9th INTERNATIONAL SYMPOSIUM HYDROGEN & ENERGY

Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materials

The 9th International Symposium “Hydrogen & Energy” serves as an information platform of the fundamental science and the frontiers of research in Sciences and Technology of Hydrogen & Energy (Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory and Modelling, Fuel Cells, Batteries, Synthetic fuels). The symposium consists of invited keynote lectures reviewing the key elements of the hydrogen cycle, i.e. the hydrogen production, hydrogen storage and hydrogen combustion and fuel cells. Furthermore, contributions on the conversion of renewable energy in general and energy carriers beside and beyond hydrogen are very welcome. The world leading experts present the current research challenges and most important results in invited and contributing talks. Early stage and experienced researchers present their newest results and the open questions on posters as well as in a one slide presentation. The conference will take place in the hotel Seeblick in Emmetten close to Lucerne in Switzerland. Emmetten is very close to the "Rütli" the origin of Switzerland (year 1291) and connected by ropeway to the skiing resort Klewenalp. The number of participants is limited to 120.

25. - 30. January 2015

Hotel SEEBLICK AG Hugenstrasse 24, CH-6376 Emmetten Telefon: +41 41 624 41 41 e-mail: [email protected] http://www.hotelseeblick.ch

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ACKNOWLEDGEMENT

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CONTENTS

Timetable

Abstracts

SUNDAY afternoon Chair: Andreas Züttel 17 17:10 - 18:00 I: Klaus LACKNER: Closing the Carbon Cycle with 17 Synthetic Fuels and Capture of Carbon Dioxide from Ambient Air

MONDAY morning Chair: Shin-Ichi ORIMO 18 09:00 - 09:20 I: Ronald GRIESSEN: H ABSORPTION IN PALLADIUM 18 NANOCUBES 09:20 - 09:40 09:40 - 10:00 T: Svetlana SYRENOVA: Indirect Plasmonic 19 Nanospectroscopy of the Hydride Formation Thermodynamics in Individual Shape-Selected Pd Nanocrystals with Different Size 10:00 - 10:20 T: Petra E. DE JONGH: The Size Dependence of the 20 hydrogen desorption and absorption for carbon-supported MgH2 particles 10:20 - 10:40 T: Sveinn OLAFSSON: RYDBERG MATTER OF 21 HYDROGEN NEW PHYSICS Coffee break 11:10 - 11:30 T: Alex LAIKHTMAN: INTERCALATION OF PLASMA- 22 ACTIVATED DEUTERIUM IN INORGANIC WS2-BASED NANOPARTICLES

11:30 - 11:50 T: Yixiao FU: SYNTHESIS OF Mg@MgF2 CORE-SHELL 23 NANOPARTICLES TO STUDY ITS THERMODYNAMICS DURING DE/HYDROGENATION 11:50 -12:10 T: Philippe MAURON: Hydrogen sorption in metal 24 intercalated fullerides 12:10 - 12:30 T: Tayfur ÖZTÜRK: Carbon Coating Mg-Ni Nanoparticles 25 via Thermal Plasma

MONDAY afternoon Chair: Michael HIRSCHER 26 14:00 - 14:20 I: Bernard DAM: A new class of photochromic materials. 26 14:20 - 14:40 14:40 - 15:00 T: Diogo M. F. DOS SANTOS: HYDROGEN EVOLUTION 27 AT NANOSTRUCTURED NI-CU FOAMS

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

15:00 - 15:20 T: Nikola BILISKOV: Synthesis and characterisation of new 28 amidoboranes 15:20 - 15:40 T: Shumin HAN: Preparation and electrochemical 29 characteristics of single-phase La-Mg-Ni-based alloys with super-stacking structures Coffee break 16:10 - 16:30 T: Yijing WANG: NBN NANOPARTICLES AS ADDITIVE 30 FOR THE HIGH DEHYDROGENATION PROPERTIES OF LITHIUM ALANATE 16:30 - 16:50 T: Gang WANG: THE PREPARATION OF MESOPOROUS 31 SILICA SUPPORTED COPPER BASED PHOTOACTIVE NANOPARTICLES WITH TUNABLE SIZES 16:50 - 17:10 T: Nicholas STADIE: The Equilibrium Dehydrogenation 32 Pressure Of Magnesium Borohydride: Revisited 17:10 - 17:30 T: Dieter PLATZEK: New concept for thermal management 33 in a hydrogen tank

MONDAY evening POSTER Chair: Min ZHU 34 20:00 - P: Georgia CHARALAMBOPOULOU: THERMAL 34 COUPLING POTENTIAL OF SOFCs WITH METAL HYDRIDE STORAGE TANKS P: Jasmina GRBOVIC NOVAKOVIC: IN SITU 35 DESOPRTION OF MgH2-TiO2 THIN FILMS P: Md Amirul ISLAM: potential of algae for bio hydrogen 37 production P: Gisela M. ARZAC: HYDROGEN-OXYGEN 38 RECOMBINATION REACTION FOR TREATMENT Of EXHAUST GASES FROM FUEL CELLS P: Aferdita PRIFTAJ VEVECKA: MECHANICAL 39 PROPERTIES OF NANOSTRUCTURED AL ALLOYS PRODUCED BY ECAP. P: Hui WANG: Mg-In-Ni Ternary Alloys for Reversible 40 Hydrogen Storage: Structure and properties P: Sathiskumar JOTHI: Hydrogen Embrittlemnet in 41 aerospace materials -21:30 P: Ales JÄGER: Preferential Sites for Hydride Formation in 42 Commercially Pure Titanium

TUESDAY morning Chair: Ronald GRIESSEN 43

09:00 - 09:20 I: Min ZHU: LiBH4 destabilization system and its hydrogen 43 storage performance 09:20 - 09:40

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09:40 - 10:00 T: Olena ZAVOROTYNSKA: IN-SITU RAMAN STUDY OF 44 H - D EXCHANGE IN γ-Mg(BH4)2 10:00 - 10:20 T: Zuleyha Ozlem KOCABAS ATAKL: Catalyzed Hydrogen 45 Sorption Mechanism in Alanates 10:20 - 10:40 T: Stefano DELEDDA: Structural changes observed during 46 the reversible hydrogenation of Mg(BH4)2 with Ni-based additives Coffee break 11:10 - 11:30 T: Baozhong LIU: IMPROVING THE HYDROGEN 47 STORAGE PERFORMACNES OF MAGNISIUM HYDIRDE BY ADDING CATALYSTS 11:30 - 11:50 T: Anna-Lisa CHAUDHARY: REACTIVE HYDRIDE 48 COMPOSITE SYSTEMS FOR BOROHYDRIDE DESTABILISATION

11:50 -12:10 T: Yigang YAN: Circumventing the formation of [B12H12]2- 49 species for reversible hydrogen Storage

12:10 - 12:30 T: Fadime HOSOGLU: Energy and CO2 at cement industry 50 for future

TUESDAY afternoon Chair: Bernard DAM 51 14:00 - 14:20 I: Hubert GIRAULT: Redox flow batteries for on demand 51 hydrogen production 14:20 - 14:40 14:40 - 15:00 T: Michael RANFT: HIGH PRESSURE ALKALINE 52 ELECTROLYSIS 15:00 - 15:20 T: Mariana SPODARYK: Gas atomised hydrogen storage 54 alloys 15:20 - 15:40 T: Ansuncion FERNANDEZ: INVESTIGATION OF A Pt 55 CONTAINING WASHCOAT ON SIC FOAM FOR HYDROGEN COMBUSTION APPLICATIONS coffee break 16:10 - 16:30 T: Ansuncion FERNANDEZ: PREPARATION OF CO AND 56 CO-B SUPPORTED CATALYSTS BY MAGNETRON SPUTTERING: A STEP FORWARD IN UNDERSTANDING THE ACTIVE PHASE AND DEACTIVATION PROCESSES IN SODIUM BOROHYDRIDE HYDROLYSIS 16:30 - 16:50 T: Domenico DE LUCA: A Matlab/Simulink design 57 procedure for Proton Exchange Membrane Fuel Cells. 16:50 - 17:10 T: Didier BLANCHARD: LIBH4: AN ELECTROLYTE FOR 58 ALL SOLID-STATE LI-ION BATTERIES

17:10 - 17:30 T: Marco HOLZER: AEROGELS FOR CO2 CAPTURE 59

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

TUESDAY evening POSTER Chair: Akihiro NAKANO 60 20:00 - P: Shunsuke KATO: In Situ X-Ray Photoelectron 60 Spectroscopy Studies On Hydrogen Storage And Catalysis P: Yali DU: Kinetics study on hydrolytic dehydrogenation of 61 alkaline sodium borohydride catalyzed by amorphous Mo- modified Co-B nanoparticles P: Martin PANHOLZER: Catalytic effects of magnesium 62 grain boundaries on H2 dissociation P: Klaus TAUBE: BOR4STORE - Development of an 64 integrated boron hydride based hydrogen tank - SOFC system P: Meiqin ZENG: The Phase Transition and Hydrogen 66 Storage Properties of Mg-Ga Alloys

P: Marco HOLZER: AEROGELS FOR CO2 CAPTURE AND 67 H2 DRIVEN DESORPTION P: Bojana PASKAS MAMULA: Nature of bonding in 68 MgH2:TM doped systems P: Andreas ZÜTTEL: FROM HYDROGEN TO SYNTHETIC 70 HYDROCARBONS -21:30 P: Marco CALIZZI: LOW TEMPERATURE CYCLING OF 71 MG-TI NANOPARTICLES FOR HYDROGEN STORAGE

WEDNESDAY morning Chair: Hubert GIRAULT 72 09:00 - 09:20 I: Nigel BRANDON: Materials Engineering for Solid Oxide 72 Fuel Cells and Electrolysers 09:20 - 09:40 09:40 - 10:00 T: Christiaan BOELSMA: A New Class of Hydrogen 73 Sensing Materials 10:00 - 10:20 T: Torben R. JENSEN: NEW MATERIALS FOR 74 HYDROGEN STORAGE 10:20 - 10:40 T: David MILSTEIN: Discovery of New Hydrogen Storage 75 Systems based on Organic Liquids Coffee break 11:10 - 11:30 T: Giovanni CINTI: RENEWABLE ELECTRICITY TO 76 METHANE: INTEGRATION OF HIGH TEMPERATURE ELECTROLYZER AND METHANATION REACTOR 11:30 - 11:50 T: Günther DOLLINGER: 3D-HYDROGEN MICROSCOPY 77 11:50 -12:10 I: Thomas Justus SCHMIDT: Introduction to the Swiss 79 Competence Center for Energy Research (SCCER) Heat & 12:10 -12:30 Electricity Storage

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

THURSDAY morning Chair: Olaf JEDICKE 80 09:00 - 09:20 I: Olaf JEDICKE: Research Infrastructures for Research 80 and development of Hydrogen and Fuel Cell Technologies 09:20 - 09:40 09:40 - 10:00 T: Elsa CALLINI: Hydrogen Storage in the framework of 82 H2FC 10:00 - 10:20 Coffee break 10:50 - 11:10 T: Pietro MORETTO: TECHNOLOGY AND SAFETY 83 ISSUES RELATED TO REFUELING OF HYDROGEN 11:10 - 11:30 CARS 11:30 - 11:50 T: TBA: 84 11:50 -12:10 12:10 -12:30

THURSDAY afternoon Chair: Olaf JEDICKE 85 14:00 - 14:20 T: Ulrich ULMER: TOWARDS HARMONIZED 85 MEASUREMENTS OF INVESTIGATIONS OF SOLID 14:20 - 14:40 HYDROGEN STORAGE MATERIALS 14:40 - 15:00 I: Vladimir MOLKOV: HYDROGEN SAFETY: THE STATE- 86 OF-THE-ART 15:00 - 15:20 15:20 - 15:40 Coffee break 16:10 - 16:30 Round Table Discussion: : Round Table Discussion 16:30 - 16:50 16:50 - 17:10 17:10 - 17:30

FRIDAY morning Chair: Bjørn HAUBACK 89 09:00 - 09:20 I: Björn C HAUBACK: Structural studies of complex 89 hydrides 09:20 - 09:40 09:40 - 10:00 I: Shin-ichi ORIMO: Cool Hydrides, Again ! 90 10:00 - 10:20 10:20 - 10:40 T: Jjanmei HUANG: ZIRCONIUM BOROHYDRIDE 91 OCTAAMMONIATE Zr(BH4)4-8NH3: SYNTHESIS, STRUCTURE AND DEHYDROGENATION ENHANCEMENT Coffee break

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

11:10 - 11:30 I: Akihiro NAKANO: EXPERIMENTAL STUDY OF A 92 METAL HYDRIDE TANK WITH DOUBLE COIL TYPE 11:30 - 11:50 HEAT EXCHANGER BELOW 1.0 MPa (G) OPERATION 11:50 -12:10 I: Michael HIRSCHER: PORSPECTS FOR POROUS 93 MATERIALS IN HYDROGEN STORAGE AND GAS 12:10 -12:30 SEPARATION

SCIENCE OF HYDROGEN & ENERGY AWARD 95

List of Participants 117

Information 127

Notes 137

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devices like fuel cells would extend the efficiency of CLOSING THE CARBON CYCLE synthetic liquid fuels even more. This leads to WITH SNYTHETIC FUELS AND scenarios in which most energy resources would initially produce electricity often without regard to CAPTURE OF CARBON DIOXIDE instant demand profiles, with excess power being FROM AMBIENT AIR converted to liquid fuels. Electricity and synthetic fuels would then be the main energy carriers, with Klaus S. Lackner advanced electrochemical technologies converting

one into the other. CO2 produced in synthetic fuel Arizona State University, Center for Negative Carbon consumption is recovered by air capture and reused in Emissions making fresh fuels. The development of energy systems is path dependent. Because these paths start in the past, For these scenarios to be relevant, air capture as well current trajectories already constrain future scenarios. as energy conversion must become economically The latest IPCC report suggests that the world has affordable. Today, it is the high cost of input electricity waited too long, and that avoiding dangerous climate that is most limiting in the development of such a conditions will require net negative carbon emissions scenario. For air capture, the low concentration of for a large part of the next fifty years. Reversing 100 carbon dioxide in air makes it is difficult to repurpose ppm of past emissions would require the development existing industrial gas separation technologies. of technologies to remove carbon dioxide from the air However, novel technologies have the potential for affordable implementations. Our own approach uses and about 1500 Gt of CO2 storage capacity, which exceeds the emissions of the 20th century. Assuming humidity changes to allow sorption on a sorbent in the that humanity succeeds in solving this existential dry state and release of carbon dioxide in the wet challenge, one may conclude that air capture state. The process is fast, reversible and efficient in technology will be developed and carbon storage terms of cost and energy. It is much simpler, and capacity will be a scarce commodity, reserved for requires far less material than a different air-capture storing carbon recovered long after it has been process, which based on a study by the American emitted. This eliminates fossil carbon as a viable Physical Society would cost $600 per ton of CO2 in a source of energy. Carbon free energy sources first-of-a-kind implementation. Using cost reductions including solar and nuclear energy will therefore be at experienced in windmills and solar panels as a guide, a premium. $600 per ton seems not very high for an initial cost. Solar energy prices dropped 100 fold and wind energy It is here that air capture could have another important costs roughly 40 fold since the 1960s. role. The transport and storage of energy can take advantage of carbon-based, synthetic fuels, as long In summary, air capture, which will be driven by the as air capture technology can recover their carbon need to remove carbon from the atmosphere, can also emissions. Liquid, carbon-based fuels have the support the development of non-fossil energy advantage of a long history of use, they are also resources by connecting them to liquid synthetic fuels genuinely attractive because they are easily handled, which are the most efficient way of carrying large transported and stored. Advanced energy conversion amounts of energy on board of a car, a plane or a ship.

Klaus S. Lackner, [email protected], +1 (480) 727-2499 Director, Center for Negative Carbon Emissions Professor, School of Sustainable Engineering and Built Environment, Fulton Schools of Engineering, Arizona State University

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HYDROGEN ABSORPTION IN PALLADIUM NANOCUBES

R. Griessen1 and N. Strohfeldt2 1 Faculty of Sciences, Division of Physics and Astronomy, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands 2 4th Physics Institute and Research Center SCoPE, University of Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart, Germany

Abstract: The recent experimental data on ab- and desorption of hydrogen in Pd nanocubes obtained by Darbhan et al [1], Baldi et al [2] and Guanggin Li et al [3] are well reproduced by a mean-field model that involves bulk and subsurface sites, elastic coupling between outer shell and bulk, elastic and electronic effective H-H interaction and disorder. The model can also be used for the interpretation of data on other nm sized particles.

Introduction Several articles on the interaction of H with Pd [1] and Baldi et al. [2] is obtained with an enthalpy of nanocubes and nanoparticles have recently been solution for subsurface sites of -20 kJ/molH, a shell published [1-4]. Each article provides detailed data on thickness of » 1 nm and a weak clamping effect. In specific aspects of H in nanoparticles and proposes ad particular the p-c isotherms and critical temperatures of hoc mechanisms for their interpretation. In this work we ensembles of Pd nanocubes [1], the size dependence of show that: i) on the basis of a scaling law the hysteresis the plateau pressures of single nanocubes [2] and the is consistent with a coherent interface model and ii) all increased concentration range of the dilute -phase are essential features of the literature data are quantitatively well reproduced. reproduced by a mean field model. The data in [3] can only be reproduced if the surrounding MOF extracts electrons from the underlying Pd and The scaling law reduces the shell thickness to zero (i.e. there are no Assuming that the upper spinodal pressure is equal to subsurface sites). the H absorption plateau, all the nanocube data collapse together when plotted as a function of Tc /T, the ratio of critical temperature and measurement temperature. The Conclusions clear difference with Pd bulk data shows that incoherent The shape of the model p-c isotherms confirms that in interfaces are not occurring during H loading. nanocubes H loading occurs coherently and unloading partially incoherently. The huge difference between bare The model Pd nanoparticles and HKUST-1 coated Pd in [3] is The basic assumption of the model is that H can be probably due to kinetic effects. Our model provides also a accommodated at subsurface sites and inner sites. As valuable framework for the quantitative interpretation of the enthalpy of solutions of the subsurface sites is more data on the absorption of H in few nm particles for which negative than that of the inner sites, the surface H defects, disorder and surface tension effects are concentration is larger than inside the nanoparticle. This essential [4-6]. leads to H dependent internal stresses and, References consequently, to H dependent enthalpies in addition to [1] Bardhan et al., Nature Materials 12 (2013) 905 the usual elastic and electronic effective H-H interaction [2] Baldi et al., Nature Materials (2014) which are assumed to be the same as in bulk Pd. In [3] Guangqin Li et al, Nature Materials13 (2014) 802 addition, the model takes also surface energy and [4] Wadell et al., Chemical Physics Letters 603 (2014) clamping contributions to the enthalpy of hydride 75–81 and C. Langhammer, private communication. formation. [5] Sachs et al., Phys. Rev. B64 (2001) 075408 Results [6] Salomons et al., Europhys. Lett. 5 (1988) 449 Agreement with the experimental data of Bardhan et al.

Ronald Griessen (1945) studied physics at the Eidgenössische Technische Hochschule in Zürich. After his PhD at the same university he went to the McLennan Laboratory of the University of Toronto. In 1976 he joined the VU university in Amsterdam as head of the Condensed Matter Physics department and worked on superconductivity, metal-hydrides and switchable mirrors. From 2005 till 2010 he was Chairman of FOM (Fundamental Research of Matter) and Chairman of the Physics Division of NWO (Netherlands Organisation for Scientific Research). He is since 2010 a lecturer at the Amsterdam University College and presently guest professor at the University of Stuttgart where he works on switchable plasmonic nanoantennas in the group of Harald Giessen. R. Griessen

Corresponding author: Griessen, [email protected], Tel.0031 35 656 1451

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INDIRECT PLASMONIC NANOSPECTROSCOPY OF THE HYDRIDE FORMATION THERMODYNAMICS IN INDIVIDUAL SHAPE-SELECTED PD NANOCRYSTALS WITH DIFFERENT SIZE Svetlana Syrenova†, Tina A. Gschneidtner‡, Yuri A. Diaz Fernandez‡, Giammarco Nalin‡, Dominika Świtlik§, Fredrik Westerlund‡, Tomasz J. Antosiewicz†§, Kasper Moth-Poulsen‡ and Christoph Langhammer†

† Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden ‡ Department of Chemical and Biological Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden § Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warsaw, Poland

Abstract We study hydride formation thermodynamics in individual Pd nanocrystals with different size (from 45 to 20 nm) and shape (cube, rod and octahedron). Nanospectroscopic readout of the hydride formation process is achieved through the use of a plasmonic Au nanoantenna adjacent to the Pd particle of interest. These Au-Pd heterodimers are made by electrostatic self-assembly of the consitituents1.

Size and shape of functional nanoparticles determine not a b only their physicochemical properties but also their technological relevance in a wide range of applications like, e.g., heterogeneous catalysis, where they may serve to significantly increase reaction efficiency and selectivity. Other examples are information and energy storage 100 nm technologies where phase transitions are of particular importance, and where controlling particle size and c shape offers unique prospects to manipulate and control the latter. Experimental investigations of such effects are traditionally conducted on nanoparticle ensembles and are thus plagued by inhomogeneous sample material 100 nm averaging effects. These can be entirely eliminated in individual nanoparticle experiments. Here we present the Figure 1. a, An artists view on the indirect plasmonic first complete and comprehensive experimental study of nanospectroscopy arrangement used to probe an the hydride formation thermodynamics in individual individual Pd nanocube by an attached spherical Au single-crystalline Pd nanoparticles of different size and plasmonic antenna. As H2 molecules (red) dissociate and shape, using non-invasive plasmonic nanospectroscopy. are absorbed into the Pd cube, the process can be We find consistent size- and shape-independent detected by the plasmonic Au particle via its near field, thermodynamics, in agreement with the classic and read-off at the single particle level owing to its large understanding of the first order phase transition for scattering cross-section at visible frequencies. b & c, hydride formation in metals. Our results provide thus a Side-view and top-view SEM images of an Au-Pd cube generic experimental blueprint for in situ studies of and Au-Pd octahedron arrangements, respectively. individual nanoparticles that can provide unprecedented References insight into correlations between nanoparticle, size, shape, and the targeted functionality. [1] Gschneidtner, T. A.; Fernandez, Y. A. D.; Syrenova, S.; Westerlund, F.; Langhammer, C.; Moth-Poulsen, K. Langmuir 2014, 30, (11), 3041-3050

August 2012 – current: Ph.D. student at the school of Materials Science, Department of Applied Physics, Chalmers University of Technology, Sweden June 2012: M.Sc. in Nanoscience and Nanotechnology, Department of Applied Physics, Chalmers University of Technology, Sweden June 2008: B.Sc. in Nanotechnology, Department of Radio technology, electronics and physics, NSTU Novosibirsk, Russia Svetlana Syrenova

Corresponding author: Svetlana Syrenova, [email protected], +46 (0)31-772 3007.

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THE SIZE DEPENDENCE OF THE HYDROGEN DESORPTION AND ABSORPTION FOR CARBON-SUPPORTED MGH2 PARTICLES Y.S. Au1, Suwarno1, F. Cuevas2, C. Zlotea2, P.E. de Jongh1

1Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands 2ICMPE/CNRS, UPEC UMR 7182, 2-8 rue Henri Dunant, Thiais, France

Abstract: Due to the natural abundance and high hydrogen content, magnesium hydride-based materials are widely studied as potential hydrogen storage materials. It is known that decreasing the particle size allows faster kinetics, and better reversibility of the hydrogen sorption. However, it has not been clarified before which steps are exactly rate limiting under given conditions. Based on series of measurements on carbon-supported MgH2 nanoparticles with well defined sizes (<20 nm as well as um sized) studied while applying different driving forces for hydrogenation, we discuss the origin of the size-dependent kinetics.

Introduction

Nanostructured metal hydrides, for instance MgH2 based, are of potential interest for solid state hydrogen storage, but also for other applications such as rechargeable batteries and hydrogenation catalysts. Our group was the first to report a strategy to prepare carbon supported nanoparticles by simply mixing MgH2 with a porous carbon support, and heating the mixture to above the melting point of magnesium [1]. It is known that particle size can have a strong impact on hydrogen sorption properties [2,3], but more detailed insight has been hampered by the great challenge to prepare small and well-defined light metal hydride particles. In this contribution we discuss recent progress in the preparation of carbon-supported MgH2 nanoparticles with tunable particle sizes, and the size-dependent rd Figure: Size-dependent hydrogen sorption (3 cycle) at hydrogenation and dehydrogenation kinetics. o 250 C and 18 bar H2 pressure Results While for micrometers-sized particles indeed solid- We found vapor-phase transport (at temperatures state diffusion can be rate limiting, this is not the case for (b) (c) below the melting point of Mg) to be able to transport Mg the <20 nm particles. The difference in hydrogen kinetics from larger crystallites to small nanoparticles being between nanometers and micrometers sized MgH2 formed inside the carbon support pores at higher particles were for the first time corroborated by intrinsic loadings than previously possible, and I will discuss hydrogen dynamics data obtained by solid state 1 H possible origins of this counter-intuitive effect. Fast and NMR. [3]. For <20 nm particles both surface-limited reversible hydrogen sorption was maintained during processes as well as nucleation barriers can play an cycling of these supported particles material, showing the important role in limiting the sorption kinetics, depending ability of the carbon support to stabilize the small on the exact experimental conditions. nanoparticles. We were able to vary in a controlled [1] P.E. de Jongh et al. Chem Mater. 19 (2007), 6052. manner the MgH2 particle size between 6 and 20 nm by [2] P.E. de Jongh, C. Zlotea et al, MRS Bull,. 38 (2013), adjusting the support porosity, allowing us to measure 488. the size-dependent hydrogen absorption and desorption [3] C. Zlotea et al. Farad. Discuss. 151 (2011), 117. rates, and attain information on the rate limiting factors as [4] Y.S. Au, et al. Adv. Func. Mater. 24 (2014), 3604. a function of size and experimental conditions.

Petra de Jongh received a PhD in photoelectrochemistry in 1999, and after 5 years working at Philips Research, joined Utrecht Utrecht University in 2004. She is currently chair of Inorganic Nanomaterials at the Debye Institute for Nanomaterials Science, working on nanostructured materials for applications in catalysis and energy storage and conversion.

Petra de Jongh

Corresponding author: Petra de Jongh, [email protected], +31 30 253 1747

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RYDBERG MATTER OF HYDROGEN, NEW PHYSICS Sveinn Ólafsson

Science Institute University of Iceland Dunhaga 3 107 Reykjavík Iceland

Rydberg matter of H or D is a condensed phase of Rydberg H or D atoms forming clusters with large atomic distances 2 d=2.9aon . The Rydberg atoms can be formed inside a catalytic material such as Fe2O3:K. Rydberg matter can also be described as frozen plasma state of plasma. The formed Rydberg matter has been shown to be able to transform to new ultra dense state of matter HN(0) or DN(0) d=2.3pm where N stands for number of atoms in the ultra-dense cluster matter. This new ultra dense state can be named Dirac matter since relativistic quantum theory is the only quantum theory that can have stable quantum solutions for the hydrogen atom on this length or density scale. The ultra-dense DN(0) Dirac matter has been shown to under low energy Laser pulsing to induce D+D fusion [1,2,3]. In this talk the state of Rydberg matter and ultra dense hydrogen is reviewed and some new experimental work is presented. A possible link for ultra dense hydrogen being the underlying reason for the reported excess heat in cold fusion experiments for the last 25 years will be discussed.

Rydberg Matter and ultra-dense hydrogen Ultra dense hydrogen was reported by Leif Holmlid first 2008. Since then he has in number of 10 to 15 peer reviewed publications he has reported on the properties of this exotic state of matter. His work has been largely unnoticed due to the revolutionary character of his work and also since no one has tried for same reason to replicate his work. The author presenting this contribution has visited his lab and in a sense replicated small portion of his work using his own setup. In this talk a short summary will be given about his results. Experimental setup is presented and interpretation of some data is The Rydberg matter is condensed on top of surface of given. Laser induced fusion [2-3] will also be described ultra thin Pt film grown on MgO. and discussed. In the end experimental link to coldfusion References experiments in electrochemistry and gas phase will be giving by presenting simple Gamov based calculation [1] Excitation levels in ultra-dense hydrogen p(−1) and d(−1) clusters: Structure of spin-based Rydberg that indicate that ultra dense DN(0) d=2.3pm matter will fuse with rate of 10-5s-1. This can be converted to energy Matter. Leif Holmlid. International Journal of Mass Spectrometry 352 (2013) 1–8 production rate of 100kw per mole of DN(0). Probing the formation of Rydberg matter [2] Laser-induced fusion in ultra-dense deuterium D(1): Optimizing MeV particle emission by carrier material Properties of ultra dense Dirac matter has so far only selection. Leif Holmlid. Nuclear Instruments and been studied by laser induced breakup, time of flight and Methods in Physics Research B 296 (2013) 66–71 radioactivity measurements. Here is a measurement setup designed to interface electrically to the ultra-dense [3] Electron, ion and neutral particle emission from laser- phase in order to see dynamics of formation of such induced processes: nuclear fusion in ultra-dense phase as function of gas pressure and temperature. The deuterium D(0) Leif Holmlid*, Johan Boman and first conductivity measurements of ultra matter H and D Sveinn Ólafsson To be Submitted des. 2014 phases will be reported and discussed.

Research on growth of thin films by sputtering and physics of hydrogen in metals. Growth of nano- structured materials with STM. Surface science work at MaxLab Laboratory Lund Sweden and defects studies of semiconductors at ISOLDE lab CERN Switzerland: PhD 1995 Uppsala University Sweden. Post Doc 1995-1998 IFM Linköping University Sweden. Senior research scientist 1998- 2006. Research Professor since 2006 at Science Institute University of Iceland Teaching at University of Iceland since 1998. Supervising 6 PhD students and a number of masters students. Chairman of the Icelandic Physical Society 2008-2013. Co-chairing MH 2008 conference in Sveinn Ólafsson Reykjavik Iceland.

University of Iceland, emai: [email protected] hompage: http://uni.hi.is/sveinol/

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INTERCALATION OF PLASMA-ACTIVATED DEUTERIUM IN INORGANIC WS2-BASED NANOPARTICLES Alex Laikhtman1, Alla Zak1, Amnon Fruchtman1, Gennady Makrinich1, Marius Enachescu2, and Meltem Sezen3

1Sciences Department, Holon Institute of Technology (HIT), 52 Golomb St., Holon 5810201, Israel

2Center for Surface Science and Nanotechnology, Politehnica University of Bucharest, Splaiul Independentei 313, 060042 Bucharest, Romania

3Nanotechnology Research and Application Center, Sabanci University, Orhanli, Tuzla 34956, Istanbul, Turkey

The use of hydrogen in a distributed system requires an effective, safe, and stable storage solution. Nanostructured materials such as inorganic nanotubes (INT) and inorganic fullerene-like (IF) nanoparticles are appealing because of their extremely high surface area and layered structure, where potentially many sites can either chemi- or physisorb hydrogen. A newly developed technology enables the synthesis and production of pure IF and INT phases of WS2 in commercial quantities, beyond tens of kg. This is why we initiated a project to test WS2 INT and IF as possible candidates for hydrogen storage. These materials may allow hydrogen to be either chemi- or physisorbed inside their crystalline structure, inside hollow core of fullerenes/nanotubes or in the open interstitial pore spaces between the nanoparticles or nanotubes, on the surface or in the open interstitial pore spaces of nanotubes’ powder mesh. Exposure to high pressure molecular hydrogen at 77-720 K was found to have measurable but limited absorption rate - up to 0.36 wt.%. Whereas treatment of the WS2-INT and WS2-IF by hydrogen and deuterium activated by microwave (MW) or radiofrequency (RF) plasma resulted in much higher value of absorbed hydrogen of ~ 0.5-1 wt.% so far. These results could be attributed to more effective interaction of activated vs. molecular hydrogen with nanoparticles substrate surface due to the strong either chemisorption of MW plasma activated hydrogen compared to weaker physisorption of molecular hydrogen, or to higher energy and momentum of the hydrogen molecules in the RF plasma. In addition, plasma originated ions and electrons interact with the nanoparticles and then can produce new or modify existing defects and pores, and so contribute to hydrogen diffusion and its stability following exposure to ambient atmosphere.

To determine the chemical nature of so absorbed deuterium, micro-Raman measurements were performed. For the RF plasma deuterated samples, a small peak centered at ~ 2970 cm-1 was observed. This feature was previously attributed to the D–D stretching mode, and, therefore, its appearance in our spectra proves that deuterium is present in the -1 molecular form, as D2. To finally prove that the Raman feature measured at 2970 cm is indeed due to D2, both IF and INT RF plasma deuterated samples were heated in vacuum to 450 ºC for 90 min. The intensity of the above Raman peak decreased to nearly zero supporting our assumptions.

TEM investigation of the deuterated WS2 nanoparticles showed some increase of the interlayer distance as compared to reference materials along with notable changes in the defects distribution.

To investigate the possible effect of ions on both types of the target materials (IF and INT of WS2), they were exposed to FIB of Ga+ ions for different doses. Following ion bombardments, the samples were analyzed by SEM, EDS, and micro- Raman. The primary effect was in the drastic change of the near surface structure and morphology of the bombarded region. From SEM images, melting or sublimation with subsequent recrystallization of the nanoparticles takes place. This is confirmed by micro-Raman measurements showing degradation of the crystalline perfection by decrease in the intensities of the characteristic peaks of WS2. However, no contamination, oxidation, or decomposition of the substrate materials was detected after FIB treatments. These results can explain why physisorbed hydrogen is stable at the room temperature in the plasma-treated IF and INT, indicating that such “melting” could happen then resulting in closing some of the pores through which hydrogen atoms diffuse inside these layered nanoparticles.

PhD in interaction of low energy electrons, photons and ions with diamond surfaces (Technion, Israel), 2003. Positions held: 2003-2004 Postdoctoral scientist, the Laboratory of Molecular Photophysics, Orsay (France) 2004-2007 Research Scientist, the lab. of materials for space environment, Soreq Nuclear Research Center (Israel) From 2007: senior lecturer in physics and head of the Microscopy Labs, Holon Institute of Alex Laikhtman Technology (HIT) (Israel)

Corresponding author: Alex Laikhtman, [email protected], Tel. +97235026830

22 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

SYNTHESIS OF MG@MGF2 CORE-SHELL NANOPARTICLES TO STUDY ITS THERMODYNAMICS DURING DE/HYDROGENATION Y. X. Fu a,b, , H. Wang a,b, and M. Zhu a,b a School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China b Key Laboratory of Advanced Energy Storage Materials of Guangdong Province Abstract: This work aims to create adequate core-shell structure to study the effect of elastic constrain has on thermodynamics of de/hydrogenation. Mg@ MgF 2 core-shell structure has been chosen and synthesized through surface fluorination of Mg nanoparticle by triethylamine trihydrofluoride (Et3N-3HF). XRD result shows Mg residual after reacting with excessive Et3N-3HF for 12hrs. SEM characterization shows MgF2 layer has a thickness of no more than 20nm. Introduction Theoretic calculation indicates that elastic constrain could XRD result shows coexistence of Mg and MgF2, after bring certain effect on the thermodynamics of Mg fluorination in excessive Et3N-3HF for 12hrs. Broad de/hydrogenation [1,2]. However, there is little adequate peaks of MgF2 indicate its nano-crystal structure. experimental data to support this theory. There are mainly two reasons for this shortage: 1). nano-sized Mg is highly vulnerable to oxygen and water, making it difficult to synthesize and create good connection with other constraining substances; 2). Well-connection brought by alloying with other metal elements in vacuum bring controversies about whether the effect shown on thermodynamics is introduced by elastic constrain or the intermediate alloy compound [3]. Surface fluorination of Mg nanoparticle is able to form Mg@ MgF2 core-shell structure with a passive shell layer of none absorption of H2 and well connection to the core, moreover, with less rigorous oxygen/water - free Figure 1 XRD pattern of surface fluorinated Mg environmental requirement and without the concerning of nanoparticles in excessive Et N-3HF. total consumption of Mg core during formation progress. 3 This method is able to form a compact MgF 2 shell of no References more than 20nm, which could affiliate the investigation of the effect elastic constrain has on thermodynamics. [1] A. Baldi et al., Phys. Rev. Lett, 2009, 102, 226102 Results [2] Pasquini L et al., Int. J. Hydrogen Energy, 2014; 39(5): 2115-23. Mg nanoparticle is synthesized through following reaction in THF: [3] C.J. Chung et al., Phys. Rev. Lett, 2012.108.106102

2K+MgCl2→Mg+2KCl

Before fluorination, by-product KCl is majorly washed away by DMF to minimize the formation of KMgF3. However, it greatly reduced the productivity of Mg nanoparticles by forming Mg-DMF colloid, but on the other hand, it proves the as-synthesized Mg particle is very small.

Yixiao Fu was born on 29 June 1990 in Jiangxi, China. 2011 Bachelor in Department of Materials, South China University of Technology (SCUT), Guangzhou, China. Major in Metallic Materials Science and Engineering. 2014 M.S degree at the Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, SCUT. His research is focused on reversible hydrogen storage of Mg based core-shell structure and compositing structure.

Yixiao Fu

Corresponding author: Min Zhu, E-mail: [email protected], Tel.: +86-20-39380578.

23 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

HYDROGEN SORPTION IN METAL INTERCALATED FULLERIDES Philippe Mauron1, Mattia Gaboardi2, Arndt Remhof1, Mauro Riccó2, Andreas Züttel1,3

1Empa. Swiss Federal Laboratories for Materials Science and Technology, Division ‘‘Hydrogen and Energy’’, Überlandstrasse 129, 8600 Dübendorf, Switzerland 2Dipartimento di Fisica e Scienze della Terra, Via G. P. Usberti 7/a, 43124 Parma, Italy 3Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des Sciences et Ingénierie Chimiques, 1015 Lausanne, Switzerland

Abstract For different hydrogenated metal intercalated fullerides (Na10C60, Li12C60 and Li28C60) the activation energies for hydrogen desorption were determined by DSC. The decrease of activation energy as function of the extent of conversion can be explained by an increasing charge transfer to the C60H36+y cage during desorption. Na intercalation leads to a significant thermodynamic destabilization for hydrogen desorption compared to pure hydrogenated C60.

