PROCEEDINGS 2 6Th Hydrogen & Energy Symposium Stoos, Switzerland 2012

6th INTERNATIONAL SYMPOSIUM HYDROGEN & ENERGY

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

The 6th symposium “Hydrogen & Energy” follows the 5th symposium on 23. – 28. January 2011 in Stoos with more than 80 participants. It serves as an information platform of the fundamental science and technology and the frontiers of research on hydrogen and energy. 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 conference and wellness hotel Stoos in the beautiful small village Stoos on 1'270 m above see level. The village is free of traffic on a alp above Schwyz in central Switzerland.

The number of participants is limited to 80.

22. - 27. January 2012

Seminar- und Wellnesshotel Stoos Ringstrasse 10 CH-6433 Stoos Tel.: +41 (0)41 817 44 44 Fax.: +41 (0)41 817 44 45 [email protected] http://www.hotel-stoos

1 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 2 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

CONTENTS

Timetable

Abstracts Sunday Chair: Andreas ZÜTTEL 17:00 - 18:00 Mogens Bjerg MOGENSEN, 'Electrolysis and Recycling of CO2 into CO2-neutral Fuels'

MONDAY morning Chair: Ping CHEN 08:30 - 09:30 Min ZHU, 'Tuning DE/Hydrogenation Kinetics and Thermodynamics of Magnesium Based Alloys' 09:30 - 10:00 Zhirong ZHAO-KARGER, 'Nanoconfined Metal Hydrides for Energy Storage' 10:00 - 10:30 Arndt REMHOF, 'Hydrogen Dynamics in Nanoconfined Lithiumborohydride' 11:00 - 11:30 Renato CAMPESI, 'SANS and TEM Characterization of MgH2-NaBH4 Nanoparticles Confined in Silica based Mesoporous Scaffold SBA-15' 11:30 . 12:00 Philippe MAURON, 'Hydrogen absorption in Na intercalated C60' 12:00 - 12:30 Nicholas STADIE, 'Zeolite-Templated Carbon Materials for High Pressure Hydrogen Storage'

MONDAY afternoon Chair: Min ZHU 14:00 - 15:00 Hongge PAN, 'Improved Hydrogen Storage in Li-Mg-N-H Combined System ' 15:00 - 15:30 Chaoling WU, 'Development of Low Cost Vanadium-based Hydrogen Storage Alloys in Sichuan University' 16:00 - 16:30 Alondra TORRES, 'Hydrogen Semi-Clathrate Hydrate Formation from TBAB aqueous solution: Kinetics and Evolution of Hydrate-Phase Composition by in situ Raman Spectroscopy.' 16:30 - 17:00 Timmy RAMIREZ-CUESTA, 'Determining the Energetics of molecular hydrogen adsorption using Inleastic Neutron Scattering Spectroscopy' 17:00 - 17:30 Elsa CALLINI, 'Catalysis by Metathesis'

POSTER SESSIONS

MONDAY evening Chair: Andreas BORGSCHULTE, Philippe MAURON Shunsuke KATO, 'Hydrogenation of CO2 on the hydride surface of Mg2NiH4' Peipei YUAN, 'LiBH4-based composites with metal hydrides and fluorides for hydrogen storage' Shin-ichi ORIMO, 'Synthesis and Characterizations of Complex Hydride YMn2H6' Liga GRINBERGA and Andris SIVARS, 'Activated SiO2 based materials for hydrogen storage.' Wiebke LOHSTROH, 'Gas Release from (H,D) Isotope Labeled 2LiBH4/MgH2 Composites' Michal GORBAR, 'ESEM and Raman Mapping of Polyphenylene Sulphide / Polysulfone / Olivine Diaphragms' Yuen AU, 'Improved hydrogen sorption kinetics in supported Mg2Cu nano-particles'

PROCEEDINGS 3 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

Renato CAMPESI, 'Hydrogenation of Carbon Monoxide over Nanostructured Systems: Mechanochemical Approach' Andreas ZÜTTEL, 'The Energy Density of Hydrogen Storage Systems' Riccardo SUTER, 'Sorption Enhanced Methanation of CO2' Ioseb RATISHVILI, 'Hydrogen-Metal Complexes in Metal-Hydrogen Intersittial Alloys. Description of Heat Capacity Anomalies'

TUESDAY morning Chair: Hongge PAN 08:30 - 09:30 Ping CHEN, 'Catalytic modification of Mg(NH2)2-2LiH system' 09:30 - 10:00 Daniele PONTIROLI, 'Superionic conductivity in fullerene polymers' 10:00 - 10:30 Ebrahim HAZRATI, 'A first-principles study of defects in LiNH2 and nano-sized LiBH4 clusters' 11:00 - 11:30 Haiwen LI, 'Hydrogen Pressure Dependence of Li2B12H12 Formation During Dehydrogenation of LiBH4-MgH2 Composite' 11:30 . 12:00 Inge LINDEMANN, 'Study of the Decomposition Path of Al-Li- Borohydride' 12:00 - 12:30 Wan Si TANG, 'Theoretical and Experimental Investigations of KSIH3 as a Reversible Hydrogen Storage Material'

POSTER SESSIONS

TUESDAY evening Chair: Arndt REMHOF, Michael BIELMANN Mauro RICCÒ, 'Muons probe strong hydrogen interactions with defective graphene' Yongfeng LIU, 'Hydrogen Storage Properties of LiBH4 Destabilized by in-situ Formation of MgH2 and LaH3' Mingxia GAO, 'The Destabilization of Mg(BH4)2-2NaAlH4 Combination System Doped with Titanium Fluorides' MOHAMMAD CHOUCAIR, 'Graphene Composites for Next Generation Lithium Ion Batteries' Ji Woo KIM, 'Corrosion Behaviour of Steel Interconnects and Coating Materials in Solid Oxide Electrolysis Cell (SOEC)' Arndt REMHOF, 'Solvent-free Synthesis and Decompostion of Y(BH4)3' Andreas BLIERSBACH, ‘How to Watch Hydrogen Diffuse in any Absorbing Material’ Ulrich ULMER, 'Preparation, testing and scale-up of doped, nanoscale amide systems for hydrogen storage ' Marius VAN DEN BERG, 'Modelling the melting temperature of complex hydrides' Michael BIELMANN, 'Market Potential for Hydrogen in Off-Grid Energy Systems' Klaus TAUBE, 'Hydrogen Sorption Properties of the MgB2 based CaH2 and CaH2-CaF2 Reactive Hydride Composites' Ulrich VOGT, 'Self Ignitting Catalytic Hydrogen Burner with Zero Immission' Pascal MARTELLI, 'Solid Acid Fuel cells'

PROCEEDINGS 4 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

WEDNESDAY morning Chair: Michael Felderhoff 08:30 - 09:30 John IRVINE, 'Solid State Electrochemical Conversion of Clean Electrons to Fuels' 09:30 - 10:00 Andreas BORGSCHULTE, 'Sorption Enhanced Reactions for Renewable Synfuels' 10:00 - 10:30 Gabor LAURENCZY, 'Hydrogen storage and delivery' 11:00 - 11:30 Jinbao GAO, 'Reversibility of H2 Sorption in Nanoconfined Sodium Alanate' 11:30 . 12:00 Abdelazim OMAR, 'Development Of Alkylation Toluene With Methanol for fuel On Modified ZSM-5 Zeolites By Amphoteric surfactant' 12:00 - 12:30 Christoph LANGHAMMER, 'Optical Nanoantennas Shine Light On Single Nanoparticles'

THURSDAY morning Chair: Klaus FUNKE 08:30 - 09:30 Werner SITTE, 'Long-term Stability of SOFC Cathodes' 09:30 - 10:00 Ivo TRAJKOVIC, 'Electrochemical characterisation of a small-scale alkaline electrolyzer and novel membranes' 10:00 - 10:30 Motoaki MATSUO, 'Fast-Ionic Conduction in Complex Hydrides' 11:00 - 11:30 Yigang YAN, 'Controlling the decomposition of LiBH4' 11:30 . 12:00 Christiaan BOELSMA, 'Verification of the Enthalpy-entropy Compensation Effect in Metal Hydrides' 12:00 - 12:30 Samir BARMAN, 'Functionalized Metal-organic Frameworks for Chemical Hydrogen Storage'

THURSDAY afternoon Chair: Maximilian Fichtner 14:00 - 15:00 Torben R. JENSEN, 'New Materials for Hydrogen Storage' 15:00 - 15:30 Georgios KALANTZOPOULOS, 'Mechanochemical Reaction of Sodium Borohydride with Transition Metal Fluorides' 16:00 - 16:30 Marc LINDER, 'Metal Hydride based Preheater for HT-PEM Fuel Cells' 16:30 - 17:30 Michael FELDERHOFF, 'Towards understanding the molecular rearrangements in complex hydrides'

FRIDAY morning Chair: Torben R. JENSEN 08:30 - 09:30 Klaus FUNKE, 'First and second universalities - phenomena and modelling' 09:30 - 10:00 Hans HAGEMANN, 'New experimental and theoretical studies of borohydrides involving divalent metal ions' 10:00 - 10:30 Monica TRINCADO, '"New catalytic approach for the dehydrogenation of amine boranes and organosilanes"' 11:00 - 11:30 Petra DE JONGH, 'Reversible Hydrogen Release and Uptake in NaBH4 Confined in Nanoporous Carbon Material' 11:30 . 12:30 Maximilian FICHTNER, 'Perspectives of H Storage and Electrochemical Storage Methods'

Guest Matteo ARAMINI Heinz BERKE Urs FRISCHKNECHT Mattia GABOARDI Jiri MULLER Denis SHEPTYAKOV

PROCEEDINGS 5 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

SCIENCE OF HYDROGEN & ENERGY AWARD

List of Participants

Information

Notes

PROCEEDINGS 6 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

Timetable

PROCEEDINGS 7 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 8 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

Abstracts

PROCEEDINGS 9 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 10 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

ELECTROLYSIS AND RECYCLING OF CO2 INTO CO2-NEUTRAL FUELS

Mogens Mogensen

Risø National Laboratory for Sustainable Energy, Technical University of Denmark (DTU), Frederiksborgvej 399, DK- 4000 Roskilde, Denmark.