Introduction (Li12C60Hx) and 250 °C (Li28C60Hx) compared to > 400°C for pure C H . Metal intercalated fullerides represent a new class of 60 36 compounds for reversible hydrogen storage, in which up to 3.5 [1] (Na10C60) and 5.1 [2] (Li12C60) can be stored. By intercalating alkali or alkali earth metals in to fullerene, the so called fullerides are formed, where charges from the metal atoms are transferred to the fullerene cages. Experimental

Lithium fullerides (Li12C60, Li28C60) were synthesized by ball milling a stoichiometric mixture of pure C60 with granular lithium in an inert argon atmosphere for 15 min. in a planetary ball mill. After the milling the sample was heated to 270 °C for 36h. Sodium fulleride (Na10C60) was Activation energy as function of the extend of conversion for synthesized by mixing sodium azide (NaN3) with C60 and Na10C60H36+y dehydrogenation. long annealing at 450 °C. The samples were hydro- References genated under the following conditions Na10C60: 225 °C / [1] Ph. Mauron, A. Remhof, A. Bliersbach, A. Borgschulte, A. 185 bar / 50 h, Li12C60: 350 °C / 180 bar / 50 h and Li C : 350 °C / 170 bar. Züttel, D. Sheptyakov, M. Gaboardi, M. Choucair, D. 28 60 Pontiroli, M. Aramini, A. Goerreri, M. Riccò, Reversible Results hydrogen absorption in sodium intercalated fullerenes. Int J Hydrogen Energ 37 (2012) 14307. The activation energies for hydrogen desorption are the highest for low α and decrease for increasing α, between [2] Ph. Mauron, M. Gaboardi, A. Remhof, A. Bliersbach, D. Sheptyakov, M. Aramini, G. Vlahopoulou, F. Giglio, D. around 200-145 kJ/mol (see figure) and 245-175 kJ/mol Pontiroli, M. Riccò, A. Züttel, Hydrogen Sorption in Li12C60. for the Na and Li compounds, respectively. Phys Chem C 2013, 117, 22598-602. Dehydrogenation enthalpies of 52 (Na10C60), 66 (Li12C60) and 69 kJ/mol H (Li C ) were determined. These [3] Ph. Mauron, M. Gaboardi, D. Pontiroli, A. Remhof, M. Riccò, 2 28 60 A. Züttel, Hydrogen Desorption Kinetics in Metal Intercalated values are lower compared to literature values for Fullerides. accepted in Phys Chem C 2014. desorption of pure C60H36 (74 kJ/mol H2). The onsets of hydrogen desorption are 185 °C (Na10C60Hx), 260 °C

1973 born 6. October in Fribourg, Switzerland. 1999 Diploma in experimental physics (solid state physics), University of Fribourg, Switzerland. 2003 PhD at University of Fribourg, Switzerland. 2005 Postdoc at Vrije Universiteit Amsterdam, The Netherlands. 2007 Project leader at Empa. Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland Philippe Mauron Corresponding author: [email protected], Tel. +41 58 765 4099

24 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

CARBON COATING OF Mg-Ni NANOPARTICLES VIA THERMAL PLASMA

Burak Aktekin and Tayfur Öztürk

Department of Metallurgical and Materials Engineering, Middle East Technical University, Ankara

There is a considerable interest in carbon coating of metal hydrides for energy storage purposes. This might result in improved thermal conductivity of metal hydrides, an aspect which is of considerable interest in Mg based hydrogen storage tanks. In batteries, such coatings might improve the electrical conductivity, thus obviating the need for the special additives used for such purposes in the electrode make-up. In the current work, following a successful synthesis of Mg2Ni and Mg nanoparticles using thermal plasma [1], we investigate whether in-situ encapsulation of such particles with carbonaceous material would be possible with the same method.

Initial experiments were carried out with nickel. This has A separate experiment was carried out in which the yielded carbon encapsulated nanoparticles, where Ni feeding rate of Mg to that of methane varied over a wide particles of average 56 nm in size was wrapped around interval. It was noted that with the feeding rates ratio by 3-9 graphitic layers, Fig.1(a). An important observation (mass) greater than CH4: Mg =1:7 was sufficient to make was that the size of particles obtained in this way was the powders resistant to oxidation. When the feeding rate significantly less than those obtained with direct of methane was lower this ratio the powders burned synthesis, i.e. without co-feeding of methane, implying intensely when exposed to air. that methane could be used as an agent of size reduction.

(a) (b) (c) Fig.1 a) Ni nanoparticles encapsulated by 5-8 graphitic layers, b) Mg particle wrapped around by graphitic layers in a carbonecous matrix. c) Mg nanoparticles of 5-6 nm in size embedded in carbonaceous matrix Mg-C powders which was resistant to oxidation was exposed up to 30 bar of hydrogen in a Sievert instrument. Attempts to wrap Mg particles in the same manner as Unfortunately the powders did not react with hydrogen that of Ni given in Fig.1(a) was not as successful. It was implying that the carbonaceous material wrapping the Mg true that occasionally some particles could be found nanoparticles was impermeable to hydrogen also. To where Mg could be wrapped around by carbonaceous improve the reactivity of powders they were milled for a material. But mostly the resulting material was in the form short duration. Powders in milled state did react with of carbonaceous matrix with embedded Mg particles. hydrogen. This was particularly the case when the methane feeding rate was high. Fig. 1(b) and (c) are examples of such structures where Mg particles of 5-6 nm in size are [1] B Aktekin, G Çakmak and T Öztürk, Induction thermal embedded in a graphitic matrix. plasma synthesis of Mg2Ni nanoparticles. Int. J of Hydrogen Energy, 39, 2014,9859.

Prof. Tayfur Ozturk, Middle East Technical University, Ankara has obtained his degrees; B.Sc in Istanbul Technical Univeristy and Ph.D from Cambridge University in 1978. His work concentrates on the processing methods that would yield nanostructured materials. This covers solid state processing; the classical milling as well as novel techniques such as direct synthesis of fine-particle compounds via electroreduction of mixed oxides. Recent studies concentrate in gas-phase synthesis covering thin films as well as nanopowders produced via thermal plasma. Tayfur Ozturk

Corresponding author: Tayfur Ozturk, [email protected], +90 312 210 5935.

25 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

A NEW CLASS OF HYDROGEN SENSING MATERIALS Bernard Dam, Yingying Luo, Nicky Law, Herman Schreuders

Department of Chemical Engineering - Materials for Energy Conversion and Storage, Faculty of Applied Science, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

Abstract –Recently a photochromic effect was discovered in YOyHx. Here we investigate the relation between the excitation and the bandgap. We find that excitation over the band gap is essential for the effect to occur.

Photochromism The phenomenon of photochromism – the reversible The application change of colour on exposure to light – has been known Since we can carefully tune the bandgap just beyond the for a long time. Recently a very special photochromic visible spectrum, this material allows us to design a effect was discovered in YOyHx [1]. This ternary oxy- photochromic material, which is operative behind a glass hydride is unique, since it allows for a photochromic window. Photochromic sunglasses could then be used in effect induced by light in the visible part of the optical cars. More importantly, this development allows the spectrum. Moreover, the photochromic darkening is design of photochromic window panes, where the colourless, resulting in a uniform darkening of the visible photochromic material is located at the inside of a double transparency. The photo-induced changes of optical glazing structure. For such practical applications, both properties are accompanied by persistent the contrast and the speed of the transition will need to photoconductivity. The physics of both effects has not yet be improved. been elucidated. The uniform darkening suggests an electronic phase segregation of metallic areas in a dielectric matrix, possibly induced by mobile vacancies. This would open a new perspective on the design of photochromic materials.

The excitation We are able to vary the bandgap between 2.3 and 3.1 eV by modifying the reactive gas composition of the sputter gas. We obtain the optical bandgap by extrapolating the square root of the optical absorption as a function the photon energy to zero. We find a straight line, suggesting an direct bandgap transition. After illumination with a white light source, the absorption increases for photon energies smaller than the bandgap only (fig.1). Comparing the photochromic darkening of these films, References we find that the photochromic effect decreases for larger [1] T.Mongstad, Ch. Platzer-Bjorkman, Jan Petter band gaps. By using optical filters we established that Maehlen, L. P.A. Mooij, Y.Pivak, B. Dam, E.S. when the photon energy is too small to excite an electron Marstein, B. C. Hauback, S. Zh. Karazhanov, A new hole pair over the semiconductor gap, no photochromism thin film photochromic material: Oxygen-containing is observed. yttrium hydride, Solar Energy Materials & Solar Cells 95 (2011) 3596–3599

1982 – 1986: PhD, Radboud University Nijmegen; 1986 – 1992: Philips Research Laboratories, Eindhoven. 1992 – 2009: Condensed Matter Physics, VU University, Amsterdam 2009 – Present: Head of the Materials for Energy Conversion and Storage group, Delft University of Technology.

B. Dam

Corresponding author: Bernard Dam, [email protected]

26 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

HYDROGEN EVOLUTION AT NANOSTRUCTURED NI-CU FOAMS D.M.F. Santos*, S. Eugénio, D.S.P. Cardoso, C.A.C. Sequeira, M.F. Montemor

Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal

Three-dimensional (3D) nanostructured nickel-copper (Ni-Cu) foams have been prepared by electrodeposition using a dynamic hydrogen template. These 3D materials were tested as electrodes for the hydrogen evolution reaction (HER) in 8 M KOH solutions for possible application as cathodes for alkaline water electrolysis. Their stability and activity for HER was evaluated by linear scan voltammetry (LSV) and main reaction parameters were calculated.

Introduction Results 3D nanostructured metallic foams (NMFs) are structures SEM analysis of the two Ni-Cu metallic foams revealed a of interconnected pores with nanoramified walls formed uniform morphology, with a 3D structure presenting of metallic particles, dendrites or other morphologies that nearly-circular micrometric pores with non-compact walls combine good electric and thermal conductivity with a formed of dendrites. The foams 3D structure was high surface area and low density. Electrodeposition favoured with increasing deposition time, due to increase provides a one-step, low-cost method for the fabrication of foam thickness and mass. EDS showed no significant of NMFs by taking advantage of the dynamic template differences on the foams chemical composition. formed by hydrogen bubbling that occurs simultaneously electrodeposition chemical composition to metal deposition [1,2]. In this way, self-supported conditions / at. % nanoramified foam structures with properly tailored sample -2 architectures can be designed, enhancing mass and j / A cm t / s Ni Cu charge transfer processes. Application of 3D materials for NiCu-90 3 90 52.9 47.1 HER was previously reported to be advantageous. NiCu-180 3 180 52.7 47.3 Additionally, among low-cost, non-noble metals, Ni and Ni-alloys have been extensively studied for HER [3]. This The analysis of the polarization curves enabled the work proposes the use of 3D Ni-Cu NMFs, formed by determination of relevant kinetic parameters, namely electrodeposition procedures, as cathodes for the HER. Tafel slopes, charge transfer coefficients, exchange current densities, and activation energies allowing a Experimental direct comparison of the performance of the foam Ni-Cu foams were prepared by electrodeposition on AISI electrodes for HER. 304 stainless steel from an electrolyte solution containing The results suggest that these 3D electrodes can attain the two ions, using a two-electrode cell connected to a high HER efficiencies while using low metal amounts. power source. Electrodeposition was carried out in Their low cost, one-step fabrication method presents galvanostatic mode by applying a current density of 3 A several advantages over conventional procedures, cm-2 for 90s (NiCu-90) or 180s (NiCu-180). Working making them an alternative to typical catalytic materials. electrodes were of 1 cm2 geometric surface area. References Electrochemical measurements were performed using a PAR 273A potentiostat controlled by PowerSuite [1] H.C. Shin, J. Dong, M. Liu, Adv. Mater. 15, 1610, software. The experiments were carried out in a single- 2003. compartment glass cell of 125 ml volume. 8 M KOH was [2] S. Eugénio, T.M. Silva, M.J. Carmezim, R.G. Duarte, used as the electrolyte. Linear scan voltammetry (LSV) M.F. Montemor, J. Appl. Electrochem. 44, 455, 2014. was used to scan the Ni-Cu foams potential from their [3] D.M.F. Santos, L. Amaral, B. Šljukić, D. Macciò, A. open circuit potential (OCP, ca. -1.1 V) until -1.4 V vs. Saccone, C.A.C. Sequeira, J. Electrochem. Soc. 161, SCE at a potential scan rate of 0.5 mV s-1. Temperature F386, 2014. was ranged between 25 and 85 ºC.

Diogo M.F. Santos obtained his Ph.D. at University of Lisbon (Portugal) in 2009 in Chemical Engineering for his studies on the borohydride oxidation reaction. He is currently a permanent researcher of the Center of Physics and Engineering of Advanced Materials of University of Lisbon, where his main research interests concern electrochemical energy conversion and storage, namely for the development of low cost electrocatalysts for direct borohydride fuel cells or looking for novel electrocatalysts for hydrogen production by alkaline water electrolysis. He has authored more than 60 journal papers and over 30 conference proceedings. He is currently the Assistant Director of Ciência & Tecnologia dos Materiais (Science & Technology of Materials) published by Elsevier. D.M.F. Santos

Corresponding author: D.M.F. Santos, [email protected], +351 218417765.

27 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

SYNTHESIS AND CHARACTERISATION OF NEW AMIDOBORANES Nikola Biliškova, Ivan Halasza, Elsa Callinib, Andreas Borgschulteb, Andreas Züttelb a Laboratory of Solid State and Complex Compounds Chemistry, Ruđer Bošković Institute, Bijenička c. 54, HR-10000 Zagreb, Croatia b EMPA, Materials Science and Technology, Dept. Hydrogen and Energy, 8600 Dübendorf, Switzerland A series of single- and bimetallic amidoboranes and their complexes with ammonia borane were prepared by ball milling from ammonia borane and corresponding metal hydrides. Products are characterised by means of IR spectroscopy and powder XRD. Dehydrogenation was followed by DSC and variable temperature Raman spectroscopy. All of the prepared systems dehydrogenate at considerably lower temperature with respect to ammonia borane. Introduction Results

Ammonia borane (NH3BH3, further in the text AB) is Milling of the LiH with AB in all molar ratios gives rise to extensively investigated due to its extremely high both corresponding LiAB∙mAB products. As expected, IR gravimetric and volumetric hydrogen density. However, spectrum of the product obtained by reaction of 1:1 serious drawbacks make it unfavourable system for mixture is considerably simpler than those for 1:2 and 1:3 practical onboard hydrogen storage. Its reactivity is products. largely determined by intermolecular dihydrogen bonding On the other hand, all attempts to obtain NaAB by milling + - interaction of N-H ··· H-B type, which operates in solid 1:1 mixture of NaH and AB were unsuccessful. The AB. Thus, the flexibility of this interaction is of crucial obtained product immediately decompose during the importance for fine tuning of properties of AB-based milling process due to the increase of temperature in vial. systems. A very successful approach is its chemical However, milling of the 1:2 ad 1:3 mixture of NaH and AB + modification by substitution of one H of NH3 moiety by readily gives NaAB∙mAB. (BH) region is complex, as in an electropositive element, such as alkaline or alkaline the case of Li-containing counterparts. Complexation of earth metal, which gives rise to amidoboranes [1]. This MAB considerably lower dehydrogenation temperatures substitution causes a significant destabilisation of with respect to both AB and MABs. dihydrogen bonding network, with assistance of Bimetallic amidoboranes Li Mg(AB) and Na Mg(AB) dehydrogenation via hydride transfer by intermediate MH 2 4 2 4 were successfully prepared. XRD of the product obtained species. The changes in dehydrogenation mechanism, by milling of the 2:1:4 mixture of NaH, MgH and AB as well as opportunity of tuning of thermodynamics [2] 2 corresponds to the one previously reported for make them highly promising systems for hydrogen Na Mg(AB) [5]. Combined evidence from IR spectra and storage. Additionally, complexation of amidoboranes with 2 4 XRD for prepared M MgAB systems shows that the hydrogen bond donating species, such as NH [3] or AB 2 4 3 bonding in these systems is very similar, but they are not [4] further promotes dehydrogenation. isostructural, as confirmed by structure of the Li2Mg(AB)4, Here we report a series of novel complexes of lithium and solved by Rietveld method. It revealed very similar sodium amidoborane with AB (MAB·mAB, where M = Li, coordination of M and Mg atoms in both cases. DSC Na and m = 1, 2), as well as bimetallic amidoboranes of indicates a rather extensive phase changes prior to M2MgAB4 composition. dehydrogenation in the case of Li2Mg(AB)4, which occurs above 120 °C for both Li2Mg(AB)4 and Na2Mg(AB)4, as Experimental evident from Raman spectra. Samples were prepared by high energy ball milling (Spex 8000M) of stoichiometric mixtures of AB and References corresponding metal hydrides during 30 min in argon [1] Y. S. Chua et al. Chem. Commun. 47 (2011) 5116- atmosphere. Single-reflection ATR IR spectroscopy, 5129 powder XRD were used for structural characterisation. [2] Y. S. Chua et al. Chem. Mater. 24 (2012) 3574-3581 Dehydrogenation properties were investigated by DSC [3] Y. S. Chua et al. Inorg. Chem. 51 (2012) 1599-1603 and variable temperature Raman spectroscopy. [4] C. Wu et al. Chem. Mater. 22 (2010) 3-5 [5] H. Wu et al. Chem. Commun. 47 (2011) 4102-4104

Born September 17, 1974 in Pula, Croatia. 1999 Masters degree of inorganic chemistry at Faculty of Sciences, University of Zagreb; thesis at Faculty of Science in Zagreb. 2009 PhD degree in physical chemistry at Ruđer Bošković Institute, Zagreb; thesis “” 2012 Research associate at the Laboratory of Solid State and Complex Compounds Chemistry, Division of Materials Chemistry, Ruđer Bošković Institute, Zagreb 2014 Visiting scientist at EMPA, Dept. Hydrogen and Energy, Dübendorf, Switzerland

Nikola Biliškov

Corresponding author: Nikola Biliškov, [email protected], Tel. +385 91 7209759

28 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Preparation and electrochemical characteristics of

single-phase La–Mg–Ni-based alloys with super-stacking structures Shumin Han a,b, Yuan Li b, Yali Du b, Jingjing Liu b a State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004,PR China b College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China Abstract: La–Mg–Ni-based hydrogen storage alloys are considered as a promising negative electrode candidate to [1] replace traditional AB5-type alloys due to their large discharge capacity . The preparation of single-phase La–Mg–Ni- based alloys is necessary for systematic investigation but this is full of difficulty and reports on the single-phase alloys are rare. Our group explored the formation mechanism of the super-stacking phases and succeeded in preparing the single-phase AB3-, A2B7- and A5B19-type La–Mg–Ni-based alloys by step-wise sintering and long-time annealing method [2-4]. The phase conversions during hydrogen absorption/desorption and the relationship between the super-stacking structures and the electrochemical properties were investigated. Moreover, the effects of the second phases appearing in the single phase alloys were also studied.

AB3-type single phase La–Mg–Ni-based LaNi5 and (La,Mg)2Ni7 phases during hydrogen alloy absorption/desorption jeopardized its cycle life.

The PuNi3-type single phase La0.69Mg0.31Ni3.05 alloy was A5B19-type single phase La–Mg–Ni-based prepared by step-wise sintering LaMgNi4 and LaNi5 alloy precursor powders. The alloy exhibited a maximum –1 The La0.84Mg0.16Ni3.80 alloy with only Pr5Co19-type phase discharge capacity (Cmax) of 352 mAh g and a high rate –1 was firstly prepared by our group by step-wise sintering dischargeability (HRD) of 36.6% at 1500 mA g . But its th LaMgNi4 and LaNi5 precursor powders in a temperature capacity retention was as low as 66.1% at the 100 cycle o o range of 600–980 C and then annealed at 900 C for 4 due to its unstable structure during hydrogen days. The alloy showed a relatively low discharge absorption/deosrption cycles. Introducing Ce Ni -type –1 2 7 capacity (338 mAh g ) but a promising high rate phase into the single phase alloy could improve its dischargeability (HRD = 51.5%). The introduction of overall electrochemical properties and the optimal 1500 20 wt.% Ce Ni -type phase remarkably improved its electrode performance was obtained when the ratio of 2 7 discharge capacity and cycling stability, and 20 wt.% of PuNi3- to Ce2Ni7-type phase abundance was close to 1:1. LaNi5 phase appearing in the single phase Pr5Co19-type A2B7-type single phase La–Mg–Ni-based alloy further developed its HRD. alloy References The Ce2Ni7-type single-phase La0.8Mg0.2Ni3.5 alloy was [1] Y.F. Liu, H.G. Pan, M.X. Gao, Q.D. Wang, J. Mater. prepared by long-time annealing, and it exhibited a Chem. 21 (2011) 4743-4755. cycling stability of 81% at the 100th charge/discharge cycle, which was much higher than that of the AB3-type [2] J.J. Liu, S.M. Han, Y. Li, J.L. Zhang, Y.M. Zhao, L. single phase alloy. It was found that the alloy structure Che, Int. J. Hydrogen Energy 38 (2013) 14903-14911. remained unchanged after initial hydrogen [3] L. Zhang, S.M. Han, D. Han, Y. Li, X. Zhao, J.J. Liu, J absorption/desorption cycles. But it decomposed into Power Sources. 268 (2014) 575-583. amorphous La and Mg and nanocrystalline LaNi5 and Ni [4] J.L. Zhang, S.M. Han, Y. Li, J.J. Liu, S.Q. Yang, L. phases after 20 cycles. Small amount of LaNi5 phase Zhang, J. Wang, J Alloy Compd. 581 (2013) 693-698. appearing in the A2B7-type single phase alloy could improve its HRD, but the discrete expansion between the

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials, and rare earth chemistry. In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogen storage alloys, light weight hydrogen strorage materials, rare earth–Mg–Ni-based electrode materials and hydrogen generation catalysts.

Shumin Han

Corresponding author: Shumin Han, [email protected], +86-335-8074648.

29 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

NBN NANOPARTICLES AS ADDITIVE FOR THE HIGH DEHYDROGENATION PROPERTIES OF LITHIUM ALANATE Li Li,Yijing Wang*, Lifang Jiao, Huatang Yuan

Institute of New Energy Material Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Key Laboratory of Advanced Energy Materials Chemistry (MOE), Tianjin Key Lab of Metal and Molecule–based Material Chemistry, Nankai University, Tianjin 300071, P.R. China

Abstract: The effects of NbN nanoparticles synthesized via a simple ‘‘urea glass’’ route on the dehydrogenation properties of LiAlH4 have been systematacially investigated. Surface configuration and dehydrogenation behaviors of the 2 mol % NbN−doped LiAlH4 (2%NbN–LiAlH4) system are also discussed. It is found that the 2%NbN–LiAlH4 sample starts to decompose at about 95 °C and releases total 7.10 wt. % hydrogen, which is 55 °C lower than that of as–milled LiAlH4. The isothermal dehydrogenation kinetics shows that the 2%NbN–LiAlH4 sample could release approximately 6.10 wt % hydrogen in 150 min at 130 °C, whereas as–received LiAlH4 only releases about 0.63 wt % hydrogen under same conditions, revealing that enhancements arising upon adding NbN nanoparticles are almost 8−9 times that of as−milled -1 LiAlH4. The activation energy (Ea) is calculated to be 71.91 and 90.87 kJ mol for the first and second hydrogen desorption of NbN–LiAlH4 sample, a 38% and 32% reduction relative to as–received LiAlH4, respectively. Detailed modeling study presents that the first dehydrogenation step can be sufficiently interpreted with the nucleation and growth in a one-dimensional model based on the first-order reaction. More interestingly, SEM image of dehydrogenated 8%NbN–LiAlH4 sample after HP–DSC under 5.5 MPa H2 shows that some nanorods appear.

Introduction LiAlH4 sample is lowered to about 95 °C with little decrease in dehydrogenation capacity. Isothermal Safe and efficient hydrogen storage technology is one of dehydrogenation results at 130 °C reveal that the key technical barriers to the development of a kind of approximately 7.10 wt % is released at 130 °C. The Ea suitable on−board hydrogen storage material. Among values of NbN-LiAlH4 sample decrease to 71.91 and complex metal hydrides, Lithium alanate (LiAlH ) is of -1 4 90.87 kJ mol after doping NbN nanoparticles, resulting particular interest. However, the practical application of in decline rates of 38 % and 32 %. From the above LiAlH is limited by relatively slow dehydrogenation rate 4 analyses, it is reasonable to conclude that NbN and poor reversibility. In order to overcome these nanoparticles are an effective additive for significantly drawbacks, an alternate approach to modifying the enhancing the dehydrogenation properties of as-received dehydrogenation kinetics of LiAlH4 is through altering the LiAlH4. chemical bonding of LiAlH4 by adding additives. Here, we report the synthesis o NbN nanoparticles. Their catalytic Acknowledgment effects on the kinetics and thermodynamics of LiAlH 4 We are grateful to the MOST project (2012AA051901), have been investigated. NSFC (51471089, 51171083), 111 project (B12015) and Results and conclusion MOE (IRT-13R30). SEM and TEM demonstrate that the size of NbN References nanoparticle is approximate 10 nm. The prepared NbN is [1] Schlapbach L, Züttel A. Nature, 2001, 414:353-358. a promising additive for as–received LiAlH4 that it produces a significantly reduced dehydrogenation [2] Eberle U, Felderhoff M, Schuth F. Angew. Chem. Int. temperature and dramatically enhanced dehydrogenation Ed., 2009, 48: 6608−6630. kinetics. The onset desorption temperature of 2%NbN–

Prof. Dr. Wang Major research interests focus on：Synthesis and Characteristics of Hydrogen Storage Materials and High-performance Electrode Materials.

Yijing Wang

Corresponding author: Name: Yijing Wang, E-mail: [email protected], Tel.: +86-22-23503639.

30 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THE PREPARATION OF COPPER BASED PHOTOACTIVE NANOPARTICLES SUPPORTED ON MESOPOROUS SILICA G. Wang,1 K. Bossers,1 R. van den Berg,1 K.P. de Jong,1 C. de Mello Donega,2 P.E. de Jongh1 1Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands 2Condensed Matter and Interfaces, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands

Abstract: Cu2O and CuxS attract much attention for the application in solar energy conversion and photocatalysis. Although Cu2O is subject to photocorrosion, CuxS is relatively stable in aqueous solution under illumination. The stability against growth of supported nanoparticles is influenced by their spatial distribution on support materials and particle size. We aim to control the size and distribution of Cu2O and CuxS nanoparticles using a mesoporous silica support, and obtaining nanoscale Cu2O and CuxS by conversion of well-defined CuO nanoparticles. The size of the CuO nanoparticles can be tuned by varying the pore diameter of the supporting silica and/or the loading. As a result Cu2O nanoparticles with sizes from 2 nm to 15 nm as well as supported CuxS nanoparticles were obtained.

Introduction phase was subsequently stable while holding at 250 ˚C for up to 60 min. The particle size was tuned from 2 to 15 Cuprous oxide (Cu O) is a p-type semiconductor with a 2 nm by changing the pore size of supporting silica and the band gap of 2.2 eV.[1] This makes it an interesting loading. UV-Vis results confirmed a relation between the candidate for applications in photocatalysis. However, particle size band gap. (Fig.1a). CuS and Cu S (Fig.1b) Cu O undergoes photodegradation in aqueous solutions 2 2 nanoparticles were obtained by the sulfidation of CuO and its valance band edge is not low enough to provide nanoparticles with Thioacetamide and 1-dodecanethiol. the necessary overpotential for efficient photocatalytic oxygen evolution. Copper sulphides (CuxS) are p-type (a) (b) (b) semiconductors with unusual photocatalytic properties that are relatively stable in aqueous solution. Little is known on the effect of particle size, shape and facets on photocatalytic activity and stability. Recent research in our group has led to great advances in the control over 200 nm size and location of Cu-based nanoparticles in mesoporous silica.[2] The aim of this research is to investigate how control over size and distribution of Cu O 2 Fig.1: (a) The relation between the particle size and band and Cu S nanoparticles can be obtained and related x gap of Cu O nanoparticles. (b)TEM image of supported effects on the photocatalytic properties. 2 Cu2S nanoparticles. Methods and Results Conclusion Different strategies were explored to obtain Cu O: 2 A controlled synthesis method of silica supported Cu O reduction from CuO with CO or H , oxidation from Cu 2 2 and Cu S nanoparticles with variable particle size was with limited supply of O , liquid-phase oxidation and x 2 achieved which will be useful for the investigation of the sulfidation. The gas phase reduction under CO was most particle size effect of copper based semiconductors on successful to produce Cu O because of the high 2 photocatalytic activity and stability. reproducibility and the clear two-step reduction of CuO in contrast with under H2. Careful tuning of conditions [1] A.H. Jayatissa et al., Appl. Surf. Sci. 255 (2009) 9474 allows attaining pure and crystalline Cu O nanopartucles. 2 [2] P. Munnik et al., J. Phys. Chem. C 115 (2011) 14698 XRD showed that 15 nm CuO nanoparticles were reduced completely to Cu2O within 4 min. The Cu2O

2012-Present PhD study in the group of Inorganic Chemistry and Catalysis at Utrecht University under supervision of Prof. Petra de Jongh. Topic of the research is the supported catalysts for stable solar fuels production. The research is financed by NRSC-Catalysis. 2009-2011 Master degree at Uppsala University, Sweden. Master project entitled “Investigation of Cobalt Complexes as an Alternative Redox Couple in Dye-sensitized Solar Cells” under the supervision of Dr. Gerrit Boschloo and Sandra Feldt. 2004-2008 Bachelor degree at Dalian University of Technology, China. Gang Wang

Corresponding author: Gang Wang, [email protected], +31 646806615

31 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THE EQUILIBRIUM DEHYDROGENATION PRESSURE OF MAGNESIUM BOROHYDRIDE: REVISITED Nicholas Stadie, Elsa Callini, Andreas Borgschulte, and Andreas Züttel

Empa, Hydrogen & Energy Laboratory, Dübendorf, Switzerland

Abstract: Light metal borohydrides have been the subject of active investigation as potential hydrogen storage materials for over a decade. Magnesium borohydride (Mg(BH4)2) boasts a very high content of hydrogen (14.9 wt%) and an intermediate temperature of dehydrogenation at ambient pressure (<600 K), typically measured in dynamic conditions. The kinetics of the decomposition reactions of borohydrides are often slow, hindering the practical measurement of their equilibrium properties. In this work, we reinvestigate the dehydrogenation reaction of Mg(BH4)2 by a novel technique that provides both kinetic and equilibrium information about the system under controlled pressure conditions. The results indicate much higher plateau pressures of Mg(BH4)2 than previously measured (e.g. >10 MPa at 590 K).

Dehydrogenation Thermodynamics Gamma-Phase Magnesium Borohydride

The release of hydrogen from complex hydrides during Equilibrium flow isotherms were measured of γ-Mg(BH4)2, decomposition (dehydrogenation) follows a series of non- a system in which it is crucially necessary to distinguish trivial steps compared to metal hydrides and reversibility between mass loss due to H2 release and due to is often therefore a challenge. impurities1,2. The experimental results set new bounds on the pressures and temperatures at which decomposition

can partially occur. Equilibrium Flow PCT: A New Method Typical methods for measuring thermodynamic properties of hydrides and hydrogen adsorption systems must be cautiously applied in the long-time scales characteristic of complex hydrides. Various novel strategies have been suggested (e.g., the dynamic PCT method) and in many cases, true thermodynamic equilibrium cannot easily be achieved. Herein, we apply a new strategy, varied- pressure TPD measurements, to generate a new type of pressure-controlled “equilibrium flow” PCT isotherm.

References [1] Stadie et al., JACS, 136, 8181 (2014). [2] Stadie et al., JoVE, (under review).

Nick was born in 1985 in Calgary, Alberta, Canada. He received a BS in chemistry from Arizona State University in Tempe, Arizona, USA in 2007. He received a MS and PhD in materials science at Caltech in Pasadena, California, USA with Prof. Brent Fultz and Dr. Channing Ahn, focusing on synthesis and thermodynamic characterization of physisorptive materials for hydrogen storage. In 2013, he joined Empa as a postdoc, and is supported by the EU program Bor4Store, studying new techniques for characterizing the decomposition pathways of light metal complex hydrides. Nicholas Stadie

Corresponding author: Nicholas Stadie, [email protected], +41 58 765 4153

32 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

NEW CONCEPT FOR THERMAL MANAGEMENT IN A HYDROGEN TANK D. Platzek1, H. Platzek1, A. Bianchin2, E. Forlin2, M. Testi3, F. Alberti3, N. Laidani3, R. Bartali3, L.Crema3, P. Matteazzi4, S. Ortega5, G. Noriega5, M. Bielewski6, J.C. Ruiz-Morales7

1 Panco GmbH, D - 56218 Muelheim-Kaerlich, email: [email protected], 2 Matres SCRL, I - 31100 Treviso, 3 Fondazione Bruno Kessler, I - 38122 Trento, 4 MBN Nanomaterialia S.p.A., I - 31050 Vascon di Carbonera (TV), 5 Cidete Ing. S.L., ES - 08800 Vilanova I la Geltru, 6 JRC-IET, NL - 1755 ZG Petten 7 Universidad de la Laguna, ES - 38200 La Laguna

Abstract

Hydrogen storage is well known to be the major bottleneck for the use of H2 as energy carrier. Actually there are few storage systems available for nice markets. The EDen project is addressing a technology able to store energy in form of hydrogen in a solid state material. EDEN is proposing a high density, fully integrated material – tank – engineered system. This work presents a novel approach for the thermal management of a hydrogen tank based on metal hydrides, working at temperatures around 350°C and thus compatible with SOFC.

Introduction Thermal management The development of solid state hydrogen storage A completely new concept for the heat transfer has been systems is a challenge for the whole specific sector. It is developed and is currently being installed into the system a real opportunity to apply promising materials in real prototype: Heatpipes specially engineered for the use in technologies to grant a new energy storage solution. The hydrogen tanks should transport the heat either in the research on solid state materials has already adsorption case to the ambient via thermoelectrics or in demonstrated high hydrogen storage capacity, but some the case of desorption of H2 the heatpipes should gaps are already a problem for the realization of a robust transport the necessary heat to the storage material. The technology and a real market product. Among the heat distribution from the heatpipes to the storage different design and layouts, the system hereby material has also been ensured. A control system and described has the objective to be managed in real-time, measurement of temperatures, pressure and gas flow is specifically for distributed level applications, included on considered. Simulations lead to parameters for the a specifically designed storage tank and interlinked to an application and the design of the tank. The first energy provision system able to match intermittent experiments with the tank prototype have shown that the energy sources with local energy demand (buildings, performance criteria have been matched and even beat. small dwellings). Acknowledgements EDEN is proposing a high density, fully integrated material – tank – engineered system, able to realize an The research leading to these results has received adaptable energy storage solution. Different suggestions funding from the European Union’s Seventh Framework for the hydrogen tank design have been considered. The Programme (FP7/2007-2013) for the Fuel Cells and aim was to develop a hydrogen storage tank and to Hydrogen Joint Technology Initiative under grant optimise the heat transfer, the heat exchange system, the agreement nr. 303472. heating system as well as the heat recovery system to References increase the total performance of the system. The H2 is stored in Mg-based Hydrides, which are catalysed with [1] A. Chaise, P. de Rango,Ph. Marty,D. Fruchart. (2010), International journal of hydrogen energy, Vol. 35, pp. Nb2O5 and present a gravimetric capacity of 7 wt%. The 6311-6322. tank can store 600 g H2 and has a H2 density of about 40 g/l, the heat recovery rate for adsorption is more than [2] M.Testi, F.Alberti, A.Bianchin, E.Forlin and L.Crema, 25%, the desorption rate 3 gH2/min. The adsorption and Proceedings of EFC2013 - Piero Lunghi Conference, desorption takes place at about 350°C, which has to be December 11-13, 2013, Rome, Italy managed with the tank.

1966 born in Koblenz, Germany. 1994 Diploma (Master) at the University of Bonn. 1994-1997 Scientist at the Institute of Space Simulation of German Aerospace Centre DLR Cologne. 1997 Doctorate at the University of Bonn (Ph.D., „Dr. rer. nat.“), found evidence for a liquid ferromagnet. 1997 – 1999 Scientist at the Biomagnetic Centre of the University hospital Jena, Development of active shielding for magnetic fields. 1999 – 2000 Development engineer at the company LASOS Lasertechnik Jena. development of a strong green diode laser including cooling technique. 2001 – 2009 Scientist at the Institute of Materials Research of DLR development of thermoelectric material, measurement equipment. Since 2004 CEO of PANCO GmbH, Physics Technology Development and Consulting development/manufacturing of measurement equipment as PSM, TEGeta etc. Dieter Platzek Developments in the field of thermoelectrics and thermal management.

Corresponding author: Dieter Platzek, [email protected], +49 2630 964696

33 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THERMAL COUPLING POTENTIAL OF SOFCs WITH METAL HYDRIDE STORAGE TANKS A. Yiotis, M. Kainourgiakis, L. Kosmidis, G. Charambopoulou, Th. Steriotis, A. Stubos

National Center for Scientific Research “Demokritos”, 15310 Agia Paraskevi, Athens - Greece

Abstract - We study the thermal coupling potential between high temperature metal hydride (MH) tanks and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources.

Background principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical Hydrogen storage in Metal Hydride (MH) tanks is an expressions for both the thermal power produced during exothermic process that produces significant excess SOFC operation and the corresponding thermal power heat, in the range 40 - 80 kJ/mol for most materials required for H desorption, as a function of the operating tested in the literature. Unless the produced heat is 2 temperature, efficiency and fuel utilization ratio in the efficiently removed from the tank, it results in increasing SOFC, and the MH enthalpy of desorption in the tank. tank temperatures that eventually satisfy the activation Based on these calculations, we propose an integrated energy barrier for H desorption, thus leading to 2 SOFC/MH design where heat is transferred primarily by incomplete tank chargings. The design of efficient cooling radiation to the tank in order to maintain steady-state systems for MH tanks is thus a crucial factor for exploiting desorption conditions. We develop a mathematical model the maximum theoretical storage capacity of the material. for this particular design that accounts for heat/mass Hydrogen desorption, on the other hand, is an transfer and desorption kinetics in the tank, and solve for endothermic reaction that requires sufficient heat fluxes the desorption dynamics of the system. Our results focus to be provided to the MH bed in order to maintain the primarily on tank operating conditions, such as pressure, desired desorption mass fluxes. In recent years, attempts temperature and H2 saturation profiles vs operation time. have been made to develop integrated, self-sustainable MH/Fuel Cell systems, where the excess thermal power Acknowledgments produced from fuel cells under normal operating This work is partially supported by the European Fuel conditions is redirected towards a MH tank to sustain H2 Cells and Hydrogen Joint Undertaking (http://www.fch- desorption. Most of these works have focused primarily ju.eu) under collaborative project ”BOR4STORE” (Grant on the thermal coupling between low temperature MH agreement no.: N 303428). tanks and Polymer Electrolyte Membrane (PEM) fuel cells, where the cooling air flow stream from the fuel cell References is used to heat the MH tank [1]. [1] B.D. MacDonald, A.M. Rowe, Int. J. Hydrogen Energy, 31 (2006) 1721-1731. Background [2] A.G. Yiotis, M.E. Kainourgiakis, L.I. Kosmidis, G.C. In this work, we study the thermal coupling potential Charalambopoulou, A.K. Stubos, J. of Power between high temperature MH tanks and a Solid Oxide Sources, 269 (2014) 440-450. Fuel Cell (SOFC) aiming towards the design of an efficient, self-sustainable integrated system [2]. Based on

Georgia is a Senior Researcher at the Environmental Research Laboratory of the National Centre for Scientific Research “Demokritos”, located in Athens - Greece. She is a Chemical Engineer and received her PhD in 2001 from the Chemical Engineering Department of the National Technical University of Athens-Greece. Her research interests include the development and characterization of porous materials, membranes (inorganic - polymeric) and nanocomposites for environmental & energy applications. Emphasis is on gas separations and storage (specific interest in H2, CO2, CH4 etc.) for natural gas upgrade, oil & gas technologies and hydrogen technologies. Georgia Charalambopoulou

Corresponding author: Georgia Charalambopoulou, E-mail: [email protected], Tel.: +30 210 6503404

34 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

IN SITU DESORPTION OF MgH2-TiO2 THIN FILMS S.Milošević1, R.Vujasin1, I.Milanović1, M.Lelis2, D.Milčius2, R.Zostautiene3 J.R.Ares Fernandez4,F.Leardini4, C. Sanchez4, J.Grbović Novaković1 1 Vinča Institute of Nuclear Sciences, University of Belgrade, Laboratory for Material Sciences, Belgrade, Serbia 2 Center for Hydrogen Energy Technologies, Lithuanian Energy Institute, Kaunas, Lithuania 3 Department of Physics, Faculty of Mathematics and Natural Sciences, Kaunas University of Technology, Kaunas, Lithuania 3 Dpto. de Física de Materiales M-04 Facultad de Ciencias Universidad Autónoma de Madrid

Desorption process of MgH2-TiO2 thin films obtained by RF sputtering were investigated by means of simultaneous thermal desorption spectroscopy (TDS) and in situ optical microscopy. The random nucleation of spherical Mg nuclei is observed in both samples, but the velocity of nuclei growing depends on thickness of the sample. Indeed thin sample desorbs within 180s, while for thick sample 10 minutes is needed for complete desorption. Thick film exhibits lower Tonset for desorption 389oC in comparison to 412oC for thin sample.