It is desirable to change our energy supply into 100 % sustainable energy. We in Denmark believe that this is possible. The presentation gives first a brief discussion of how this may be doable. Next the potential of synthetic fuels is explained, and finally the possibility of making synthetic CO2 neutral and affordable hydrocarbon using electrolysis to make synthesis gas is described. A viable CO2 source is, in the long term, recycling of CO2 originating from combustion of biomass derived fuels.

Introduction Electrolysis and fuel synthesis There is a great incentive for the industrialized Many types of electrolysers exist with operation countries to become less dependent on fossil fuels. temperatures from room temperature up to 1000 C. The Denmark's aim is to become independent of coal, oil and pros, cons and potentials of the various types will be gas by 2050 [1]. It is natural to look at biomass as to presented. In particular, the high temperature (600 - 1000 replace fossil fuel, but there will not be enough biomass C) solid oxide electrolyser cell (SOEC) has been available [2]. Fortunately, more than enough renewable reported practical for co-electrolysis of H2O and CO2 even energy is potentially available. The annual global influx of though it is not yet commercialized. Electrolysis of H2O + 24 energy from the sun to the earth is about 3 - 410 J, CO2 into H2 + CO (syngas) and O2 using SOEC is 20 while the marketed energy consumption is ca. 510 J, advantageous, because electrolysis is a heat consuming i.e. the earth receives ca. 6 - 8,000 times more energy process. The Joule heat contributes to the splitting of the from the sun than we need. Thus, if we use 0.2 % of the water and CO2 molecules. Thus, the higher the 2 earth’s area (ca. 1 mill. km or 15 % of Australia) and temperature, the less electrical energy is need for the have a collection efficiency of 10 %, we get the energy splitting. The SOEC may be operated self cooling if the that we need. Besides solar, including wind and hydro, operation voltage is equal to the thermoneutral voltage. we also have geothermal and nuclear (fusion and fission) potential energy sources. From syngas most hydrocarbon fuels can be synthesised using well established catalytic conversion technologies. Thus, the relevant question is: how we can make enough The simplest and cheapest synthetic hydrocarbon is CH4, affordable energy available? also called substitute natural gas (SNG), which may be Storage of sustainable electricity transported in the existing NG pipelines. Compounds like CH3OH and dimethyl ether (DME = (CH3)2O) are more There are several ways of storing sustainable energy. suitable for the transport sector (trucks, air planes, cars). They can be roughly divided into physical and chemical methods. The physical storage types are e.g. pumping References water to high altitude reservoirs, compression of air, [1] Energy strategy 2050 - from coal, oil and gas to flywheel, magnetic storage and super capacitors. They green energy, The Danish Government, 2011, are generally characterized with relatively low energy http://www.ens.dk/Documents/Netboghandel%20- density. Chemical storage types are e.g. biomass, %20publikationer/2011/Energy_Strategy_2050.pdf synthetic fuels and batteries. Great advantages of synthetic hydrocarbon fuels are their high energy density [2] H. Wenzel, “Breaking the biomass bottleneck of the and that existing infrastructure can be used without major fossil free society”, Sep. 22nd, 2010, CONCITO, modifications. http://www.concito.info/en/udgivelser.php

Research Professor, Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for Sustainable Energy, DTU; 38 years in electrochemistry; M.Sc. in 1973 and Ph.D. in 1976 from the Department of Metallurgy, DTU; Manager of numerous projects and now of Strategic Electrochemistry Research Center (SERC); 180 peer reviewed journal papers (cited more than 5000 times) and 17 patents/applications; h-index 36. Received the Christian Friedrich Schönbein Medal of Honor at The 8th European Fuel Cell Forum, 2008.

M. Mogensen

Corresponding author: Mogens Mogensen, [email protected], Tel. +45 2132 6622 11

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

TUNING DE/HYDROGENATION KINETICS AND THERMODYNAMICS OF MAGNESIUM BASED ALLOYS

M. Zhu, L. Z. Ouyang and H. Wang

School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P. R. China

Abstract By in-situ forming nanocomposite, the de/hydrogenation kinetics can be greatly improved in a Mg-Ce-Ni alloy -1 with dehydrogenation activation energy reducing to 63 KJ(mol H2) . Based on that, a Mg-Ce-Ni alloy has been developed, which has initial capacity of 4 wt. %, fast kinetics and excellent cycleabilty. By forming solid solution in Mg based binary and ternary alloys, the thermodynamics can be adjusted with fully reversible de/hydriding. For Mg90In10 and Mg85In5Al10 solid solutions, the enthalpy of dehydrogenation reaction is altered to -65 KJ/mol and -63 KJ/mol respectively.

Introduction Reversible hydriding of Solid solution

Mg based hydrides are potential candidates that satisfy The MgH2/Si system showed reduced desorption -1 the requirement for the future hydrogen energy. enthalpy of 36.4 kJ (mol H2) , which is attributed to the However, too high thermodynamic and kinetic barrier is formation of Mg2Si. However, this system suffers from still big obstacle for utilization. Substantial kinetics poor reversibility and large capacity loss [1]. We have improvement has been achieved by nanoscaling, developed a reversible de/hydriding reaction in Mg based catalyzing and alloying, but little progress in tuning the solid solution[3]. By mechanical alloying, Mg(In) solid thermodynamics unless the Mg is refined to several solution can be obtained. In the hydriding reaction, Mg(In) nanometers. Changing reaction path has tuned the transforms to MgH2 and MgIn( phase), while in the thermodynamics in Mg-Si system but the reaction is not dehydriding reaction, MgH2 and MgIn can fully reversibly reversible[1]. We present here a fully reversible transformed to Mg(In). The enthalpy of this reaction is de/hydriding in Mg based solid solution with altered obviously reduced and plateau pressure is significantly reaction enthalpy, and a kinetic improvement by in-situ increased. The reduction of desorption enthalpy is related forming nanocomposite. to In content in Mg(In) solid solution and it changes from - 78 KJ/mol for pure Mg to -65 KJ/mol for Mg90In10 with In-situ formed nanocomposite hydrogen storage capacity of more than 4.0 wt. %. This Mg-RE alloys can disproportionate to MgH2 and REH3 in concept can be extended to other systems. We also hydriding process and unique nanocomposite structure prepared solid solution in Mg-In-Al ternary system. A fully can be in-situ formed in some Mg-RE-TM systems by this reversible hydriding is also realized and the enthalpy can -1 reaction [2]. We show that the MgH2-CeH2.73-Ni be further reduced to -62 KJ(mol H2) for Mg85In5Al10 with nanocomposite has very fine lamella structure with reversible hydrogen storage capacity of more than 4.0 thickness of MgH2 and CeH2.73 less than 30 and 15 nm, wt. %. The above results provide significantly new way respectively. In addition, Ni nanoparticles exist at their for tuning the thermodynamics of Mg based hydrides. boundary. The adjoining of extremely fine CeH2.73 and Ni to Mg/MgH2 enhances de/hydriding. Indeed, a very fast References kinetics was achieved in aMg-Ce-Ni alloy with capacity of [1] J. Vajo, F. Mertens, C.C. Ahn, R.C. Bowman, B. Fultz, 4.0 wt.% and the temperature for fully de/hydrogenation J. Phys. Chem. B 108 (2004) 13977. cycle was significantly decreased to 505 K. The apparent [2] L. Z. Ouyang, X.S. Yang, H.W. Dong, M. Zhu, Scripta activation energy (Ea) for the dehydriding of the alloy was Materialia, 61 (2009) 339. lowered to 63±3 kJ/mol from 158 kJ/mol measured for [3] H.C. Zhong,H. Wang,J.W. Liu,D.L. Sun and M. MgH2. The above nanocomposite structure also Zhu,Scripta Materialia 65 (2011) 285–287 effectively inhibits phase growth, which leading long cycle life of more than 500 cycles.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Professor Min Zhu received Ph.D degree from Dalian Univ. of Tech. in 1988. He worked in TU Berlin as Humboldt Research Fellow from 1993 to 1995, and later in Tokyo Univ., NIMS, and Univ. of Sydney as visiting scientist. His research interests include hydrogen storage materials, lithium ion battery, mechanical alloying and shape memory alloys. He has published more than 100 papers in peer reviewed international journals. He received the Outstanding Young Scientist Fund Min Zhu from NSFC in 1999, and appointed as “Cheung Kong Professor” in 2002. He is a Chief Scientist of China’s “973” project on hydrogen storage materials Corresponding author: Min Zhu, [email protected], 86-20-87113924.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

NANOCONFINED METAL HYDRIDES FOR ENERGY STORAGE

Zhirong Zhao-Karger, Elisa Gil Bardají and Maxmilian Fichtner

Karlsruhe Institute of Technology (KIT), Institute of nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germany

The impacts of nanoconfinement on the hydrogen storage properties of metal hydrides and decomposition reaction pathways of complex metal hydrides have been investigated. Nanoconfinement within porous carbon scaffolds has proved to be promising for tuning the thermodynamics and hydrogen sorption kinetics of metal hydrides. As a bottom-up nanostructuring methodology, nanoconfinement is also of interest for other applications for chemical energy storage in the future.

Introduction surface and porosity analysis (BET method), solid state NMR et al. Many efforts have been devoted to synthesize nano scaled metal hydrides to improve their hydrogen sorption Results properties and make them suitable for hydrogen fuel-cell All the composites have shown remarkable decreased based applications. This is because nanostructuring can desorption temperatures compared to their bulk states. improve the kinetics of a solid state reaction by The activation energies have been lowered for shortening the diffusion lengths. In addition, at the decomposition reactions of Mg(BH ) and MgH . nanoscale, the thermodynamic stability of metal hydrides 4 2 2 can also be significantly affected by surface energy.[1] In addition to kinetic change, nanoconfined MgH2 has Nano-confinement within porous host scaffolds has also shown the change on equilibrium pressures. The proved to be an efficient method for preparing reduced enthalpy and entropy have been determined for nanoscaled metal hydrides, especially for materials with the nanoscaled MgH2 by pressure-composition isotherm a particle size below 10 nm.[2] In the present work, the (PCI) measurements. In case of nanoconfined metal thermodynamics, dehydrogenation kinetics, and reaction borohydride, the decomposition reaction pathways pathways of nanoconfined hydride materials have been significantly differ from those of bulk materials. studied. References Experimental [1] M. Fichtner Nanotechnol 20: 204009(2009). Porous carbon materials with pore width below 4 nm [2] Zh. Zhao-Karger, J. Hu, A. Roth, et al. Chem. were utilized as size controlling templates for metal Commun. 46, 8353(2010) ; S. Sartori, K. D. Knudsen, hydrides. Nanoconfined metal hydrides including MgH , 2 Zh. Zhao-Karger et al. J. Phys. Chem. C, 114, Mg(BH ) and the binary LiBH /Mg(BH ) system have 4 2 4 4 2 18785(2010) been synthesized by wet incipient impregnation or melting infiltration techniques. Characterization was performed by means of TEM, N2 physisorption based

Born 01. 11. 1970 in Nei Mongol, China. 1996 M.Sc in Chemistry in China, 2006 Dr. rer. nat. at the institute of organic chemistry, university of Hannover, Germany, 2007 Postdoc at the Catalytic Research Laboratory, university of Heidelberg, Germany, 2008 Research staff at the Institute of Nanotechnology, Karlsruhe Institute of Technology.

Zh.Zhao-Karger

Corresponding author: Zhirong Zhao-Karger, email: [email protected], Tel.(+49) 721 608 28908

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN DYNAMICS IN NANOCONFINED LITHIUMBOROHYDRIDE

Arndt Remhof1, Andreas Züttel1, Jan Peter Embs2, Peter Ngene3, Petra de Jongh3

1Empa, Hydrogen and Energy, Dübendorf, Switzerland; 2Laboratory for Neutron Scattering, ETHZ & PSI, Villigen PSI, Switzerland; 3Inorganic Chemistry and Catalysis, Utrecht University, NL-3584 CA Utrecht, The Netherlands

Nanoconfinement of LiBH4 is a promising way to enhance the hydrogen sorption kinetics and to prevent phase segregation. Quasielastic and inelastic neutron scattering reveal the stabilization of the high temperature phase at room temperature. The rotational mobility however, differs from the bulk high temperature phase. The activation energy is - enhanced and a substantial number of [BH4] ions do not participate in the fast rotational motion.

Introduction

Lithium borohydride (LiBH4) is an attractive material for solid state hydrogen storage due to its high hydrogen content of 18.5wt% [1]. Confinement of LiBH4 in small pores can increase hydrogen release and uptake kinetics We performed inelastic and quasielastic neutron spectroscopy to investigate the hydrogen dynamics in melt-infiltrated LiBH4 in graphitic porous carbon, - especially the reorientations of the [BH4] ions. Results

Figure 1 compares the time of flight spectra of bulk LiBH4 (top) and nanoconfined LiBH4 (bottom), recorded at temperatures between 300K and 500K.

In bulk LiBH4, the phase transition is clearly seen by the sudden change of the shape of the TOF spectra between 360K and 390K. In case of nanoconfined LiBH4 in carbon (15wt%), no phase transition is seen in the temperature range between 300K and 500K. The absence of the pronounced spectral features is a fingerprint of the high temperature phase [2]. Nanoconfinement stabilizes the high temperature phase at room temperature and leads to a shift of the transition temperature well below room Figure 1: (top) Time-of-flight (TOF) spectra for bulk LiBH4 temperature. In the quasielastic regime, the and of nano-confined LiBH (bottom) nanoconfined system shows enhanced rotational 4 disorder at room temperature as compared to the bulk References material. Up to 430 K the quasielastic broadening follows [1] A. F. Gross, Jwt al., J. Phys. Chem. C 112, 5651, Arrhenius behaviour with activation energy of 83meV, (2008). which is higher than in the bulk HT phase. Also the time between two consecutive rotational jumps is increased. [2] A. Borgschulte, et al., Faraday Discuss. 151, 213, The confinement favours the dynamically disordered HT (2011). phase but at the same time reduces the mobility. Above 430 K the quasielastic broadening is almost independent of temperature, probably due to a melting-like process.

1994 University Diploma with distinction of the University of Kent at Canterbury, UK. 1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France. 1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany. 1999 Guest scientist at the Universidade Sao Francisco in Itatiba, Sao Paulo, Brazil. 2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands. 2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum. From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.” 2010 Guest scientist at the Tohoku University in Sendai, Japan Arndt Remhof

Corresponding author: Arndt Remhof, [email protected] +41587654369 17

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SANS AND TEM CHARACTERIZATION OF MGH2-NABH4 NANOPARTICLES CONFINED IN SILICA BASED MESOPOROUS SCAFFOLD SBA-15 Renato Campesi1, Sebastiano Garroni2, Eva Pellicher3, M.Dolors Baró3, Chiara Milanese4, Alessandro Girella4, Francesco Dolci1, Gabriele Mulas2.

1 JRC-IET, Westernduinweg 3, 1755 ZG Petten, The Netherlands

2 Dipartimento di Chimica, Università di Sassari and INSTM, Via Vienna 2, I-07100 Sassari, Italy

3 Departament de Física, Universitat Autònoma de Barcelona, E-08193 Bellaterra, Spain

4 C.S.G.I. & Dipartimento di Chimica, Sezione di Chimica Fisica, Università di Pavia, Viale Taramelli 16, I-27100 Pavia, Italy.