Introduction desorption properties of thin films can be attributed obviously to the shorter diffusion path for H atoms. The Among various nanostructures used as potential material random nucleation of spherical Mg nuclei is observed in for hydrogen storage, MgH thin films attract attention for 2 both samples (see Figure 1). The nucleation process in variety of reasons, such as easy way of synthesis and thin sample is very fast and can be attributed the fact that low reactivity. Moreover, thin films offer the possibility to nucleation and perhaps clustering of the Mg nuclei study influence of microstructure and additives on occurs along some preferential directions determined by hydrides sorption properties in controlled way. The the vacancies. All nuclei grow together with the same activation energies for desorption varies and are caused velocity. On the other hand, in the thick sample there is by several issues [1]. Regarding the mechanism of formation of large and small nuclei alternately. There is reaction, the desorption follows nucleation and growth no color variation prior to the desorption as it for pure process, but in Pd-capped films an interface mechanism MgH film obtained by the same synthesis technique. is also proposed [2]. So, to clarify the mechanism of 2 The change in color and halos are observed around the reaction, in situ desorption from MgH -TiO films coupled 2 2 impurities (holes) in thick sample but only after the with optical microscopy were studied. complete desorption and could be a consequence of

formation of intermetalics. Experimental details

MgH2-TiO2 thin films were synthesized by RF sputtering using Kurt J. Lesker 75 PVD apparatus on quartz substrate. Two different thickness of MgH2 layer ranging were used (200 nm - S1 and 300 nm - S2) while the thickness of TiO2 films was 10 nm for all films. Deposition of TiO2 was done using pulsing DC current supply for magnetron. MgH2 decomposition was studied by means of simultaneous thermal desorption spectroscopy (TDS) and in situ optical microscopy. Optical microscope equipped with a hot stage able to a) S1 at 417 oC b) S2 at 415 oC work under inert atmosphere up to 873 K or under H2 up to 573 K in transmitted or reflected mode enables video Figure 1. Nucleation and growth process in MgH2-TiO2 acquisition and light intensity measurements during thin films with different thickness a) S1 -200 nm and b) sorption studies. Desorption were done in Ar flow of S2 – 300 nm sample 1atm. In-situ optical study [2] provides information on hydride formation or decomposition kinetics and References nucleation process. [1] J.R. Ares, F. Leardini, P. Dıaz-Chao , I.J. Ferrer, J.F. Fernandez ,C. Sanchez,Int J Hydrogen Energy 39(6); Results and discussion 2014:2587–2596 Regarding thinner film (S1), desorption starts at [2] M. Barawi, C. Granero,P.Diaz-Chao,C.V. Manzano,M. 412oC and ends at 427 oC,while thick film (S2) desorbs Martin-Gonzalez,D. Jimenez-Rey,I.J. from 389 to 434 oC. For complete desorption in sample Ferrer,J.F.Fernandez,C.Sanchez,J.R. Ares, Int J S1, 180 seconds is needed, while for thick sample Hydrogen Energy 39(18); 2014 :9865-9870 desorption is finished in 10 minutes. The improved H2

35 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Born in Belgrade, Serbia 29.09.1973. Graduate degree in physical chemistry,1999, Magisterium in physical chemistry, 2003, PhD in physical chemistry 2005. From 1999 she works in Vinca Institute of Nuclear Sciences in Laboratory of material sciences as principal researcher. 2008 Post doc in ENEA CR Casaccia, President of Serbian Society for Microscopy from 2010-2014. 2009 awarded from International Association of Hydrogen Energy with IJHE outstanding Service Award. Leader of Hydrogen storage initiative Serbia. Guest Editor: Novel Perspectives on Hydrogen Storage in Solid Media and International Journal of Hydrogen Energy.

Jasmina Grbović Novaković

Corresponding author: Jasmina Grbovic Novakovic, email: [email protected], Tel.+ 381 64 16 96 253

36 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

POTENTIAL OF ALGAE FOR BIO HYDROGEN PRODUCTION Mohamed AMIRUL ISLAM

Skolkovo Institute of Science & Technology, Energy Science & Technology, Moscow Region, Russia

Abstract Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;vText; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;

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MSc research student

Islam Md Amirul

Corresponding author: Mohamedd Amirul Islam , [email protected], Tel. +79854766037

37 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

HYDROGEN-OXYGEN RECOMBINATION REACTION FOR TREATMENT OF EXHAUST GASES FROM FUEL CELLS G.M. Arzac*, D. Hufschmidt, A. Fernández Instituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja. Seville. Spain.

Abstract The study of H2/O2 recombination reaction is key in the development of hydrogen-based technologies. One application of this reaction is the elimination of H2 in the exhaust of fuel cells. In this work the reaction was studied in conditions which simulate the exhaust gases from a fuel cell, namely 3% v/v H2/air mixture. 1% Pt/SiC and 1% Pt/TiO2 were tested as catalysts. Both materials converted hydrogen into water efficiently at room temperature and reached a steady state after a few minutes. TiO2 has demonstrated to be more efficient in terms of conversion probably due to metal-support interactions. Further investigation will be conducted to explain this phenomenon.

H2-O2 recombination reaction or catalytic hydrogen (less than 1nm) and disperse Pt nanoparticles as combustion (CHC, reaction 1) is receiving a lot of confirmed by EDX (Energy Dispersive X-Ray Absorption). attention in relation to the development of hydrogen- Catalytic activity for the 1%wt Pt/TiO2 catalyst (12mg) -1 based technologies.[1] Reaction 1 is highly exothermic (- was measured for a 200ml.min H2/air mixture flow rate. 286kJ.mol-1) and can be employed for safety and/or The reaction started at room temperature, and after a few heating purposes. minutes, conversion and temperature achieved a H2 + O2 H2O (1) stationary state. Similar results were found in the second It is known that the outlet gas from the fuel cell contains cycle but with an increase in conversion (86 vs 92%) and certain amounts of unreacted hydrogen. For making the average temperature (44 vs 46.5 ºC). exhaust gases H2 free, it is essential to process the The activity for the 1%wt Pt/SiC catalyst was also residual gas in a simple manner. At this stage, CHC is measured in the same conditions. TiO2 supported needed to convert hydrogen into water at room catalyst shows improved activity respect to the SiC temperature by using air as oxidant. [2] supported one (86 vs 75%). According to previous report, Pt is a well stablished catalyst for (1), and has the the differences could be attributed to the reducibility of capability to start up the reaction even at room Ti(IV) which generates lattice oxygen sites available for temperature. [3] For practical purposes, it is essential to the H2/O2 recombination. [4] However, further studies are have the catalyst in a supported form which improves required for a full comprehension of this effect. dispersion, prevents aggregation and facilitates its use in successive cycles. In this paper we study the Pt-catalysed reaction using 3% References v/v H2/ air mixtures simulating the conditions of the [1] V.M. Shinde, G. Madras, Catalysis Today 198 (2012) exhaust of a fuel cell. The catalysts were prepared by 270-279. incipient impregnation of Pt on commercial TiO2 and SiC [2] P. Despande, G. Madras, Appl. Catal. B Environ 100 supports and the results were compared. The kinetics of (2010) 481-490. the reaction was monitored by measuring H2 [3] M. Haruta, H. Sano, Int. J. Hydrogen Energy, 6 (1981) concentration by Gas Chromatography. 601-608 The 1%wt Pt/TiO catalyst was studied by Electron 2 [4] P. Despande, G. Madras, Phys. Chem. Chem Phys, Microscopy. The study reveals the formation of very small 13, (2011) 708-718.

I was born in Buenos Aires, Argentina. I studied Chemistry at the University of Buenos Aires (UBA). As student and also as graduated, I worked for four years at the Organic Chemistry Department of the UBA, synthesizing antitumorals. I was also teacher at the Inorganic Chemistry Department of the same university during 7 years. I did my PhD at the University of Seville, Spain on hydrogen storage through sodium borohydride hydrolysis reaction under the supervision of Dr. Asunción Fernández. At present, my postdoctoral activity is still in relationship with hydrogen technologies and now specially focused on catalytic hydrogen combustion. Gisela Arzac

*Corresponding author: Gisela M. Arzac, [email protected], +34954489552.

38 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

MECHANICAL PROPERTIES OF NANOSTRUCTURED AL ALLOYS PRODUCED BY ECAP. Aferdita Priftaj Vevecka

Polytechnic University of Tirana, Sheshi “ Nene Tereza”, N.4, Tirana, Albania. Abstract The novel multi-functional materials produced from the broad and multidisciplinary field that is nowadays called nanotechnology, can be used for sustainable energy production, transformation and use. Magnesium, aluminium or Mg– Al alloys in the form of bulk materials with nanograins, are envisaged as some of the potential optimal materials for hydrogen storage. During the last decades, fabrication of bulk nanostructured or ultrafine grained metals and alloys, using severe plastic deformation (SPD) processing, has been evolving as a rapidly advancing direction of nanomaterials science, aimed at developing materials with new mechanical and functional properties for advanced applications. Among various SPD processes, Equal Channel Angular Pressing (ECAP), is the most well developed processing technique. In the present work, the technologically interesting aluminium alloy AA6061 was selected for study. The strain rate sensitivity of AA6061 has been investigated in a conventional grain sized (CG) state and in two different ultrafine grained (UFG) conditions, processed by ECAP, for 2 and 6 passes at 100° C. Strain rate jump tests in compression were performed at different temperatures, and the strain-rate sensitivity (SRS) exponent m was determined. It is shown that both UFG microstructures, exhibit a strongly increased strain-rate sensitivity (SRS) compared to CG state.

References [3] A.Veveçka, M. Cabibbo, T. G. Langdon, “Materials [1]M. J. Zehetbauer, H. P. Stüwe, A. Vorhauer, E. Characterization” 84 ( 2 0 1 3 ) 1 2 6 – 1 3 3, Schafler, J. Kohout, Adv.Eng.Mater. 5 (2003) 330 Available online at www.sciencedirect .com [2]R. Z. Valiev, T.G. Langdon, Progress in Materials Science 51 (2006) 881-981

Education: I have finished the faculty of Physics at the University of Tirana, Albania in 1970. From 1970 to 1974 I have worked as assistant at the chair of ”General Physics” of the Faculty of Natural Sciences, University of Tirana. From 1974 to 1992 I have worked as lecturer in General Physics for students of the Engineering Faculties, at the chair of ”Materials Science”, Faculty of Natural Sciences, University of Tirana. Since 1992 I work as Lecturer in Physics at the Department of Physics, Polytechnic University of Tirana, Albania. In 1982 I qualified for the Doctor’s Degree (PhD.) with the thesis: ” Study of structural changes of aluminium and its alloys, during thermal and plastic treatments, by Transmission Electron Microscopy (TEM)”. In 1994 I received the title " Associate Professor" and in 1999, I received the title "Professor". From March 1995 until April 2004, I was for 9 years, member of the editorial board of the international premier academic journal “Materials Science and Engineering A”. In December 2008 I was elected Associate Academic member of the Albanian Academy of Science.

Name: Aferdita Priftaj - Vevecka Address: Polytechnic University of Tirana Department of Physics Sheshi “Nene Tereza”, N.4, Tirana, Albania Corresponding author: Aferdita Priftaj Vevecka, [email protected] , + 355692107327

39 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

MG-IN-NI TERNARY ALLOYS FOR REVERSIBLE HYDROGEN STORAGE: STRUCTURE AND PROPERTIES Hui Wang1,2, Yanshan Lu1,2, Jiangwen Liu1,2, Liuzhang Ouyang1,2 and Min Zhu1,2 1 School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, P. R. China 2 Guangdong Provincial Key Laboratory of Advanced Energy Storage Materials, Guangzhou, 510641, P. R. China

Abstract: A series of Mg-In-Ni alloys were prepared by sintering and ball-milling, and their structure and hydrogen storage properties were investigated. It was found that two new Mg-In-Ni ternary phases were reversibly formed in the hydrogenation and dehydrogenation, which is responsible for the reduced decomposition reaction enthalpy of MgH2, being 70.1 kJ/mol H2 for the Mg70In15Ni15 alloy. More importantly, the Ni addition could also improve the hydrogen sorption kinetics of Mg. Therefore, the hydrogen desorption temperature of Mg-In-Ni alloys could be reduced down to The results indicate that the Mg-In-Ni alloys

Introduction 3D reconstruction of transmission electron microscopy. Further, the hydrogen storage properties of all Mg-In-Ni Mg is considered to be a promising hydrogen storage alloys were compared, and the reaction mechanism of material with high gravimetric capacity and abundant several typical Mg-In-Ni alloys were investigated. resource. However, the over-high operating temperature due to unfavorable thermodynamics of magnesium hydride (MgH2) hinders its practical applications. Composition and structure modification have been proven to be effective in improving the hydrogen storage properties of MgH2. For example, we found that Mg(In) and Mg(In,Al) solid solutions could be reversibly formed as dehydriding from their hydrogenated products, and that the desorption enthalpy was reduced [1,2]. In this work, we investigate the reversible phase transformation of Mg-In-Ni ternary alloys during de-/hydrogenation cycles, and their de-/hydriding thermodynamic and kinetic Figure 1 The composition and structure of as-prepared properties. ternary Mg-In-Ni alloys Experimental results References A series of Mg-In-Ni alloys were prepared from the [1] H. C. Zhong, H. Wang, J. W. Liu, D. L. Sun, M. Zhu, elemental powders by sintering and subsequent ball- Scripta Mater. 65 (2011) 285. milling process. Figure 1 shows the composition range of alloys to be explored, and their phase structure. The [2] H. Wang, H. C. Zhong, M. Zhu, et al, Journal of crystal lattice of two new Mg-In-Ni ternary phases: Physics Chemistry C, 118(2014)12087. Mg70In15Ni15 and Mg50In25Ni25, has been determined by

Hui Wang received his PhD in Materials Processing from South China University of Technology in 2003. He is currently A.P. Professor at the Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou, China. His research interest is focused on the Mg-base alloy for solid-state hydrogen storage, utilizing the strategies of nanostructure, composite structure, alloying and catalyst doping to improve the hydrogen storage properties of Mg.

Dr. Hui Wang

Corresponding author: A. Prof. Hui Min Zhu, [email protected]

40 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THE ROLE OF HYDROGEN IN WELDABILITY OF AEROSPACE MATERIALS *S. Jothi, T. N. Croft, S. G. R. Brown College of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP, UK *[email protected]; [email protected]

Abstract: Microstructures play a prominent role in aerospace components which are typically made of high toughness, corrosion resistant and high strength structural polycrystalline metallic materials such as nickel and nickel based super alloys. Nickel and nickel based super alloys are made up of complex microstructures which are susceptible to delayed failure caused by absorption of hydrogen produced during fabrication in manufacturing process such as electrodeposition and welding. Several catastrophic failures have occurred in aerospace industries on nickel and nickel based super alloys due to hydrogen embrittlement (HE) and hydrogen stress cracking (HSC) near weld joints. HE depends on many factors including hydrogen and impurities diffusion and segregation, heat source during welding, weld residual stresses, microstructural morphology, defects and texture morphological behaviour. Multiscale technique have been employed to investigate the influence of these factors in hydrogen embrittlement both computationally and experimentally. The studies provide insights on the influence of these factors and control it strategically to reduce the susceptibility of materials to hydrogen embrittlement.

Corresponding author: Sathiskumar Jothi, [email protected]; [email protected], Tel. 00447587876010

41 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Preferential Sites for Hydrides Formation in Commercially Pure Titanium

Aleš Jäger, Walter Guy, Viera Gärtnerová, Karel Tesař

Laboratory of Nanostructures and Nanomaterials, Institute of Physics, Na Slovance 2, Prague 182 21, Czech Republic

Abstract: The aim of present study is to identify preferential sites for hydrides formation in commercially pure Titanium grade 2. Ti with an initial H concentration of <0.015% was machined by electro discharge machining (EDM) to create a surface layer with an excess of H and subsequently annealed at 900° C to enables H diffusion into bulk . The heat treatment resulted in an unusual duplex α and β microstructure with β phase decorating grain boundaries and triple junction as well as lamellar β phase in grain interiors. High resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy combined with electron energy loss spectroscopy (STEM-EELS) were mainly used to correlate relations between hydride formation and crystal structure defects such as dislocations and interfaces. It is shown that crystal structure defects serve as preferential sites for titanium hydrides creation and each type of crystal defect prefer to be occupied by particular hydride. Introduction Outline of the Results One of the most important impurities in titanium, which The microstructure after heat treatment consists of α also has potential for applications such as hydrogen phase grains and β phase mainly decorating grain storage, is hydrogen. In access of hydrogen, there are boundaries. It was observed that the β phase appears in three major titanium hydride phases described in two variations, the first along grain boundaries and triple literature, which may occur under certain conditions. Due junctions, and the second as lamellar type lathes within to the naturally high diffusivity of hydrogen, and its individual α phase grains. The heat treatment procedure relatively low solubility in titanium, gamma and delta used effectively stopped the α → β transition, which was phase titanium hydrides can naturally occur even in CP in progress when the sample was above the α transus of titanium [1]. Because of the importance and near ~887°C, and led to a duplex α+β microstructure, common inevitability of hydrides in titanium, understanding the in some titanium alloys with β phase stabilizing elements mechanisms of hydride formation in titanium has been an [2]. Nanometer scaled features of the microstructure area of active research for 30 years or more. In spite of were observed by TEM techniques. It is shown that this effort, there is still incomplete knowledge about particular titanium hydrides such as face centred defect - hydride relationship. tetragonal titanium hydride and face centred cubic titanium hydride are systematically formed around certain Experimental Part crystal structure defects. An extruded rod of commercial purity titanium grade 2, 16mm in diameter, was machined into flat samples by References wire EDM prior to heat treatment in an argon [1] Banerjee, D., & Williams, J. C. (2013). Perspectives atmosphere. The heat treatment was comprised of an on titanium science and technology. Acta Materialia, increase of 0.2°C/s up to a temperature of 900°C, w hich 61(3), 844–879. doi:10.1016/j.actamat.2012.10.043 was held for 1 hour, followed by cooling at a rate of 5°C/s back to room temperature. Transmission electron [2] Tesař, K., & Jäger, A. (2014). Electron backscatter microscopy (TEM) samples were cut into 3mm diameter diffraction analysis of the crack development induced disks with a thickness of approximately 300 microns, and by uniaxial tension in commercially pure titanium. then thinned by grinding to 50 or 100 microns before final Materials Science and Engineering: A, 616, 155–160. thinning by ion polishing or twin-jet electrolytic polishing, doi:10.1016/j.msea.2014.08.028 respectively. Two techniques of TEM sample preparation were used in order to verify the minimal impact of sample preparation procedures on hydride formation.

Aleš Jäger 1997 – 2002 Faculty of Mathematics and Physics of Charles University in Prague Master degree Head of Group Nanomaterials 2002 – 2007 Faculty of Mathematics and Physics of Charles University in Prague and Interfaces Ph.D. degree Since 2007 Institute of Physics, Academy of Sciences, Postdoc position Since 2011 Institute of Physics, Academy of Sciences, Group Leader

Corresponding author: Aleš Jäger, [email protected], Tel. 00420 266 052 870

42 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

LIBH4 DESTABILIZATION SYSTEM AND ITS HYDROGEN STORAGE PERFORMANCE Min Zhu1,2, Yijing Wang3

1. School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P. R. China. 2. Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou 510640, P. R. China. 3. Institute of New Material Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin 300071, P. R. China.

As a type of potential high-capacity hydrogen LiBH4-4LiOH, respectively. The latter exhibited faster storage material, LiBH4 has received intensive research dehydrogenation kinetics. Unfortunately, LiBH4-alkali interest over the last decade, for addressing its high metal hydroxide system was not reversible under the thermodynamics, sluggish kinetics and irreversibility. rehydrogenation conditions of 400 ºC and 10 MPa Herein, we demonstrate our latest effort on achieving a hydrogen pressure. reversible high hydrogen system with superior de-/re- For achieving superior reversibility with enhanced hydrogenation properties, through introducing thermodynamic and kinetic behavior, nanostructured nanosized NdH , alkali metal hydroxides and 2+x CoB of different morphologies, being rod-like, flake-like, nanostructured CoB with different morphologies into chain-like, waxberry-like and mulberry-like, was LiBH by ball milling. The enhanced hydrogen storage 4 synthesized by controlling chemical reduction process, performace was realized and the mechanism was also and then doped into LiBH by ball milling [3]. The revealed. 4 catalytic activity of CoB is in the order of mulberry-like > A destabilized reversible reaction, 4LiBH4+NdH2↔ waxberry-like > chain-like > flake-like > rod-like, which NdB4+4LiH+7H2Fehler! Eine Ziffer wurde erwartet., is in accordance with their specific surface area from has been established [1]. The dehydrogenation kinetics high to low. This led to the different de-/re- of this reaction are fast, 6.0 wt.% hydrogen was hydrogenation performance of CoB doped LiBH4 at 200 released within 1.5 h at 370 ºC. Significantly, we found °C and 350 °C. In contrast to other three CoBs, that it is a nanosize-controlled reversible LiBH4-NdH2+x mulberry-like and waxberry-like ones dramatically system. The destabilization reaction could not proceed enhanced dehydrogenation of LiBH4 below 200 °C. 4.6 upon dehydrogenation-rehydrogenation cycling, and 4.8 wt.% hydrogen was rapidly released from LiBH4 because of significant growth of the NdH2+x particles. in 3 h respectively, and more than 2 wt.% hydrogen However, the presence of NdH2+x continued to have a was reversible for the later. For dehydrogenation at 350 positive effect upon the dehydrogenation kinetics of °C, mulberry-like CoB showed the best catalytic effect LiBH4. In a word, this novel finding is beneficial for than other CoBs, with which 10.4 wt.% hydrogen modifying the reversibility of the reactive hydride liberated from LiBH4 within 1 h. Significantly, full composite systems through nanosize-controlling. reversibility was achieved under 400 °C and 10 MPa hydrogen pressure, and reversible 9.6 wt.% To futher reduce the dehydrogenation temperature, dehydrogenation capacity was acquired at the fourth alkali metal hydroxides were adopted to facilitate - cycle. To our knowledge, it is the first time to report the hydrogen through H+/H coupling mechanism [2]. The catalytic effect of CoB through optimizing the main dehydrogenation temperature decreased to 207, nanostructure on the dehydrogenation and 221, and 230 °C for LiBH4-LiOH, 2LiBH4-NaOH, and rehydrogenation of LiBH4. 2LiBH4-KOH, respectively. Further investigation in LiBH4-xLiOH (x = 1, 1.36, 4) indicated that destabilization arose from different reaction pathways in References the composites, which depended on the LiBH4: LiOH ratio. The dehydrogenation temperature increased from [1] M. Zhu, et al. J. Phys. Chem. C, 2013, 117, 9566. 207 to 250 °C, upon increasing the ratio of LiOH in [2] M. Zhu, et al. RSC Advances, 2014, 4, 3082. LiBH4-LiOH from 1 to 4. 4.1 and 6.5 wt.% of hydrogen [3] M. Zhu, et al. Nano energy, 2014, 10, 235. was liberated within 10 minutes by LiBH4-LiOH and

Corresponding author: Min Zhu, [email protected], Tel. +86-20-87113924

Min Zhu is a professor in South China University of Technology. He received his Ph.D. from Dalian University of Technology in 1988. His main research interest lies in the fields of advanced energy storage materials, such as hydrogen storage materials, lithium ion battery materials, and electrode

materials for super-capacity. Zhu has published more than 200 journal articles. Prof. Min Zhu

43 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

IN-SITU RAMAN STUDY OF H → D EXCHANGE IN γ-MG(BH4)2 O. Zavorotynska,1 G. Li,2 M.Matsuo,2 S. Deledda,1 S.I. Orimo,2 B.C. Hauback1

1Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway

2Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Abstract. Hydrogen-isotope exchange in γ-Mg(BH4)2 was studied by in-situ Raman spectroscopy. When γ-Mg(BH4)2 was gradually heated in 0.3MPa D2 atmosphere, the first evidence of isotope exchange appeared as already at 373 K, and below the temperature reported earlier for α-Mg(BH4)2. Gradual formation of BDH3, BD2H2, BD3H and BD4 anions was followed at various temperatures until the formation of strongly fluorescent phase(s) at 498 K and above. Isothermal steps allow us to follow the kinetics of isotopic exchange reaction.

Introduction BH4-xDx ions. Isotope-exchange reactions were followed isothermally at several steps, allowing us to study the Isotope spectroscopy can provide useful insight into isothermal reaction kinetics. The relative concentrations molecular structure and bonding. Due to the large mass of BH D ions were related to the integrated areas of the difference of H and D, vibrational spectra of the 4-x x corresponding symmetric B-D stretching. Experimental molecular groups containing the two isotopes are easily data of the reaction rates at isothermal steps will be distinguished and can be used to study the mechanisms compared to various theoretical kinetic models. of various intermolecular processes. Isotope spectroscopy of complex hydrides, for example LiBH4 Acknowledgements and Mg(BH ) , have been used to investigate synthesis, 4 2 This work was financed by the EU 7FP BOR4STORE diffusion, decomposition and also thermodynamic and the iTHEUS project funded by the ERA-NET properties [1-3]. In this work in-situ isotope Raman CONCERT-Japan cooperative program spectroscopy was applied to study the H-D exchange in (http://www.concertjapan.eu/). Mg(BH4)2 between300 and 543 K. Methods and Results References [1] H. Hagemann, V. D'Anna, J.-P. Rapin, K. Yvon, Commercial γ-Mg(BH ) was used in this study. The 4 2 Deuterium-Hydrogen Exchange in Solid Mg(BH ) , J. sample was soaked in 0.3MPa D at 300 K and gradually 4 2 2 Phys. Chem. C, 114 (2010) 10045-10047. heated at 5 K/min rate. Simultaneously Raman spectra [2] A. Borgschulte, A. Jain, A.J. Ramirez-Cuesta, P. were recorded with a Nicolet Almega micro-Raman Martelli, A. Remhof, O. Friedrichs, R. Gremaud, A. Züttel, spectroscope with 532 nm excitation wavelength. The Mobility and dynamics in the complex hydrides LiAlH first evidence of H-D exchange appeared at 373 K as a 4 and LiBH , Faraday Discuss., 151 (2011) 213-230. peak at 1717 cm-1 and assigned to the B-D stretching 4 [3] R. Gremaud, A. Borgschulte, O. Friedrichs, A. Züttel, mode in BDH . With increasing temperature, we were 3 Synthesis Mechanism of Alkali Borohydrides by able to record well-resolved peaks due to the B-D Heterolytic Diborane Splitting, J. Phys. Chem. C, 115 stretching in various (2011) 2489-2496.

Dr. Olena Zavorotynska obtained her Specialist degree in Physics from Kyiv-Mohyla Academy in Kyiv, Ukraine, in 2006. She continued her studies in the University of Turin, Italy, where she earned her PhD degree in Materials Science in 2010 under the supervision of Prof. Giuseppe Spoto. During her doctorate studies, she worked on hydrogen storage via adsorption in porous materials. The work was mainly focused on characterization of the materials’ surfaces (zeolites, MOFs, polymers) with variable-temperature vibrational spectroscopy of probe molecules, and enhancement of the adsorption properties of these materials. In 2010-2012 she worked as the research assistant in University of Turin, studying metal borohydrides for hydrogen storage applications. She continues this research at present at the Institute for Energy Technology in Norway, where she works as post Olena doctorate fellow since 2012 in the group of Prof. Bjørn Hauback. Zavorotynska

Corresponding author: O. Zavorotynska, [email protected], +47 466 21 096

44 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

CATALYZED H SORPTION MECHANISM IN ALANATES Zuleyha Özlem Kocabas Atakli a, Elsa Callini a, Shunsuke Kato a and Andreas Züttel a,b* a EMPA, Swiss Federal Laboratories for Materials Research and Testing, CH-8600 Dübendorf, Switzerland b Ecole polytechnique fédérale de Lausanne (EPFL), Institut des sciences et ingénierie chimiques, CH-1015 Lausanne, Switzerland

Abstract: The hydrogen sorption pathways of alkali alanates were analyzed and a mechanism for the catalytic hydrogen sorption was developed. Gibbs free energy values of each possible step were calculated based on experimental determined thermodynamic data (enthalpies and entropies) of individual hydrides, MAlH4, M3AlH6, and MH. The values + - for the activation energies, based on the intermediates M , H , MH, and AlH3 were obtained. The mechanism of the catalysis was unclear despite the large number of proposed models since the discovery of the catalytic activity of Ti in NaAlH4 in 1996 by Boris Bogdanovic [1]. We present an atomistic model, where MAlH4 desorbs hydrogen through the + - intermediates M , H , MH, and AlH3 to the hexahydride M3AlH6 and finally the elemental hydride MH. The catalyst acts as + - - - 3- a bridge to transfer the M and H from MAlH4 to the neighboring AlH4 forming AlH6 and finally isolated MH leaving AlH3 behind which spontaneously desorbs hydrogen to Al and 1.5 H2. The proposed mechanism is symmetric in the direction of the hydrogen sorption mechanism.

Introduction Quite a number of possible mechanisms for the hydrogen were systematically investigated by considering Gibbs sorption in MAlH4 have been proposed [2]. However, all free energy of their starting materials, intermediates, and these approaches suffer from the fact that Ti catalyzes products. The Gibbs free energy diagrams were both hydrogen desorption steps as well as the adsorption constructed according to the published experimental of hydrogen. We presented a completely symmetric thermodynamic parameters [3]. MAlH4 (where M= Li, Na, mechanism where the function of the catalyst is well- and K) is known to release hydrogen in two distinct steps; defined. Firstly, we focused exclusively on understanding M3AlH6 and MH partially dehydrogenated phases appear the main intermediate steps in the dehydrogenation and in the dehydrogenation process. In all cases, it was rehydrogenation of MAlH4 and M3AlH6 (where M= Li, Na, obtained that two appearing intermediate phases at the and K) based on thermodynamic considerations. With first dehydrogenation step and one possible intermediate this aim, Gibbs free energy values of each possible for the second dehydrogenation step. It was shown that compound were calculated from the experimental (de)hydrogenation happened in two-step processes + - thermodynamic properties of individual hydrides, MAlH4, including M , H , MH, and AlH3 phases. We proposed that M3AlH6, and MH. Secondly, the activation barriers, with the task of Ti as catalyzed in rehydrogenation reaction is + - the intermediates M , H , MH, and AlH3, for the first and followed same path with the dehydrogenation steps. second step were obtained. Lastly, we presented an atomistic model, where the catalyst acted as a bridge to References - 3- transfer the M+ and H- from AlH4 to AlH6 and finally to [1] B. Bogdanovic, M Schwickardi J. Alloys Compd., 253- form MH based on thermodynamic considerations.The 254 (1997), pp. 1. proposed mechanism was symmetric and the catalyst [2] A. Leon, O. Kircher, M. Fichtner, J. Rothe, D. Schild could be active on the intermediates M+, H-, MH, and J. Phys. Chem. B, 110 (2006), pp. 1192-1200. AlH3 for the (de)hydrogenation. Result and Discussion [3] Z. Özlem Kocabas Atakli, Elsa Callini, Andreas Züttel, J. Alloys and Compounds (2015),to be In order to tailor the thermodynamic stabilities, the published (de)hydrogenation of LiAlH4, NaAlH4, and KAlH4 at 453 K

Short CV Züleyha Özlem Kocabas Ataklı received a doctorate from department of material science and engineering from Sabanci University in 2013 for her work on fabrication of porous and nanomaterials as adsorbent materials for water treatment application. She is currently Postdoctoral Researcher at Empa, Swiss Federal Laboratories for Materials Science and Technology. Her research interests are in the area of adsorption, synthesis of nanomaterials, surface properties of porous and nano materials, carbonaceous material chemistry, heterogeneous catalysis, photocatalytic oxidation, and hydrogen storage.

Corresponding Author: Andreas Züttel, [email protected], +41 21 693 97 34.

45 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

STRUCTURAL CHANGES OBSERVED DURING THE REVERSIBLE HYDROGENATION OF Mg(BH4)2 WITH Ni-BASED ADDITIVES I. Saldan1,2, S. Hino1, T. D. Humphries1, O. Zavorotynska1, M. Chong3, C.M. Jensen3, S. Deledda1, B.C. Hauback1

1Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway,

2Department of Physical and Colloid Chemistry, Ivan Franko National University of L’viv, UA-79005 L’viv, Ukraine

3Department of Chemistry, University of Hawaii, Honolulu, HI 96822, USA

Abstract -Mg(BH4)2 ball milled together with 2 mol% of Ni-based additives – Ninano; NiCl2; NiF2; Ni3B – has been investigated during one hydrogen desorption-absorption cycle. Powders were sampled after milling and hydrogen desorption-absorption in order to monitor the structural changes in the hydrogen- containing phases with PXD, XAS, NMR and IR spectroscopies. Hydrogen desorption results in the formation of a 11 reversible phase which was identified by B NMR as Mg(B3H8)2. However, IR could not confirm the presence of the B– H–B bridged bonds, characteristic of Mg(B3H8)2

Introduction formed in the composite containing Ni3B. Analysis by X- ray Absorption Spectroscopy (XAS) performed after ball Magnesium borohydride, Mg(BH ) , is one of the most 4 2 milling, after desorption and after absorption shows that promising hydrogen storage materials due to its the Ni B additive remains unaffected, whereas NiCl and theoretical hydrogen capacity of 14.9 wt% [1]. However, 3 2 NiF additives react with Mg(BH ) during the hydrogen its application is hindered by poor kinetics and lack of 2 4 2 desorption-absorption, and forming compounds with a reversibility. The development of additives that might local structure very similar to that of amorphous Ni B. change and speed up the H-sorption reaction pathway, 3 Multinuclear NMR spectroscopy confirms the partial inhibiting the formation of stable higher polyboranes, is reversibility of the system, as well as the formation of currently being extensively explored in order to improve 2– [B10H10] during hydrogen absorption. The presence of the kinetics and reversibility of H-sorption in Mg(BH ) . In 2– 4 2 [B H ] (n = 10; 12) was also detected by infrared (IR) the present work, four different Ni-based additives have n n spectroscopy of the dehydrogenated and rehydrogenated been investigated as possible catalysts towards samples. The IR measurements give no clear indication reversible Mg(BH ) decomposition. 4 2 that ions containing B–H–B bridged hydrogen groups Experimental methods and results were formed during the H-sorption cycle.

-Mg(BH4)2 was ball milled together with 2 mol% of Acknowledgments different Ni-based additives (Ni ): Ni ; NiCl ; NiF ; add nano 2 2 This work was supported by the Norwegian Research Ni B. Under the applied ball-milling conditions, no 3 Council within the NANOMAT and FRIENERGI -Mg(BH ) and 4 2 programs, and by the European Fuel Cells and Hydrogen Ni were observed. Hydrogen desorption carried out at add Joint Undertaking (http://www.fch-ju.eu) under temperatures 220-264 ºC resulted for all samples, in collaborative project “BOR4STORE” (Grant agreement partial decomposition of Mg(BH ) and formation of 4 2 no.: N° 303428). amorphous phases, as seen by Powder X-ray Diffraction (PXD). PXD analysis after rehydrogenation at References temperatures 210-262 ºC and at pressures between 100 [1] Orimo, S.; Nakamori, Y.; Eliseo, J. R.; Züttel, A.; and 155 bar revealed increasing - Jensen, C. M. Chem. Rev. 2007, 107, 4111–4132 Mg(BH4)2, indicating a partial reversibility of the – composite powders. The highest amount of [BH4] is

Dr. Stefano Deledda received his Master in Chemistry from the University of Sassari, Italy, and his PhD in Chemistry from the Dresden Technical University, Germany. He has a 15-year-long experience in the synthesis and characterization of metastable and nanocrystalline alloys and compounds processed by non-equilibrium techniques. At IFE since 2005, his research activities include the synthesis of complex hydrides, multicomponent alloys and composites by ball milling and their structural and thermodynamic characterization. He has authored and co-authored more than 40 publications. He is now project responsible for the construction of the new high-resolution neutron Stefano powder diffractometer, work-package leader in an EU Project on hydrogen storage materials Deledda (BOR4STORE) and scientific contact for one on advanced magnetic materials (NANOPYME).

Corresponding author: Stefano Deledda, email: [email protected], Tel.: +47 407 26 921

46 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

IMPROVING THE HYDROGEN STORAGE PERFORMACNES OF MAGNISIUM HYDIRDE BY ADDING CATALYSTS Baozhong Liu1,2,*, Yanping Fan1, Yuan Li2, Shumin Han2

1 School of Material Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, China

2 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China

Abstract: Adding the catalyst is an effective methods to improve hydrogen sorption performance of MgH2. Recently, we studied the infulunce of the various catalysts, including MoS2, MoO2, Fe3S4, WS2, LaFeO3, MgTiO3 and 2D TiC MXene, on the hydrogen absorption/desorption kinetics of MgH2. The dehydrogenation temperature, hydriding/dehydriding rate and the activation energy of the hydrogen desorption process are estimated, and the catalytic mechanism of the catalysts has also been analyzed.