Abstract: The confinement via melt infiltration of MgH2 and NaBH4 nanoparticles within the pores of a silica based mesoporous scaffold (SBA-15) was studied either by small angle neutron scattering (SANS) or by transmission electron microscopy (TEM). The coupling of SANS and TEM techniques allowed to confirm that the synthesis route adopted for the preparation of MgH2-NaBH4/SBA15 nanocomposite, enabled the dispersion of the hydride nanoparticles, with a good extent, within the pores of the SBA-15 scaffold. The nanoparticles dispersion was studied on the as synthesized materials as well after hydrogen des-absorption cycles. Introduction Results Among the several techniques exploited so far in order to SANS measurements showed the appearance of a new improve hydrogen storage properties of the so called peak centered at around 2 nm-1 (figure 1a). This new Reactive Hydride Composites (RHC), nanoconfinement reflection suggested that new ordered scatterers with a of the hydride phases in porous materials sounds very size smaller then the pores of the SBA-15 are present in interesting [1] . At least in principle the confinement could the MgH2-NaBH4/SBA-15 nanocomposites. Taking into hinder the growing of the hydride particle size during the account that the scaffold displays only three main peaks synthesis process and allows the dispersion of the active centered at 0.66, 1.14 and 1.32 nm-1, respectively; the phases in the support material. The resulting benefit new peak could be attributed to MgH2 and NaBH4 would be reduced particle size which is recognized to nanoparticles. It is also interesting to note that this have a great influence in improving the kinetic and reflection is present only in the pattern of the desorbed or thermodynamic as well as to facilitate the interaction re-absorbed materials. This means that the hydride between the hydride phases during the hydrogenation nanoparticles confined within the pores of the SBA-15 process. In that respect we synthesized nanocomposite maintained their size even after the hydrogen desorption by melt infiltration of MgH2 and NaBH4 in the pores of and desorption process. To further investigate the well ordered silica based porous material (SBA-15). TEM dispersion of MgH2 and NaBH4 nanoparticles in the SBA- and SANS techniques showed as the melting process led 15 scaffold, the as synthesized materials as well as the to the dispersion of nanoparticles either within (< 5nm) or cycled ones were investigated by transmission electron outside the SBA-15 pores. microscopy (TEM), the image (figure 1b). shows that the nanocomposites are mainly composed by nanoparticles Experimental dispersed inside the pores of the scaffold. STEM-EDX SBA-15 were synthesized from TEOS and a co-block chemical analysis also confirmed that both MgH2 and polymer P-123, following a procedure reported in NaBH4 were infiltrated in the SBA-15 pores. literature by Zhao et al. [2]. The SBA-15 were then mixed References with MgH2 and NaBH4 and heated up to 450 °C under Ar atmosphere for 1 h. The structural characterization of the [1] A. F Gros, J. J Vajo, S.L Van Atta, G. L. Olson, S. L. samples was carried out by TEM (Jeol-JEM 2011, 200 Skeith, F. Mertens, J. Phys. Chem. C 2008 112 5651 kV, Tecnai F24) and SANS at the ILL-D22 beam line. [2] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. Fredrickson, The samples were also desorbed and re-absorbed using B. Chmelka, G. Stucky, Science 279 (1998) 548-52. a volumetric apparatus (PCT-pro 2000, Setaram)

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Was born in Olbia, Sardegna, Italy on the 15-01-1981

Graduated in Chemistry at the Universita’ di Sassari in 2005

PhD in Engineering Science and Environment, Universite’ de Paris-Est in 2008

Currently working as a researcher at the JRC-IET in Petten, the Netherlands

Renato Campesi

Corresponding author: Renato Campesi, [email protected], Tel. +31224565228

a) b)

Figure 1. a) SANS patterns of the SBA-15 and the MgH2-NaBH4/SBA-15 nanocomposites as synthesized ad after cycling; b) tilted TEM images of the MgH2-NaBH4/SBA-15 nanocomposite, the circle highlights the filled channel.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN ABSORPTION IN SODIUM INTERCALATED FULLERENES

Philippe Mauron,1 Michael Bielmann,1 Arndt Remhof,1 Andreas Borgschulte,1 Mohammad Choucair,2 Mattia Gaboardi,2 Daniele Pontiroli,2 Denis Sheptyakov,3 Mauro Riccò,2 Andreas Züttel,1

1Empa. Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2Dipartimento di Fisica, Università di Parma, Via G. Usberti 7/a, 43100 Parma, Italy

3Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

The hydrogen absorption of sodium intercalated fullerenes (Na10C60) was investigated volumetrically with a pcT system. Hydrogenation was done at pressures up to 200 bar and at temperatures up to 450°C. 2 mass% of hydrogen can be reversibly stored in Na10C60. The samples were investigated by XRD, Raman spectroscopy and neutron diffraction.

Introduction Results Hydrocarbons have a high hydrogen storage capacity Up to 2 mass% of hydrogen can be reversibly stored in e.g. up to 25.1 mass% for methane and >12.4 mass% for Na10C60. During hydrogen absorption the crystal lattice of alkanes CnH2n+2. In hydrocarbons the hydrogen is Na10C60 is expanded and a new phase was formed as covalently bond to the carbon and the desorption shown by XRD (Fig. 1) and neutron diffraction. temperature is too high for mobile applications. For physisorbed molecular hydrogen on high surface area 160 2nd abs (200°C, 200 bar) 1st H2 des (400°C) 140 carbon materials the binding energy is too low and liquid 1st H2 abs (350°C, 200 bar) nitrogen temperatures are required. An intermediate 120 Na10C60

100 binding energy of 20 – 40 kJ/mol H2 would be needed for practical applications. This can be obtained by means of 80 60 an additional attracting force between hydrogen molecule Intensity [a.u.] and the host material, which could originate from an 40 electrostatic (dipole or quadrupole) or orbital interaction 20 0 (e.g. Kubas) [1]. 10 20 30 40 50 60 70 Experimental Angle [2 Fig. 1: XRD patterns of the hydrogen absorption of Na10C60 The Na10C60 samples were synthesised by decomposing a mixture of sodium azide and C60 [2] pressed into a References pellet at temperatures between 380 and 450 °C. [1] G.J. Kubas, R.R. Ryan, B.I. Swanson, Ph.J. Hydrogenation/deuteration was performed at pressures Vergamini, H.J. Wasserman, J. Am. Chem. Soc. 106 up to 200/100 bar respectively at temperatures up to (1984) 451. 450°C for several hours. [2] K. Imaeda, I.I. Khairullin, K. Yakushi, M. Nagata, N. Dehydrogenation was done by applying a temperature Mizutani, H. Kitagawa, H. Inokuchi, Solid State ramp up to 400 °C at 1 bar hydrogen or at constant Comm. 87 (1993) 375. volume.

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 21

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

ZEOLITE-TEMPLATED CARBON MATERIALS FOR HIGH PRESSURE HYDROGEN STORAGE

Nicholas P. Stadie1,2, John J. Vajo3, Philippe Mauron2, Andreas Borgschulte2, Andreas Züttel2, Channing C. Ahn1, Brent Fultz1

1W. M. Keck Laboratory, California Institute of Technology, Pasadena, California 91125, USA

2EMPA, Swiss Federal Laboratories for Materials Research and Testing, CH-8600, Dübendorf, Switzerland

3HRL Laboratories, LLC, Malibu, California 90265, USA

The hydrogen storage capacity reported for zeolite-templated carbon (ZTC) is among the highest for physisorptive materials (including porous carbons, carbon nanotubes, zeolites, and metal-organic frameworks): 6 wt% at 2 MPa and at 77 K. Measurements at 298 K have been performed to determine the viability of room temperature hydrogen storage by pure physisorption. At pressures up to 30 MPa, hydrogen uptake is found to be dependent on specific surface area, even across numerous different materials, despite earlier reports otherwise.

Zeolite-Templated Carbon Experiment These materials are obtained via a templating method; a We prepared high surface area carbons by the ZTC suitable polymeric carbon precursor is inserted into the method; materials with BET surface areas of up to 3800 channels of a zeolite by mixing, then polymerized to m2/g were readily produced in multi-gram quantities. create a solid hydrocarbon with analogous structure to Measurements of N2 and CO2 adsorption were performed the zeolite. The polymer/zeolite composite is treated at to analyse the difference in pore character between ZTCs high temperature and the polymer is pyrolyzed to carbon. and other carbons. Hydrogen uptake measurements at This replicate carbon, ZTC, is then freed from the zeolite 77, 87, and 298 K were performed with a gravimetric template by dissolution in HF, yielding porous zeolite-like balance and a custom, volumetric Sieverts apparatus (to structures with extremely high surface areas (>3000 10 MPa). A second, high pressure Sieverts apparatus m2/g) and large micropore volume.1 was designed and constructed to measure hydrogen uptake at pressures up to 70 MPa. Remarkable Hydrogen Storage at 298 K? Gibbs excess hydrogen capacity across all materials measured corresponded to specific surface area, even at high pressure. The highest measured capacity was ~1 wt% which is well below the target values for a viable storage material. Physisorbent materials are not suitable for hydrogen storage at room temperature. It was reported that room temperature hydrogen uptake in zeolite-templated carbon (ZTC) materials exceeds that References of materials with similar specific surface area, such as [1] Yang et al., “Enhanced Hydrogen Storage Capacity of 2 superactivated carbon MSC-30, by up to 100%. While High Surface Area Zeolite-like C Materials,” JACS, this effect was not reported to be observed at standard 2007. measurement pressures (1-10 MPa), it was claimed to be [2] Kyotani et al., “High-Pressure Hydrogen Storage in evident in the regime of 20-34 MPa. Few suitable Zeolite-Templated Carbon,” J Phys Chem C, 2009. apparatus for measurement at these pressures exist.