Background (2) The synthesized Fe3S4 and WS2 were applied as the catalyst to improve the hydrogen storage properties. The Magnesium (Mg) is considered a promising candidate dehydrogenation temperature of MgH by ball-milling with material for reversible hydrogen storage owing to its high 2 Fe S and WS were markedly reduced by 90 K and 60 K, hydrogen storage capacity, outstanding reversibility and 3 4 2 respectively. MgH +20 wt.% Fe S and MgH +20 wt.% low cost [1]. However, the hydrogen desorption 2 3 4 2 WS could release 3.8 wt.% and 4.2 wt.% hydrogen temperature of Mg hydride is usually very high due to the 2 within 21 min at 623 K, respectively, while MgH was only strong affinity between magnesium and hydrogen. 2 2.3 wt.%. These existed new Fe and MgS or W and MgS Therefore, it becomes a critical issue to improve derived from the reaction between MgH and Fe S or hydrogenation and dehydrogenation kinetics for the 2 3 4 WS , and the synergetic effect of Fe or W and MgS was widespread application of hydrogen storage materials 2 responsible for the improvement of the hydrogen containing Mg. It is confirmed that adding various performances. catalysts is one of the effective methods to decrease the hydrogen sorption temperature and improve the rate of (3) The synthesized LaFeO3 or MgTiO3 was applied as hydrding/dehydriding. the catalyst to improve the hydrogen storage properties, The dehydrogenation temperature of MgH was reduces Present work 2 by adding LaFeO3 and MgTiO3, and the hydrogen (1) MoS2 has a superior catalytic effect over MoO2 on sorption kinetics were improved. And the dehydriding improving the hydrogen kinetic properties of MgH2 [3]. activation energy was also reduced by ball-milling with The hydrogen desorption temperature decreased from LaFeO3 or MgTiO3. 662.10 K (pure MgH ) to 650.07 K (MgH +20 wt.%MoO ) 2 2 2 (4) The hydrogen sorption performances of MgH were and 640.34 K (MgH +20 wt.%MoS ). According to the 2 2 2 improved by adding 2D TiC MXene prepared by Kissinger plot, the activation energy of the hydrogen exfoliating the MAX phases. desorption process is estimated to be 101.34 kJ/mol of MgH2 with MoO2 and 87.19 kJ/mol of that with MoS2, References indicating that the dehydriding process enhancement of [1] Lu J, Choi YJ, Fang ZZ, et al. J. Am. Chem. Soc. 2009; the hydriding/dehydriding kinetics of MgH is attributed to 2 131: 15843-52. the presence of MgS and Mo or MgO and Mo, which catalyze the hydrogen absorption/desorption behaviour of [2] Bogdnovic B, Harwing TH, Spliethoff B. Int. J. MgH2. The comparisons between MoS2 and MoO2 Hydrogen Energy 1993; 18: 575-89. suggest that S anion has superior properties than O [3] Jia Y, Han SM, Zhang W, Zhao X, et al. Int J anion on catalyzing the hydriding/dehydriding kinetics. Hydrogen Energy 2013, 38:2352-6.

Baozhong Liu was born on 18 September 1976 in Qinhuangdao city, China. 2000 Bachelor in Department of Chemistry, Yanshan Univeristy, Qinhuangdao, China. 2007 Ph.D. in State Key Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun, China. 2009 Postdoctor in AIST, Japan. 2014 Professor in College of Materials Science and Engneering, Henan Polytechnic University, Jiaozuo, China, Research field: Hydrogen storage materials, Hydrogen storage electrode alloys, nickel/metal hydride (Ni/MH) secondary battery Baozhong Liu

Corresponding author: Baozhong Liu, email: [email protected], Tel. +86-391-3989859

47 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

REACTIVE HYDRIDE COMPOSITE SYSTEMS FOR BOROHYDRIDE DESTABILISATION

Anna-Lisa Chaudhary,1 Nils Bergemann,1 Guanqiao Li,2 Motoaki Matsuo,2 Chiara Milanese,3 Shin-ichi Orimo,2 Claudio Pistidda,1 Thomas Klassen1 and Martin Dornheim1

1Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Geesthacht , Germany

2WPI-Advanced Institute for Materials Research, Tohoku University, Sendai, Japan 3 Pavia H2 Lab, Department of Chemistry, Physical Chemistry Division, University of Pavia, Pavia, Italy

Abstract

Hydrogen as an energy carrier can be used in combination with renewable technologies as a complete clean, green energy source compared to current fossil fuel driven technologies. An effective hydrogen system requires suitable hydrogen storage to enable the storage of excess energy produced by renewable energy to be used at times when direct production from renewables is low. This then allows for continuous clean energy supply. One such storage solution is the use of metal hydrides as they are able to store and release hydrogen by forming and breaking chemical bonds. Complex hydrides are, especially, very promising as hydrogen-storage materials, due to their high gravimetric and volumetric capacities. New combinations of complex metal borohydrides ball milled with the transition metal complex hydrides, ScH2 or Mg2FeH6 are characterised and compared. Initially, the Reactive Hydride Composite (RHC) systems of Li, Mg and Ca borohydrides are combined with ScH2 and desorption properties studied using techniques such as in situ synchrotron X-ray analysis and coupled differential scanning calorimetry with Sieverts apparatus. The effect of ScH2 on the borohydrides did have some destabilization effect; however, reaction kinetic limitations did not allow the systems to achieve theoretical thermodynamic equilibrium. Other RHC systems containing light metal borohydrides MBH4 (where M = Li, Na, Mg, K or Ca) are milled with Mg2FeH6 and desorption properties characterised using thermal property analysis, mass spectrometry and X-ray diffraction. It was found that these borohydrides combined with Mg2FeH6, at a specific anionic ratio, underwent simultaneous desorption of the two hydrides, which resulted in a single event of hydrogen release. These borohydrides-Mg2FeH6 systems also show cationic independence since, all five light metal borohydride mixtures desorbed hydrogen within a narrow temperature range centering around 300 C.

Short CV for Anna-Lisa Chaudhary Anna-Lisa studied chemical engineering including a Master’s degree at the University of Queensland in Brisbane, Australia. Whist studying her Master’s degree, she also spent 4 years living and working as an English teacher in Kyoto Japan, occasionally visiting Tsukuba for some in situ X-ray diffraction experiments. She was fortunate to be asked to work for Plantic Technologies Limited in Melbourne after completing her studies. After some time, she then went on to complete a Ph.D. at Curtin University in Perth. Currently, she is working as a research scientist at the Helmholz Zentrum Geesthacht in Germany whilst travelling to Japan and Italy for collaborative research.

Corresponding author: Anna-Lisa Chaudhary, [email protected], +49 (0) 4152 87 2647

48 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

2- CIRCUMVENTING THE FORMATION OF [B12H12] SPECIES FOR REVERSIBLE HYDROGEN STORAGE

1Yigang YAN, 1Arndt Remhof, 2Daniel Rentsch, 1Andreas Züttel

1Empa, Hydrogen & Energy, Dübendorf, Switzerland 2Empa, Functional Polymers, Dübendorf, Switzerland

There is a common belief that [B12H12] compounds (e.g., MgB12H12) form as intermediates and serve as boron sinks 11 preventing the re-hydrogenation for metal borohydrides such as Mg(BH4)2 and Ca(BH4)2. In this study, detailed B NMR measurements provide evidences that [B12H12] compounds can be avoided/circumvented in the hydrogen sorption process of Mg(BH4)2 and Ca(BH4)2.

Introduction Results 11 1 Metal borohydrides display high hydrogen densities and Figure 1 shows B{ H} NMR spectra of DMSO-d6 thereby offer the hope to overcome the challenges solutions of decomposed Mg(BH4)2 and the reference associated with solid hydrogen storage. samples. MgB12H12, a DMSO soluble compound, was not observed in the DMSO-d6 solutions of all decomposition In order to develop a reversible storage system toward [2] products of Mg(BH4)2 from 265 to 400ºC. For Ca(BH4)2, the practical applications, the hydrogen desorption CaB12H12 was also not observed in the solid residues of pathway and the key intermediates involved need to be decomposition under vacuum. known. Many efforts have been raised to identify the reaction intermediates during the decomposition process. There is a common belief that [B12H12] compounds (e.g., MgB12H12) form as intermediates and serve as boron sinks preventing the re-hydrogenation for metal [1] borohydrides such as Mg(BH4)2 and Ca(BH4)2. However, it is still lacking of firm evidences for the formation of MB12H12 (M = Mg, Ca) and their roles in the hydrogen sorption process need to be further elucidated. Therefore, we carried out detailed 11B NMR measurements to identify the intermediates forming during the desorption processes of Mg(BH4)2 and Ca(BH4)2.

Experimental 11 Solution-state B NMR spectra were recorded on a 5 11 mm inverse broadband probe at 298 K. For each Figure 1. B NMR spectra of DMSO-d6 solutions of Mg(BH4)2 decomposed at 265 to 400°C under dynamic vacuum, referred measurement, amounts of ≈ 10 mg solid samples and to Mg(BH4)2 and MgB12H12. about 5 mL of water or DMSO were weighed into tight vials 11B NMR chemical shifts are reported in parts per References million (ppm), externally referenced to a 1.0 M B(OH)3 [1] S. J. Hwang et al., J. Phys. Chem C, 2008, 112, 3164. aqueous solution at 19.6 ppm, and 1H NMR chemical [2] Y. Yan et al., Chem. Comm., 2015, DOI: shifts are referenced to the resonances of water (4.7 ppm) 10.1039/C4CC05266H or DMSO (2.49 ppm).

2004-07 PhD student at Institute of materials science and engineering, Sichuan University, China. 2007-08 Senior engineer at SAE Magnetics (H.K.) Ltd, China. 2008-09 Postdoctoral Fellowship at Institute for Materials Research, Tohoku University, Japan. 2009-11 JSPS Postdoctoral Fellowship at Institute for Materials Research, Tohoku University, Japan. 2011-12 Postdoctoral Fellowship at Empa, Switzerland. 2012 Visiting Scientist in Utrecht University, the Netherlands. 2012- Scientist at Empa, Switzerland.

Corresponding author: Yigang YAN, [email protected], +41 58 765 40 82

49 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

ENERGY AND CO2 AT CEMENT INDUSTRY FOR FUTURE Fadime HOSOGLU

Holcim Technology Ltd., Im Schachen, CH-5113 Holderbank AG, Switzerland

Abstract Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;vText; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text; Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;Text; Text; Text; Text; Text; Text;Text; Text; Text; Text;

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Dr. Fadime Hosoglu has finished school of Engineering in the Environmental engineering in university of Mersin on 2008. During Engineering school have studied Polytechnic of Valencia on 2005. I have studied my Master at University Marne La Vallée in environmental department on 2009. After my master, I have studied my PhD about: “Production of 1-propanol and 1-butanol from the mixture methanol and ethanol over hydrotalcite catalyst” at university Science and Technology of Lille 1 on 2012. From 2012 to 2014 I was Post. Doc. in the team of Prof. Andreas Züttel "Hydrogen and Energy" at Empa in Switzerland were I developed a new experimental setup for the Fadime investigation of CO2 reduction catalyst and I synthesised new catalysts. Since Sept. 2014 I'm a HOSOGLU project manager at Holcim Technology in Switzerland.

Corresponding author: Fadime HOSOGLU, [email protected], Tel.

50 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Redox&flow&batteries&for&on&demand&hydrogen&production& Véronique Amstutz, Heron Vrubel, Pekka Peljo, Hubert Girault Laboratoire d’électrochimie physique et analytique, Ecole Polytechnique Féderale de Lausanne

Graphical Abstract

Subtitle We shall discuss here nanoparticles Recently, we have shown that it was supported on silica or other ceramics. Two possible to couple a vanadium redox flow redox half-reactions take on the battery with two external circuits to carry nanoparticle, e.g. hydrogen evolution and out indirect and intermittent water V(II) oxidation, and we shall discuss both electrolysis. the thermodynamic and the kinetic The gist of this approach is to store “junk aspects. electricity” in a redox flow battery when its prize from the grid or from renewable More generally, we shall discuss strategies sources is low and to use this stored redox to develop fuelling stations for tomorrow’s energy to carry out indirect electrolysis. cars.

Here, Vanadium(II) can be used to References produce hydrogen whilst Vanadium(V) can Renewable& Hydrogen& Generation& from& a& be used to oxidise SO2 to generate Dual;Circuit&Redox&Flow&Battery& protons and sulfuric acid. Alternatively, V.& Amstutz,& K.E.& Toghill,& F.& Powlesland,& H.& cerium can be used such that cerium IV Vrubel,&C.&Comninellis,&X.&Hu&and&H.H.&Girault& can oxidise water to oxygen. Energy Env. Sci., 7 (2014) 2350-2358 To perform these reactions in external reactors, it is important to use nanoparticle catalysts.

Prof.&Hubert&Girault& & Professor,(Laboratory(of(Physical(and(Analytical( Electrochemistry,(EPFL( ( & & 51 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

1) HIGH PRESSURE ALKALINE ELECTROLYSIS Michael Ranft , Thomas Jordan1), Andreas Class2)

1) Institute for Nuclear and Energy Technology, Karlsruhe Institute of Technology 2) Areva Nuclear Professional School, Karlsruhe Institute of Technology

A hydrogen filling station stores hydrogen at a pressure of 450bar. Producing hydrogen at this pressure level with an alkaline electrolyser would avoid the need of an external compressor. The approach leads to a less complex system with an increased overall efficiency. Additional a numerical tool reflecting H2 and O2 bubble behaviour at high pressure in potassium hydroxide solution is developed and validated against appropriate experiments.

Motivation The Karlsruhe Institute of Technology (KIT) operates a filling station which provides hydrogen for the two fuel cell-based buses that connects the different locations of KIT. Currently an external supplier provides the required hydrogen on a weekly basis. In the future “green” hydrogen shall be produced directly at KIT. Besides the possible hydrogen sources VERENA [1] and bioliq [2] at Campus North of KIT, a high pressure alkaline electrolyser is planned which uses the excessive electric Figure 1: Sketch of the high pressure experiments energy from the combined heat and power unit or from solar-panel installations within the Campus North. Expected Results Alkaline electrolysers are a well-known technology with At the end of the project a numerical tool exists which high purity of produced H2 and good scalability. In reflects H2 and O2 bubble behaviour at high pressure combination with our partner Instituto Tecnológico de alkaline electrolysis. Construction rules are established Buenos Aires (ITBA) from Argentina a high pressure based on the simulation results for a better gas phase electrolysers is planned that provides H2 directly at a transport inside the electrolyser and for optimizing the pressure of about 450bar. The abstinence of a gas/electrolyte separation. compressor prevents efficiency losses due to H2 compression and yields to a higher reliability, due to less complexity of the whole system. Approach With the aid of two-phase flow simulation and supported experiments an optimized design of the electrolyser is developed with enhanced gas phase transport from cell stack to gas-liquid separator and improved separation process of H2 and O2 bubbles from the electrolyte The simulation is based on solving an transport equation for gas mass fraction probability density function (pdf): Figure 2: Sketch of the gas-liquid separator

��� ���(�)� (1) + � ∙ ��� + The construction of the electrolyser is done in �� �� collaboration with ITBA. They are responsible for the ⟨ ⟩ 1 � � − � electrolyser with the gas separator and KIT for the safety = � ∙ � ��� + �� 2 �� � assessment and the integration of the whole system in the existing hydrogen fuel station. Instead using a standard Lagrange approach this pdf is approximated by a finite number of stochastic fields [3]. A transport equation for each stochastic field is solved in References the Eulerian framework. This method avoids the Euler- [1] VERENA Pilot Plant, Lagrange coupling. In addition a new model is developed http://www.ikft.kit.edu/english/138.php describing the bubble/bubble and bubble with free surface interaction of both H2 and O2 bubbles in [2] bioliq Plant, http://www.bioliq.de/english/index.php potassium hydroxide solution at pressures up to 450bar. [3] L. Valiño, Flow, Turbulence and Combustion 60 Validation experiments are done investigating the bubble (1998) 157-172. production at the electrode surface at high pressure. In a second series of experiments H2 bubbles are charged in a water column and their behaviour is analysed up to background pressures of 450bar.

52 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Michael Ranft finished his studies of Aerospace Engineering at the TU Dresden, Germany in 2012. He participated in two semesters abroad at the Universidad del Valle de Atemajac (UNIVA) in Guadalajara, Mexico and in a half year internship at Airbus in Bremen, Germany. In 2012 he wrote his diploma thesis in collaboration with MTU Friedrichshafen, Germany at the Karlsruhe Institute of Technology (KIT) about the implementation of a new combustion model in the free C++ library OpenFOAM. After a short period as scientific assistant Michael Ranft started his PhD work on high pressure alkaline electrolysis at KIT. Michael Ranft

Corresponding author: Michael Ranft, [email protected], Tel. +49 721 608-24897

53 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

GAS ATOMISED HYDROGEN STORAGE ALLOYS Mariana Spodaryk1*, Larisa Shcherbakova1, Anatoliy Sameljuk1, Oleg Khyzhun1, Yurii Solonin1, Philippe Mauron2, Arndt Remhof2, Andreas Züttel 2, 3 1 Institute for Problems of Materials Science, NAS of Ukraine, 3, Krzhyzhanovsky Str., 03680, Kyiv-142, Ukraine 2 Division ‘‘Hydrogen and Energy’’, EMPA Materials Science and Technology, 8600 Dübendorf, Switzerland 3 Ecole polytechnique fédérale de Lausanne (EPFL), Institut des sciences et ingénierie chimiques, CH-1015 Lausanne, Switzerland

The phase composition, morphology, structure, and the surface state of gas atomised AB5 type hydrogen storage alloys have been investigated. The influence of the production method and the alloy composition on the electrode properties are discussed in detail. We propose a mechanism for the capacity degradation of the gas atomised alloy electrodes.

Introduction decreases the surface energy of the alloys, thus leading to a less spherical shape [3,4]. The gas atomised alloy The alloy production method, defines the alloy micro- electrodes show high electrochemical stability and structure, influences the electrochemical reaction hydrogen storage capacity. The activation, kinetics and kinetics, storage capacity, and especially the cycle hydrogen storage properties of gas atomised alloys stability of the metal hydride electrodes. High pressure improve with increasing particle size, and this gas atomisation (HPGA) is a technology with a rapid 6 improvement is even more pronounced for Co-containing cooling rate of up to 10 K/s, which allows to produce alloys. Using impedance spectroscopy we found that the intermetallic alloy powders of spherical shape directly in reaction resistance is determined by the surface the µm size range. Large quantity of material can be composition of the activated alloys. Co-free alloys produced (up to 10 kg/h) and directly results in uniform, activate within a few cycles, show better high rate well-defined particles, does not require the standard discharge ability (4-17C) as compared to Co-containing timely grinding process of the AB -type alloys for battery 5 alloys, which exhibit the highest cycle stability due to the electrodes Gas atomized alloy powders are sophisticated passivation of the surface. We propose an alloy non-equilibrium materials with unique properties for Ni- electrodes degradation mechanism based on the MH batteries, e.g. a surface with enhanced corrosion corrosion and decrepitation due to volume expansion [4]. resistance, leading to an increased cycle stability [1]. According to it Co-containing alloy electrodes mostly However, the electrochemical and hydrogen storage loose the cycle stability because of mechanical properties of gas atomized materials are discussed decrepitation, whereas the Co-free alloys mostly controversially from the viewpoint of application [1,2], degradate from selective dissolution of aluminum. therefore, the results of a comprehensive study on four representative gas atomized alloys are presented.. References

[1] Yu.M. Solonin, V.V. Savin, S.M. Solonin et al., J. Results and Discussion Alloys Compd. 253–254 (1997) 594–597. The phase composition, morphology, structure, and the [2] K. Young, T. Ouchi, A. Banik et al., J. Alloys Compd. surface state of gas atomised AB5-type hydrogen storage 509:10 (2011) 4896–4904. alloys, where Ni was partially substituted by Co and Al and La by Mm have been investigated. All samples [3] M. Spodaryk, L. Shcherbakova, A. Sameljuk et al., J. Alloys Compd. 607 (2014) 32–38. exhibit the hexagonal CaCu5−type structure. The alloy composition affected the morphology of the gas atomised [4] M. Spodaryk, L. Shcherbakova, A. Sameljuk et al., J. particles: Co-free alloys are spherical and Co-containing Alloys Compd. 621 (2015) 225–231. alloys are irregularly shaped. The addition of Co

Short CV of Mariana SPODARYK Born 17th of October 1988 in Ivano-Frankivsk, Ukraine. 2011 Master Degree on Technical Electrochemistry in Kyiv National University of Technology and Design, Ukraine 2011 - 2014 PhD student in the Institute for Problems of Materials Science, Ukraine National Academy of Sciences in Kyiv, Ukraine

2013 - 2014 Guest Scientist at EMPA Materials Science & Technology, Switzerland Mariana Spodaryk

Corresponding author: Mariana Spodaryk, email: [email protected], Tel. (+38) (068) 5417935

54 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

INVESTIGATION OF A Pt CONTAINING WASHCOAT ON SIC FOAM FOR HYDROGEN COMBUSTION APPLICATIONS A. Fernándeza,b,*,G.M. Arzaca, U.F.Vogtb,c, F.Hosoglub, A.Borgschulteb, M.C. Jimeneza, O. Montesa, A. Züttelb a Instituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja. Seville. Spain.b EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland.c Department Crystallography, Institute of Earth and Environmental Science, Albert-Ludwigs-University of Freiburg, Germany

Abstract: A commercial Pt based washcoat (Pt/SiC), was studied for the first time as catalyst for hydrogen combustion. Structural characterization was performed using Electron Microscopy, X-Ray diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS). The reaction was monitored for the first time following water concentration by Fourier Transform Infrared spectra (FTIR). The Pt/SiC catalyst has demonstrated to be active enough to start up the reaction very quickly at room temperature and very small amounts of material were used to achieve the kinetic regime. The material has been -1 -1 able to convert as much as 18.5Lhydrogen.min gPt in conditions of excess of catalyst. The activation energy obtained in kinetic conditions was (35±1) kJ.mol-1. ______Catalytic hydrogen combustion (CHC, reaction (1)) is a start up the reaction very quickly at room temperature key reaction in the “hydrogen economy” which can be and very small amounts of material were used to achieve employed as a means of heat production as well as for the kinetic regime. The material has been able to convert -1 -1 safety purposes. [1,3] as much as 18.5Lhydrogen*min gPt in conditions of excess of catalyst. Pt/SiC was studied after use by H + ½ O → H O (1) 2 2 2 means of XPS and no significant changes on Pt oxidation Reaction (1) is highly exothermic (-286kJ.mol-1) and can states were found with respect to the fresh one. be controlled using appropriate catalysts, in contrast to Catalytic activity was studied in kinetic regime as a flame combustion which produces NOx and presents function of temperature. The Arrhenius plot permitted to safety issues. Thinking of a practical application for (1), obtain a (35±1) kJ.mol-1 activation energy. catalyst should be prepared in supported form, which improves dispersion, prevents aggregation and facilitates References its use in successive cycles. For heating purposes, [1] V.M. Shinde, et al Catalysis Today 198 (2012) 270- silicon carbide should be the support of election. To our 279. knowledge, SiC has not been employed for CHC before. [2] A. M. Venezia, et al Surface and interface analysis, In this work we used for the first time a commercial Pt 19, (1992) 543-547 washcoat on highly porous SiC foams (Pt/SiC) as catalyst for CHC for lean (1% v/v) H2/air mixtures. Kinetic studies [3] U. F. Vogt, B. Fumey, M. Bielmann, V. Siong, N. were conducted using a novel method which consists of Gallandat, A. Züttel, Catalytic Hydrogen Combustion measuring water concentration by FTIR in the exhaust on Porous SiC Ceramics, European Fuel Cell Forum gas. This method is advantageous with respect to gas 2011, 28 June -1 July 2011, Lucerne Switzerland, chromatography because permits to monitor the reaction Fuel Cell Applications II, chapter 15 – Session B07 second-to-second. The material was characterized by pp. 45-54, XRD, XPS, Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM). The catalyst is composed of 9-20 nm disperse Pt nanoparticles decorating a mixture of SiC, Al2O3, SiO2 and small amounts of ceria. Pt particle size was estimated using Scherrer´s formula (111) resulting in 17 nm. Pt/SiC has demonstrated to be active enough to Born May 1958 in Vigo, Spain, Prof. Asunción Fernández graduated in Chemistry at the University of Cádiz (Spain) (1980) and in Physics at UNED (Spanish Open University) (1984). She carried out her PhD work at Max-Planck Institut für Strahlenchemie in Mülheim a.d. Ruhr (Germany) obtaining the Dr. rer. nat. degree at the University of Dortmund (Germany) in June 1983 on the subject of photocatalytic H2 production from water solutions. In 1984 she joined the Materials Science Institute of Seville (Spain), a mix-centre of the Spanish Research Council (CSIC) and the Univ. Seville; where she is leading the “Nanostructured Materials & Microstructure” group and the “Advanced Laboratory for Nanoscopies and Spectroscopies”. Her actual research is devoted to the fabrication and ASUNCIÓN FERNÁNDEZ characterization of nanostructured coatings by PVD and the study of materials for H2 storage/production for portable applications. *Corresponding author: Asunción Fernández, [email protected], +34-954489531

55 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

PREPARATION OF CO AND CO-B SUPPORTED CATALYSTS BY MAGNETRON SPUTTERING: A STEP FORWARD IN UNDERSTANDING THE ACTIVE PHASE AND DEACTIVATION PROCESSES IN SODIUM BOROHYDRIDE HYDROLYSIS V. Godinhoa, G.M. Arzacb, M. Paladinic, D. Hufschmidta, L.C. Gontarda, M.C. Jimeneza, A. Fernándeza,* a Instituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja. Seville. Spain. In this work we report on the preparation and characterization of Co and Co-B catalysts prepared by magnetron sputtering supported on polymeric membranes for sodium borohydride hydrolysis. The preparation of both reference materials with similar microstructure is an intrinsic capability of the sputtering technique and permits us to give new insights into the study of the active phase and deactivation process, both being at present under intense discussion.

Over the last decade the hydrolysis of hydrogen We have recently reported the preparation of storage materials such as sodium borohydride (NaBH4, supported Co metallic catalysts as thin films by SB) has been one of the most investigated approaches magnetron sputtering for sodium borohydride hydrolysis. for hydrogen generation. SB is stable in dry air and [3] Magnetron sputtering is a very versatile technique that combines lightweight with high hydrogen content (10.8 permitted us to deposit highly columnar coatings, with wt%). high surface area to be used as catalysts. NaBH4 + 2H2O → 4H2 + NaBO2 (1) In this work we report on the preparation and Tough spontaneous, SB hydrolysis (reaction 1) characterization of Co and Co-B coatings prepared by needs catalysts to occur at appreciable rates. Co has magnetron sputtering supported on polymeric demonstrated to be a good choice because its membranes for sodium borohydride hydrolysis. Catalytic compromise between activity and cost. However, its activity of Co and Co-B films is investigated. Techniques major drawback is related to stability: these materials usually applied in the characterization of thin films will be deactivate upon cycling. here employed for the analysis of supported catalysts Despite the great number of papers reporting Co before and after catalytic test. Advanced Electron and Co-B based catalysts, the nature of the active phase Microscopy techniques will be also employed to fully is still under intense discussion. Several compounds characterize samples from a chemical and structural 0 have been proposed such as Co , CoxBy (cobalt borides), point of view. The preparation of Co and Co-B reference 0 0 Co(BO2)2, (CoB)5H3, or mixtures of Co and B , etc. [1] materials with similar microstructure is an intrinsic The major difficulty in the elucidation of the active phase capability of the sputtering technique and permits us to is SB itself: its reducing and boron-donating capabilities give new insights into the study of the active phase and modify catalysts´ surface during the reaction. Most often deactivation process. Co-B catalysts are prepared as ultrafine amorphous powders by using a boron-containing reducing agent References (usually SB). This permits to obtain Co in metallic state [1]Demirci, U. B et al. Physical Chemistry Chemical because the protective role of boron compounds forms Physics 2014, 16 (15), 6872-6885. altogether a complex Co-B material. [2] The preparation [2]Arzac, G. M et al. Chemcatchem 2011, 3 (8), 1305- of Co nanoparticles (without boron) of similar size and 1313. crystallinity than the Co-B nanopowder is really [3]Paladini, M. et al. Applied Catalysis B-Environmental challenging because, in absence of capping agent, the 2014, 158, 400-409. oxidation of cobalt would be inevitable.

Born May 1958 in Vigo, Spain, Prof. Asunción Fernández graduated in Chemistry at the University of Cádiz (Spain) (1980) and in Physics at UNED (Spanish Open University) (1984). She carried out her PhD work at Max-Planck Institut für Strahlenchemie in Mülheim a.d. Ruhr (Germany) obtaining the Dr. rer. nat. degree at the University of Dortmund (Germany) in June 1983 on the subject of photocatalytic H2 production from water solutions. In 1984 she joined the Materials Science Institute of Seville (Spain), a mix-centre of the Spanish Research Council (CSIC) and the Univ. Seville; where she is leading the “Nanostructured Materials & Microstructure” group and the “Advanced Laboratory for Nanoscopies and Spectroscopies”. Her actual research is devoted to the fabrication and ASUNCIÓN FERNÁNDEZ characterization of nanostructured coatings by PVD and the study of materials for H2 storage/production for portable applications. *Corresponding author: Asunción Fernández, [email protected], +34-954489531

56 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

A MATLAB/SIMULINK® DESIGN PROCEDURE FOR PROTON EXCHANGE MEMBRANE FUEL CELLS Domenico De Luca, Petronilla Fragiacomo, Giuseppe De Lorenzo University of Calabria, Department of Mechanical, Energy and Management Engineering, Rende (CS), Italy

Abstract The paper shows and examines a design procedure for performances estimation of Proton Exchange Membrane Fuel Cells (PEMFCs), which are expressed through the analytical formulation of polarization curve, power output and inlet hydrogen flow rate. The procedure, which has been set up using a Matlab/Simulink® model, is based on the equations derived from the theory of electrochemistry and thermodynamics of PEMFCs. The analytical expressions of performances can be used in order to evaluate the behaviour of a PEMFC in a power generating system.

Introduction exchange current density i0, limiting current density iL, transfer coefficient , amplification constant , mass During the past few decades, PEMFCs have received an 1 transport k and internal resistance r. The operating increasing attention especially for use in transportation in variables are: operating temperature T, ambient innovative powertrains as substitute of the Internal temperature T , , operating pressure p, relative humidity Combustion Engine (ICE). [1] ext In this work, a design procedure has been developed , stoichiometric ratio at anode StH2 and at cathode StO2. through a model, shown in Fig. 1, which allows the The cell specifications are: cell area Acell, number of cells definition of the characteristics of PEMFCs, in terms of Ncells and membrane thickness tm. voltage, power and consumption using input data inside Results each block. The results show the graphs in which voltage (V), power (W) and hydrogen consumption (g/s) are plotted over current, as shown in Fig. 3.

Fig. 1 – Matlab/Simulink® model for performances calculations.

Then, the analytical expressions obtained are used as Fig. 3 – Results of design procedure. look-up tables in the block diagram, shown in Fig. 2, which contains the simulation of a PEMFC. Model validation The model validation was done by the comparison between the results of design procedure and the technical datasheet of main PEMFCs manufactures (Horizon, Ballard and Nuvera). References [1] X. Zhang, J. Guo, J. Chen: “The parametric optimum Fig. 2 – Block diagram for PEMFC simulation. analysis of a PEM fuel cell and its load matching”, Energy, Vol. 35 (2010), pp. 5294-5299. Input data [2] M.G. Santarelli, M.F.Torchio, P. Cochis: “Parameters The most important input data used in the model can be estimation of a PEM fuel cell polarization curve and classified in empirical parameters, operating variables analysis of their behavior with temperature”, Journal and cell specifications. [2] The empirical parameters are: of Power Source, Vol. 159 (2006), pp. 824-835.

Born in 1979. He received a Master Degree in Mechanical Engineering in 2004 at the University of Calabria. In 2004 he attended a fellowship project at ENEA, Research Center for Energy and Environment in Rome, about “Development of Fuel Cell Use in Railway Field”. From 2005 to 2008 he worked in the R&D departments of private automotive companies in Turin. In 2008 he received a specialization diploma for teaching at the Polytechnic of Turin and from 2009 to 2013 he worked in a high school as teacher of Mechanics. In 2013 he was visitor student at Hochschule Esslingen, Germany. He is currently developing a PhD program about “Innovative design of hybrid powertrain Domenico De Luca equipped with fuel cells” with Prof. Petronilla Fragiacomo. Corresponding author: Domenico De Luca, [email protected], Tel. +39 333 6575192

57 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

LIBH4: AN ELECTROLYTE FOR ALL SOLID-STATE LI-ION BATTERIES Didier Blanchard1, Dadi Sveinbjörnsson1, Suwarno2, Tejs Vegge1, and Petra E. de Jongh2 1Department of Energy Conversion and Storage, Technical University of Denmark, Denmark 2Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands

Lithium borohydride, LiBH4, is potentially interesting as a solid state electrolyte for Li-ion batteries. It consists of a lattice + - o of Li cations and BH4 anions and displays high lithium mobility, not at room temperature but above 110 C at which a transition to a high temperature hexagonal structure occurs. This hexagonal and highly Li+ conducting phase can be stabilized at room temperature forming a solid solution with lithium halides, with a LiBH4-LiI solid solution yielding the highest Li+ conduction. Another strategy to stabilize the high temperature polymorph below 110 oC is to nano-confine LiBH4 into mesoporous scaffold, leading to conductivities three orders of magnitude larger than for bulk LiBH4.

Lithium solid electrolytes: a Holy Grail electrolytes in all-solid-state cells, but the solid solution electrochemical stability is reduced to 3 V compared to For quantum leap improvements of the Li-ion battery 5 V for the pure LiBH . [3,4] energy densities, safety and lifetimes, the use of solid 4 electrolytes is a must. Conventional Li-ion batteries We recently found [5] that confining the hydride in contain organic liquids or gels as electrolytes. These mesoporous silica scaffolds decreases the phase + transition temperature and brings the conductivity to electrolytes have high Li conductivities but are -1 flammable and allow lithium dendrite formation, causing values as high as 0.1 mS.cm at room temperature, thus capacity fades and shortened lifetimes. Solid electrolytes three orders of magnitude higher than for bulk LiBH4. The system is stable over extended ranges of temperature enable the assembly of all-solid-state cells with superior o thermal and mechanical stabilities. They allow the use of (up to 140 C) and potentials (up to 6 V) which makes it lithium metal as anode, which has a higher gravimetric compatible with high voltage cathodes. The stability energy density than any electrodes used with liquid against lithium metal as well as the use of this new type electrolytes, and as dendrite formation is suppressed, the of solid electrolyte in all-solid-state battery has been space between the electrodes can be reduced. successfully tested. Furthermore, high energy density sulphur cathodes can This discovery opens up new possibilities for the be used, as solid electrolytes suppress the dissolution of production of efficient all-solid-state batteries. polysulphides. References A new type solid electrolyte [1] H. Oguchi, et al., Appl. Phys. Lett. (2009), 94, 141912 + Lithium borohydride, LiBH4, exhibits a high ionic Li [2] J. S. G. Myrdal, et al., J. Phys. Chem. C (2013), 117, conductivity in its high temperature polymorph (~1 9084. mS.cm-1 at 120 oC). This high temperature phase can be stabilized at room temperature by forming a solid solution [3] D. Sveinbjornsson, J. Electrochem. Soc. (2014), 161, with Li-halides [1]. Using Density Functional Theory A1432. calculations, Quasi-Elastic Neutron Scattering [4] M. Matsuo et al., Adv. Energy Mater. (2011), 1, 161. measurements [2] and positron annihilation spectroscopy, we have studied in detail the mechanism [5] D. Blanchard et al., Adv. Funct. Mater. (2014), DOI: of the Li+ conduction in such solid-solutions. We have 10.1002/adfm.201402538 shown that these solid solutions can be used as

D. Blanchard is, since 2013, Senior Researcher at the Technical University of Denmark, department of Energy Conversion and Storage (Group leader Tejs Vegge). He joined the group in 2008, as postdoctoral researcher and then scientist. His research focuses on materials for energy storage: solid-electrolytes, metal hydride batteries, ammonia storage and hydrogen storage in complex hydrides. He developed this later field of research while being postdoctoral researcher in Bjorn Hauback’s group at the institute for Energy Technology, Norway. D. Blanchard received his Ph.D. from the Université Joseph Fourier, Grenoble (France), after a curriculum in applied physics, geophysics and chemistry of the atmosphere. Didier Blanchard

Corresponding author: Didier Blanchard, [email protected], +45 46775899.

58 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

AEROGELS FOR CO2 CAPTURE Marco HOLZER1,2, Shanyu ZHAO2, Matthias KÖBEL2, Wim J. MALFAIT2, Andreas ZÜTTEL1,2 1) École Polytechnique Fédérale de Lausanne (EPFL), 2) EMPA Materials Science and Technology

Abstract CO2 may be captured via ad- and desorption from a solid sorbent, often assisted by grafted amine groups . Aerogels were synthesised with aminosilianes, designed to capture CO2 from 400 ppm in air. A novel silica aerogel absorber shows high CO2 absorption capacities combined with a high surface area, good mechanical strength and open pore structure resulting in a high performance nanomaterial for CO2 capture.

O=C=O

O=C=O O=C=O

O=C=O

Overview O=C=O Hydrocarbons played a crucial role in the development of O=C=O our society and are the most important energy vector for mobility. Thus, our society requires synthetic hydrocarbons for our future. Burning fossil fuels releases Figure 2. Amine silanes, the building gaseous products in the atmosphere. This causes a rise blocks of aerogels absorbing CO2 in CO2 concentration, disturbing the fragile equilibrium of our ecosystem. Hydrocarbons derived from atmospheric CO2 are carbon neutral, can be synthesized upon This is the thermodynamic optimum, resulting in the demand and have the energy density required to fly, corresponding minimum cost assuming electricity is contrary to H2. used. However, there is no technology operating even close to this value. The energy intensive step is the CO2 capture sorbent regeneration where vacuum and heat are applied In April 2014, the northern hemisphere exceeded 400 to remove CO2. Aerogels have unique properties, such ppm CO2 in the atmosphere [1]. In order to concentrate as very low density and high surface area. By using CO2 from such a low concentration, work has the be amine silanes (Fig. 2), the basic groups are an intrinsic delivered: material property resulting in high stability and mechanical strength. !"$/!"! !"#$ !"ℎ $ References !!"# = !"#$ = 0.13 !!! ↔ !! 9.10! 400!!" !"#!"! !"#!"! [1] World Meteorological Org., Press Release No. 991

2005 - 06 Exchange Program Milwaukee, USA 2011 Internship University Strathclyde, Glasgow, Scotland 2013 Master degree Chem. Bio. Eng. ETH Zürich 2014 Swiss Federal Laboratories, Dübendorf: Alkaline Electrolysis 2014 - PhD EPFL Sion LMER: H2 driven desorption of CO2 sorbents

Marco Holzer [email protected], [email protected]

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

IN SITU X-RAY PHOTOELECTRON SPECTROSCOPY STUDIES ON HYDROGEN STORAGE AND CATALYSIS Shunsuke KATO,1 Andreas ZÜTTEL1,2 1. Empa, Swiss Federal Laboratories for Materials Science and Technology, Switzerland 2. École Polytechnique Fédérale de Lausanne (EPFL), Switzerland

The aim is to develop X-ray photoelectron spectroscopy for in situ investigations relevant to a wide range of research fields such as heterogeneous catalysis and energy storage. Near ambient pressure X-ray photoelectron spectroscopy has become an emerging tool for determining electronic structure and depth resolved chemical composition for interfacial reactions.

In Situ X-ray Photoelectron Spectroscopy and the dependence of surface properties on pressure (XPS) can be analysed in situ with respect to elemental composition, oxidation state, and chemical specificity. A Near ambient pressure XPS provides information about correlation between surface chemistry and surface the electronic structure of matter (gas, liquid, solid) under properties is determined by in situ XPS analysis. defined conditions and bridges the pressure gap between an ultra-high vacuum-based surface-science experiment and an experiment simulating realistic conditions at mbar pressure, thus providing valuable information about interfacial reactions, gas-solid, gas-liquid, and liquid-solid reactions.

Fig. 2 Surface analysis by ultrahigh vacuum (UHV) XPS vs. ambient pressure XPS.

References [1] S. Kato, M. Ammann, T. Huthwelker, C. Paun, M. Lampimäki, M.-T. Lee, M. Rothensteiner, J. A. van Bokhoven, Quantitative depth profiling of Ce3+ in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere, Phys. Chem. Chem. Phys., 2015, in Fig. 1 Potential curves for activated chemisorption of press. hydrogen on a metal surface covered with a surface layer [2] M.-T. Lee, M. A. Brown, S. Kato, A. Kleibert, A. and exothermic solution in the bulk. Türler, M. Ammann, Competition between organics Therefore, this direct surface analysis has become an and bromide at the aqueous solution–air interface immerging tool in a wide range of applications such as as seen from ozone uptake kinetics and X-ray heterogeneous catalysis [1], environmental science [2], photoelectron spectroscopy, J. Phys. Chem. A, and electrochemistry. In heterogeneous catalysis, for 2015, in press. example, restructuring of the surface during reactions

2005 Master of Engineering from Tokai University, Japan. 2007 PhD student at the Laboratory for Hydrogen & Energy, Empa, Swiss Federal Laboratories for Materials Science and Technology, and at the Department of Physics, the University of Fribourg, Switzerland. 2012 Dr. rer. nat. from the University of Fribourg. The thesis: Surface properties of hydrides and reactions. 2012 Postdoc at Laboratory of Radio- and Environmental Chemistry, Paul Scherrer Institute, Switzerland. Since 2014 Postdoc at Empa, Swiss Federal Laboratories for Materials Science and Technology.

Shunsuke KATO

Corresponding author: Shunsuke KATO, [email protected], Tel. +41 58 765 6086

60 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Kinetics study on hydrolytic dehydrogenation of alkaline sodium borohydride catalyzed by amorphous Mo-modified Co-B nanoparticles Yuan Li b, Dandan Ke b, Yali Du b, Shumin Han a,b,* a State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, China b College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China

Abstract: NaBH4 is a good candidate solid hydrogen carrier to supply pure hydrogen for portable application owing to its combined merits of high hydrogen storage gravimetric efficiency [1]. Some non-noble metallic boride (M-B) or phosphide [2] (M-P) show excellent activity in catalyzing hydrolysis of NaBH4 . Co-B is shown to be an effective catalyst in NaBH4 hydrolysis reaction, and some modification to Co-B compound has been reported [3]. In our study, Molybdenum-modified Co-B nanoparticles are obtained by the co-deposition chemical reduction method. The relationship between microstructure, catalytic activity and kinetic performance for H2 generation by hydrolysis of alkaline NaBH4 is studied. The synthesized nanoparticles are characterized by amorphous structure with smooth surface and homogeneous particle size around 30 nm. Mo promoter in the Co-Mo-B catalyst plays an important role for the high catalytic activity of NaBH4 hydrolysis, in which the formed molybdenum oxides on the Co-B surface weaken the bond strength of the H-OH facilitating the dissociation of water, and promote the whole hydrolysis reaction. As a result, Mo induced Co-B nanoparticles with the optimal Co/Mo molar ratio of 3:1 exhibit enhanced hydrogen generation rate as high as 4200 , which is about 2.5 times higher than that of the undoped Co-B catalyst. The promoting effect of Mo in the Co-Mo-B catalyst also results in lower activation energy of 43.7 kJ mol1 as compared to 52.6 kJ mol1 of pure Co-B catalyst. Kinetic studies reveal that, in low concentration, first-order reaction is observed with respect to NaBH4, indicating that surface adsorption - of BH4 is the rate-limiting step, whereas, at high concentration, hydrolysis reaction conforms to zero-order reaction owing to that the hydrolysis rate depends on surface reaction of adsorbed molecules. This work represents a substantial improvement in the synthesis of non-noble transition metal catalyst, opening the path for the application on catalytic hydrogen generation of NaBH4. Keyword: Mo-modified Co-B catalyst; Sodium borohydride hydrolysis; Hydrogen generation; Kinetics analysis

Fig. 1. TEM images of Co-B samples (a), Co-Mo-B Fig. 2. Hydrogen generation volume of alkaline Fig.3. Proposed mechanism for NaBH4 hydrolysis (Co:Mo=3:1) samples (b) and the corresponding EDAX NaBH4 hydrolysis in the presence of Co-B and catalyzed by Mo-modified Co-Bcatalyst. spectrum of Co-Mo-B (Co:Mo=3:1) samples (c). Co-Mo-B catalysts

References [1] H.B. Dai, Y. Liang, L.P. Ma, P. Wang, J. Phys. Chem. C, 112 (2008) 15886–15892. [2] S. Carenco, D. Portehault, C. Boissière, N. Mézailles, C. Sanchez, Chemical Reviews, 113 (2013) 7981–8065. [3] Y. Guo, Z. Dong, Z. Cui, X. Zhang, J. Ma, Int. J. Hydrogen Energy, 37 (2012) 1577–1583.

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials, and rare earth chemistry. In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogen storage alloys, light weight hydrogen strorage materials, rare earth–Mg–Ni-based electrode materials and hydrogen generation catalysts.

Shumin Han

Corresponding author: Shumin Han, [email protected], +86-335-8074648.

61 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

CATALYTIC EFFECTS OF MAGNESIUM GRAIN BOUNDARIES ON H2 DISSOCIATION Martin Panholzer1, Markus Obermayer1, Iris Bergmair2 and Kurt Hingerl1

1 Center for Surface and Nanoanalytics, Johannes Kepler University Linz

2 Profactor GmbH,Steyr-Gleink, Austria

Abstract: The influence of a Σ10(1124)/[1100] grain boundary in magnesium on the dissociation of the hydrogen molecule has been investigated by ab initio calculations. It is found that the dissociation barrier is indeed lowered by 0.115eV, including zero point motion, compared to the clean surface. This results in a 25 fold increase in the transition rate, at desorption temperature of 572K. Furthermore different diffusion paths of hydrogen in and out of the grain boundary plane are investigated.

Introduction we investigated a specific magnesium GB. We found that for the rather dense GB H2 diffusion is not possible, but Magnesiumhydride is, due to its high volumetric and propose this possibility for less dense GB. This would gravimetric hydrogen density, an attractive hydrogen drastically increase the effective surface area and as storage material. But there are two major drawbacks consequence the kinetics of the hydrogenation process. which hinder this storage material from commercial Another effect of the GB on the dissociation rate occurs usage, i) the high desorption energy (resulting in a for GB ending at the surface. A hydrogen molecule can desorption temp. of 300°C) and ii) the poor kinetics. enter the “GB surface layer” with a very low potential Large progress has been made in the last few years in barrier and reach the transition state. improving the kinetics. The main improvements are Furthermore the GB will not be as dense as in the bulk achieved by addition of catalysts and nano structuring of and will therefore have lower potential barriers for further the materials. The latter is done either by high energy ball diffusion. milling (HEBM) which reduces the particle size to some nm, or by serve plastic deformation (SPD) which The results also show that the zero point motion has a increases the density of defects, i.e. grain boundaries large effect on the energy barrier and the transition rates, (GB) and dislocations. also through the pre factor. The contribution of the zero point motion mainly contributes to the 25-fold rate It has been found by Vegge [1] that dissociation of H2 is increase at desorption temperature of 572K. the rate limiting step in ad- and desorption. From that point of view it is clear that reduction of particle size We conclude that the results are a strong hint on a results in an increase of kinetics. On the other hand catalytic effect of GB either ending at surfaces or, for Skripnyuk et al. [2] found that ECAP (equal channel rather wide GB, even allowing H2 diffusion, which angular pressing, a method which falls in the class of drastically increases the effective surface. Further work is SPD) processed material shows similar kinetics necessary in order to determine which kind of GB or compared to the HEBM treated [3]. This is rather dislocation has the strongest effect and to reduce surprising, since the particle size of the ECAP material, uncertainties due to the real path of the reaction. some microns, is huge compared to the HEBM powder. Therefore naturally the question arises what exactly is References the effect of GB on the dissociation dynamics. In this [1] Tejs Vegge. Phys. Rev. B, 70(3):035412, July 2004 paper we investigate possible reaction paths and [2] V.M. Skripnyuk, E. Rabkin, Y. Estrin, and R. Lapovok. examine a potential catalytic effect of GB’s. Int. J. Hydrogen Energy, 34(15):6320–6324, August Results and Conclusion 2009. The aim of this presentation is to clarify the effects on [3] M. Krystian, M.J. Zehetbauer, H. Kropik, B. Mingler, dissociation of H2 in a material with a high density of and G. Krexner. J. Alloys Compd., 509:S449–S455, defects, as introduced by SPD methods. For that purpose June 2011.

62 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Date and Place of Birth: February 5, 1980, Linz Marital status: Partner Martina, Children: Tobias, Olivia, Emma Nationality: Austria Employment and education: 2007-2010 Dissertation at Johannes Kepler University Linz (advisor E. Krotscheck). Title: Pair excitations and exchange effects in the dynamics of strongly correlated Fermiuids 26.8.2010 Promotion passed with distinction Martin Panholzer 9.-12.2010 Post doc at the Institute for Theoretical Physics, JKU Linz 2011-2013 Post doc at the Institute for electrical drives and power electronics, JKU Linz; ACCM since 5.2013 Post doc at the Center for Surface and Nanoanalytics, JKU Linz; Project: H2desorb Scientific interest: Hydrogen storage in metalhydrides, photocatalysis (theoretical modeling) Development of microscopic quantum many-body methods for strongly correlated systems Selected Publications: H. Godfrin, M. Meschke, H.J. Lauter, A. Sultan, H. M. Boehm, E. Krotscheck, and M. Panholzer. Observation of a roton collective mode in a two-dimensional Fermi liquid. Nature, 483:576–579, MAR 2012. H. M. Boehm, R. Holler, E. Krotscheck, and M. Panholzer. Dynamic many-body theory: Dynamics of strongly correlated Fermi fluids. PHYSICAL REVIEW B, 82(22), DEC 6 2010. M. Panholzer, H. M. Boehm, R. Holler, and E. Krotscheck. Exchange Effects and the Dynamics of He-3. J. OF LOW TEMP. PHYS., 158(1-2,Sp. Iss. SI):135–140, JAN 2010.

Corresponding author: Martin Panholzer, [email protected], Tel. +4373224681478

63 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

BOR4STORE – DEVELOPMENT OF A BORON HYDRIDE BASED INTEGRATED SOFC – METAL HYDRIDE TANK SYSTEM Klaus Taube1, José Bellosta von Colbe1, Giovanni Capurso1, Julian Jepsen1, Claudio Pistidda1, Andreas Yiotis2, Michael Kainourgakis2, Athanassios Stubos2, Deniz Yigit3, Henning Zoz3, Thomas Klassen1, Martin Dornheim1

1 Helmholtz-Zentrum Geesthacht, Geesthacht, Germany; 2 National Centre for Scientific Research „Demokritos“, Athens, Greece; 3 Zoz GmbH, Wenden, Germany

In the frame of the FCH JU project BOR4STORE – “Fast, reliable and cost effective boron hydride based high capacity solid state hydrogen storage materials” (grant 303428), a metal hydride tank containing ca. 10 kg of a boron hydride based storage material and storing ca. 1 kg of hydrogen shall be thermally integrated with a high temperature solid oxide fuel cell (SOFC). Factors like required hydrogen flow for the SOFC at maximum power level, electric efficiency, fuel consumption, reaction kinetics and engineering and safety requirements lead to a tank design, where the heat from the SOFC exhaust gases is transferred via a heat exchanger system to the metal hydride tank. The complete system will be set up in 2015 and tested for verification of the concept and stability of the hydrogen storage capacity during cycling.

Introduction reaction thermodynamics and kinetics of the Li-RHC, a modular tank design was chosen, consisting of 10 - 20 BOR4STORE (www.bor4store.eu) is a European project tubes and containing ca. 500 - 1000g each of the storage with the target of a) investigating various kinds of boron material. hydride based hydrogen storage materials and b) selecting the most suitable for a metal hydride tank to be The SOFC delivers an outgas flow of ca. 200 Nl/min at thermally integrated with a SOFC. Then, a prototype of ca. 900°C after an integrated afterburner, used to burn such an integrated system shall be constructed. any unreacted hydrogen and thus consisting of an air/water vapour mixture. Model calculations, based on Selection of storage material preliminary considerations [2], showed, that this gas The selection of the special kind of boron hydride based stream delivers enough heat flow at a sufficiently high storage material was based on the following temperature and homogeneity of the temperature requirements: distribution via an inert gas based heat exchanger 3 system to the metal hydride tank for fulfilling the hydrogen capacity 8 wt.%, 80 kg H2/m requirements for hydrogen supply of the SOFC. hydrogen release temperature <450°C Reaction enthalpy < 40 kJ/(mol H2) Outlook loadable to full capacity in less than 1 hour Due to the expected high temperature of operation of the high stability of capacity over several tens of heat exchanger between SOFC and metal hydride tank loading and unloading cycles of ca. 600 – 650°C, safety of the system against potential for reaching competitive cost to accidental hydrogen release and ignition is of uppermost compressed hydrogen stores under mass importance in all design considerations. production conditions Currently, the tank design is discussed with certification In the broad range of boron based storage materials bodies in order to fulfill requirements of European PED investigated in BOR4STORE, so far only one material, and AD2000 directives. The final design and construction the Lithium based Reactive Hydride Composite 2LiBH4- is expected for early 2015, and testing of the whole MgH2 (Li-RHC) exhibited the required combination of integrated system shall start in early summer 2015. properties. Especially with respect of stability of capacity most of the investigated materials failed, whereas the Li- References RHC exhibited stable properties over several tens of [1] J. Jepsen, C. Milanese, A. Girella, G.A. Lozano,l J. cycles. From PcI measurements of Li-RHC, reaction Puszkiel, B. Schiavo, J.M. Bellosta von Colbe, A. st enthalpies of 75 kJ(mol H2) for the 1 desorption step Marini, S. Kabelac, T. Klassen, M. Dornheim; (MgH2 Mg + H2) and of 52.6 kJ/(3mol H2) (2LiBH4 + „Fundamental thermodynamic and kinetic properties nd Mg 2LiH + MgB2 + 3H2) for the 2 were obtained, of the Li-RHC system for hydrogen storage”, yielding an average of 32 kJ(mol H2). [1] submitted Tank design [2] A. G. Yiotis, M. E. Kainourgiakis, L. I. Kosmidis, G. C. The BOR4STORE tank shall be used for supply of a Charalambopoulou, A. K. Stubos, “Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride commercial 1.3 kWelectric SOFC. With the electrical efficiency of nominally 40%, an average fuel consumption tanks: Thermodynamic and design considerations of 80% of the input hydrogen flow, a required hydrogen towards integrated systems”, Journal of Power flow at maximum power of 15 Nl/min and the known Sources 269 (2014) 440 - 450

64 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

1979-1986: Study of physics at the University of Hamburg, 1987-1991: PhD Thesis at the Philips Research Laboratory Hamburg, Dept. Thin Films, 1991-2000: Scientist at the Fraunhofer Institute for Surface Technology and Thin Films, Braunschweig, 2000-2001: Head of Dept. Forming Technology at IFU Institute for Forming Technology, Lüdenscheid, since 2002:Scientist at the Institute of Material Science at Helmholtz-Zentrum Geesthacht Research Centre Coordinator of the FCH JU Collaborative Project "BOR4STORE" (2012 – 2015, www.bor4store.eu/) and of the Marie Curie ITN ECOSTORE (2013 – 2017, www.ecostore.eu) Dr. Klaus Taube

Corresponding author: Dr. Klaus Taube, [email protected], Tel. +49 4152 87 25 41

65 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THE PHASE TRANSITION AND HYDROGEN STORAGE PROPERTIES OF Mg-Ga ALLOYS Daifeng Wua,b, Liuzhang Ouyanga,b,c, Meiqin Zeng a,b*, Hui Wanga,b, Jiangwen Liua,b, Min Zhua,b

aSchool of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou, 510641, PR China bChina-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou, 510641, PR China cKey Laboratory of Fuel Cell Technology of Guangdong Province, South China University of Technology, Guangzhou, 510641, PR China

The preparation of Mg-Ga alloys Mg(Ga) + H2 ↔ Mg2Ga + MgH2 (1)

To obtain Mg-Ga alloys, Mg and Mg5Ga2 were mixed at According to the van’t Hoff equation the enthalpy change weight ratio 10:1, considering the solid solubility of Ga is (ΔH) of dehydrogenation reaction of Mg-Ga alloys are 5wt. % at 573K, under Dielectric Barrier Discharge calculated to be 76.9kJ/mol H2 , which are slightly lower Plasma (DBDP) assisted ball milling for 9 hours. Mg5Ga2 than pure Mg measured at the same conditions was prepared by vacuum induction melting in a magnesia (79.1kJ/mol H2). Also, DSC test shows that the only crucible under the protection of pure argon atmosphere. dehydrogenation peak is located at 673K and around 10K lower than pure Mg. According to the above results, Phase transition of Mg-Ga alloys during the improved thermodynamics and related mechanism of hydrogenation and dehydrogenation the present Mg-Ga alloys should be the same as those process for the Mg(In) solid solution. XRD patterns show that the as-melted and the Dehydrogenation kinetics of Mg-Ga alloys dehydrogenation samples are mainly made up of Mg5Ga2 phase, with a few Mg Ga phases. And the hydrogenation Mg-Ga hydrides thoroughly released 6.5 wt% H2 in 90 2 minutes at 598K. With the temperature rise, the sample is composed of MgH2 and Mg2Ga and Mg5Ga2 phases. These results show the hydrogenation and thoroughly dehydrogenation time is reduced to 15 dehydrogenation process of Mg-Ga alloys is a reversible. minutes and 10 minutes at 623K and 658K, respectively. By fitting the dehydrogenation kinetic curves to JMAK Thermodynamic properties of Mg-Ga alloys equation, the dehydrogenation activation energy of Mg- PCI results show that the reversible hydrogen storage Ga alloys was calculated to be 153kJ/mol, which is lower than that of pure Mg. capacity Mg-Ga alloys is 6.7wt%H2. With the increase of temperature, dehydrogenation and hydrogen plateau References pressures rise. Besides, the hysteresis between hydrogenation and dehydrogenation are pretty small. [1] L. Z. Ouyang, et al. J. Alloys Compd. 2014, 586,113

As there is a single plateau pressure during hydrogenation and dehydrogenation process, it can be confirmed that Mg(Ga) solid solution can be formed during hydrogenation and dehydrogenation process at relatively high temperature (above 573K) , and the reaction equation should be as follow :

Ms Zeng is associate Professor in South China University of Technology. Her research interest lies in the fields of mechanical alloying, hydrogen storage materials, and hardmetals.

Meiqing ZENG Corresponding author: Meiqing Zeng, [email protected], Tel. +86-20-87112762

66 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

COMBINED CO2 AND H2 DRIVEN DESORPTION AND CO2 REDUCTION Marco Holzer, Andreas Züttel École polytechnique fédérale de Lausanne (EPFL), EMPA Materials Science and Technology

Abstract

Materials absorbing atmospheric CO2 are known and used in cyclic processes such as Temperature Vacuum Swing Adsorption (TVSA). However, the energy intensive step is the regeneration of the sorbent producing pure CO2, which is than in a latter step mixed with H2 to produce Hydrocarbons. The author proposes to directly produce a H2/CO2 mixture by using H2 as a purge gas for sorbent regeneration. Alkaline electrolysis produces H2 at the temperature used in the TVSA process and excess heat. The reactive mixture of H2/CO2 can be processed to many Hydrocarbons we need in our daily life such as Methanol, Dimethylether, Gasoline, Ethan and many more depending on the choice of the catalyst.

Sorbent

Amine modified aerogels absorb CO2 from atmospheric air. Many sorbent based on amine impregnated Silica frameworks are known, however, Aerogels have unique properties in regard of density and surface area, a key feature in adsorption. Desorption

Once the sorbent is loaded, CO2 has to be removed. This may be done by TVSA approached, where 50 mbar and 85-95°C are applied to the sorbent. This is very energy example is the Fischer Tropsch process, where an intensive since the sorbent is moist due to coabsorption Iron/Cobalt system produces a wide mixture, from C to of water on the basic sorbent [1]. 1 C20. Another established process is Methanol synthesis Hydrogen where CuZnO/Al2O3 is used. In one step Methanol can be altered to Dimethylether, a candidate for synthetic fuel. The Hydrogen required to reduce CO2 can be produced by alkaline electrolysis, a green process requiring only water and electricity. This process operates at 85°C and an efficiency of 80%. In order to regenerate an amine References sorbent, also a temperature of 85-95°C is required. The [1] C. Gebald, J. a Wurzbacher, A. Borgschulte, T. author proposes a synergy between the two processes. Zimmermann, and A. Steinfeld, “Single-component The desorption of CO2 from the sorbent can be enhanced and binary CO2 and H2O adsorption of amine- with moist H2 as a purge gas, producing directly the functionalized cellulose.,” Environ. Sci. Technol., vol. mixture of CO2 and H2, ready for the reduction to the 48, no. 4, pp. 2497–504, Feb. 2014. desired hydrocarbon. [2] M. Müller: "Dimethyl Ether“, Ullmann's Encyclopedia CO2 Reduction of Industrial Chemistry, Electronic Release, Wiley- VCH, Weinheim 2012. With H2, CO2 can be reduced to many hydrocarbons our society needs. The key is the catalyst. One well-known

2005 - 06 Exchange Program Milwaukee, USA 2011 Internship University Strathclyde, Glasgow, Scotland 2013 Master degree Chem. Bio. Eng. ETH Zürich 2014 Swiss Federal Laboratories, Dübendorf: Alkaline Electrolysis 2014 - PhD EPFL Sion LMER: H2 driven desorption of CO2 sorbents

Marco Holzer [email protected], [email protected]

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

NATURE OF BONDING IN MgH2:TM DOPED SYSTEMS B.Paskaš Mamula, J.Grbović Novaković, B.Kuzmanović, N.Ivanović,N.Novaković 1 Vinča Institute of Nuclear Sciences, University of Belgrade, Laboratory for Nuclear and Plasma Physics, Belgrade, Serbia

Ab initio electronic structure calculations of the Mg15TMH32 (TM –transition metal) systems for the entire 3d TM series have been performed using full-potential (linearized) augmented plane waves method with addition of the local orbitals). Details of bonding and the mechanism of the TM impurities influence on stability of MgH2 were investigated by means of electronic structure change after the TM impurities insertion into MgH2 and using the “atoms in molecules” (AIM) Bader’s charge density topology analysis. Obtained trends show that nature of TM-H bonding along the series change in a sense of directional bonding contribution rise, with maximum effect for late 3d metals Co and Ni. The effect of charge redistribution is nevertheless local and it in general weakens Mg-H bonds and the surrounding MgH2 matrix.

Introduction (NN) bonds, charge density topology analysis of pure MgH reveals existence of second neighbour (SN) longer It is found that MgH sluggish kinetics can be 2 2 H-H bond with directional character and possible improved and rather high desorption temperature contribution to and impact on overall stability of this significantly decreased by nanostructuring (mechanical system. Introduction of TM changes this picture. NN milling, addition of transition metals, their oxides and bonding paths persist while SN H-H bonds are missing intermetallics [1]. in all TM doped systems. We conclude that the bonding In our previous work [2], we have used the 2x2x2 is more directional with significant redistribution of supercell approach to investigate the influence of Ti and available charge (TM are acting as electron donors) Co dopants on MgH stability. It has been found that 2 towards NN TM-H direction. The rise of charge density these dopants lower the overall stability of MgH , and that 2 values in bonding critical points (Fig. 1a) goes in favour stronger bonding of TM and surrounding H atoms of such a conclusion. weakens the rest of the structure, at least locally. Rise of covalent contribution of these bonds should Here, we emphasize the importance of charge density be accompanied with specific properties of charge properties to get bonding nature details and mechanisms density laplacian. The value of this property is connected of observed MgH matrix destabilization. This was 2 to the ionic-covalency ratio in chemical bonding. The achieved by means of "atoms in molecules" theory and results are given in fig 1b. The trend obtained does not peculiarities of charge density in bonding critical points follow the trend in TM-H bond lengths and in-between (bCP's). bCP's charge density values. The reason for this could be spatial localization of 3d orbitals and specifics of Calculations details sp3d2-dX (X-number of the remaining d electrons in the 3d-shell) hybridization. All calculations have been performed using

(L)APW+LO(lo) method. Supercell was constructed by 2x2x2 stacking of MgH2 rutile unit cell using its previously optimized cell parameters and ionic coordinates. One Mg atom was substituted with TM and relaxation of ionic coordinates was again performed without further optimization of supercell parameters. Every TM atom is octahedrally coordinated with 6 H atoms at almost equal distances. Systems were not treated in spin independent manner. Obtained charge densities were used as input for further Bader charge analysis. a) b)

Results and discussion Figure 1. a) charge density and b) laplacian in bonding CP’s in first TM coordination. Both NN H2 and Ionic relaxation have confirmed that 3d TM's (with the H4 bCP’s are presented, along with SN (b2) and third exception of Sc) tend to form shorter and stronger bonds nearest (b3) neighour bCP’s. with their first coordination H atoms. The shortest bonds are found for Fe and Co (~1.65 Å), while the longest (and of comparable length as Mg-H in pure MgH2 (~ 1.95 Å) References for Sc and Zn. The distribution of so called bonding critical points [1] Bassetti A, Bonetti E, Pasquini L, Montone A, Grbovic (obtained from zero charge density gradient and specific J, Vittori Antisari M. Eur Phys J B; 2005; 43:19-27 saddle point configuration conditions) and bonding paths [2] N.Novaković, Lj. Matović, J. Grbovic Novaković, connecting two atomic sites gives us information about I.Radisavljevic, M. Manasijevic, B.Paskaš Mamula, N. the existence, strength and nature of atomic interactions Ivanović, Int.J.Hyd. Energy 35; 2010; 598-608 in the system. Beside expected Mg-H nearest neighbour

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Born in Kraljevo, Serbia 23.10.1977. Graduate degree in physics 2005, Ph.D. candidate at Faculty of Physics, University of Belgrade since 2010. From 2010 works in Vinča Institute of Nuclear Sciences in Laboratory for Nuclear and Plasma Physics as an research associate.

Bojana Paskaš Mamula

Corresponding author: Bojana Paskaš Mamula, email: [email protected], Tel.+ 381 11 3408 610

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

FROM HYDROGEN TO SYNTHETIC HYDROCARBONS Andreas ZÜTTEL1,2, Philippe MAURON1,2, Elsa CALLINI1,2, Shunsuke KATO1,2, Marco HOLZER1,2, Jianmei HUANG1,2

1) Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), École polytechnique fédérale de Lausanne, EPFL Valais/Wallis, Switzerland, 2) EMPA Materials Science and Technology, Dübendorf, Switzerland

Hydrogen is produced from water by means of electrolysis with renewable energy. CO2 is abundant in the atmosphere at a concentration of 400 ppm. The extraction of CO2 and reduction with hydrogen to hydrocarbons leads to synthetic and CO2 neutral fuels. Furthermore, the controlled reaction to a specific product like C10H22 would allow to store large quantities of renewable energy in easy way based on established technology for diesel. Two major challanges have to be overcome: 1) energy efficient extraction of CO2 from the atmosphere and concentration to pure CO2 at 1 bar, and to develop new reaction pathways which allow to reduce CO2 to a specific product.

CO2 FROM THE ATMOSPHERE Thermodynamically the reduction of CO2 follows the established paths of the reversed water gas shift The extraction of CO from the atmosphere (400 ppm = 2 reaction, Fisch-Tropsch synthesis or the Sabatier 0.04%) to 1 bar pure CO requires the Gibbs free 2 reaction. enthalpy ΔG = 20 kJ/mol which corresponds to 0.126 kWh/kgCO2. However, with the today known adsorption processes approximately 1.5 to 2 kWh/kgCO2 of heat are necessary in order to concentrate CO2 [1]. Therefore, new processes working close to the thermodynamic limit have to be developed.

CO2 REDUCTION WITH HYDROGEN

Fig. 2. Free enthalpy of the CO2 reduction along the established reaction paths (red). The new controlled reaction path (blue) will be investigated.

References Fig. 1. Schematig representation of the various reduction [1] http://www.climeworks.com/co2-capture-plants.html paths of CO on a surface with adsorbed H. 2 [2] Y. Hori, Modern Aspects of Electrochemistry 42, The reduction path of CO2 on a surface depends on the (2008), pp 89-189. Electrochemical CO2 Reduction on reaction conditions e.g. temperature, hydrogen partial Metal Electrodes. pressure, and on the surface composition as well as the local surface structure. CO2 is reduced to methane (CH4) on Ni and C-C coupling (C2H4) was only found on Cu [2].

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf, Switzerland. 1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr. rer. nat. from the science faculty UniFR. 1994 Post doc "Amorphous hydrides and optical films" with AT&T Bell Labs in Murray Hill, New Jersey, USA. 1997 Lecturer at the Physics Department UniFR. 2003 External professor at the Vrije Universiteit Amsterdam, Netherlands. 2004 Habilitation in experimental physics at the science faculty UniFR. President of the Swiss Hydrogen Association „HYDROPOLE“. 2006 Head of the section “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics Andreas department UniFR. 2009 Guest Professor at IMR, Tohoku University in Sendai, Japan. 2012 Visiting ZÜTTEL Professor at Delft Technical University, The Netherlands. 2014 Full Prof. in Physical Chemistry and head of the Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), École polytechnique fédérale de Lausanne, EPFL Valais/Wallis, Switzerland

Corresponding author: Andreas ZÜTTEL, email: [email protected], Tel. +41 79 484 2553

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

LOW TEMPERATURE CYCLING OF MG-TI NANOPARTICLES FOR HYDROGEN STORAGE Marco Calizzia, Luca Pasquinia aDepartment of Physics and Astronomy - University of Bologna, viale Berti-Pichat 6/2, 40127 Bologna, Italy

In the field of solid state hydrogen storage magnesium is an element of great interest because of the desirable properties of its hydride (MgH2): it is abundant, cheap and light. The two big obstacles that are yet to be overcome are the high working temperatures and the slow sorption kinetics of the bulk system. In this work we show how the Mg/MgH2 system can be improved to have better storage properties combinig the addition of a catalyst with the production of nanoparticles.

Synthesis and characterisation Hydrogen storage properties The samples were syntesised evaporating Mg with the Reaction kinetics and pressure-composition isotherms technique of the Inert Gas Condensation (IGC), a are measured with a homemade Sievert apparatus. In physical deposition technique, resulting formed by this work we focused on the low-temperature range, that nanoparticles (NPs). Nanostructuring the system means for Mg-based systems below 300°C, in order to increases the surface to volume ratio and reduces H limit the coarsening and degradation of the diffusion paths enhancing material's sorption kinetics. nanostructure. For these samples the enthalpy of hydride Together with Mg is evaporated another element, titanium formation is unaltered, compared with that of bulk Mg, but (Ti), which is known to be a good catalyst [1-3] and has the kinetics are faster by orders of magnitude: these Mg- the best combination of price and weight among the Ti NPs at 225°C already absorb hydrogen within 200 s at transition metals. The NPs are collected on a liquid 1,3 bar and desorb in 400 s starting from vacuum. nitrogen-cooled rotating cylinder and then in situ transferred to a secondary chamber where they are References hydrogenated at 150°C under 133 mbar of H pressure for [1] A. J. Du et al. J. Phys. Chem. B 109 (2005) 2h. Characterisation is performed with x-ray diffraction [2] S. X. Tao et al., Phys. Rev. B 79 (2009) (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analyses. From SEM and [3] Cuevas, Korablov, Latroche, PCCP 14 (2012) XRD, NPs turn out to be in the 10-20 nm size range. Mg and Ti are immiscible with each other, but in these NPs is observed a metastable substitutional hcp alloy in the metallic phase before hydrogenation. The samples are succesfully hydrogenated after the mild in situ treatment.

Born 10/10/1989 in Bologna. 2011 – Bachelor degree in Physics at University of Bologna, Italy; 2013 – Master degree in Physics at University of Bologna, Italy with thesis “The nanostructured Mg- Ti system for solid state hydrogen storage” in collaboration with ICMPE-CNRS in Paris, France with Dr. F. Cuevas; since January 2014: PhD student in Physics at University of Bologna, Italy with Dr. L. Pasquini. Marco Calizzi Corresponding author: Marco Calizzi, [email protected], +39 051 2095133

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

MATERIALS ENGINEERING FOR SOLID OXIDE FUEL CELLS AND ELECTROLYSERS Nigel Brandon

Imperial College London

The paper will present work within the authors group on the use of 3D imaging and analysis, and Raman spectroscopy, to understand the properties and behaviour of porous electrodes for use in solid oxide fuel cells and electrolysers. A brief overview of technology status in the UK in these areas will also be presented.

Introduction Raman spectroscopy There is increasing interest in both high temperature solid Raman spectroscopy is particularly sensitive to the oxide fuel cells for the production of heat and power, and presence of carbon on electrode surfaces. An in the use of high temperature electrolysers for the electrochemical cell has been developed that allows such production of hydrogen from steam, and/or the reduction measurements to be made under SOC operating of carbon dioxide to carbon monoxide. Whilst conditions. Both ex-situ and in-situ measurements have encouraging progress continues to be made, there been used to explore the formation of carbon during the remain challenges regarding the long term durability of electrolysis of carbon dioxide to carbon monoxide, and electrodes for both applications. Work in the authors the addition of ceria at the electrode-electrolyte has been group is seeking to understanding and mitigate these shown to inhibit carbon formation [3]. issues through the application of advanced 3D imaging and analysis of electrode microstructure, to inform a References design led approach to the fabrication of optimum [1] Tariq F, Kishimoto M, Yufit V, Cui G, Somalu M, electrode structures, and the application of Raman Brandon NP, 2014, 3D imaging and quantification of spectroscopy to understand carbon formation during CO2 interfaces in SOFC anodes, JOURNAL OF THE electrolysis, and fuel cell operation on hydrocarbon fuels. EUROPEAN CERAMIC SOCIETY, Vol: 34, Pages: 3755-3761. 3D imaging and analysis [2] Kishimoto M, Lomberg M, Ruiz-Trejo E, Brandon NP, Recent advances in experimental methods allows us to 2014, Enhanced triple-phase boundary density in image, quantify and model the properties of the porous infiltrated electrodes for solid oxide fuel cells composite electrodes used in Solid Oxide Cells (SOCs) demonstrated by high-resolution tomography, [1]. An example from a recent paper is presented below JOURNAL OF POWER SOURCES, Vol: 266, Pages: [2], showing the reconstructed image of a porous Ni- 291-295. doped ceria electrode (sample shown has a size of around 2x2x4 µm), fabricated from a ceria ceramic [3] Duboviks V, Maher RC, Kishimoto M, Cohen LF, scaffold impregnated with nickel particles, where the Brandon NP, Offer GJ, 2014, A Raman spectroscopic scaffold is shown in grey and the nickel particles in study of the carbon deposition mechanism on Ni/CGO green. electrodes during CO/CO2 electrolysis, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, Vol: 16, Pages: 13063-13068.

Prof Nigel Brandon (NPB) OBE FREng is Director of the Sustainable Gas Institute at Imperial College London. He is an electrochemical engineer whose research interests lie in electrochemical devices for energy applications, with over 150 peer reviewed papers and 12 patents in the field. He is Director of the Hydrogen and Fuel Cell SUPERGEN Hub and Co-Director of the Energy Storage SUPERGEN Hub. He was awarded the RAE Silver Medal in 2007, the Baker Medal in 2011 for his work on microgeneration, the ASME Francis Bacon Medal in 2014, and co-founded the fuel cell company Ceres Power in 2001 based on his research. Corresponding author: Prof Nigel Brandon OBE FREng, [email protected], Tel. +44 20 7594 5704

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

A NEW CLASS OF HYDROGEN SENSING MATERIALS C. Boelsma1, R. J. Westerwaal1, and B. Dam1

1 Department of Chemical Engineering - Materials for Energy Conversion and Storage, Faculty of Applied Science, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

Abstract – We recently discovered a new class of optical hydrogen sensing materials. We demonstrate this by the case of hafnium hydride, which shows a well-defined relation between the optical response and the applied hydrogen pressures over a very large pressure range (> 7 orders of magnitude. We do not observe any signs of hysteresis, while observing a high degree of stability upon cycling. Remarkably, the optical contrast decreases with increasing hydrogen content.

Optical Fiber Sensors are a 10 000 to 1 000 000 times more sensitive than Mg- based and Pd-based compounds, respectively. The In a sustainable economy with hydrogen as a major sensors show a high stability upon cycling (the sensors energy carrier, a sensitive hydrogen sensor is can be reactivated after 6 months in air without the use of indispensable. We focus on optical fiber sensors, which a protective layer) with good kinetics (response time is in are ideal for continuous sensing hydrogen in small the range of seconds to minutes at elevated spaces and/or in atmospheres that can form explosive temperatures, depending on the pressure change), while mixtures. we found no signs of hysteresis. In literature usually two classes of optical hydrogen sensing materials are reported. The first class consists of Optical Contrast Pd-based compounds. These compounds show fast and Although electronic and structural properties as function reversible kinetics and are very stable, but the optical of the hydrogen content are different for the group IV and contrast is rather low with a small detectable range of group V elements, their sensing behavior is the same. partial hydrogen pressure (103 – 105 ppm) [1,2]. The They all show a significant decrease in optical contrast second class consists of Mg-based compounds where with increasing hydrogen content. This is remarkable, as the optical contrast is superior compared to Pd-based other optical sensing materials (e.g., Mg-based and Pd- compounds, but the detection range spans also only two based compounds) all show an increase in optical orders of magnitude (101 – 103 ppm) [3]. Furthermore, contrast with increasing hydrogen content. Here we Mg-based compounds exhibit a large hysteresis, limiting discuss the origin of this effect. the possibility to monitor fluctuations in hydrogen concentration. References [1] R.J. Westerwaal et al., International Journal of A New Class Hydrogen Energy, 38 (2013). Here we introduce a new class of hydrogen sensing [2] R.J. Westerwaal et al., Sensors and Actuators B, 165 materials. This class consists of a group IV (Ti, Zr, Hf) (2012). and group V (V, Nb, Ta) elements of the periodic table. We demonstrate their behavior by means of HfHx, which [3] M. Slaman et al., Sensors and Actuators B, 123 shows a well-defined relation between optical response (2007). and the pressures over a very large range of at least 7 orders of magnitude. First results show that we are able to detect hydrogen at partial pressures as low as a few ppb up to a hundred ppm. This means that these sensors

2004 – 2008: Bachelor Physics and Astronomy, VU University Amsterdam; 2008 – 2011: Master Physics, Specialization Advanced Matter and Energy Physics; 2011 – Present: Ph.D. in Chemical Engineering, Materials for Energy Conversion and Storage, Delft University of Technology.

C. Boelsma

Corresponding author: Christiaan Boelsma, [email protected], 0031-15 27 83891

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

NEW MATERIALS FOR HYDROGEN STORAGE

Torben R. Jensen

Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Denmark.