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, focusing on synthesis of novel metal-organic framework materials with Prof. Michael O’Keeffe. He now carries out graduate studies and research at California Institute of Technology in Pasadena, California, USA with Prof. Brent Fultz and Dr. Channing Ahn. The focus of current research is synthesis and characterisation of high surface area materials for hydrogen storage applications. He expects to graduate with a PhD in Materials Science in 2012. During 2010, Nick spent 6 months at EMPA in Dübendorf, Switzerland performing CO2 adsorption experiments on porous materials as a technique for the characterisation of extremely narrow microporosity. N. Stadie

Corresponding author: Nicholas P. Stadie, [email protected], +1-626-395-2329 23

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

IMPROVED HYDROGEN STORAGE IN LI-MG-N-H COMBINED SYSTEM

Hongge Pan, Yongfeng Liu, Mingxia Gao

Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China.

Abstract reaction, a three-dimensional diffusion controlled kinetic mechanism was definitely identified for the first time by Hydrogen is the most ideal fuel in the comprehensive analyzing isothermal hydrogen desorption curves using a clean-energy concept. However, hydrogen storage is still linear plot method. In addition, improved hydrogen a major technical barrier for its on-board application as a storage properties were achieved for the Mg(NH ) -2LiH transportation fuel. Recently, metal-N-H systems have 2 2 system by introducing various additives, such as NaOH, been attracting significant attention owing to their high NaBH , and so on. The role played by the additives were gravimetric hydrogen density. Among them, the Li-Mg-N- 4 analyzed and discussed. H material is regarded as one of the very promising systems due to its good reversibility, comparatively high References hydrogen content and favorable thermodynamic [1] P. Chen, Z. Xiong, J. Luo, J. Lin, K. Tan, Nature properties. Unfortunately, a relatively high kinetic barrier 2002, 420, 302-304. retards its practical applications for hydrogen storage. In this talk, we present our recent work on improving the [2] Z. Xiong, G. Wu, J. Hu, P. Chen, Adv. Mater. 2004, hydrogen storage thermodynamics and kinetics of the Li- 16, 1522-1525. Mg-N-H combined system by size effect, composition [3] W. Luo, J. Alloys Compd. 2004, 381, 284-287. adjustment and catalyst addition. It is found that the reaction pathways for dehydrogenation/hydrogenation of [4] Y. Liu, K. Zhong, M. Gao, J. Wang, H. Pan, Q. Wang, the LiNH2-MgH2 (1:1) system depends strongly on the Chem. Mater. 2008, 20 3521-3527. milling duration due to the presence of two competing [5] Y. Liu, K. Zhong, K. Luo, M. Gao, H. Pan, Q. Wang, J. reactions in different stages including ball milling and Am. Chem. Soc. 2009, 131, 1862-1870. heating process. This fact explains reasonably the discrepancies in the experimental results of the LiNH2- [6] C. Liang, Y. F. Liu, K. Luo, B. Li, M. X. Gao, H. G. Pan MgH2 (1:1) system reported previously by several and Q. D.Wang, Chem. Eur. J., 2010, 16, 693-702. research groups. Moreover, Li2MgN2H2 was synthesized [7] C. Liang, Y. F. Liu, Y. jiang, Z.J. Wei, M. X. Gao, H. G. by sintering a mixture of Mg(NH2)2-2LiNH2 and its size- Pan and Q. D.Wang, Phys. Chem. Chem. Phys., dependent hydrogen storage performances were 2011, 13, 314-321. investigated systematically. A dramatically enhanced kinetics for hydrogen absorption/desorption was achieved with a reduction in the particle size. For dehydrogenation

Hongge Pan received his PhD in Materials Science and Engineering from Zhejiang University in 1996 under a joint program between Zhejiang University and Institute of Physics, Chinese Academy of Science. Later that year he joined Zhejiang University and became a Professor in 1999. He awarded the Chinese 2000 National Excellent Doctoral Dissertation Award. His research is focused on energy materials for solid-state hydrogen storage and lithium batteries.

Hongge Pan

Corresponding author: Hongge pan, [email protected], [email protected]; +86-571-87952615.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

th 6 Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

DEVELOPMENT OF LOW COST VANADIUM-BASED HYDROGEN STORAGE ALLOYS IN SICHUAN UNIVERSITY

1 2 1 1 1 Chaoling Wu, Yigang Yan, Fei Yang, Linshan Luo, Yungui Chen 1 College of Materials Science and Engineering, Sichuan University, Chengdu 610064, China 2 EMPA, Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland

Abstract Vanadium (V)-based hydrogen storage alloys show attractive absorption capacity up to 3.8wt% and good kinetics at near room temperature. However, the cost of alloy hinders their applications, due to the high price of pure V (25,000 Euro/ton). After several years of efforts, Sichuan University made a big progress in preparing low cost V-based alloys by using cheap FeV80 master alloy. The cost of alloy was significantly decreased by about 90%. The cyclic stability and the applications of the alloys have been investigated. 2.5 kg V-based alloys prepared from FeV80 were filled in two containers to supply the hydrogen for a fuel cell bicycle, which shows a cruise of around 100 km after one full charge.

Establishment of V-Ti-Cr-Fe alloy system Application of V-based hydrogen storage A V-Ti-Cr-Fe quarternary alloy system was developed alloys with the V content varying from 20~60 mol%. The 2.5 kg of the V-based alloy, prepared by arc-melting optimum compositions among this system show under vacuum, was stored in two containers as the desorption capacities ≥ 2.1 wt% at room-temperature [1]. hydrogen supply to a fuel cell bicycle. The bicycle is able The ab/desorption capacities were found to strongly to run 100 km (40 km / kg alloy) after being fully charged. depend on lattice parameters and electron In comparison, the same bicycle carrying 3 kg of the concentrations. Based on this system, the addition of commercial alloy (AB5 type) only runs 56.5 km (18.8 km / manganese further improve the desorption capacity to kg alloy) after one charge. 2.43 wt% at room-temperature and 3.0 wt% at 80 ℃.

Cyclic stability of the alloys Cyclic stability of two alloys of Ti-Cr-(VFe)48 and Ti-Cr-

(VFe)72 were investigated [2]. The desorption capacity decreases sharply during the first 10 ab/desorption cycles, while keeping steady after that. Ti-Cr-(VFe)72 alloy shows better cyclic stability than Ti-Cr-(VFe)48. The Container贮氢器 Fuel燃料电池 cell microstrain inside the lattice was found to be strongly related with the decrease in desorption capacity. On the other hand, the surface poisoning by the impurities in the hydrogen sources was also found to reduce the cyclic life. Alloys prepared from FeV80 master alloy The price of FeV80 master alloy is even lower than 10% Figure 1. The fuel cell bicycle carrying 2.5 kg V-based of that of pure V metal in current market. We succeeded hydrogen alloys in two containers. in preparing the V-Ti-Cr-Fe-based alloys from the cheap FeV80 master alloy, due to their similar V/Fe ratio [3]. For References example, V-Ti-Cr-Fe-Mn prepared from FeV80 shows [1] Y. Yan, et al, J. Alloys Comp. 441, 297 (2007). almost the same desorption capacity and a slight [2] C. Wu, et al, Int. J. Hydrogen Energy 35, 8130 (2010). increase in plateau pressure from 0.35 to 0.45 MPa. [3] Y. Yan, et al, J. Power Source 164, 799 (2007).

Born 20th July, 1974 in Chongqing City, China. 1997 bachelor in department of metal materials and heat- treatment, Chengdu University of Science and Technology, Chengdu, China. 2000 Master in College of Materials Science and Engineering, Sichuan University, Chengdu, China. 2003 Ph.D. in College of Materials Science and Engineering, Sichuan University. 2003 Lecturer in College of Materials Science and Engineering, Sichuan University. 2007 Associate professor in College of Materials Science and Engineering, Sichuan University. 2007 Assistant director in Engineering Research Center of Alternative Energy Materials & Devices, Ministry of Education of China. 2008 Chief Engineer in Sichuan Baosheng New Energy Materials Co., Ltd. Chengdu, China. Research field: Hydrogen production, hydrogen storage and system, electrode materials in batteries. 2012 Guest Professor in Prof. Züttel Lab in EMPA Swiss Federal Laboratories for Wu Chaoling Materials Science and Technology, Switzerland.

Corresponding author: Chaoling Wu, [email protected], 86-28-85466916 27

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN STORAGE IN TETRA N-BUTYL AMONIUM BROMIDE SEMI- CLATHRATE HYDRATES: KINETICS AND EVOLUTION OF HYDRATE- PHASE COMPOSITION BY IN SITU RAMAN SPECTROSCOPY Alondra Torres Trueba,1 Ivona Rodovic,1 John F. Zevenbergen,2 Cor J. Peters,1,3,4 Maaike C. Kroon4*

1 Department of Process & Energy, Delft University of Technology, Delft, Netherlands 2 TNO Defense, Security and Safety, Lange Kleiweg 137, 2288 GJ Rijswijk, Netherlands 3 Chemical Engineering Program, Petroleum Institute, Abu Dhabi, United Arab Emirates 4 Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, Eindhoven, Netherlands

In order to elucidate the potential of H2-TBAB semi-clathrate hydrates for H2 storage, kinetic data and in situ Raman spectroscopy measurements were obtained for two TBAB concentrations (2.6 mol% and 3.7 mol% in the liquid solution) in a pressure range of 5 – 16 MPa. The influence of pressure, TBAB concentration and formation method (T-cycle method and T-constant method) on the hydrate nucleation, hydrate growth and H2 storage capacity was determined. The results showed that kinetics are favored at higher pressures and solute concentrations. Less stochastic nature was observed when the T-cycle method was applied. The inclusion of H2 in the semi-hydrate phase was confirmed.