Hydrogen is recognized as a potential and extremely interesting energy carrier, which can facilitate efficient utilization of unevenly distributed renewable energy. Here we report an overview of our recent results within new materials for hydrogen storage: (i) synthesis of novel metal borohydrides and studies of their properties, (ii) tailoring materials properties by formation of eutectic melting systems, and (iii) in situ powder X-ray diffraction for studies of hydrogen release and uptake reactions. We conclude that the chemistry of hydrides is very divers, towards multi-functional materials, including ion-conductors for batteries, methanisation of carbondioxide etc.

Metal borohydrides Multi-functionality Hydrogen has the highest gravimetric energy density of A series of 30 new complex hydride perovskite-type all known substances and is attractive for future storage materials and new synthesis protocols involving rare of renewable energy [1]. We have recently developed earth elements was recently presented [7]. new synthesis strategies combining mechano-chemical Photophysical, electronic and hydrogen storage and solvent based methods for synthesis of new properties was discovered along with trends in structural hydrides. The metal borohydrides MM’BH4, typically behaviour. In this view, homopolar hydridic di-hydrogen contain an alkali metal, M, and a di- or tri-positive cation, contacts arise as a potential tool to tailor crystal M’. Apparently, the structural complexity increase with the symmetries, hence merging concepts of molecular increasing size of the alkali metal and also the tendency chemistry with ceramic-like host lattices. Furthermore, to form mixed borohydride-halide compounds and ternary anion-mixing provides a link to the known ABX3 halides. chlorides [1-4]. A fascinating structural chemistry is discovered within metal borohydrides, e.g. interpene- Some metal hydrides are found to react with carbon trated ‘MOF-like’ networks or zeolite-type structures with dioxide and provide a new approach for direct up to 30% ‘empty’ space in the porous structures of metahanisation of CO2. In this talk, we will also illustrate that in situ powder X-ray diffraction is a unique, sensitive Mg(BH ) , M = Mg or Mn, which additionally can 4 2 and informative technique for probing gas-solid reactions. physisorp molecular hydrogen, e.g. Mg(BH4)2~2H2, m = ~20 wt% H2 [5,6]. Another polymorph has extremely dense packing of hydrogen, Mg(BH4)2, V = 147 g H2/L. References Recently, we stabilized NH4BH4 with extreme hydrogen density, 24.5 wt% H2, as NH4Ca(BH4)3 (15.7 wt% H2) with [1] M. B. Ley, et al, Mater. Today, 2014, 17, 122. [2] higher decomposition temperature, Tdec = 97 C [7]. Rude, et al, Physica Status Solidi 2011, 208 1754. [3] L. Jepsen, et al, Mater. Today, 2014, 17, 129. [4] J. Huot, et Ion conductors for batteries al. Prog. Mater. Sci. 2013, 58, 30. [5] E. Roedern, et al, Recently, a series of new fast Li-ion conductors, J. Phys. Chem. C, 2014, 118, 23567. [6] Filinchuk, et al, Angew. Chem. Int. Ed. 2011, 50, 11162. [7] P. LiM(BH4)3Cl, M = La, Ce, Gd, Pr or Nd, which simultaneously store significant amounts of hydrogen Schouwink, Nature Comm. 2014, DOI: 10.1038/ was discovered. The conductivity is due to unoccupied ncomms6706. [8] Ley et al. Chem. Mater. 2012, 24, cation position around the large cubane like composite 1654. anions [8]. Closo-boranes containing large anions of 2 2 B12H12 or B10H10 are of increasing interest and may provide ion conductors.

Torben received his Ph.D. degree in materials chemistry and did postdoctoral research at Risø National Laboratory and DESY, Hasylab, Hamburg. He became Assistant Professor (2000) and Research Associate Professor (2002) at the Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University. He was awarded a Steno research stipend (2002) by the Danish research council, a Carlsberg research stipend (2005) form the Carlsberg Foundation and a doctor of science degree from the faculty of science and technology at Aarhus University. His research interests are focused on synthesis, structural, physical and chemical properties of new inorganic materials and utilisation of synchrotron X-ray radiation for materials characterization. Corresponding author: Torben R. Jensen, [email protected], +45 87155939 (mobile: +45 2272 1486).

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

DISCOVERY OF NEW HYDROGEN STORAGE SYSTEMS BASED ON ORGANIC LIQUIDS David Milstein

Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel

The ability to store and transport H2 within a liquid carrier at standard temperatures and pressures provides many advantages over current H2 storage methods. However, although potentially significantly more cost efficient than high- pressure or cryogenic tanks, the development of efficient liquid-organic hydrogen carrier systems (LOHCs) remains challenging.

We have developed new catalytic reactions of organic compounds capable of efficiently releasing hydrogen gas

(“acceptorless dehydrogenation”) [1], such as dehydrogenative coupling of alcohols to form esters and H2 [2], dehydrogenative coupling of alcohols and amines to form amides and H2 [3], and oxidation of alcohols to carboxylic acids using water as oxidant, with liberation of H2 [4]. We have also developed the reverse hydrogenation reactions under very mild pressure and temperatures reactions. These reactions now provide a foundation for novel hydrogen storage systems. We will describe novel LOHC systems based on new catalysts using inexpensive organic hydrogen carriers capable of high hydrogen storage capacity. The performance of these systems will be compared with those of reported LOHC systems.

References [2] C. Gunanathan, D. Milstein, Metal-Ligand Cooperation by Aromatization-Dearomatization: A New Paradigm in [1] C. Gunanathan, D. Milstein. Applications of Bond Activation and “Green” Catalysis, Accts. Chem. acceptorless dehydrogenation and related Res. 2011, 44, 588-602 transformations in chemical synthesis. Science, 2013, 341, 1229712 (review) [4] E.Balaraman, E. Khaskin, G. Leitus, D. Milstein, Catalytic transformation of alcohols to carboxylic acid [3] C. Gunanathan, Y. Ben-David and D. Milstein. Direct salts and H using water as the oxygen atom source. Synthesis of Amides from Alcohols and Amines with 2 Nature Chemistry, 2013, 5. 122-125 Liberation of H2. Science, 2007, 317, 790-792

David Milstein is the Israel Matz Professor of Chemistry and the Director of the Kimmel Center of Molecular Design at the Weizmann Institute of Science in Israel. He received his Ph.D. degree at the Hebrew University in 1976 and performed postdoctoral research at Colorado State University, where together with his advisor, John Stille, he discovered the Stille Reaction. In 1979 he joined DuPont Company’s CR&D department and in 1986 he moved to the Weizmann Institute, where he headed the Department of Organic Chemistry in 1996-2005. His research interests include fundamental organometallic chemistry, particularly the activation of strong bonds, and the design and applications of environmentally benign processes and sustainable energy related processes catalyzed by transition metal complexes. Awards include: the Kolthoff Prize (2002); the Israel Chemical Society Prize (2006); the ACS National Award in Organometallic Chemistry (2007); the RSC Sir Geoffrey David Milstein Wilkinson Award (2010); the Humboldt Senior Award (2011); and the Israel Prize (2012, Israel’s highest honor). He was also awarded several lectureships and visiting professorships, and he serves on several Editorial Boards. He is a member of the Israel National Academy of Sciences and Humanities, and the German National Academy of Sciences-Leopoldina.

Corresponding author: David Milstein, [email protected] Tel. +972-89342599

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

RENEWABLE ELECTRICITY TO METHANE: INTEGRATION OF HIGH TEMPERATURE ELECTROLYZER AND METHANATION REACTOR Arianna Baldinelli, Linda Barelli, Gianni Bidini, Giovanni Cinti*

Affiliation : Department of Engineering, University of Perugia Abstract : The increased production of energy from renewable sources has recently introduced critical issues, such as grid congestion and perturbation. Because of the unpredictable, intermittent and fluctuating character of these sources, such as sun and wind, the integration of energy storage in the energy system at both local and systemic level is required. This to mitigate grid interconnection issues due to RES plants and to increment their exploitation avoiding curtailments. To this end, chemical storage is one of the most promising direction, due to high energy density and the possibility of long term storage application, particularly at local and small grid level [1]. This study presents the concept of a high temperature solid oxide electrolyzer (SOE) integrated with a methanation reactor (MR). Operating the SOE in co-electrolysis mode [2], the electricity is converted into hydrogen and CO which are then transformed into methane. The main advantage of this solution is that methane can be distributed by means of a widespread existing net, avoiding the need of a hydrogen storage. At the same time CO2 from an external local source can be turned back into fuel, realizing CO2 separation and reuse. As a consequence, the infrastructure costs are strongly less than the ones that a hydrogen-based system would have to face. Starting from the experimental activity, a SOE model was developed. Then, the complete system was designed and overall performances were evaluated.

Experimental obtained integrating the two units and balance of plant components. CO and electricity are fed to the system by A 4 cells SOE was operated in co-eletrcolysis mode to 2 external sources. Efficiency was calculated as the ratio get experimental data and develop the model. Operative between total input energy and produced chemical temperature was kept at 750°C while inlet composition energy stored into methane. was varied, in particular H2O/CO2 ratio was changed keeping a 10% content of H2 in the inlet flow. Total flow System study was kept constant at 190 Nl/h. For each composition a The model design was tested in different operative polarization curve was performed up to 0.5 A/cm2. Outlet conditions varying temperature, pressure and gas mix.; gas composition was measured during polarization. For each condition the integrated system efficiency, as Model defined above, was determined. Temperature decrease strongly effect system efficiency and, in several Based on experimental data the model of the stack was conditions, methanation occurs directly inside the stack. developed in Aspen Plus. The electrodes were modelled On the other hand, temperature reduction increases considering electrochemical equilibrium while voltage losses into SOE unit; consequently the optimize was calculated starting from experimental data. A gibbs operation point was individuated increasing active area. reactor was added to the model after the electrochemical equilibrium. This latter permits to reach gas composition References equilibrium in accordance to gas analysis. Once enthalpy [1] H. Chen, T.N. Cong, W. Yang, C. Tan, Y. Li, Y. due at operative reactant utilization was calculated the Ding, Prog. Nat. Sci. 19 (2009) 291. polarization curves were used to calculate active area at [2] C. Graves, S.D. Ebbesen, M. Mogensen, Solid thermoneutral conditions. Also methanation reactor was State Ionics 192 (2011) 398. modelled using available data in literature considering all occurring reactions. Heat balance of the system was

Researcher at FCLab of Department of Engineering. Member of research units within projects developed by University of Perugia in the fuel cell area. Competences in the microCHP fuel cell based system design and test. Specifically, the latter relates to experimental test on SOFC and SOEC. SOFC studies focus mainly on effect of innovative fuels (syngas, ammonia, biogas) in terms of efficiency and system integration issues. Contaminant effect is part of these studies with particular attention to H2S and TAR as contaminant of biogas and syngas respectively. Due to the high interest in energy storage, research activity was extended to hydrogen production and, in particular, to high temperature electrolyzes both in electrolysis and in co-electrolysis, analyzing through experimental investigation the impact of temperature equilibrium on thermal and energy balance. Giovanni Cinti

Corresponding author: Giovanni Cinti, [email protected], +390755853991.

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

3D-HYDROGEN MICROSCOPY G. Dollinger1, M. Moser1, P. Reichart1, S. Wagner², A. Pundt² 1) Universität der Bundeswehr München, LRT2, 85579 Neubiberg, Germany 2) Universität Göttingen, Institut für Materialphysik, 37077 Göttingen, Germany

Proton-proton scattering at the Munich microprobe SNAKE gives the unique possibility for sensitive 3D hydrogen microscopy [1]. It is especially well suited to investigate microdistributions of hydrogen in any material that interacts with or contains hydrogen. We have shown detection limits as low as 0.08 at-ppm and a submicrometer resolution. A main advantage of the method is that standardless quantification is possible without any matrix effects. Thus, in terms of lateral resolution, sensitivity and quantification it is the method of choice for hydrogen microscopy in any kind of material. We show results of 3D-hydrogen microscopy on niobium, tungsten and diamond in order to demonstrate the potential of this method for applications in hydrogen storage and fuel cell materials.

Description of 3D-hydrogen microscope measuring the sum energy of the coincidently detected The method of 3D-hydrogen microscopy relies on the use proton pair. fig. 1 of 20 MeV protons that are delivered at the Munich 14 Applications MV tandem accelerator. The proton beam is focused to a The first prove of sub-0.1 at ppm sensitivity and sub-µm submicrometer sized beam spot by means of the resolution was obtained when analyzing hydrogen at microprobe SNAKE (Superconducting Nanoscope for grain boundaries in chemical vapor deposition (CVD) Applied nuclear (Kern-) physics Experiments). Protons of grown diamond [2] using 3D-hydrogen microscopy. the beam may be elastically scattered from hydrogen Regarding hydrogen storage applications, we obtained atoms in the sample, thus creating two protons that are laterally resolved measurements of inhomogeneous emitted on the back side of the sample – if it is thinner hydrogen distributions in niobium thin films when the than about 100 µm - and detected in coincidence (fig. 1). solution limit for hydrogen of 0.13 H/Nb in the clamped - By scanning the beam across the sample a two- niobium is passed and islands of -niobium show up that dimensional image of the hydrogen distribution is are detached from their silicon substrate [3]. Fig. 2 shows obtained that quantitatively shows the lateral hydrogen an optical micrograph (left) and the corresponding distribution in the sample. The depth of origin of each of hydrogen distribution in one of the films (right). Thus we the detected hydrogen atoms is analyzed in addition by were able for the first time to demonstrate inhomogeneous hydrogen loading due to the microscopic evolution of phase changes in the material during hydrogen loading. fig. 2

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Referencs [2] P. Reichart, et al., Science 306 (2004) 1537. [1] P. Reichart, et al., Nucl. Instr. and Meth. B197 (2002), [3] S. Wagner et al, Int. J. Hydr. Energy 38 (2013) 13822. pp. 134-149.

Prof. Dr. rer. nat. GÜNTHER DOLLINGER

* August 02, 1960 in Kempten, Germany Universität der Bundeswehr München Fakultät für Luft- und Raumfahrttechnik Institut für Angewandte Physik und Messtechnik, LRT 2 Werner-Heisenbergweg 39 D-85577 Neubiberg, Germany Phone: +49 89 6004 3505 Fax: +49 89 6004 3295 E-mail: [email protected]

http://www.unibw.de/lrt2/

EDUCATION Jun. 1998 Habilitation in Experimental Physics, TU München Feb. 1990 Ph.D. in Physics, TU München Dec. 1985 Staatsexamen Lehramt für Gymnasien 1980-1985 Studies of Physics and Mathematics, TU München

ACADEMIC CAREER Since 2004 Professor (head of institute) for Applied Physics and Metrology, Faculty for Aerospace Sciences, Universität der Bundeswehr München 2001-2004 Permanent Staff and Lecturer, Physics Department, TU München 2000-2001 Senior Researcher at National Accelerator Center (now iThemba Labs) Somer Set West, South Africa 1988-2000 Member of Staff, Physics Department, TU München 1986-1988 Research Scholar, Physics Department, TU München

RESEARCH FOCUS Experimental Physics/Materials Science/Metrology/Radiobiology. Ion-matter interaction, Positron- matter interaction, Ion microscopy: development and application in materials science and radiobiology. Positron microscopy: development and application in materials science

HONORS

Prize for most excellent PhD in Physics, TU München, 1990

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

THE SWISS COMPETENCE CENTER FOR ENERGY RESEARCH: HEAT AND ELECTRICTY STORAGE Thomas J. Schmidt

Electrochemistry Laboratory, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland

The establishment of eight Swiss Competence Centers for Energy Research (SCCER) within the so-called Action Plan Coordinated Energy Research is part of the Swiss Energy Strategy 2050. Besides other topics – Energy Supply, Grids, Efficiency in Mobility, industrial process and buildings, Biomass, and Economy, Environment, Law, Behavior – the SCCER Heat & Electricity Storage plays a key role. In this contribution, this SCCER is introduced with its contents, goals and current achievements.

Introduction Her the focus is on Li- and Na-type batteries in terms of energy density, cost and the high explorative area of The future of the Swiss energy supply, after the nuclear beyond Li-ion technologies. energy phase out, will heavily rely on intermittent renewable energies such as solar or wind. To guarantee Thermal Energy Storage the continuous (temporal and regional), reliable, and with a focus on buildings and processes by exploring cost-efficient supply of power, heat, and fuels derived advanced adiabatic compressed air storage (AA-CAES), from these energy sources, it is critical to develop the pumped heat electric storage (PHES) and high- science and technology of electricity storage comprising temperature process heat. advanced rechargeable batteries and synthetic fuels (hydrogen, hydrocarbons), respectively. In the heat Hydrogen Generation and Storage storage domain short-term and seasonal heat storage by exploring emerging technologies in the field including solutions also call for new developments. redox flow batteries, radically lower cost catalysts, and The establishment of the Swiss Competence Centers for high energy density liquid storage routes. Energy Research (SCCER) is a key-element to realize Development of advanced catalysts for CO2 the Swiss Energy Strategy 2050. It addresses the inter- reduction university coordination of energy research across Switzerland. For the period of 2013 to 2016, a total of Within this work package, the reduction of CO2 by CHF 72 million has been spoken to the set-up SCCER in catalytic and electrocatalytic (co-electolysis) means is seven predefined action areas including energy storage. studied aiming at high efficiencies selectivities for The implementation of the SCCER is supervised by the syngas/hydro-carbons production Commission for Technology and Innovation (CTI). Technology Interaction of Storage Systems The SCCER Heat & Electricity Storage explores the storage technology in a wider context to Within the framework of these seven SCCER, the make the SCCER more powerful. Questions of SCCER on Heat and Electricity Storage is dedicated to technology interaction is part of the research, covering a active research on different related topics organized in wide range of aspects from socio-economical aspects to five work packges. system integration and modeling Advanced Battery and Battery Materials

In February 2011, Thomas J. Schmidt became Chair of Electrochemistry at ETH Zurich, combined with the appointment as Head of the Electrochemistry Laboratory at Paul Scherrer Institute in Villigen, Switzerland. Since 2014 Prof. Schmidt is Director of the Swiss Competence Center for Energy Research (SCCER) Heat & Electricity Storage. After graduating from University of Ulm, Germany (2000), he spent time as Post-Doc at Lawrence Berkeley National Laboratory (2001) and Paul Scherrer Institut (2002), before he continued his career in industries at BASF Fuel Cell GmbH, where he led the R&D activities as Director R&D. He received the Charles W. Tobias Young Investigator Award from the Electrochemical Society in 2010. He was awarded the Otto-Monsted Visiting Professorship at the Technical University of Denmark (Lyngby) in 2013.

T. J. Schmidt

Corresponding author: T.J. Schmidt, [email protected], Tel. +41-56-310-5765

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

RESEARCH INFRASTRUCTURES FOR RESEARCH AND DEVELOPMENT OF HYDROGEN AND FUEL CELL TECHNOLOGIES Olaf Jedicke

Karlsruher Institute of Technology; Hermann-von-Helmholtz Platz 1; 76344 Eggenstein-Leopoldshafen; GERMANY

Abstract

Successful research and development base especially on the availability of modern laboratories, technical research installations and in some specific cases, also on big research facilities, such as neutron sources or synchrotron radiation dedicated to material investigation. Nowadays, this does apply for nearly all kind of scientific work. “Hydrogen technology” covers very different aspects of essential research and development and thus requires sophisticated experimental installations and research facilities, to proceed effectual, to generate new and novel results. However, what sounds reasonable often lacks success while general instructions do not exist how to determine experimental installations and/or research facilities to solve or investigate more detailed problems in research and development or to examine scientific ideas. The Integrating European Infrastructure was created 2011 to resolve this problem. Even more, the integrating infrastructure likes to support research and development regarding hydrogen and fuel cell technologies towards the European strategy of sustainable, competitive and secure energy.

H2FC European Infrastructure

H2FC European Infrastructure project was formed 2011 to integrate the European research and development community around rare and/or unique infrastructure elements that will facilitate and significantly enhance the research and development of hydrogen and fuel cell technology in a broad scope. The project is coordinated by Karlsruher Institute of Technology (KIT) and combines 19 European’s research centers and universities. The total project budget of € 10.147.583,60 is dedicated to support external research and development by offering free access to technical research installations, to modify and improve existing research installations according the necessities and to team and strengthen the up to now separated communities (e.g. fuel cell-, safety- and Fig. 1.0 Structure of H FC European Infrastructure hydrogen technology communities). 2 project H2FC Major Targets Major targets of H2FC European Infrastructure based H FC Objectives (Joint Research) upon identified needs of the different communities within 2 fuel cells and hydrogen technology: The total budget of € 10.147.583 H2FC European Infrastructure forebodes the importance of the specific 1. Transnational Access to research installations theme and challenges associated. Main challenge of the and infrastructures project is to originate a coordinated and integrated 2. Joint research on improvements and further alliance based on complementary, state-of-the-art, or development of research infrastructures even beyond state-of-the-art unique infrastructures, to 3. Teaming of the different communities by serve the necessities of the scientific hydrogen and fuel compiling and exchange of general and specific cells community and to facilitate world class research. knowledge The key research topics identified are described by the Three main pillars govern the project work, networking work package headings and focus basically on the activities, joint research activities and transnational integration, enhancement and improvement of existing access activities, further subdivided in 23 work packages, technical research infrastructures: whereat each work package has its own objectives 1. Facility improvements for investigation of basic [fig.1.0] hydrogen properties and material behaviour 2. Facility improvements for investigation of components and systems of the hydrogen energy chain

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

3. Methods, protocols and benchmarking on fire development and generation of knowledge [fig.2.0]. resistance, solid storage materials, fuel cell Access activities are divided into 7 calls and announced degradation and fuel quality each separately; no exclusion of submitted proposals is 4. Development of a cyber-laboratory and central effected by. Access activities in the special concern “free database to practice simulation and modelling of charge” ends with the project in October 2015. on fuel cells and hydrogen safety aspects Performance & Durability SolidSolid StorageStorageMaterialsMaterials FCFC PerformancePerformance HYSORB,HYSORB, SOLTEFSOLTEF H2QF,H2QF, ETC,ETC, FCLabFCLab H2FC Objectives (Networking) H2H2 PermeationPermeation FCFC DurabilityDurability The networking activities are heading the R&D GASTEFGASTEF DurSOFCDurSOFC,, FCTESTFCTEST communities in concerns of: Embrittlement,Embrittlement, LifeLife timetime analysisanalysis PretHy,PretHy, HyCyHyCy 1. Relevant education and training actions BasicBasic MaterialMaterial InvestigationsInvestigations 2. Foresight, knowledge and innovation on SINQ,SINQ, IFEIFE NeutronNeutron BeamBeam

hydrogen technologies and especially to H2 Production Storage Transport Fuel Cells Other H2 Application

investigate existing scientific bottlenecks but H2H2 SensorsSensors also to inform and discuss with national and SenTeFSenTeF,, SensSens international authorities about necessities and FlowFlowandand MixingMixing HySacHySac,, HiPresHiPres,, TunEnTunEn,, TTSTTS demands IgnitionIgnitionandand CombustionCombustion 3. Dissemination and public relations to inform HySacHySac,, HyKaHyKa(PROFLAM),(PROFLAM), ExCellExCell communities and strengthen collaboration and Hazards, Risks & Safety transfer of knowledge to generate impact in industrial aspects Fig.2.0 Experimental and technical portfolio of H2FC 4. Long term perspectives to develop and install European Infrastructure instruments for sustaining communication and

collaboration Acknowledgement H2FC Objectives (Transnational Access) H2FC European Infrastructure is funded by European Main support to European’s hydrogen and fuel cell Commission under FP7 framework und Capacities, communities will be given through the transnational project no. 284522 access activities, by offering very different technical and http://www.h2fc.eu experimental facilities to external users. Approximately 52 different technical installations are offered by the http://ec.europa.eu/research/infrastructures/pdf/h2fc_dec consortium free of charge to the fuel cell and hydrogen 12.pdf communities to support scientific ideas, technical

Physicist and Mathematician; studies elementary particle physics and mathematics at University of Karlsruhe, scientist at Fraunhofer Community (Institute for Chemical Technology, Pfinztal) science 1992 to developed digital, optical high speed measurement techniques to investigate practically fast dynamic deformation behavior of polymeric materials. Modeling of polymeric material behavior. Parallel investigation and application of sub- and super critical water conditions, to use its properties to extract fine chemicals from biomass and especially lignocelluloses materials. In 2005 Olaf Jedicke took up a lead position at Project Management Agency, which acts in behalf of the National Ministry of Education and Science (BMBF), to develop and arrange national research- and investigation Olaf Jedicke programs. Teaching Fluid Dynamics at the University of Cooperative Education since 1994, Higher Mathematics and Numeric since 2000. Olaf Jedicke started working with EU Framework programs already in the 3rd FP, act as project coordinator of BIONIRS, co-coordinator of e.g. HySafe, NanoHy, ScinTax, RELATE, EUMINAfab and is coordinator of the European infrastructure projects H2FC European Infrastructure. Since 2011 senior scientist at Institute of Nuclear- and Energy- Technologies, “Hydrogen Safety Group” in 2011.

Olaf Jedicke; [email protected]; Phone +49 (0) 721 6082 5274

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

HYDROGEN STORAGE IN THE FRAMEWORK OF H2FC E. Callini1, A.Borgschulte1, A. Züttel1,2

1 Empa, Ueberlandstrasse 129, 8600 Duebendorf, Switzerland.

2 EPFL, SB, ISIC, 1015 Lausanne, Switzerland.

Abstract: H2FC European Infrastructure Project is intended to integrate European Infrastructure and support science and development of Hydrogen and Fuel Cell Technologies towards European Strategy for Sustainable Competitive and Secure Energy. The Project addresses 4 different aspects of hydrogen related research: Storage, Production, End-use / Systems and Safety. This contribution will focus on the state of the art of Hydrogen Storage and how this topic is tackled in the framework of H2FC project.

Hydrogen Storage – State of the Art [2]http://www.linde- gas.com/internet.global.lindegas.global/en/images/LT There are 3 different ways to store hydrogen [1], as 01_2011_GB17_19666.pdf illustrated in Figure 1: liquefied [2], as compressed gas [3] and in solid [4] or liquid hydrogen containing species. [3] GreenPower project, Nano-Tera plenary annual The latter category can moreover been differentiated meeting, 2011. weather the hydrogen is physisorbed or chemisorbed into [4] E. Callini, et al., APL 94, 221905 (2009). the compounds. For all these different systems this contribution will summarize the state of the art, present [5] www.h2fc.eu the current technology and underline the challenges to still be addressed.

Hydrogen Storage – H2FC In the framework of the H2FC project [5], most of the research efforts have been focused on storing hydrogen in solid or liquid hydrides. Several Trans National Actions have been involved in this topic and Empa is one of the host centres for synthesis and characterization of hydrogen containing materials. An overview of the projects and scientific highlights will be presented to illustrate the work and the collaboration within the H2FC platform.

References [1] A. Züttel, A. Borgschulte, L. Schlapbach, (eds.) Hydrogen as a Future Energy Carrier, Wiley-VCH, Figure 1: Different ways of storing hydrogen. Top as Heidelberg 2008 compressed gas [3], bottom as metal hydride [4], right liquefied [2].

Born 13.1.1982 in Varese, Italy. In 2011 she graduated in Physics in Bologna, Italy, with Prof. E. Bonetti. During her studies she collaborates with the Danish Technical University in Copenhagen, Denmark, with Prof. T. Bohr; the Department of Chemistry of the Aarhus University in Denmark, with Prof. T. R. Jensen and with the California Institute of Technology in Pasadena (CA), with Prof. B. Fultz and Dr. C. Ahn. Since 2011 she is PostDoc in the Complex Hydrides Group in the Laboratory Hydrogen & Energy at Empa, Dübendorf, Switzerland.

Elsa Callini

Corresponding author: Elsa Callini, [email protected], +41 587654933.

82 9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

TECHNOLOGY AND SAFETY ISSUES RELATED TO REFUELING OF HYDROGEN CARS Pietro MORETTO

DG Joint Research Platform, Petten, The Netherlands

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Corresponding author: Name, email, Tel.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

TOWARDS HARMONIZED MEASUREMENTS OF INVESTIGATIONS OF SOLID HYDROGEN STORAGE MATERIALS

Ulrich Ulmera, Maximilian Fichtnera, Pietro Morettob, Marek Bieliewskib, Christoph Frommenc, Magnus H. Sorbyc, Georgia Charalambopouloud, Thanos Stubosd, Phillipe Maurone, Andreas Borgschultee, Vasile Iosubf, Olivier Gilliaf a Karlsruhe Institute of Technology, Institute of Nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germany b Institute for Energy and Transport, European Commission DG-JRC, P.O. Box 2, 1755 ZG, Petten, The Netherlands c Institute for Energy Technology, P.O. Box 40, 2027 Kjeller, Norway d National Center for Scientific Research Demokritos, P.O. Box 60037, 15310 Athens, Greece e Division of Hydrogen and Energy, Department of Mobility, Energy and Environment, EMPA, Swiss Federal Laboratories for Materials Testing and Research, 8600 Dübendorf, Switzerland f CEA Grenoble, DRT/LITEN/DTH, 17 rue de Martyrs, 38054 Grenoble, France

Abstract: The progress in the development of methods and protocols for a harmonization of the investigation of solid state hydrogen storage materials in the framework of the H2FC European infrastructure project is presented.

For the implementation of a hydrogen economy, safe and external) around the world. The emphasis is put on efficient storage of hydrogen is one of the key issues. calorimetric measurements. Large amounts of hydrogen can only be stored when bound to a carrier material. That can be an organic liquid, For efficient safety assessment of H storage materials a physisorption material at cryogenic temperatures, or a and systems it is necessary to develop a procedure metal hydride. Such materials must be qualified before where the safety characteristics of a new H storage they can be used in an application relevant technical material can be assessed at an early stage, with typical environment. Thus it is necessary to develop harmonised amounts of material and in a way that is also characterization methods which are targeted at transferrable to real storage devices. application relevant parameters. In this respect, a method which correlates microstructural The accurate and reliable assessment of the H2 storage and chemical changes in a material with a slowdown of performance of candidate solid stores remains a critical absorption/desorption rates and decreased cycling and controversial issue, severely plaguing solid storage capacity has been developed at KIT. These efforts have research by incorrectly measured and overestimated been complemented by the improvement at JRC of a capacity values mainly due to the complexity of the cycling test device capable of thousands of experimental parameters involved. These problems need hydrogenation cycles. Regarding the system design, the to be identified and methods need to be tested to COMEDHY installation at CEA that allows the circumvent these problems. measurement of hydride materials swelling and shrinking when absorbing and desorbing hydrogen between 20 °C The partners performed a literature review on existing and 200 °C under 0-200 bar, had its resolution increased data of most relevant solid storage materials. A critical to obtain accurate and quantitative information of the analysis of these results allowed the identification of swelling phenomenon under controlled loading with lacks and controversial issues. Smart, in-situ sorption respect to the hydride container. methodologies were developed with a special attention to interfaces and sample environments/cells were designed It is expected that the development of these partly unique to couple gas sorption concepts and rigs with calorimetry, experimental and modelling capabilities coupled with mass spectrometry, spectroscopy or XRD/neutron harmonized round robin approaches will have a scattering. significant impact on the deployment of solid hydrogen storage materials. To validate the new characterization platform an inter- laboratory comparison on MgH2 is currently performed with participation of laboratories (H2FC internal and

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

HYDROGEN SAFETY: THE STATE-OF-THE-ART Vladimir Molkov

Hydrogen Safety Engineering and Research Centre, University of Ulster, Newtownabbey, BT37 0QB, UK

Abstract. The state-of-the-art and future tasks in hydrogen safety engineering are presented. Calculation of deterministic separation distances for unignited and ignited releases using the similarity law and the universal flame length correlations is demonstrated. Spontaneous ignition of hydrogen during the sudden release of hydrogen is discussed. The effect of a release diameter on delayed ignition overpressure is demonstrated. The increase of local overpressure when using barriers is described. Unique for hydrogen so-called the pressure peaking phenomenon is explained. Calculation of parameters of the hydrogen ventilation system is explained. New correlations for venting of hydrogen-air deflagrations for mixtures occupying the whole enclosure and only its part are presented. Peculiarities of well-ventilated and under- ventilated fires are discussed in detail. Some important knowledge gaps and technological bottlenecks are identified.

Introduction 51.7 mm, laminar and turbulent flows, sub-sonic, sonic, and super-sonic velocities of release. Hydrogen Safety Engineering is defined as the application of scientific and engineering principles to the protection of life, property and the environment from the adverse effects of accidents involving hydrogen [1]. The state-of-the-art in hydrogen safety engineering is presented along with some future tasks. Deterministic separation distances Concentration decay in expanded and under-expanded jets is described by the similarity law validated against a wide range of experiments at pressure up to 400 bar, and release diameters 0.25-25 mm (Fig. 1). Hazard example include an intake of flammable mixture into the nearby building ventilation system that can cause an explosion, etc.

Figure 2. The universal flame length correlation.

There are three separation distances for jet fires. o Separation distance 1: 2xLF is the “death” limit (300 C, 20 o s); Separation distance 2: 3xLF is the pain limit (115 C, 5 min); Separation distance 3: 3.5xLF is the “no harm” limit (70oC). Figure 1. The similarity law for hydrogen concentration “Unexpected” conclusion: all three separation distances decay in momentum-dominated expanded and under- for hydrogen jet fire are longer than distance to the lower expanded jets. flammability limit (LFL) of 4% of hydrogen in air [1]. Selected issues of hydrogen safety The universal flame length correlation allows calculation The LES model of spontaneous ignition of hydrogen by of flame length for all regimes of hydrogen fires (Fig. 2). It “diffusion mechanism” during the sudden release into a gives dependence of the dimensionlised by release T-shaped channel reproduced experimental results. The diameter flame length LF/D as a function of the product of model is based on the eddy dissipation concept and two ratios: a ratio of density of hydrogen in the nozzle includes reduced chemistry of hydrogen oxidation in air. (can be calculated by means of Cyber-Laboratory, www.h2fc.eu) to density of surrounding air, and a ratio of Experimental study of HSL demonstrated that hydrogen velocity in the nozzle to the speed of sound of overpressure during delayed ignition of hydrogen jet hydrogen in the nozzle. The correlation is validated in the strongly depends on release diameter. At storage range of pressure 0.1-90 MPa, release diameters 0.4- pressure 20 MPa the overpressure of delayed deflagration of the jet was 16.5 kPa for 9.5 mm diameter

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015 release pipe and there was no overpressure at all for 1.5 New vent sizing correlation for layers of flammable mm diameter. The conclusion is to reduce the piping hydrogen-air mixtures is developed and validated for the diameter (in case of full bore rupture) as low as first time (Fig. 5). reasonably practical for technological purposes. Introduction of a barrier reduces the separation distance based on the flame length. However, the overpressure increases from 16.5 kPa to 42 kPa for 90o barrier and to 57 kPa for 60o barrier posing potentially higher harm to people nearby. The pressure peaking phenomenon has been recently released phenomenon characteristic for hydrogen. Figure 3 demonstrates overpressure dynamics in the SAE garage of size 4.5x2.6x2.6 m (volume 30.4 m3) with a “brick” vent (sizes 25x5 cm, i.e. area of 0.0125 m2). Release from thermally activated pressure relief device (TPRD) installed at vehicle’s onboard storage is with a mass flow rate 390 g/s (350 bar, TPRD diameter D=5.08 mm). It can be concluded from Fig. 3 that such garage will be demolished in 1-2 s. Figure 5. Vent sizing correlation for layers of hydrogen-air mixture in enclosures.

General rules for indoor fire regimes in an enclosure with one vent are derived by numerical study: there is well- ventilated fire for small leak rates; then there is a transition to under-ventilated fire with an external flame for moderate release rates; then under-ventilated fire with self-extinction is observed for higher flow rates; and finally again under-ventilated fire with external flame takes place with very high flow rates. Figure 6 shows dynamics of external fire (left) and self-extinction regime (right).

Figure 3. Pressure peaking phenomenon for four gases in SAE garage with a vent of one brick size.

The study within the HyIndoor project has shown that passive ventilation equation should be used instead of former natural ventilation equations. The difference between the two methods is described by a function f(X). Underestimation by natural ventilation equations is x2 Figure 6. Two regimes of under-ventilated fire: external times for lean hydrogen-air mixtures, and overestimation flame (left) and self-extinction (right). is x2 times for rich mixtures.

Some gaps and bottlenecks in safety The main objective of hydrogen safety is life safety. Innovative safety strategies and engineering solutions yet to be developed to make hydrogen and fuel cell systems and infrastructure even inherently safer. Comparatively large deterministic separation distances from unignited release, jet fire, blast wave and fireball during high pressure vessel rupture have to be reduced. It can be achieved by a coupled action of reducing the release (piping, TPRD) diameter and increasing fire

resistance rating of the storage tank. Figure 4. Passive ventilation (solid line) against natural ventilation.

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

A promising system of multi-level thermal protection of Figure 7. A system of thermal protection of high pressure on-board storage tank with the use of Intumescent paint storage tank. and external protective low pressure vessel is shown in Fig. 7. It is expected that fire resistance rating for the protected tank can reach 1-2 hours instead of current 6- References 12 minutes. [1] V. Molkov, Fundamentals of Hydrogen Safety Engineering (free download eBook, http://bookboon.com, available since October 2012)

Prof Vladimir Molkov is a physicist graduated from Moscow Institute of Physics and Technology (MIPT). He received PhD degree in Chemical Physics, including Physics of Combustion and Explosion from MIPT, and DSc degree in Fire and Explosion Safety from All-Russian Research Institute for Fire Protection (VNIIPO). Before joining the University of Ulster (UU) as Professor of Fire Safety Science in 1999, he worked at VNIIPO as a Head of Department. In 1997-1998 he carried out joint research with Prof Toshisuke Hirano at the University of Tokyo (UT) as a Fellow of Japanese Society for Promotion of Science, and in 2012 visited UT as an advisor of their explosion research Vladimir Molkov programme. Since 2004 he is specialising in hydrogen safety with thrust on modeling and numerical simulations. Research interests include but not limited to under-expanded jet releases and dispersion outdoors and indoors, ventilation of unscheduled hydrogen releases, spontaneous ignition of hydrogen during sudden releases to oxidizer, well- under-ventilated hydrogen fires, including self-extinction and re-ignition phenomena, modeling and simulations of large-scale deflagrations and detonations, thermal protection of on-board storage, blast waves and fireballs from high-pressure hydrogen storage tank rupture, mitigation techniques, including deterministic separation distances, etc. In 2008 he has established and directs the Hydrogen Safety Engineering and Research Centre (HySAFER) at the University of Ulster, one of key providers of hydrogen safety research and education globally. He has coordinated and participated in major European and UK projects relevant to hydrogen safety. Since 2012 he is a Visiting Professor at Karlsruhe Institute of Technology, HECTOR School of Engineering and Management (Germany). Since 2013 he is UK expert in ISO TC/197 “Hydrogen technologies”.

Corresponding author: Vladimir Molkov, [email protected], +447790026451

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

STRUCTURAL STUDIES OF COMPLEX HYDRIDES Bjørn C. Hauback, Stefano Deledda, Christoph Frommen, Magnus H. Sørby

Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway

Neutron diffraction is the main method to determine hydrogen/deuterium positions in metal hydrides. For complicated structural features the combination of X-ray (including synchrotron radiation) and neutron diffraction is needed to obtain a complete description of the crystal structures. The rare-earth borohydrides show a big structural diversity, with anion substitution, polymorphism, different coordination numbers and multiple oxidation states of the rare-earth. Selected detailed crystal structure studies and in-situ sorption experiments will be described.