Introduction Additionally, a new apparatus was built and tested to study the hydrate phase formation and dissociation for a Tetrabutylammonium bromide (TBAB) semi-clathrate solution of 2.6 mol% of TBAB in situ by using the Raman hydrates, or TBAB semi-hydrates are crystalline inclusion spectroscopy technique. The inclusion of H in the semi- compounds formed by H O molecules and by TBAB 2 2 hydrate phase was confirmed. Results showed the salts. Recently, TBAB semi-hydrates have been importance of H2 mass transfer on the storage capacity of proposed as potential H2 storage materials [1]. In order to the H2-TBAB semi-hydrates. develop semi-hydrate based technology for H2 storage, it is necessary to take into account the optimal kinetics of Conclusions formation, which depends on the conditions applied. In order to developed semi-clathrate hydrate based Therefore, time-dependent experiments were performed technology for H storage, higher pressures and solute in this study in order to determine the optimal formation 2 concentrations should be used to assure optimal kinetics. kinetics as well as the H storage potential of H -TBAB 2 2 The T-cycle method should be applied to reduce the semi-hydrates. stochastic nature of the semi-hydrate formation. Finally, Results to assure optimal H2 storage, the H2 mass transfer limitations should be eliminated by means of increasing The influence of pressure (5-16 MPa), TBAB the contact surface area by the liquid and gas phases or concentration (2.6 mol% and 3.7 mol%) and formation the hydrate and gas phases. method (T-cycle method and T-constant method) on the hydrate nucleation, hydrate growth and H2 storage References capacity was determined. The results showed that [1] Hashimoto S, Murayama S, Sugahara T, Sato H, kinetics are favored at higher pressures and solute Ohgaki K. Thermodynamic and Raman spectroscopic concentrations. It was also observed that the H -TBAB 2 studies on H2+tetrahydrofuran+water and H2+ tetra- semi-hydrate formation at constant cooling rate (T-cycle n-butyl ammonium bromide+water mixtures method) exhibited shorter induction times with a less containing gas hydrates. Chem Eng Sci stochastic nature compared to the T-constant method. 2006;61(24):7884-8. There was not observed any influence of the formation method on the hydrate growth and amount of H2 consumed.

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.

Alondra Torres

* Corresponding author. Cor J. Peters, E-mail: [email protected], Tel.: +31-15-2782660 29

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

STUDYING HYDROGEN ADSORPTION ON MOF FRAMEWORKS A.J. Ramirez-Cuesta

ISIS Facility, Rutherford Appleton Laboratory, STFC, Chilton, Didcot, OX11 0QX, United Kingdom

The interaction of molecular hydrogen with surfaces and porous materials can be studied with Inelastic Neutron Scattering Spectroscopy (INS). In particular the rotational line of hydrogen is very sensitive to the interaction of the molecule with the adsorption site. A series of results arising from the interaction of hydrogen with different system is presented. From the weak interaction of molecular hydrogen with carbon to the stronger interaction with metal organic frameworks.

Introduction Where J and M are the rotational quantum Inelastic neutron scattering spectroscopy (INS) is numbers. In the case hydrogen, the rotational an ideal technique to study hydrogen containing constant B is 7.35 meV. With INS, due to the nature materials.[1]. Another great advantage of INS is of the neutron with matter, we can measure an that allows a more direct comparison between extremely sharp line corresponding to the rotational experimental results and theoretical calculations transition J(1←0) (para to ortho-hydrogen), that has than is the case for optical spectroscopies (Raman an energy of 2B (14.5 meV) [1,2]. and Infra-red). All experiments have been made in When the hydrogen molecule interacts with a TOSCA, which is the world’s higher resolution surface, the rotational line can experience a shift broadband INS spectrometer. It measures a range and splitting. In the case of graphite, there is a very of 3-1000 meV (24-8000 cm-1). small widening of the rotational line. For carbon nanotubes, the effect, due to the curvature of the Theory surface is more pronounced but still small. For The rotational levels for the hydrogen molecule, in metal oxides, MOF, zeolites etc, the interaction of the case of solid hydrogen (negligible interaction molecular hydrogen is large, so are the rotational between molecules) are given by: line shifts [5]. For MOFs, a very exquisite EJM=J(J+1) Brot assignment of the adsorption sites can be done. References [1] PCH Mitchell, SF Parker, AJ Ramirez-Cuesta and J Tomkinson “Vibrational Spectroscopy with Neutrons” World Scientific, London, (2005). [2] Ramirez-Cuesta, AJ;et al; Journal Of Materials Chemistry, 17: 2533 (2007) [3] Ulivi, L; Celli, M; Giannasi, A; Ramirez-Cuesta, AJ; Bull, DJ; Zoppi, M, PRB, 76: 161401 (2007) [4] Ramirez-Cuesta, A. J.; Mitchell, P. C. H. Catalysis Today 2007, 120 (3-4), 368-373. Fig 1. The INS spectra of hydrogen in HKUST as [5] AJ Ramirez-Cuesta, MO Jones, WIF David, function of loading, 4 different sites are apparent; the Materials Today, 12, 2009, 54-61. population is monitored by the area of each peak.

AJ (Timmy) Ramirez-Cuesta is Senior Instrument Scientist of the TOSCA spectrometer at the ISIS Facility, Rutherford Appleton Laboratory in the United Kingdom. He has been working on computational modeling of experimental data for over 25 years and has been involved in the use of neutrons for over a decade. Scientific interests are: Lattice Dynamics Calculations. Characterization of hydrogen storage systems, metal hydrides and porous materials using Inelastic Neutron Scattering and ab-initio Computational methods. Interactions of molecules with surfaces. Modeling of surface reactions and catalysis using classical and quantum methods. Timmy

Corresponding author: AJ (Timmy) Ramirez-Cuesta, [email protected], Tel.+44 1235 446510 31

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

CATALYSIS BY METATHESIS

E. Callini1, A. Borgschulte1, A.J. Ramirez-Cuesta2, B. Probst1, A. Züttel1

1Empa, Swiss Federal Laboratories for Materials, Testing and Research, CH-8600 Dübendorf, Switzerland 2ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, United Kingdom

Understanding complex hydrides decomposition paths is a crucial issue to store hydrogen. Through the information we can get from such an analysis, tuned and focused attempts to obtain their reversibility can be possible. Here we present combined thermogramivetric (TG) and infra-red (IR) measurements which shed a new light on the problem. The support of the computational modelling is complementary to determine the decomposition reaction. The system under investigation is Ti(BH4)3 which is an interesting room temperature liquid complex hydride.

Hydrogen in Complex Hydrides The storage of hydrogen in liquid complex hydrides is an attractive option, since these materials contain up to 20 wt% of hydrogen [1]. Synthesis and handling these materials is not simple. This therefore yields to difficulties in their characterization and the identification of the decomposition reactions with particular emphasis on gaseous products. Combined TG-IR measurements The method presented here is an innovative combination of different techniques and approaches [2]. The weight loss associated with the release of hydrogen is monitored by a thermogravimetric balance, while the decomposition gas is detected by an infrared spectrometer, which gives This observation and the computational modelling may a quantitative measure of the amount of each gas connect this system to the role of Ti halides frequently component. In this way we provide a real time in situ used as additives to enhance desorption kinetics. The composition analysis of the desorption gas. exchange of Ti-ions with Li-ions may catalyse the desorption of LiBH4 via the intermediate formation of Ti(BH4)3 Ti(BH4)3: One of the most promising materials in the class of the nLiBH + TiCl => Ti(BH ) +3LiCl + (n-3)LiBH => room temperature liquid complex hydrides is the Ti(BH ) , 4 3 4 3 4 4 3 3(B+3/2 H ) + Ti(BH ) + 3LiH + 3LiCl + (n-6)LiBH since it can store around the 13 wt% of hydrogen. 2 4 3 4 We investigated metasynthesis of Ti(BH4)3 by ball milling This reaction cannot be reversed, and thus TiCl3 does not powders of TiCl3 and LiBH4 or by adding TiCl4 (liquid) to catalyse effectively for absorption, in good agreement the powder of LiBH4. In the case of the liquid-solid with empirical data. We demonstrate the required high synthesis, the initial emission of diborane and HCl is ionic mobility by exchange experiments. almost suppressed by the emission, at around 45 °C, of References Ti(BH4)3. In the solid synthesis the emission of Ti(BH4)3 starts already at room temperature (see the IR spectra in [1] A. Züttel, A. Borgschulte, L. Schlapbach, (eds.) the picture) and most likely the detected diborane is an Hydrogen as a Future Energy Carrier, Wiley-VCH, effect of the decomposition of Ti(BH4)3. The difficulties in Heidelberg 2008 detecting the Ti(BH4)3 are due to the fact that we found it [2] A. Borgschulte, et al., J. Phys. Chem. C, 2011, 115 to be an extremely unstable compond: it decomposes (34), pp 17220–17226 within few hours at RT.

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. 33

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Hydrogenation of CO2 on the hydride surface of Mg2NiH4

Shunsuke Kato,1 Michael Bielmann,1 Benjamin Probst,1 Riccardo Suter,1 Davide Ferri,2 Andreas Borgschulte,1 Andreas Züttel1

1Empa, Laboratory for Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2Empa, Laboratory for Solid State Chemistry and Catalysis, CH-8600 Dübendorf, Switzerland

This study focuses on a catalytic property of the hydrogen-rich surface of a hydride in the hydrogenation reactions of CO2. The surface processes on Mg2NiH4 were investigated by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS). The hydrogenation reactions of CO2 on the hydride surface were analyzed by means of catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. The hydrogen-deuterium exchange measurements evidence the interactions of the gas molecules CO2, CH4 and H2O with the hydride surface. Dissociation of H2 molecules is not the rate controlling step on the hydride catalyst. From the viewpoint of catalyst preparation, this study implies great potential for reutilization of hydrogen storage alloys as a CO2-reduction catalyst.

Introduction molecules and subsequent hydrogenation of the intermetallics Mg Ni. The way towards a chemical energy carrier from 2 renewable energy may be taken via two strategies: the Hydrogenation reaction of CO2 on Mg2NiH4 first one develops technologies to make hydrogen from The In the CO hydrogenation process on the hydride water the novel energy carrier; the second is the 2 surface, the hydrogen desorption does not determine the implementation of processes for the production of reaction rate but the dissociative adsorption of CO established fuels such as hydrocarbons from CO , water 2 2 molecules on the hydride facilitates the rate of and renewable energy [1,2]. Interestingly, many scientific methanation. The precipitated Ni-clusters on the oxidized questions in hydrogen storage have their counterpart in surface are attributed to the catalytic activity of the the catalytic processes during the synthesis of hydrides surface, i.e. for dissociative adsorption of CO hydrocarbons from hydrogen and CO .[3] In this study 2 2 molecules and their subsequent hydrogenation. The the catalytic interactions of the hydride surface of continuing disproportionation reaction of the hydride Mg NiH with CO during the hydrogen desorption was 2 4 2 induces a rough surface structure. As more and more Ni investigated and the surface processes were studied in particles are formed during decomposition, the modified great detail in the view of a novel class of methanation surface becomes further active in the CO methanation. catalysts on one hand, and to understand the poisoning 2 processes on surfaces of Mg2Ni when exposed to contaminated hydrogen on the other. References Surface properties [1] A. Züttel, A. Remhof, A. Borgschulte, O. Friedrichs, The formation of surface oxide layers on Mg2NiH4 upon Phil. Trans. R. Soc. A, 2010, 368, 3329. exposure to CO hinders the decomposition of the 2 [2] C. Graves, S. D. Ebbesen, M. Mogensen, K. S. hydride. The surface oxidation is accompanied by Lackner, Renewable and Sustainable Energy segregation of Mg oxides and Ni at the disproportionated Reviews, 2011, 15, 1. surface on Mg2NiH4X. The active Ni sites at the surface are associated with the ready dissociation of hydrogen [3] W. E. Wallace, Chemtech, 1982, December, 752.

Born 10. 6. 1976 in Ise, Japan. 2005 Master of Engineering in Applied Science, Tokai University, Japan. Research into gas-solid reactions: reactivity of gases (H2, O2, H2O) with metal surfaces under ultrahigh vacuum condition. 2005-2007 NEDO research assistant at Tokai University, Japan, "Advanced metal hydrides with high volume density of hydrogen". Since 2007 PhD student at Empa, Div. Hydrogen & Energy, and University of Fribourg, Switzerland.

Shunsuke Kato

Corresponding author: Shunsuke Kato, email: mailto:[email protected], Tel. (+41) (44) 823 4327

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

LiBH4-based composites with metal hydrides and fluorides for

hydrogen storage Pei Pei Yuan and Bin Hong Liu Dept. of Materials Sci. & Eng., Zhejiang University, Hangzhou 310027, P.R. China

Abstract

LiBH4-based reactive composites are promising hydrogen storage materials. In this study, we developed a new composite based on 6LiBH4+CaF2. It has a theoretical hydrogen capacity of

9.6 wt% and a slightly decreased thermodynamic stability compared with pure LiBH4. The new composite demonstrated good reversibility in spite of the hydrogen back pressure during dehydrogenation. Further comparative studies of four composites 6LiBH4+CaX2 and

2LiBH4+MgX2 (X=H and F) revealed their similarities and differences in hydrogen storage properties. In general, the composites with fluorides had similar hydrogen storage properties with those containing corresponding hydrides. However, LiBH4/MgX2 and LiBH4/CaX2 (x=F, H) demonstrated large differences because the hydrogen storage performance of LiBH4/MgX2 showed a strong dependence on hydrogen back pressure. The structural difference between MgB2 and

CaB6 may partially account for the observed phenomena for these LiBH4-based composites.

37 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

INCREASING HYDROGEN DENSITIES OF METAL HYDRIDES BY USING CONTINUOUS TRANSFORMATION INTO COMPLEX HYDRIDES Guan-Qiao Li1, Nao Hiyama1, Mika Kano1, Shigeuyki Takagi1, Motoaki Matsuo1, Satoshi Semboshi1, Kazutoshi Miwa2, Shin-ichi Orimo1

1 Institute for Materials Research, Tohoku University, Sendai, 980-8577, Japan 2 Toyota Central R&D Laboratories, Inc., Nagakute 480-1192, Japan

Recent experimental and computational results on YMn2 hydrides provide us a new guideline for designing advanced hydrogen storage materials, that is, “increasing hydrogen densities of metal hydrides by using continuous transformation into complex hydrides”.

Background on YMn2 hydrides hydrogenation below 5 MPa (at 423 K for 12 h). Hydrogenation of YMn2 has been studied because hydrogen induces strong modify- A new guideline for hydrogen storage cations in its materials properties. After materials [6] hydrogenation at ambient hydrogen pressures and temperatures, YMn2Hx shows a Further studies should provide us with unique continuous increase in the cubic cell guidelines for designing advanced hydrogen parameter up to x = 3.5, a two phase range storage materials; increasing hydrogen with a mixture of cubic and rhombohedral densities of metal hydrides by using conti- phases for 3.5 < x < 4 and a rhombohedral nuous transformation into complex hydrides. phase for 4 < x < 4.5 [1-3]. Wang et al. and Paul-Boncour et al. have reported that x This research was funded by Funding reaches 6 when the hydrogenation is carried Program for Next Generation World-Leading out at a high hydrogen pressure of 170 MPa Researchers (GR008) and the Integrated at 473 K for 12 h [4,5]. Project of ICC-IMR.

Low-pressure synthesis of YMn2 hydrides [6] References First-principles calculations were performed [1] J. Przewoznik et al., JALCOM 225, 436 (1995). for a complex hydride YMn2H6 to investigate [2] M. Latroche et al., JALCOM 274, 59 (1998). its electronic structure and thermodynamic [3] V. Paul-Boncour et al., Faraday Discuss. stability. Based on the enthalpy change of 151, 307 (2011). −65 kJ/mol estimated from the calculation, [4] C.-Y. Wang et al., Solid State Commun. 130, 815 (2004). we experimentally verified a possible low- [5] V. Paul-Boncour et al., J. Solid State Chem. pressure synthesis of YMn2H6 from a metal 178, 356 (2005). hydride YMn2H4.5. X-ray diffractometry [6] M. Matsuo et al., APL 98, 221908 (2011). confirmed the formation of YMn2H6 after

Born 11. 2. 1966 in Hiroshima, Japan. 1993-1995 JSPS Research Fellow, 1995 Ph.D. degree, 1995-2002 Research Associate, in/from Hiroshima University. 1998-1999 Guest Researcher in Max-Planck Institute for Metal Research awarded Alexander von Humboldt Fellowship and MEXT Fellowships. 2002 Associate Professor, Institute for Materials Research (IMR), Tohoku University. 2010 Full-Professor, Head of the Section and Deputy of the Research Center “Integrated Materials Research Center for a Low-Carbon Society (LC-IMR)”. http://www.hydrogen.imr.tohoku.ac.jp/ Shin-ichi Orimo Corresponding author: Shin-ichi Orimo, Email: [email protected], Tel. (+81) (22) 215 2093

39 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

ACTIVATED SiO2-BASED MATERIALS FOR HYDROGEN STORAGE

Liga Grinberga, Andris Sivars, Janis Kleperis

Institute of Solid State Physics, University of Latvia, Kengaraga Street 8, Riga, Latvia

SiO2 based materials (glass, zeolite) under normal conditions are not absorbing hydrogen in notable amounts. We used extractive-pyrolytic method to activate glass and natural clinoptilolite zeolite with palladium nano-particles. Ion exchange method was applied to adjust natural clinoptilolite for hydrogen storage. The volumetric and thermogravimetric methods were used to study hydrogen absorption in samples at room and elevated temperatures and hydrogen pressures up to 10 bars. Different amount of sorbed hydrogen in the investigated samples is observed although it varies by method used in the experiments.