Introduction samples. TG-DSC, TPD combination with mass spectrometry and Sieverts apparatus are used for the Detailed knowledge about the positions of the atoms is of characterization of the hydrogen storage properties. major importance both for development of new metal hydrides and for understanding of their properties. Results Neutron diffraction is a unique tool for studies of metal Selected detailed crystal structure studies and in-situ hydrides since it is the only method to determine the desorption and absorption diffraction experiments will be positions of the hydrogen/deuterium atoms in the crystal described. The presentation will address some of our structures. For structural studies the use of deuterium is recent studies on complex hydrides. By in-situ high crucial due to the challenge with incoherent scattering pressure NMR and combination of in-situ SR-PXD and with normal hydrogen. Furthermore for studies of boron- PND the hydrogenation of NaAlH have been studied in based compounds, borohydrides, the 11B isotope has to 4 details [1]. We have performed a systematic investigation be used because of the strong absorption of neutrons in of the rare-earth borohydrides, and the big structural normal boron (mainly 10B). The weak interaction of diversity will be discussed [2]. In these compounds there neutrons with most elements results in determination of are anion substitution, polymorphism, different real bulk properties and easy use of complex sample coordination numbers and multiple oxidation states of the environments. Examples of structural studies of novel rare-earth. The combination of neutron and synchrotron aluminium and boron-based complex hydrides will be radiation X-ray scattering is in particular important and presented. will be emphasized. Experimental Acknowledgements The boron-based samples are prepared using ball milling Financial support from The Research Council of Norway, techniques by mixing LiBH and the corresponding rare- 4 EU 7FP projects FLYHY, BOR4STORE, H2FC and ERA- earth chlorides in different ratios. For neutron diffraction NET CONCERT-Japan We acknowledge the skilful double labelled Li11BD is used as the starting material. 4 assistance from the staff of SNBL at ESRF. Most of our powder neutron diffraction (PND) experiments are performed with the high-resolution References powder diffractometer PUS at the JEEP II reactor at IFE. [1] T. Humphries, D. Birkmere, B.C. Hauback, G.S. For studies of complex structures and samples McGrady, C.M. Jensen, Phys. Chem. Chem. Phys. containing different phases, the combination of PND and (2013) 15, 6179-6181; T. Humphries, J.W. X-ray diffraction is needed. For very complicated Makepeace, S. Hino, W.I.F. David, B.C. Hauback, J. structural features and in-situ experiments, the use of Mater. Chem. A (2014) 2, 16594-16600 synchrotron radiation powder X-ray diffraction (SR-PXD) is important. The SR-PXD experiments are performed at [2] J.E. Olsen, C. Frommen, T.R: Jensen, M.D. Riktor, the Swiss-Norwegian Beamlines (SNBL) at the ESRF in M.H. Sørby, B.C. Hauback, RSC Advances (2014) 4, France. IR, Raman and NMR methods are used in order 1570-1582; to characterize the non-crystalline components in the

Bjørn C. Hauback is Department Head of the Physics Department at Institute for Energy Technology and adjunct professor of Physics at the University of Oslo. He has a PhD in physics from Norwegian Institute of Technology from 1989. His main interests are structure-property relationships of hydrogen storage materials and neutron diffraction. He is a member of Norwegian Academy of Technological Sciences and led the Task 22 on hydrogen storage materials of the IEA Hydrogen Implementation Agreement in 2006-2012. He will be co-chair of the Gordon Research Conference Hydrogen-Metal Systems in July 2015. B.C. Hauback

Corresponding author: Bjørn C. Hauback, [email protected], tel: +47 97 40 88 44.

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

Cool Hydrides, Again ! Shin-ichi ORIMO1,2 1 WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan 2 Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

The significance of the research on materials containing hydrogen has increased rapidly and extensively due to the consideration of hydrogen as a future energy source/carrier. Accumulation of knowledge of hydrogen behavior in metallic, inorganic, and polymer-like materials is vital in order to develop hydrogen production, storage, and transportation technologies. Besides the practical aspects, fundamental studies of hydrogen in materials are indispensable to understand the intrinsic properties of the materials, and in many cases, to modify/improve their properties. In this presentation, some selected research topics and trends currently underway in Japan will be discussed (partially “reviewed” according to the presentation in MH2014).

- Commercialization of fuel cell vehicles planned in the next year (recently announced “December 15, 2014”), and on-going improvements of related infrastructures and legal systems.

?

http://toyota.jp/sp/fcv/catalog/performance.html “Evolution” of Fe-based Complex Hydrides

- Focused research on liquid-state hydrides (ammonia - Multiplicity of complex hydrides, including all-solid-state and methylcyclohexane (MCH), etc.) as hydrogen/energy battery device studies and applications. carriers.

3H MCH 2 Toluene C H CH + C H CH 6 11 3 6 5 3 Li

- Research progress in solid-state hydrides, especially using advanced neutron and synchrotron beam B techniques, combined with high-pressure technique. H

- Recent studies on iron-hydrogen systems in both - New phenomena observed in hydrogen-dope materials; materials science (hydrogen embrittlement/storage) and superconductivity and electronic properties. earth science.

Shin-ichi ORIMO received his Ph.D. in materials science/physics from Hiroshima University in 1995. He was a JSPS research fellow (1993-1995), a research associate in Hiroshima University (1995-2002), and a guest researcher of Max-Planck Institute for Metal Research awarded by Alexander von Humboldt Fellowship and MEXT Fellowship (1998-1999); and is a professor of WPI-AIMR / IMR, and the Head of Integrated Materials Research Center for a Low-Carbon Society, Tohoku University. His research interests are fundamentals and energy-related applications of hydrides. He was awarded “The Prize for Science and Technology (Research Category), The Commendation for Science and Technology by the Minister, MEXT (2012)”. Shin-ichi ORIMO http://www.hydrogen.imr.tohoku.ac.jp/

Corresponding author: Shin-ichi ORIMO, Email: [email protected], Tel. (+81)22-215-2093.

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

NH3BH3 MODIFIED Zr(BH4)4·8NH3 WITH ENHANCED DEHYDROGENATION PROPERTIES Jianmei Huanga*, Xuebin Yub, Liuzhang Ouyanga, Min Zhua aSchool of Materials Science and Engineering and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641, China bDepartment of Materials Science, Fudan University, Shanghai 200433, China

A new complex system, Zr(BH4)4·8NH3-nNH3BH3 (n = 2, 3, 4, 5), was prepared via ball milling of Zr(BH4)4·8NH3 and NH3BH3 (AB). The combination of two compounds effectively reduced the ammonia release and the dehydrogenation temperature when compared to the individual compounds. In the optimal composition, Zr(BH4)4·8NH3-4AB, the hydrogen purity was improved to 96.1 mol.% and 7.0 wt.% of hydrogen was released at 100 C. These remarkable improvements are attributed to the interaction between AB and the NH3 group in Zr(BH4)4·8NH3, which enables a more active δ+ -δ interaction of H ··· H. These advanced dehydrogenation properties suggest that Zr(BH4)4·8NH3-4AB is a promising candidate for potential hydrogen storage applications.

Introduction

Zr(BH4)4·8NH3 shows the highest coordination number of NH3 groups among all the known metal borohydride ammoniates. It could fast release hydrogen close to ambient conditions. Hence, Zr(BH4)4·8NH3 is considered as a promising chemical hydrogen storage materials. However, 16.3 mol.% of ammonia is released during the dehydrogenation process of Zr(BH4)4·8NH3, which reduces the hydrogen purity and amount. Herein, ammonia borane was applied to inhibit the release of ammonia.[1] Fig.1 Summary of hydrogen release capacity, purity and Synthesis and Dehydrogenation temperature.

The combination system of Zr(BH4)4·8NH3 and NH3BH3 was prepared through ball milling. When compared to Mechanism 11 Zr(BH4)4·8NH3 and pure AB, these composites show a From the FTIR and B NMR results, the mutual dehydrogenation improvement in terms of dehydrogenation of Zr(BH4)4·8NH3-4AB occurs through reduced toxic by-product gas release, decreased the interaction between AB and the NH3 groups in hydrogen evolution temperature, and enhanced Zr(BH4)4·8NH3, resulting in a decrease in the dehydrogenation kinetics. As shown in Fig.1, the coordination number of NH3 on the Zr cations. The gas hydrogen purity in the gaseous products is improved with impurities released from AB as well as Zr(BH4)4·8NH3 increasing the amount of AB, and reaches a maximum of were simultaneously reduced. An amorphous B-N based 96.1 mol.% for Zr(BH4)4·8NH3-4AB. This composite also polymer was found to be the final product. shows a reduced dehydrogenation temperature from 130 C to 85 C and releases 7.0 wt.% of hydrogen within 45 Reference min at 100 C. [1] J. M. Huang et al, J. Mater. Chem. A., accepted.

Born 1987 in Guangxi, China. Jianmei Huang is a PhD student of Materials Processing at South China University of Technology. Her current research interests are focused on novel borohydride- based hydrogen storage materials. 2009.9-present: A student for continuous Master and PhD study, School of Materials Science and Engineering, South China University of Technology 2013.4-2014.6: Guest PHD student, Department of Materials Science, Fudan University 2014.7-present:Guest PHD student, Empa-Swiss Federal Laboratories for Materials Science and Jianmei Huang Technology

Corresponding author: Jianmei Huang, email: [email protected], Tel.: +41 768143314

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

EXPERIMENTAL STUDY OF A METAL HYDRIDE TANK WITH DOUBLE COIL TYPE HEAT EXCHANGER BELOW 1.0 MPa (G) OPERATION Akihiro Nakano a,*, Hiroshi Itoa, Satya Shekhar Bhogillaa, Theodore Motykab, Claudio Corgnaleb, Scott Greenwayc, Bjørn C. Haubackd a National Institute of Advanced Industrial Science and Technology (AIST) b Savannah River National Laboratory (SRNL) c Greenway Energy LLC d Institute for Energy Technology (IFE)

A metal hydride tank, which is operated below 1.0 MPa (Gauge), has been developed with the aim of recovering the reaction heat of metal hydride for the Totalized Hydrogen Energy Utilization System application. The hydrogen mass flow data from hydrogen production by renewable energy (solar power) and the fuel cell operation, which were obtained at SRNL, were used for the testing at AIST and the reaction heat recovery rates were evaluated.

Introduction and outlet temperatures of the circulation water. Temperature drops are presented in Fig. 1c, when the A metal hydride tank has been developed for the hydrogen flow rate was diminished. It is also noted from Totalized Hydrogen Energy Utilization System (THEUS) Figs. 1b and 1c that the temperature is more sensitive to application1. The metal hydride tank, which had the same the hydrogen flow rate as compared with the pressure. geometrical configuration set at SRNL, was fabricate with The metal hydride reaction heat recovery rate was 83 %. a different composition of the metal hydride alloy for On the other hand, the fuel cell at SRNL was capable of operation below 1.0 MPa (G). By using the mass flow producing 5 kW net of DC power. Since the hydrogen controller, the data for the hydrogen production from supply capability of the metal hydride tank was small, renewable energy and the fuel cell at SRNL were small electric loads were selected in the experiments at reproduced at AIST. The absorption and desorption tests SRNL. In case of the experimental simulation using the were carried out and the reaction heat recovery rates of hydrogen flow rate data with the load of 0.5 kW, the the metal hydride tank were investigated in this study. reaction heat recovery rate was 86 %. The details of the Experimental set-up experimental results will be reported in the symposium.

A double coil type heat exchanger was installed in the metal hydride tank for recovering the reaction heat of the metal hydride. 50kg of MmNi5 (AB5) metal hydride alloy was placed in the tank. The hydrogen was provided from hydrogen cylinders. The hydrogen flow rate was controlled by a mass flow controller (MFC) and a personal computer. When the experimental simulations were carried out, the mass flow data obtained from SRNL were read into the personal computer and the hydrogen Fig.1 Experimental simulation results. (a) Reproduced hydrogen flow rate was reproduced by the MFC. flow rate. (b) P-C isotherm. (c) The temperatures in each position in the tank and the inlet and the outlet temperatures of Experimental results and comments the circulation water. Fig. 1 presents the experimental results for absorption. The circulation water temperature was set at 32 °C. Fig. References 1a shows the reproduced hydrogen flow rate. 6451 NL of [1] Masuda M, Kato A, et.al. Energy efficiency evaluation hydrogen was absorbed in this case. Fig. 1b shows the of totalized hydrogen energy utilization system for P-C isotherm. The maximum pressure was 0.974 MPa. commercial buildings. Proc. of 17th world hydrogen The hydrogen was fully charged in the metal hydride tank. energy conference 2008; Paper No.260, CD-ROM. Fig. 1c shows the temperature in the tank, and the inlet

1993: Doctor of Philosophy in Engineering of University of Tsukuba. 1994-1996: NASA Jet Propulsion Laboratory (JPL) (Guest Researcher) 1996-2000: Mechanical Engineering Laboratory (MEL) 2001- : National Institute of Advanced Industrial Science and Technology (AIST). (2011) Savannah River National Laboratory (Guest Researcher) & University of South Carolina (Visiting Professor) (2012-13) Energy Tech. Research Institute (ETRI), Integrated Hydrogen System Group Leader. Akihiro Nakano (2014- ) ETRI, Hydrogen Energy Technology Group Leader.

Corresponding author: Akihiro Nakano, email [email protected], Tel. +81-29-861-7250

9th Int. Symposium Hydrogen & Energy Emmetten, Switzerland 2015

PORSPECTS FOR POROUS MATERIALS IN HYDROGEN STORAGE AND GAS SEPARATION Michael Hirscher

Max Planck Institute for Intelligent Systems, Stuttgart, Germany

In the past 10 years the number of known porous structures is basically exploded, since new types of porous framework materials, e.g., MOFs, ZIFs, COFs etc., have been synthesized. These novel materials possess extremely high specific surface areas combined with a well-defined uniform pore size distribution. The presentation will give an overview on the progress and the limitations of hydrogen storage via physisorption. Furthermore, possible applications in gas separation and especially for hydrogen isotope separation will be discussed.

Porous Materials the enhancement of the storage capacity at room temperature by metal doping will be critically assessed. For a long time the field of porous materials was In general the enhancement is very small and below any dominated on the one side by activated carbons, technological relevance [5]. possessing an amorphous-like structure and high surface areas, and on the other side by zeolites, which are H2/D2 Isotope Separation crystalline with well-defined pores, however, limited in In microporous materials hydrogen isotopes can be specific surface area below 1000m2/g. The field has separated by two principles: i) confinement in small pores tremendously grown, when porous coordination polymers i.e. “Kinetic Quantum Sieving” [2,6] ii) strong adsorption or framework materials could be prepared with a stable sites i.e. “Chemical Affinity Quantum Sieving” [7]. For and robust structure after removal of solvent molecules, different framework materials, experimental results will be exhibiting ultra-high porosity and large specific surface presented for the selectivity directly measured by thermal areas [1]. Different classes of these novel highly porous, desorption spectroscopy after exposure to isotope crystalline structures, e.g., metal-organic frameworks mixtures of H and D . Both sieving mechanisms will be (MOFs), zeolitic imidazolate frameworks (ZIFs) or 2 2 discussed regarding possible technical applications. covalent organic frameworks (COFs), have been extensively studied for applications in gas storage. References Frameworks with small pores and/or even smaller [1] G. Férey, Chem. Soc. Rev., 37 (2008) 191; S. apertures can be designed enabling sieving effects for Kitagawa et al., Angew. Chem. Int. Ed., 43 (2004) gas separation. Recently, quantum sieving in nanopores 2334; O.M. Yaghi et al., Nature, 423 (2003) 705; with a diameter near the kinetic extension of the X.C. Huang, Y.Y. Lin, J.P. Zhang, X.M. Chen, Angew. hydrogen molecule was proposed as one promising Chem. Int. Ed., 45 (2006) 1557. possibility for separating D2/H2 isotope efficiently and effectively [2]. [2] J.J.M. Beenakker et al., Chem. Phys. Lett., 232 (1995) 379. Hydrogen Storage [3] M. Hirscher, Angew. Chem. Int. Ed. 50 (2011) 581. For the maximum hydrogen uptake at high pressure and 77 K an almost linear correlation with the specific surface [4] M. Hirscher, M. Schlichtenmayer, J. Mater. Chem., area is found for many different nanoporous framework 22 (2012) 10134. materials [3]. Furthermore, frameworks possessing [5] C. Zlotea et al., J. Am. Chem. Soc., 132, (2010) 2991; smaller pores show typically a higher heat of adsorption. S.B. Kalidindi et al., Chem. Eur. J., 18 (2012) 10848. Both, maximum hydrogen storage capacity and heat of adsorption have to be considered to optimize the [6] J. Teufel et al., Adv. Mater. 2013, 25, 635. materials for their potential application [4]. Furthermore, [7] H. Oh et al., ACS Nano, 2014, 1, 761.

Michael Hirscher is group leader at the Max Planck Institute for Intelligent Systems, Stuttgart, Germany. He studied physics at the University of Stuttgart, Germany and at the Oregon State University, Corvallis, USA, receiving a Master’s degree, a Diploma, and Ph.D. degree in 1982, 1984, and 1987, respectively. For his achievements he was awarded the Otto Hahn Medal of the Max Planck Society in 1988. Prior to taking his position in Stuttgart, he spent a post-doctoral fellowship at the University of Pennsylvania, Philadelphia, USA. He published over 100 papers and edited recently the “Handbook of Hydrogen Storage”. Since 2013 he is Operating Agent of Task 32 “Hydrogen-based Energy Storage” in the Hydrogen Implementation Agreement of the IEA. His M. Hirscher current research interests focus on nanoporous materials for gas storage and separation.

Corresponding author: Michael Hirscher, [email protected], Tel. +49-711-689-1808

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD

The “Science of Hydrogen & Energy” award is a price, just similar to the Nobel price, for an extraordinary contribution to the sciences of hydrogen. The aim is to award a prize to a distinct scientist for his scientific work of a life time.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2007

Ronald Pierre Griessen, was born March 7, 1945 in Switzerland. He received 1964 his Baccalauréat, from Gymnase français in Bienne, Switzerland. From 1964 – 1969 he studied Physics and Mathematics at the Swiss Federal Institute of Technology (ETH) in Zürich and finished with a Diploma-thesis on: "Magnetostriction of type-II superconductors". From 1969 – 1973 he was PhD student in the Low Temperature Physics Group of Prof.dr J.L. Olsen at the ETH. PhD-thesis on: "Oscillatory Magnetostriction and the stress dependence of the Fermi Surface of Al, In, Zn and Mg". From 1974 – 1976 he was Research Associate at the McLennan Physical Laboratory of the University of Toronto, Canada where he worked on the electronic structure of spin- density-wave systems and quantum oscillations.In 1976 he was visiting scientist at the ETH, Zürich and from 1976 – 1980 senior lecturer at the Vrije Universiteit in Amsterdam. Since 1980 he is Prof. Dr. Ronald Griessen Full Professor in charge of the Department of Condensed Matter Physics.

Ronald Griessen has investigated the thermodynamics of palladium films and the isotope effect on the electronic structure of hydrides. Furthermore, the effect of anharmonicity and Debye-Waller factor on superconductivity of PdHx and PdDx have been studied by Ronald before he developed a semi-empirical model for the heat of solution of hydrogen in transition metals. He also studied the trapping energy for hydrogen on lattice defects as well as the heat of solution of disordered transition metals. The volume expansion upon hydrogen absorption, the Gorsky-effect, the diffusion, electromigration and the hydrogen diffusion in magnetig fields are just a few other subjects treated and described by Ronald Griessen. Then Ronald decided to test the world of high pressure hydrogen and described the properties of hydrides formed at very high pressure as well as the properties of hydrogen gas in a wide temperature and pressure range. During the intense investigation of superconductors and metal hydrides under high hydrogen pressure in a diamond anvil cell, Ronald has discovered the switchable optical properties of yttrium and lanthanum hydride films. This has then stimulated Ronald to investigate thin films with optical methods and to develop new methods for the combinatorial search of new hydride phases as well as for the determination of the thermodynamic parameters e.g. stability and kinetics of the hydrides. Furthermore, new applications for hydrides as hydrogen detectors and optical filters have been developed in his group.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2008

Louis Schlapbach, born March 4, 1944 in Belp Switzerland. He graduated from the Swiss Federal Institute of Technology Zurich (ETHZ) in Experimental Physics and got his PhD in Solid State Physics – Magnetism also at ETHZ. As a postdoc at a CNRS laboratory in Paris, he studied hydrogen storage in intermetallic compounds. Back at ETHZ, he developed the surface science aspects of the hydrogen interaction with metals and alloys. From 1988 till 2001, Louis Schlapbach was Full Professor for Physics at the University of Fribourg. As such he built up a research team of 20-25 people working on the topic „New Materials and their Surfaces“ resulting in about 40 PhD, 200 scientific papers and some patents. A strong collaboration with industry was established. In spring 2001, he has been appointed CEO of Empa, the materials science and technology institution of the Prof. Dr. Louis Schlapbach ETH domain with 750 coworkers in Dübendorf, St. Gallen and Thun.

Louis Schlapbach started his scientific work in 1970, 38 years ago, with the investigation of the Hall effect, electrical transport and magnetic susceptibility of liquid rear earth elements like Cerium. 30 years ago in 1970 he was coauthor with Busch and Waldirich on a paper about the hydrides of La-Ni compounds. LaNi5 was subsequently investigated in view of the structure, surface segregations, hydrogen occupation of interstitial sites and as electrode material.LaNi5 is still the base material for most of the electrochemical applications of metal hydrides today. The work on LaNi5 was complemented by the research on FeTi. Louis Schlapbach realized the importance of the surface composition for the hydrogen sorption process and he was able to describe the role of the surface-active species. Furthermore, he investigated the changes of the surface composition of LaNi5 and FeTi in oxidizing atmospheres and he found the formation of metallic clusters as superparamagnetic particles acting as the active sites in hydrogen dissociation and recombination. The investigation of the surface of metal hydrides was further intensified by means of X-ray photoelectron spectroscopy. Louis Schlapbach was the first scientist correctly describing the activation process of a metal hydride and, furthermore, to model the chemical composition and states of the elements in a surface profile. He also succeeded to analyze the electronic structure of raere earth elements and their hydrides by means of photoemission spectroscopy. In 1990 Louis Schlapbach edited the two books "Hydrogen in Intermetallic Compounds I & II" of the Springer Sereies. The books became a very important reference for all the researchers active in the field of hydrides.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Gary Sandrock received his master from the Institute of Technology, Cleveland in 1965 and his Ph.D. from the Western Reserve University, Cleveland in 1971. He worked from 1962- 1969 as a research metallurgist in the NASA Lewis Research Center, Cleveland, Ohio. From 1971-1983 he was Section Manager of Energy Systems at Inco Research and Development Center, Suffern, NY. From 1983-1991 he was Vice President and Director of Technology at Ergenics, Inc., Ringwood, NJ. From 1992-1993 Gary Sandrock was visiting professor at the Kogakuin University, Hachioji, Tokyo, Japan where he developed a new chemical surface treatment and investigated the activation characteristics of chemical treated AB5 alloys. Gary then became the president of SunaTech, Inc., Ringwood, NJ, where he Dr. Gary Sandrock developed reversible hydrogen storage systems. At the same time Gary Operating Agent, International Energy Agency Hydrogen Implementing agreement Tasks 12 & 17 (Hydrogen Storage Materials) and worked as a consultant for the US DOE via Sandia National Laboratories, Livermore, CA.

In 1995 Gary Sandrock started to creat and mainten Hydride Databases of IEA(HIA)/DOE/SNL (http://hydpark.ca.sandia.gov) and he is author of several book chapters and review papers e.g. “A panoramic overview of hydrogen storage alloys from a gas reaction point of view”. His recent research concentrates on the catalysis of the hydrogen desorption from alanates and most recently Gary investigated the hydrogen desorption behavior of AlH3 and explaned the mechanism of the kinetic stabilisation of aluminumhydrid. Furthermore, he published a paper entitled “Accelerated thermal decomposition of AlH3 for hydrogen-fueled vehicles” where he shows the possible ways to change the activation barrier for the hydrogen desorption in a controlled way. Gary Sandrock not only made significant achevements in understanding metal hydrides he also built the bridge from sciences to application. Furthermore, his scientific review papers and the hydride database are inestimably value for the hydride society.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Jens Norskov was born on September 21 in 1952. He received his Master dgree in physics and chemistry from the University of Aarhus, Denmark in 1976 and his PhD in theoretical physics in 1979. During his PhD he published papers about the electronic structure of H and He in metal vacancies and the contraction of diatomic molecules upon chemisorption. Jens Norskov was a Post Doc at IBM in Yorktown Heights, New York in 1979 and was affiliated with Nordita, (Nordic Institute for Theoretical Physics) in Copenhagen before he became a member of the scientific staff of Haldor Topsøe A/S, Lyngby in 1981. He continued the investigation of gas molecules at the surface of metals and developed a picture of adsorption and desorption of hydrogen emerging from self-consistent model calculations. In 1992 he was Prof. Dr. Jens Norskov appointed as a professor of theoretical physics in the department of physics at the Technical University of Denmark, Lyngby and became the director of the Center for Atomic-scale Materials Physics (CAMP), Department of Physics, Technical University of Denmark, Lyngby.

Recent research of the group of Jens Norskov covers several of the most relevant topics: 1) The development of theoretical methods e.g. “Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces”; 2) Theoretical surface science e.g. “Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces”; 3) Nanostructures and materials properties e.g. Atomic-scale imaging of carbon nanofiber growth”; 4) Heterogeneous catalysis e.g. “Ammonia synthesis from first principles calculations”; 5) Biomolecules e.g. “Biomimetic hydrogen evolution”; 6) Electrochemistry and fuel cells e.g. “The origin of the overpotential for oxygen reduction at a fuel cell cathode”; 7) Hydrogen storage e.g. “Metal ammine complexes for hydrogen storage” Jens Norskov is not only a creative and brilliant scientist, he also belongs to the few scientist able to successfully combine theoretical approches with experimental observations for the understanding of the basic phenomena. It is always a great pleasure to listen to Jens Norskovs talks, which are exciting eye opening stories combined with some great new stimulating ideas.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Rüdiger Bormann was born September, 14 1952 in Germany. He received 1977 his diploma in physics (Metalphysics), from the University Göttingen and 1979 his Dr. rer. nat. from the University Göttingen. From 1981 to 1982 he was visiting scientist in the Dept. of Applied Physics at Stanford University, U.S.A. From 1982 to 1988 he was Assistant Professor (Hochschulassistent) at the University Göttingen where he received the Habilitation University Göttingen, venia legendi in 1988. From 1989 to 1997 he was Professor of Metalphysics (GKSS Research Centre, Geesthacht and Hamburg University of Technology) and from 1996 to 2009 he was director of the Institute for Materials Research, GKSS Research Centre, Geesthacht and since 2009

he is Professor of Applied Materials Physics and President of the Prof. Dr. Rüdiger Bormann University of Bayreuth. Rüdiger Bormann died on 13. January 2013 in an accident in Cologne, Germany.

Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses, metastable crystalline and amorphous alloys as well as the thermodynamics and kinetics of the amorphous phase formation by mechanical alloying. This was the basis for the investigation of Mg and Mg-Ni hydrides and the thermodynamics of nanoscale magnesim hydride. The discovery catalytic effect of metal oxides on the hydrogen sorption kinetics of magnesium was a great step forward in the development of hydrogen storage materials. Furthermore, very important was also the interpretation of the role of the grain boundaries for the diffusion of hydrogen in the passivating hydride phase formation. Recently the discovery of the so called reactive hydride composites by the combination of two hydrides has opened a new field of materials design for hydrogen storage. Therefore, we aword Prof. Rüdiger Bormann with the Science of Hydrogen & Energy prize 2010.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Ivor Rex Harris was born August 31, 1939 in United Kingdom. In 1960 he rewceived his B.Sc. in Physical Metallurgy from the University of Birmingham), 1964 his Ph.D and became a ICI Research Fellow. From 1966 he was lecturer in the Department of Physical Metallurgy and1988he became a full Professor of Materials Science. From 1989 to 2002 he was Head of School, Metallurgy and Materials and from 2004 to 2005 acting director of the Institute for Energy Research and Policy. Since 2008 he is Honorary Professor of Materials Science of the School of Metallurgy and Materials at the University of Birmingham.

Prof. Dr. Ivor Rex Harris

For around 40 years, Rex Harris was leader of the Applied Alloy Chemistry Group (AACG) in Metallurgy and Materials. During this time he maintained a long-standing research interest in the fields of rare earth alloys, permanent magnets and hydrogen purification and storage materials. He developed a close synergy between these fields with the development and application of the Hydrogen Decrepitation (HD) process to the manufacture of NdFeB magnets. The HD process resulted in up to a 25% saving in production cost and is now used world-wide in the fabrication of NdFeB sintered magnets. These materials are playing a vital role in the production of energy efficient electric drives, actuators and generators. The latest development within the group is the use of the HD process in the recycling of 2/17 and NdFeB magnets. His research also made a very significant contribution to the development and understanding of the Hydrogenation, Disproportionation, Desorption and Recombination (HDDR) process which enabled coercive powder and hence bonded magnets to be formed from bulk NdFeB alloys. He has published over 500 scientific papers and edited and co-edited a number of books. During these years he has successfully supervised around 120 postgraduate students, many of whom are still working in applied materials science and occupy senior positions in industry, government and academia throughout the world. Since stepping down as group leader and head of school he has focused his activities on the application of NdFeB magnets and hydrogen storage materials to practical demonstrators such as the Ross Barlow hybrid canal boat. This zero- carbon emission craft is serving to highlight the huge potential of magnets and hydrogen in the drive towards a sustainable transport system and he has given a large number of public lectures on this subject with the aim of raising public awareness of the dual threats of climate change and resource depletion. He continues to be very active in this campaign which he considers to be of paramount importance. Therefore, we award Prof. Rex Harris with the Science of Hydrogen & Energy prize 2010.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Rainer Kirchheim was born May 24, 1943 in Halle/Saale, Germany. He studied Physics at the University of Stuttgart from 1966-1971 and received the diploma for the work “Electrochemical studies of oxygen solid solutions in high melting metals” at the Max-Planck-Institut für Metallforschung/University of Stuttgart. He received his Ph.D. for the thesis entitled “Thermo- and electrotransport of oxygen and nitrogen in Va metals “ from the University of Stuttgart, Max-Planck-Institut für Metallforschung in 1973. In 1988 he received the Habilitation “Measurements and modelling of hydrogen solubility and diffusivity in disordered metal lattices“ from the University of Stuttgart, Faculty of Chemistry Metallurgy. Since 1993 he is Full Professor (Gustav Tamman Chair) Prof. Dr. Rainer Kirchheim University of Göttingen Göttingen Germany and Director Georg- August-Universitaet Goettingen, Institut für Materialphysik Göttingen Germany .

Prof. Rainer Kirchheim has investigated 30 years ago oxygen in metals, especially diffusion, thermo-transport and thermo-power of oxygen in transition metals and alloys. In 1980 he started to study diffusion of hydrogen in dillute alloys of copper and niobium in palladium. He developed an electrochemical method for the measurement of the hydrogen diffusion in palladium and palladium alloys and performed fundamental studies on the diffusion mechanism of interstitial species. The interaction of hydrogen with dislocations in palladium and the interpretation with a model based on the Fermi- Dirac distribution are of great importance for the understanding of the interstitial site occupation of hydrogen in alloys and amorphous metals. For the enormous contributions on the hydrogen dynamics and thermodynamics in metals as well as the hydrogen interaction with dislocations, grain bounderies and interfaces we award Prof. Rainer Kirchheim with the Science of Hydrogen & Energy prize 2010.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2011

Koji Hashimoto was born October 23, 1935 in Japan. He received the M. Sc. In Chemistry from the Faculty of Science of the Tohoku University, Sendai, Japan. In 1966 he received the Doctor degree in sciences from the Tohoku University and in the same year he became an associate professor in the Institute for Materials Research (IMR) of the Tohoku University. From 1967 to 1969 he was a Post Doctorate Fellow in the Division of Applied Chemistry of the National Research Council in Canada. From 1987 to 1999 he was a Professor in the Institute for Materials Research (IMR) of the Tohoku University and from 1999 to 2006 he was Professor at the Tohoku Institute of Technology.

Prof. Dr. Koji Hashimoto

Prof. emeritus Koji Hashimoto has published over 520 papers in scientific journals in addition to review articles and book chapters. He has worked on corrosion-resistant alloys, electrolysis, especially he pioneered the electrolysis of seawater. He tailored the catalysts for carbon dioxide methanation, in particular, he has built a prototype plant for global CO2 recycling in 1995 on the roof top of the Institute for Materials Research, Tohoku University. The plant consists of power generation by photovoltaic cells, hydrogen production by seawater electrolysis and methane formation by the reaction of carbon dioxide with hydrogen, carbon dioxide recovery at an energy consuming district, and transportation of carbon dioxide. The plant uses tailored key materials with high performance and durability, that is, cathodes for hydrogen production, anodes for only oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for rapid and selective production of methane by the reaction of carbon dioxide with hydrogen. The performance of the plant has substantiated that global CO2 recycling can supply abundant energy generated from solar energy on deserts in the form of methane and can really prevent global warming induced by carbon dioxide emissions. In 2003, he has built a pilot plant of global CO2 recycling at Tohoku Institute of Technology which is the minimum unit of industrial scale for seawater electrolysis and carbon dioxide methanation. He is in the Editorial Board of "Corrosion Science", a Member of NACE International, the Electrochemical Society and the International Society of Electrochemistry. Member of Japan Society of Corrosion Engineering, the Japan Institute of Metals, the Surface Finishing Society of Japan, the Iron and Steel Institute of Japan, the Electrochemical Society of Japan, the Society of Chemical Engineers, Japan, the Chemical Society of Japan, and other scientific societies in Japan. He received many awards among those also The Electrochemical Society Fellow Award in 1997 in recognition of contribution to the advancement of science and technology, for leadership in electrochemical and solid state science and technology and for active participation in the affairs of the Electrochemical Society, Inc. We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogen and the use of hydrogen for the reduction of CO2 with the Science of Hydrogen & Energy prize 2011.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2012

Mogens Mogenson is research professor in the fuel cells and solid state chemistry division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark (DTU). He has spent 37 years in electrochemistry. He received his MSc in 1973 and PhD in 1976 from the Department of Metallurgy, DTU. After a postdoctoral period at the Department of Chemistry A, DTU, and a short period in the battery industry (Hellesens A/S), he was employed at Risø National Laboratory in 1980. He was manager for numerous projects and programs (mainly within R&D of practical electrochemical cells such as solid oxide fuel cells) and now the Strategic Electrochemistry Research Center (SERC). He has coauthored more than 250 scientific papers and reports,

and has 16 patents/patent applications. Prof. Dr. Mogens MOGENSON

Prof. Mogens Mogensen from the Risø National Laboratory for sustainable Energy made an enormous contribution in the development for electrochemical systems like SOFCs (High Temperature Solid Oxide Fuel cells), SOEC (Solid Oxide Electrolyser Cells) as well as oxygen separation membranes over the last 20 years. His topics in this field include the material development for electrodes, electrolytes as well as interconnects, coatings and sealing’s. Mogens is known for his broad knowledge and understanding of the total systems and especially the deep knowledge of the thermodynamics and electrochemical behavior of the cells. The driving force behind his research activities are the principle understanding of the aging mechanisms in SOEC and SOFC systems, the electrochemical behavior, but also the development of new materials for better performance and competitive prices. In the field of advanced materials he was very active and successful in the development of catalytic metal oxides with fluorite and perovskite related structures. These compounds are extremely flexible with respect to substitution of host cations and non-stoichiometry. By this purpose he has done “material engineering” by tailoring the basic materials properties for aspects like high electronic and ionic conductivity, matching thermal expansion coefficient, stability in hydrogen and/or oxygen atmosphere, etc. The development of novel materials was leading to the “world record” in power density for electrochemical cells, accompanied by a low aging- and degradation rate (>1%/1000h) and an outstanding mechanical strength and flexibility. Mogensen was also very active in cells and stack development with high electrical efficiency and fuel flexibility including natural gas, biogas, diesel, LPG, methanol, DME and ethanol. Recently his topic and interest are the synthetic fuels derived from water and CO2. This is interesting as the produced syngas (H2 + CO) can react to form methane, which is a more suitable energy carrier. In this process, the catalytic process is taking place inside the cell, so the reaction heat can be utilized.

We award Prof. Mogens Mogenson for his outstanding work on the electrochemistry of electrolysers and fuel cells with the Science of Hydrogen & Energy prize 2012.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2013

Graduated Nagoya University with Msc applied physics and Bsc in physics.. Joined Toyota Motor Corporation in 1981, then working as engineer in production engines and advanced engine systems. Later working as Toyota Engine representative at Toyota Europe in Brussels. Involved for first hybrid (Prius) development as manager for emission and fuel economy. In later years working as a planner for world hybrid deployment. From 2004 fuel cell development manager. Currently project general manager at R&D management division and Energy Affairs department.

Mr. Katsuhiko HIROSE

Katsuhiko HIROSE has a very important role in the development of hydrogen for mobility by building the bridge between industry (Toyota) and academia as well as the bridge between Asia and Europe.

He initiate the hydrogen's economical value assessments. Hydrogen fuel is valuable for the economy as well as for the environment. The value-chain analysis of Fuel Cell vehicles and Hydrogen Energy analysis identifies the big economical value of the use of hydrogen as a fuel. This analysis has re-ignited many activities on hydrogen all over the world He also initiated the H2Mobility activities and brought many OEM and stakeholder into these activities. Resulting in the German H2mobility report. A portfolio of power-trains for Europe: a fact-based analysis, which stimulated the hydrogen activities world wide again. The large number of key-note speeches in both engineering conference and academic conference stand for his continuous efforts as an interpreter between the industries and academic scientists. He is responsable for the world leading research in hydrogen storage by means of hybrid tank systems, i.e. the combination of pressurized hydrogen gas and metal hydrides, which leads to a hydrogen storage with greater gravimetric and volumetric hydrogen density as compared to the individual system. Furthermore, he also developed a Cryo-adsortion tank system.

We award Mr. Katsuhiko HIROSE for his outstanding work on the implementation of hydrogen for mobility and for linking the key people worldwide together with the Science of Hydrogen & Energy prize 2013.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2013

Hans Geerlings studied experimental physics in Amsterdam, where he received his PhD degree in 1987. In that year he moved to Shell, where he worked in research on a number of topics including synthesis gas conversion, hydrogen storage and CO2 capture and storage. In 2007 he was appointed as a part time professor at the Delft University of Technology. His current research interests are in the area of ‘Solar Fuel synthesis’ and ‘Mineralization of CO2’.

Prof. Dr. Hans GEERLINGS

Hans Geerlings has worked on complex hydrides, i.e. alanates, especially on the synthesis and the characterization of MgAlH4 and CaAlH4, before he focused on the CO2 capture and mineralization. Recently, he published a paper in Environmental Science entitled “Efficient Production of Solar Fuel Using Existing Large Scale Production Technologies” in which the efficient production of solar fuels today using existing technologies is described. The feasibility of liquid hydrocarbon fuels production from CO2 and water with efficiencies approaching 10% from solar energy is demonstrated, this is about an order of magnitude higher than alternative technologies currently under development. The reduction of CO2 with hydrogen for the production of synthetic fuels is a new challenging research branch with an enormous potential for the future energy economy.

We award Prof. Hans Geerlings for his outstanding work on the hydrogen production and storage as well as his effort to open new fields in a world leading oil producing company with the Science of Hydrogen & Energy prize 2013.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2014

Qidong WANG is a professor of Department of Materials Science and Engineering, Zhejiang University. He was born in 1921, and obtained his BSc degree in 1943 from Zhejiang University of China, MSc degree in 1948 from Stanford University and PhD in 1951 in the University of Iowa of USA, majoring in the heat power of mechanical engineering. He returned China in January of 1951 to teach and do research in Zhejiang University until he retired in 2011. His main research work focuses on hydrogen storage materials and their actual applications. Besides the researching tasks and teaching, he has also done many administrative and social services.

Prof. Dr. Qidong WANG

Prof. Qidong WANG from the Department of Materials Science and Engineering of Zhejiang University was involved in the fields of mechanical engineering, metallurgical engineering and functional materials in his 60 years’ research career. He has made many outstanding contributions in the topics such as process intensification of melting procedure in cupola, precision casting of high speed steel cutting tools and developments of new hydrogen storage materials and systems. In particular, he is well known as a pioneer in the development and applications of hydrogen storage alloys in China. He has done a lot of excellent work in the research fields of rare earth based hydrogen storage materials and new metal-hydride systems. His research interests also focus on the purification and transportation of hydrogen as well as Ni-MH batteries. Since 1978 he devoted himself into the research on hydrogen storage alloys and compounds and their applications for storing and transporting hydrogen and the use of hydrogen as supplementary fuel for internal combustion engines. He firstly used lanthanum-rich mischmetal, which has almost the same hydrogen storage capability but the cost of the alloy lowers by one third, to replace the pure lanthanum. Moreover he firstly employed mechanical milling method to prepare mischmetal cathode materials for hydrogen storage batteries, which hereafter were widely accepted by peers. He has contributed with his coworkers more than 500 scientific papers and reports and he has 18 patents and more than 20 awards on his contributions in scientific researches, teaching and social contributions. So far, his scientific papers have been cited more than 5000 times and his H-index reached as high as 33. Even though at an advanced age, he is still concerning on the development of hydrogen economy. His endurance and diligence are the merits we scientific workers should learn from.

We award Prof. Qidong WANG for his outstanding work on hydrogen storage materials and their applications with the Science of Hydrogen & Energy prize 2014.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2014

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf, Switzerland. 1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr. rer. nat. from the science faculty UniFR. 1994 SNF Post doc with AT&T Bell Labs in Murray Hill, New Jersey, USA. 1997 Lecturer at the Physics Department UniFR. 2003 External professor at the Vrije Universiteit Amsterdam, Netherlands. 2004 Habilitation in experimental physics at the science faculty UniFR. President of the Swiss Hydrogen Association „HYDROPOLE“. 2006 Head of the section “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics department UniFR. 2009 Guest Professor at IMR, Tohoku

University in Sendai, Japan. 2012 Visiting Professor at Delft Prof. Dr. Andreas ZÜTTEL Technical University, The Netherlands

Andreas Züttel has worked on metal hydride electrodes and developed new overstoichiometric AB2 Laves-phase alloys wher the B atoms partially occupy A-sites. He developed a mathematical model for the capacity of a metal hydride electrode. With the discovery of carbon nanotubes and first reports about the great hydrogen storage capacity of single wall carbon nanotubes he started to investigated the interaction of hydrogen with nanostructures by means of electrochemical sorption measurements and described the relationship between the hydrogen density and the materials surface area of nanostructures. Furthermore, the size dependent hydrogen sorption properties of monodisperse Palladium clusters as small as 55 atoms were investigated electrochemically and modeled by A. Züttel. He intitiated the research on borohydrides for hydrogen storage 10 years ago and published together with S.I. Orimo important papers on the properties of borohydrides e.g. a model for the stability and the hydrogen sorption mechanism. Recently his activities have expanded to the reduction of CO2 with hydrogen for the production of synthetic hydrocarbons as fuels. This is the basis to close the materials cycle for hydrocarbons as energy carriers.

We award Prof. Andreas Züttel for his outstanding work in the science on the interaction of hydrogen with solids e.g. intermetallic compounds, nanostructures and complex hydrides with the Science of Hydrogen & Energy prize 2014.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2015

After the Thorbecke Scholengemeenschap Arnhem Gymnasium Beta (1969 – 1975) Bernard Dam studied chemistry at the Radboud Universiteit Nijmegen (1975 – 1982) where he graduated (cum laude) in EPR-spectroscopy and solid state chemistry, with a minor in philosophy of science. His PhD in physical chemistry he received from the Radboud Universiteit Nijmegen (1982 – 1986) for the thesis: "Growth and morphology of classical and superspace crystals". He joined Philips Research Laboratories (NatLab) where he worked on the growth and properties of metallic, superconducting and complex oxide thin films by various vapor deposition techniques (Sputter Deposition, Pulsed

Laser Deposition and Molecular Beam epitaxy) from April Prof. Dr. Bernard DAM 1986 – May 1992. He became Associate Professor at the vrije universiteit amsterdam, with the main areas of research: HTc-superconductivity, switchable mirrors, hydrogen storage, hydrogen sensing. He is co-founder of the Bachelor program 'Science, Business and Innovation' researcher (May 1992 – January 2009). Since January 2009 he is full professor in chemistry at Delft University of Technology, Department of Chemical Engineering, Head of the section 'Materials for Energy Conversion and Storage', Scientific director Sustainable Energy Technologies-3TU, Chair of the exam committee of the applied science faculty

Bernard Dam's goal is to develop new materials for sustainable energy applications. He want's to contribute to scientific breakthroughs and see his research transformed into commercial products. His field is functional thin film materials science: find relations between growth, (defect) structure and physical properties in relation to their application. At present he aims for applications based on metal hydrides, such as hydrogen sensors, hydrogen storage, hydrogen membranes and chemochromic windows. In addition, he investigate the mechanism of photo- electrochemical water splitting. The direct conversion of sunlight into fuel has the advantage that, as compared to electricity, such fuels can be more easily stored.

We award Prof. Bernard Dam for his outstanding work in the science of hydrogen in thin films witch lead to the "hydrogenography" as a new experimental method for the investigation of the hydrogen diffusion in solids as well as the screening of hydries and the development of a new type of hydrogen detector with the Science of Hydrogen & Energy prize 2015.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2015

1993-1995 JSPS (Japanese Society for the Promotion of Sciences) Research Fellow. 1995 Ph. D., Fac. Integrated Arts and Sci., Hiroshima University, 1995 - 2002 Research Associate, Hiroshima University. 1998 - 1999 Guest Researcher, Max-Planck Institute for Metal Research, as Alexander von Humboldt Foundation and Japanese Ministry of Education Fellows. 2002 Associate Professor, Institute for Materials Research (IMR), Tohoku University. 2009 Professor, Institute for Materials Research (IMR), Head of Hydrogen Functional Materials Division, Tohoku University

Prof. Dr. Shin-Ichi ORIMO

Shin-Ichi Orimo's early work was on composite hydrides based on Mg where he synthesised new materials by mechanical alloying and characterized their hydrogen sorption properties. His fundamental achievements on Mg based composits and nanomaterials e.g. grain boundary diffusion, amorphisation and kinetics of the hydrogen sorption process is of great importants for Mg based hydrogen storage materials. From the year 2000 on he investigated the hydrigen interaction with nanostructured graphite and crabon materials and combined carbon with metal nanoparticles. In 2003 the paper entitled "Material properties of MBH4 (M = Li, Na, and K)" which presented the beginning of the worldwide intense research on complex borohydrides. Many essential contributions for the understanding of the structure, the reaction mechanism and the hydrogen sorption kinetics came from Orimo's group. Especially to mention the relationship of the hydrogen desorption temperature and the cation electronegativity. Very early Orimo's group also worked on the combination of complex hydrides and amides. Recently, the high - temperature phase of LiBH4 was stabilized by a partial substitution of the [BH4] with the iodin- ions leading to a very high ionic conductivity at ambient temperature.

We award Prof. Shin-Ichi Orimo for his outstanding work in the science of hydrides, the discovery of new hydride systems and tunable properties of hydrides with the Science of Hydrogen & Energy prize 2015.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2015

Michael Hirscher is group leader “Hydrogen storage” at the Max Planck Institute for Intelligent Systems, Stuttgart, Germany. He studied physics at University of Stuttgart, Germany and Oregon State University, Corvallis, USA. For his achievements during his PhD he was awarded the Otto Hahn Medal of the Max Planck Society in 1988. Prior to taking his position in Stuttgart, he spent a post-doctoral fellowship at the University of Pennsylvania, Philadelphia, USA. Recently, he edited the “Handbook of Hydrogen Storage” and is operating agent of IEA-HIA Task 32 “Hydrogen-based energy storage” since 2013. His current research interests focus on nanoporous and nanoscale

materials for gas storage and separation. Dr.Michael HIRSCHER

Michael Hirscher investigated the hydrogen adsorption in carbon nanostructures from the beginning of there discovery and especially after the publication of Michael Heben (Heben, M. J.; Dillon, A. C., “Room-temperature hydrogen storage in nanotubes” Science 2000, 287, (5453), 593-593.) which turned out to be a missinterpretation of the measurements. M. Hirscher carefully investigated the surface site occupation of the carbon nanostructures and the interaction energy. His present studies focus on novel nanoporous framework materials, e.g., metal-organic frameworks (MOFs), with high specific surface area and microporosity, which can be applied for cryo-adsorption tanks.

Furthermore, these crystalline, nanoporous framework materials are investigated for their ability to separate isotopes of light gases, e.g., hydrogen-deuterium mix--tures, by quantum sieving.

We award Dr. Michael Hirscher for his outstanding work in the science of the interaction of hydrogen with porous nanostructures, the investigation and description of the quantity of hydrogen as well as the adsorption energy of the Van-der-Waals interaction of hydrogen with various nanoporous materials with the Science of Hydrogen & Energy prize 2015.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SCIENCE OF HYDROGEN & ENERGY AWARD 2015

Head of Physics Department, Institute for Energy Technology (IFE), 2011- Scientific responsible Energy Storage, IFE, 2009- Principal Scientist New Materials, IFE, 2007- Adjunct Professor of Physics, University of Oslo (UiO), 2000- Deputy Head of Physics Department, IFE, 2001- 2011 Principal Research Scientist, Physics Department, IFE, 1993-2007. Postdoctoral Associate, NTH, 1988-1991; IFE, 1991-1993. Fellow, NTH and Research Council of Norway (RCN), 1983-1988. Dr. ing. (PhD) Norwegian Institute of Technology (NTH), Trondheim, Norway 1988. Siv. ing. (Master degree) NTH, Trondheim, Norway 1981.

Prof. Dr. Bjørn HAUBACK

Bjørn Hauback has made enormous contributions to the structure determination of intermetallic hydrides and complex hydrides, i.e. deuterides. Furthermore, he is an expert in the charge and magnetic ordering of intercalated compounds as well as oxydes. Hs group was the first determining the structure of the LiAlD4 and NaAlD4 in the years 2002 and 2003 and he investigated the hydrogen desorption reaction of alanates and borohydrides in great detail by synchrotron and neutron diffraction. Bjørn Hauback was Operating Agent for IEA Hydrogen Implementation Agreement Task 22 - "Fundamental and Applied Hydrogen Storage Materials Development" from 2006. Within this task an enormous progress on the investigation and understanding of complex hydrides was achieved.

We award Prof. Bjørn Hauback for his outstanding work in the structur determination of hydrides and the host materials as well as the complicated structures of substituted complex hydrides and composite hydrides with the Science of Hydrogen & Energy prize 2015.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

BEST POSTER AWARD 2011

Ms. Alondra TORRES TRUEBA

“Hydrogen Storage in Structure II Clathrate Hydrates with Various Promoters”

Department of Process & Energy, Delft University of Technology, Delft, Netherlands

M.Sc. Alondra Torres earned her bachelor degree from Universidad Autonoma del Estado de Mexico and her master degree (cum laude) from Universidad Iberoamericana in Mexico City. Currently Alondra Torres is appointed as a Ph.D. student at Delft University of Technology in the Netherlands. During her studies Alondra Torres has been involved in several projects including; heavy metals removal from waste water with organic material and the formation of polymeric membranes with supercritical CO2 for gas separation. Her current Ph.D. project involves the study of the potential of clathrate hydrates for hydrogen storage.

Hydrogen Storage in Structure II Clathrate Hydrates with Various Promoters

Hydrogen (H2) is a promising alternative to fossil fuels, because it offers a solution for three main global challenges: (i) reduction of greenhouse gas emissions, (ii) fulfilment of energy requirements and (iii) reduction of local air pollution. However, due to the difficulty in finding an effective storage medium, the application of H2, for instance in the automotive sector, is currently limited. Clathrate hydrates, have been regarded as a favorable alternative for H2 storage. Their profitability, safety, fast and high reversibility and efficient production make them more suitable for this application than other H2 storage materials.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

BEST POSTER AWARD 2012

Mr. Andreas BLIERSBACH

“How to Watch Hydrogen Diffuse in any Absorbing Material”

Department of Physics and Astronomy, Materials Physics Division, Uppsala University, Sweden.

Born 1986 in Cologne, Germany. 2011 Diploma in physics at the Rheinische Friedrich-Wilhelms University Bonn, Germany. 2008 – 2009 studies and research, as exchange student, at Uppsala University, Sweden. 2010 – 2011 research on hydrogen diffusion in nano sized materials by direct imaging at Uppsala University, Sweden. Since December 2011 PhD student at EMPA, Dübendorf, Switzerland and involved in smart carbon based hydrogen storage materials.

“HOW TO WATCH HYDROGEN DIFFUSE IN ANY ABSORBING MATERIAL”

The kinetics of interstitial hydrogen are of great interest and importance for many technologies. In particular nano-sized materials motivate fascinating applications and scientific questions. Even though diffusion is one of the most studied phenomena the complex combination of quantum effects and dynamic interplay with the displacement of host atoms [1,4] is still only partially understood. We present a method to quantify chemical diffusion of hydrogen in nano- sized materials. The changes in the absorptance of a vanadium single crystal thin-film, induced by hydrogen, are observed visually and in real-time as a function of position. Concentration profiles and their evolution in time, during chemical diffusion, can be measured down to a hydrogen content corresponding to just a few effective monolayers, randomly distributed within VHx.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

BEST POSTER AWARD 2013

Mr. Moreno DE RESPINIS

“Optimization of Anneal Procedure in Metal Oxides: Case Study of Nanostructured Tungsten Processed via Low-Energy Helium-Ions”

Delft University of Technology, Faculty of Applied Siences, Department of Chemical Engineering, Materials for Energy Conversion and Storage; Julianalaan 136, 2628 BL Delft, The Netherlands

Moreno de Respinis received his bachelor degree in physics at the University of Milan in 2008, and earned his master degree

in sustainable energy with study line hydrogen and fuel cells at the Technical University of Denmark (DTU) in 2011. He concluded his master with a fellowship at the Lawrence Berkeley National Laboratory with Dr. Heinz M. Frei’s group, in which he performed mechanistic studies of water photo- oxidation by visible-light driven Co3O4 catalyst. He is currently a Ph.D. student at Delft University of Technology where he is researching on photoanodes for solar water splitting.

“Optimization of Anneal Procedure in Metal Oxides: Case Study of Nanostructured Tungsten Processed via Low-Energy Helium-Ions”

One challenge in developing highly efficient nanostructured photoelectrodes is to control their morphology, crystal phase and stoichiometry. We present a novel physical processing route that uses high-flux of low-energy helium- ion to generate porous structures on tungsten targets. Optimal anneal condition to form WO3 photoanode is determined via in-situ XRD. SEM images show mesoporous crystalline structure, and feature sizes depend on substrate temperature and can be tuned between 30 nm and 1 µm. Our research shows that a two-step anneal procedure is optimal to oxidize surface nanostructures into crystalline WO3, preserving the bulk as metallic W for good electrical contact. As a result, IPCE of 20% is obtained, resulting in an AM1.5 2 2 photocurrent of 0.75 mA/cm at 1.23 VRHE (compared to 0.15 mA/cm after standard thermal oxidative anneal). The excellent control over feature size offers an exciting new processing route to nanostructure materials for e.g. solar water splitting.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

BEST POSTER AWARD 2014

Mr. Yixiao FU

"Study on the hydrogen exchange behavior in the metal hydride-LiBH4 composite"

School of Materials Science and Engineering, South China University of Technology, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, P. R. China

Born 1990 in Jiangxi, China. 2011 Bachelor in Metallic Materials Science and Engineering in Department of Materials, South China University of Technology (SCUT), Guangzhou, China. He is currently a M.S candidate at SCUT. Focused on LiBH4-MgH2 system and Magnesium core-shell structure.

"Study on the hydrogen exchange behavior in the metal hydride-LiBH4 composite"

Hydrogen-exchange effect discovered in hydride composite gives an angle to study the non- reaction interaction between components and to study detailed desorption mechanism. Although obvious phenomena had been observed to prove the existence of this effect, the detail mechanism has not been proposed. Our research presents a desorption model relating to H exchange and proves that interface between two hydrides and mobile H atoms from both hydrides are crucial for the exchange to happen. Desorption gas specie in LiBH4-VD2 system drastically changed after melting of LiBH4 and only then showed obvious H-D exchange phenomena, in LiBH4-MgD2 system inhibition of desorption of MgD2 by 4MPa H2 nearly annihilate B-D signal in FTIR indicating nearly no D atoms was found in LiBH4.

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

PARTICIPANTS

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Gisela ARZAC (Dr) Instituto de Ciencia de Materiales de email: [email protected] Sevilla Tel.: +34954489552 Av. Américo Vespucio 49, Isla Cartuja mobil: Seville Spain Nikola BILISKOV (Dr.) Rudjer Boskovic Institute email: [email protected] Bijenicka c. 54 Tel.: +38514561084¸ 10000 Zagreb mobil: +385917209759 Croatia

Didier BLANCHARD (Dr.) DTU email: [email protected] Frederiksborgvej 399 Tel.: +45 46775899 Roskilde mobil: +45 50394893 Denmark

Christiaan BOELSMA TU Delft email: [email protected] (Mr.) Granaat 8 Tel.: 1703BC Heerhugowaard mobil: Netherlands

Nigel BRANDON (Prof., Imperial College London, Sustainable email: Director) Gas Institute [email protected] 11 Princes Gardens Tel.: +442075945704 London mobil: United Kingdom Elsa CALLINI (Dr.) EMPA Materials Science & Technology email: [email protected] Ueberlandstrasse 129 Tel.: 8600 Dübendorf mobil: Switzerland

Georgia National Center for Scientific Research email: [email protected] CHARALAMBOPOULOU "Demokritos" Tel.: +30 210 6503404 (Dr.) Patriarchou Gregoriou & Neapoleos mobil: +30 6977 201516 15310 Agia Paraskevi Attikis Greece Anna-Lisa CHAUDHARY Helmholtz Zentrum Geesthacht email: anna- (Dr) Max-Planck Strasse [email protected] Geesthacht Tel.: +4916093473360 Germany mobil: +4916093473360

Giovanni CINTI (Dr) University of Perugia email: [email protected] via Duranti 69 Tel.: +390755853991 6125 Perugia mobil: +393406141983 Italy

Bernard DAM (Prof. Dr.) TU Delft email: [email protected] julianalaan 136 Tel.: 2595 GE Delft mobil: Netherlands

Petra DE JONGH (Prof.) Debye Institute for Nanomaterials email: [email protected] Science, Utrecht University Tel.: Universiteitsweg 99 mobil: 3584 CG/Utrecht Netherlands

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Domenico DE LUCA (M. UNIVERSITY OF CALABRIA email: ENG.) PONTE BUCCI 44/C 5TH FLOOR [email protected] 87036 Calabria Tel.: +39.0984.494942 Italy mobil: +39.333.6575192

Stefano DELEDDA (Dr.) Institute for Energy Technology email: [email protected] P.O. Box 40 Tel.: +47 407 26 921 2027 Kjeller mobil: Norway

Günther DOLLINGER Universität der Bundeswehr München email: (Prof. Dr.) Werner Heisenberg Weg 39 [email protected] D-85577 Neubiberg Tel.: +49 89 6004 3505 Germany mobil:

Yali DU (Ms.) Yanshan University email: [email protected] 438 Hebei Street Tel.: +86-335-8074648 066004/Qinhuangdao mobil: China

Adrian EPPRECHT (Mr.) EMPA Materials Science & Technology email: Überlandstrasse 129 [email protected] 8600 Dübendorf Tel.: Switzerland mobil: +41 79 253 1668

Asuncion FERNÀNDEZ Instituto de Ciencia de Materiales de email: [email protected] (Dr.) Sevilla Tel.: +34954489531 Av. Américo Vespucio 49, Isla Cartuja mobil: Seville Spain Yixiao FU (Mr.) South China University of Technology email: [email protected] PanYu district Tel.: Guanzhou mobil: +86 13068708656 China

Viera GÄRTNEROVÀ Institute of Physics email: [email protected] (Ph.D.) Na Slovance 1999/2 Tel.: +420 266 052 870 182 21 Prague 8 mobil: Czech Republic

Hans GEERLINGS (Prof. Shell / TU Delft email: Dr.) Grasweg 31 [email protected] 1031 HW Amsterdam Tel.: +31206302393 Netherlands mobil: +31655123169

Hubert GIRAULT EPFL (Ecole Polytechnique Fédérale email: [email protected] (Professor) de Lausanne) Tel.: +41216933145 SB-ISIC-LEPA Station 6 mobil: +41 79 560 2164 1015 LAUSANNE Switzerland Jasmina GRBOVIC Vinca Institute of Nuclear Sciences email: [email protected] NOVAKOVIC (Dr.) M.Petrovica Alasa 12-14 Tel.: +381 11 3408 662 11000 Belgrade mobil: + 381 64 16 96253 Serbia and Montenegro

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Ronald GRIESSEN (Prof. VU university email: [email protected] Dr.) Emmaweg 29 B Tel.: +31-35-6561451 1241 LG Kortenhoef mobil: +31 62033 6322 Netherlands

Shumin HAN (Prof.) Yanshan University email: [email protected] 438 Hebei Street Tel.: +86-335-8074648 066004/Qinhuangdao mobil: China

Bjørn C. HAUBACK Institute for Energy Technology email: [email protected] (Professor) P.O. Box 40 Tel.: +47 9740 8844 Kjeller mobil: Norway

Michael HIRSCHER (Dr.) Max-Planck-Institut für Intelligente email: [email protected] Systeme Tel.: Heisenbergstr. 3 mobil: 70569 Stuttgart Germany Marco HOLZER (Mr.) EPFL & EMPA email: [email protected] Überlandstrasse 129 Tel.: +41 79 763 37 93 8600 Dübendorf mobil: 0 Switzerland

Fadime HOSOGLU (Dr.) Holcim Ltd. email: Schaffhauserstrasse 272 [email protected] 8007 Zurich Tel.: +41 79 961 5364 Switzerland mobil: +41 79 961 5364

Jianmei HUANG (PHD EMPA & South China University of email: [email protected] student) Technology Tel.: Ueberlandstrasse 129 mobil: +41 76 814 3314 8600 Duebendorf Switzerland Md Amirul ISLAM (Mr.) Skoltech - www.skoltech.ru email: Novaya 100, Skolkovo [email protected] 143025 Moscow Region Tel.: Russian Federation mobil:

Aleå¡ JAGER (PhD.) Institute of Physics email: [email protected] Na Slovance 1999/2 Tel.: +420 266 052 870 182 21 Prague 8 mobil: Czech Republic

Olaf JEDICKE (Dr.) Karlsruher Institute for Technology email: [email protected] Hermann-von-Helmholtz-Platz 1 Tel.: +49 721 6082 5274 76344 Eggenstein-Leopoldshafen mobil: +49 173 697 0210 Germany

Torben R. JENSEN iNANO and Department of Chemistry, email: [email protected] (Assoc. Prof. D.Sc.) Aarhus University Tel.: Langelandgade 140 mobil: 8000 Aarhus Denmark

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Sathiskumar JOTHI () Swansea University email: [email protected] singleton park Tel.: +447587876010 Swansea mobil: +44 758 787 6010 United Kingdom

Xin JU (Prof.) Department of Physics, University of email: [email protected] Science and Technology Beijing Tel.: +86-10-62333921 30 Xueyuan Road, Haidian District mobil: +86 1358520 9127 Beijing 100083 China Shunsuke KATO (Dr.) EMPA Materials Science & Technology email: [email protected] Überlandstrasse 129 Tel.: +41 58 765 6086 8600 Dübendorf mobil: +41 79 949 34 63 Switzerland

Zuleyha Ozlem EMPA Materials Science & Technology email: KOCABAS ATAKLA (Dr.) Überlandstrasse 129 [email protected] 8600 Dübendorf Tel.: Switzerland mobil:

Christian KRELL (Dr.) Fronius International GmbH email: Günter-Fronius-Strasse 1 [email protected] 4600 Wels Tel.: +43 664 602415786 Austria mobil:

Klaus LACKNER (Prof., Arizona State University, Center for email: [email protected] Director) Negative Carbon Emissions Tel.: +1 (480) 727 2499 660 South College Avenue, PO Box mobil: 873005 85287-3005, Tempe, AZ United States Alexander LAIKHTMAN Holon Institute of Technology (HIT) email: [email protected] (Dr.) 52 Golomb St. Tel.: 5810201 mobil: Israel

Yuan LI (Dr.) Yanshan University email: [email protected] 438 Hebei Street Tel.: 066004/Qinhuangdao mobil: China

Baozhong LIU (Dr.) School of Material Science and email: [email protected] Engineering, Henan Polytechnic Tel.: +86 391-3986901 University mobil: +86 391 3989859 2001 Century Avenue, Jiaozuo China Philippe MAURON (Dr.) EMPA Materials Science & Technology email: Überlandstrasse 129 [email protected] 8600 Dübendorf Tel.: Switzerland mobil:

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

David MILSTEIN (Prof.) Weizmann Institute of Science email: 1 Herzl St [email protected] Rehovot Tel.: +972 8934 2599 Israel mobil: +972 8934 2599

Vladimir MOLKOV Ulster University email: [email protected] (Professor) Shore Road Tel.: +44 2890 368731 Newtownabbey mobil: +44 7790 026451 United Kingdom

Jiri MULLER (Dr.) IFE email: [email protected] Tel.: 2027 Kjeller mobil: Norway

Akihiro NAKANO (Ph.D.) AIST email: [email protected] Tsukuba East 1-2-1 namiki Tel.: +81-29-861-7250 305-8564/Tsukuba mobil: +81-80-4327-6564 Japan

Sveinn OLAFSSON Science Institute University of Iceland email: [email protected] (Research Professor) Dunhaga 3 Tel.: +354 525 4693 Reykjavík mobil: +354 525 4693 Iceland

Shin-Ichi ORIMO WPI-AIMR / Institute for Materials email: [email protected] (Professor) Research, Tohoku University Tel.: +81-22-215-2093 2-1-1 Katahira, Aoba-ku mobil: Sendai, 980-8577 Japan Tayfur OZTURK (Prof.) Middle East Technical University email: [email protected] Dumlupinar Bulvari No 1 Tel.: +90 312 210 5935 06800 Ankara mobil: +90 532 4566352 Turkey

Martin PANHOLZER (Dr.) Johannes Kepler University Linz email: [email protected] Altenberger Str. 69 Tel.: +43 7322468 1478 4040/Linz mobil: Austria

Bojana PASKAS Vinca Institute of Nuclear Sciences, email: [email protected] MAMULA (M.Sc.) University of Belgrade Tel.: +381 11 340 8610 PO Box 522 mobil: 11001 Belgrade Serbia and Montenegro Dieter PLATZEK (Dr. rer Panco GmbH email: [email protected] .nat.) Kaerlicher Str. 7 Tel.: 56218 Muelheim-Kaerlich mobil: Germany

Aferdita PRIFTAJ Polytechnic University of Tirana email: [email protected] VEVECKA (Professor) Sheshi "Nene Tereza", N.4 Tel.: +355 42 222 7914 10023 Tirana mobil: +355 69 210 7327 Albania

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Michael RANFT (Dipl.- Karlsruhe Institute of Technology email: [email protected] Ing.) Hermann-von-Helmholtz-Platz 1 Tel.: +49 721 608 24897 76344 Eggenstein-Leopoldshafen mobil: Germany

Diogo SANTOS (Dr.) Instituto Superior Tecnico email: Pavilhao de Minas, Piso 4, Av. Rovisco [email protected] Pais Tel.: 1049-001 Lisboa mobil: Portugal Thomas Justus Paul Scherrer Institut email: SCHMIDT (Prof. Dr. ) OLGA/113 [email protected] 5232 Villigen PSI Tel.: +41 56 310 57 65 Switzerland mobil:

Ulrich SCHMIDTCHEN BAM Fed. Inst. for Mat. Res. and email: (Dr.) Testing [email protected] Unter den Eichen 87 Tel.: +49 30 8104 4402 12205 Berlin mobil: +49 173 621 1533 Germany Sok Gun SONG (Mr.) National industrialization company email: [email protected] P.O. Box 26707 Riyadh 11496 Tel.: Riyadh mobil: +966 540 304 279 Saudi Arabia

Mariana SPODARYK Institute for Problems of Materials email: [email protected] (Ms.) Science Tel.: Verhovynna str.85, ap.48 mobil: +380 68541 7935 03176 Kyiv Ukraine Nicholas STADIE (Dr.) EMPA Materials Science & Technology email: [email protected] Überlandstrasse 129 Tel.: +41 58 765 4153 8600 Dübendorf mobil: Switzerland

Svetlana SYRENOVA Chalmers University of Technology email: [email protected] (Ms.) Department of Applied Physics, Divison Tel.: +46 31772 3007 of Chemical Physics mobil: +46 76344 2249 41296, Göteborg Sweden Osman TAHA (Sinor Hamad Medical Corporation email: [email protected] Radiation Physicist ) Qatar - Doda PO 3050 Tel.: 974 mobil: Qatar

Klaus TAUBE (Dr.) Helmholtz-Zentrum Geesthacht email: [email protected] Max-Planck-Strasse 1 Tel.: +49 4152 87 25 41 Geesthacht mobil: +49 175 59 16 984 Germany

Ulrich ULMER (Dr.) Karlsruhe Institute of Technology email: [email protected] Hermann-von-Helmholtz-Platz 1 Tel.: 76344 Eggenstein-Leopoldshafen mobil: Germany

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Name Address email, tel.

Izumi UMEGAKI (Dr.) Toyota Central R&D Labs., Inc email: 41-1, Yokomichi, Nagakute [email protected] Aichi Tel.: +81-561-71-8111 Japan mobil:

Gang WANG () Utrecht University email: [email protected] Universiteitsweg 99 Tel.: 3584 CG Utrecht mobil: +31 64680 6615 Netherlands

Hui WANG (Dr.) South China University of Technology email: [email protected] Tel.: 510640 Guangzhou mobil: China

Yijing WANG () Institute of New Energy Material email: [email protected] Chemistry Tel.: 94 Weijin Road mobil: Nankai District, Tianjin 30071, P.R.China Yigang YAN (Dr.) EMPA Materials Science & Technology email: [email protected] Überlandstrasse 129 Tel.: 8600 Duebendorf mobil: Switzerland

Olena ZAVOROTYNSKA Institute for Energy Technology email: [email protected] (Dr) Tel.: +4746621096 P.O. Box 40 mobil: NO-2027 Norway Meiqin ZENG () South China University of Technology email: [email protected] Tel.: 510640 Guangzhou mobil: China

Min ZHU (Prof. Dr.) South China University of Technology email: [email protected] Tel.: 510640 Guangzhou mobil: China

Andreas ZÜTTEL (Prof. EPFL & EMPA email: [email protected] Dr.) Überlandstr. 129 Tel.: 8600 Zürich mobil: +41 79 484 2553 Switzerland

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Information

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Map from Zürich (upper left corner) to Emmetten (center bottom)

Map of the region Emmetten

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

Travel to Emmetten from Zürich airport:

Please go to the ticket counter in the airport and ask for a ticket to Emmetten (roundtrip). Please also ask the person at the counter to print you the timetable for your connection e.g.:

Station/Stop Date Time Platform Travel with Comments Zürich Flughafen So 25. 1. 15 dep 13:47 4 IR 2653 Direction: Luzern

Luzern arr 14:49 6 Luzern dep 15:10 13 IR 2976 Direction: Engelberg

Stans arr 15:23 1 Stans dep 15:51 Bus 311 Direction: Seelisberg

Emmetten Post arr. 16:24

Duration: 2:37; runs daily

http://www.sbb.ch/en/home.html

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

EMERGENCY TELEPHONE NUMBERS

country code for Switzerland +41... POLICE 117

FIRE FIGHTERS 118

AMBULANCE 144

RESCUE HELICOPTER (REGA) 1414

Adrian EPPRECHT 079 253 1668 Administration / Organizer

Andreas ZÜTTEL 079 484 2553 Organizer

Hotel SEEBLICK AG 041 624 41 41 Hugenstrasse 24 CH-6376 Emmetten email: [email protected] URL: http://www.hotelseeblick.ch

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

CLIMATE

Average air temperature in Emmetten in °C

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

SOCIAL EVENTS

Rütli Bus to Beckenried, Ship to the "Tellplatte" and short walk to "Rütli". Gided tour with information about the cradle of Switzerland.

Skiing Free skiing, skipass will be provided (depending on the snow condition)

Sledging Free sledging (depending on the snow condition)

Snowwalk Guided tour (depending on the snow condition)

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

HISTORY OF SWITZERLAND

From the beginnings to the present. Much of the territory covered by present-day Switzerland is mountainous. For this reason, the Alpine passes have played a significant role in the development of the country, as have the powers that sought to control these important communication and trade routes. The inaccessible mountains with their particular living conditions provided the area with protection and a great deal of freedom because they made it difficult for foreign powers to enforce their control in the longer term. This enabled the population to develop its own traditions and forms of government. This situation also favoured the neutrality that has been in force since 1515 and which has also served the neighboring countries by forming a safety zone between the European states. The state of Switzerland as we know it today only assumed its current form in 1848. Prior to this time there was no real Swiss history as such; rather, it was the history of the various territories that gradually coalesced up until 1848 in order to form modern-day Switzerland.

From the The oldest traces of human existence are about 150,000 years old, while the oldest beginnings to the flint tools that have been found are about 100,000 years old. The territory of the Romans present-day Switzerland developed in a similar way to that of the rest of Europe. Under Roman In 58 BC, the Mittelland-based Helvetians tried to avoid the Germanic incursion influence, 58 BC from the west and migrate to the south of France. But Caesar sent them back and settled them as a "buffer people". Switzerland after After the departure of the Romans, the Alemanni gradually colonised Switzerland the Romans from the north. Western Switzerland was ruled by the Burgundians, while the Alpine regions were dominated by local Gallo-Roman rulers. The rise of Initially brought to Switzerland by the Romans, Christianity only really started to Christianity, 6th spread in the 6th century when the wandering monks from Ireland began century establishing monasteries. Under German rule Supported by noble families, non-aristocratic landowners, abbots and bishops, the German Emperor Conrad II ruled over large parts of western and central Europe – and united the Swiss territories in 1032. Switzerland in the 1291 is traditionally regarded as being the founding year of the Confederation – this late Middle Ages was when three rural valley communities banded together in order to be better prepared for attacks from the outside. In the 14th and 15 centuries there developed a loose federation with rural and urban members. By the end of the 15th century it was strong enough to affect the balance of power in Europe. Various wars were fought in which the Confederates displayed courage and ingenuity, and they gained a reputation as a formidable opponent in combat. The Confederation was enlarged in various ways with some areas joining voluntarily and as equal members while others were more or less forced. The members of the Confederation mainly administered the affairs of their own regions but representatives of each area also met regularly to discuss issues of common interest. Rise of the Swiss The desire for freedom on the part of rebellious miners in their ancestral country Confederation prompted the Habsburgs to enforce their claims to power by the force of arms. In the process they suffered heavy losses - while the Confederates grew increasingly confident. Dissension and the The relationships between the Confederates and other parts of what is now Burgundian Wars Switzerland were very diverse. At the instigation of Bern and of the French king, the Confederates went to war against the Burgundian duke, Charles the Bold, who

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

suffered a crushing defeat in three battles. Independence and Following the success of the Swabian wars the interest of those in central the end of Switzerland now turned towards the south. The Confederates’ dreams of having expansion great power finally came to an end with their crushing defeat at Marignano. Reformation and The 16th century in Western Europe was dominated by the Reformation, a the 17th century movement which divided western Christianity into two camps. Although the riots and destruction were fought on a religious level, this reflected, above all, the desire for social change and the social tensions that existed primarily between town and country. The 17th century saw three further landmarks in the development of modern-day Switzerland. All came as a result of the 30 Years' War (1618-48). While large parts of Europe were involved in this war, the Confederation remained neutral. An important consequence of the Thirty Years' War was Swiss independence from the Holy Roman Empire, which was formally recognised by the Treaty of Westphalia. Two Reformers: The 16th century was marked by reformations, counter-reformations and religious Zwingli and Calvin wars - and also by renewal within the Catholic Church. Political structure in The rights and freedoms within the Confederation varied greatly depending on the the 17th century location. There were rural cantons, city cantons, cities dominated by aristocrats, common lordships ruled by bailiffs as well as subject territories. Thirty Years’ War The Confederation was able to keep out of the Thirty Years’ War – had it been and independence involved, it would have led to the collapse of the Confederation due to confessional differences. Peasant revolts and Whereas a currency devaluation led to a peasant uprising, it was the confessional religious peace divide that sparked the Villmergen Wars that led to the restoration of a balanced religious peace and an end to Catholic hegemony. 18th and 19th In 1798, French troops invaded Switzerland and proclaimed a centralised state. century Later, the old cantonal system was restored - albeit in a more centralised form. In 1798, French troops invaded Switzerland and created the centralised Helvetic Republic. For the first time in its history, Switzerland was forced to abandon its neutrality and to provide troops for France. After the Sonderbund War, the foundations for the modern Switzerland were finally laid down with the adoption of

the Constitution of 1848. It brought about a more centralised form of government and a single economic area, which put an end to the cantonal rivalries and enabled economic development. Despite this progress, the 19th century was a difficult time for many people in Switzerland. Poverty, hunger and poor job prospects led to a wave of emigration, including to North and South America. 20th century The 20th century was generally marked by a series of striking developments in the political, economic and social arenas. Domestically there was a shift towards a multi-party system. While at the beginning of the century one party occupied all the positions in the government (Federal Council), there were four parties represented there at the end of the century. Agrarian Switzerland developed into an industrial state with the result that there were more immigrants than emigrants and the standard of living rose significantly. Working conditions and social security steadily improved and there was greater access to a more extensive range of consumer goods. The development of the export sector changed the country’s relationship with Europe and the rest of the world. Although Switzerland remained politically neutral – it did not actively participate in either of the two World Wars – neutrality remained the subject of intense debate.

Ref.: http://www.myswitzerland.com/

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

KLEWENALP Region

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

NOTES

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015

9th Int. Symposium Hydrogen & Energy Emmetten, SWITZERLAND 2015