Experimental SiO2 glass. It can be assumed that the material with larger surface area absorbs more hydrogen due to the SiO2 based samples in the form of composite materials greater amount of potential interaction sites that would be used in this research consist of Pyrex glass (PG), SiO2 exposed to hydrogen. However, hydrogen sorption glass (SiO2), silica gel (SG), zeolite (ZE), and palladium kinetic measurements with volumetric method showed (Pd). Palladium nanoparticles with nominal metal loading that the materials with the less specific surface area from 1.25 to 10 wt% onto carrier powders (PG, SiO2, SG, absorb more hydrogen than the other ones. Potential ZE) were prepared by extractive-pyrolytic method [1]. explanation is related with the spill-over effect [2]. The Hydrogen sorption experiments were performed with results of thermogravimetric results show that the mass PCTPro-2000 (SETARAM). Initial treatment of the of zeolite activated with 1.25 wt% Pd is increasing by 4-5 samples includes vacuuming and annealing at 200°C for wt%. This work demonstrates the possibility to use silica 1h and cooling to 26°C. Differential thermogravimetric based materials doped with palladium for hydrogen analysis was performed on Shimadzu DTA-60. After storage. initial heat treatment the samples were heated up to 200 or 300 oC at the rate 10 deg/min in argon atmosphere, Acknowledgements and cooled down to room temperature in hydrogen Authors acknowledge the ERDF Projects No. atmosphere at the rate 5 deg/min. Both argon and 2010/0204/2DP/2.1.1.2.0./10/APIA/VIAA/010. and hydrogen were supplied with flow rate 50 ml/min. 2010/0188/2DP/2.1.1.1.0/10/APIA/VIAA/031. Results References XRD and SEM analysis of silica/Pd based composite [1] V.Serga, M.Maiorov, A.Petrov, A.Krumina (2009), materials showed that not only the pure nanocrystalline Integrated Ferroelectrics, No.103 (1), p. 18-24. Pd but also PdO are located on the external surfaces of silica based material nanoparticles. BET surface analysis [2] L.Grinberga, J.Kleperis, G.Bajars, G.Vaivars, A.Lusis showed that porous silica gel and zeolite has (2008), Solid State Ionics 179, p. 42-45. considerably larger specific surface area than Pyrex and

A. Sivars is the 3 grade bachelor student of the faculty of Physics and Mathematics, University of Latvia. Currently works also in the Institute of Solid State Physics, University of Latvia, in the Laboratory of Hydrogen and energy technology materials. Already is co-author of the 3 conference thesis and 2 articles.

Andris Sivars PhD degree in Material Sciences of University of Latvia, works in the in the Institute of Solid State Physics, University of Latvia, in the Laboratory of Hydrogen and energy technology materials since 1999. The scientific research topic has changed from gas sensors and electronic nose to the hydrogen storage materials on 2004. The title of the PhD thesis: ‘New materials for hydrogen storage’ where the investigated material was composite of AB5 and glass. She is author and coauthor of more than 20 articles and 1 book chapter.

Liga Grinberga

Corresponding author: Liga Grinberga, email: [email protected], Tel. +371 67262145 41

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

GAS RELEASE FROM (H,D) ISOTOPE LABELED 2LiBH4/MgH2 COMPOSITES

W. Lohstroha,b, N. Boucharatb, E. Gil Bardajib, M. Fichtnerb a Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München, 85747 Garching, Germany, b Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany

The decomposition of (H,D) isotope labeled 2LiBD4+MgH2 and 2LiBH4+MgD2 composites has been investigated using thermogravimetry, differential scanning calorimetry and mass spectrometry. Significant isotope scrambling is observed once the decomposition process has started. For samples 2LiBD4 + MgH2 the majority gas species is D2 while 2LiBH4+MgD2 predominantly emit HD. The addition of Ti-isopropoxide does not change the ratios.

Introduction mass spectrometry (Sensys Evo, Setaram, and DSC 204 HP Netzsch), XRD and FTIR were used to study the The 2 LiBH +MgH composites are intensely investigated 4 2 phase composition. as hydrogen storage material. Hydrogen release occurs in a two step reaction: Significant isotope scrambling is observed once the 2LiBH4+MgH2 -> 2LiBH4+Mg + H2 -> 2LiH + MgB2 +4H2 decomposition has started: samples 2 LiBH4 + MgD2 release predominantly HD while the majority gas species and in total 10.5 wt% H2 are released [1,2]. Additions of Ti-isopropoxide improve the kinetics of hydrogen release for 2LiBD4 + MgH2 is D2. Above T>400°C, the relative and ameliorate reversibility of the system. This ratio of the gas species D2, HD and H2 remains constant. For Ti-isopropoxide samples gas release is shifted to improvement is thought to be due to the formation of TiB2 lower temperatures but the gas species distribution is acting as nucleation site of MgB2 during desorption [3-5]. similar compared to the undoped case. The results The formation of MgB2 (instead of amorphous boron) has been identified as crucial point for the reversibility of the indicate that H/D exchange during decomposition is system. To further elucidate the rate limiting factors of the easily possible and we propose the following model for decomposition reaction and the effect of the Ti- the initial step for the decomposition: hydrogen (either H isopropoxide additive we studied the gas release in or H2) released from magnesium hydride gets scrambled with the more abundant gas species either at the isotopically labelled samples 2LiBD4 + MgH2 and 2 LiBH4 MgH2/LiBD4 interface or during diffusion through the + MgD2. liquid LiBD4 layer. Experimental and Results

LiBH4 (Sigma-Aldrich, 95%), LiBD4 (KatChem 98%), References MgH2 (Alfa Aesar,98%) and Ti-isopropoxide (Alfa Aesar) [1] J.J. Vajo et al. Physical Chemistry Letters B 109, were obtained commercially. MgD2 was produced by 2005, 3719-3722 cycling commercial MgH2 in a Sieverts’ apparatus under D2 gas. High energy ball-milling (Retsch PM400 planetary [2] U. Bösenberg et al. Acta Mater. 55 (2007) 3951–3958 mill) at a 400 rpm rotation speed has been used to [3] U. Bösenberg et al Acta Materialia 58 (2010) 3381– produce the nanocomposites. For the additive free 3389 samples premilled LiB(H,D)4 and Mg(H,D)2 were mixed and ball milled together for 13 h. Ti-isopropoxide doped [4] E. Deprez et al. Acta Materialia 58 (2010) 5683–5694 samples have been prepared by mixing premilled [5] E. Deprez et al. J. Phys. Chem. C 114 (2010) 3309– Mg(D,H)2 powder with 5 at% Ti-isopropoxide for 13h and 3317 subsequently mixing it with premilled LiB(H,D)4 for additional 5h. The gas release was studied using thermogravimetry, differential scanning calorimetry and

1996 Diploma in Physics, Georg-August Universität Göttingen, Germany 1999 Dr. rer. nat. from the science faculty Georg-August Universiät Göttingen, Germany 2000 Post Doc at the Clarendon Laboratory, Condensed Matter Physics, Oxford University 2003 Post Doc at the Department of Physics and Astronomy, Condensed Matter Physics at the Vrije Universiteit Amsterdam, The Netherlands 2005 Research Staff at the Institute of Nanotechnology, Karlsruhe Institute of Technology 2011 Instrument Scientist at Technische Universität München, Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM2) Wiebke Lohstroh

Corresponding author: Wiebke Lohstroh, [email protected], Phone: 49 (0)89 289 14735 43

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

ESEM AND RAMAN MAPPING OF POLYPHENYLENE SULPHIDE/ POLYSULFONE / OLIVINE DIAPHRAGMS

Michal Gorbar1,2, Marcus Pohl1,3, Andreas Borgschulte1, Ulrich F. Vogt1,5, Ernest Burkhalter4 and Andreas Züttel1,2

1EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland

2University of Fribourg, Dept. of Physics, Fribourg, Switzerland

3University of Applied Science, Faculty of Chemical Engineering, Münster, Germany

4IHT, Monthey, Switzerland

5Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

PPS-PSU-olivine diaphragms were manufactured and investigated aiming at replacing chrysotile-asbestos diaphragms in alkaline electrolysers. The chemical information was drawn from a mapping of the specific Raman transitions of olivine, polysulfone and polyphenylene sulphide with a spatial resolution of around 3 mm. The interval between the measured spots was chosen 5 mm in x- and y-direction. The distribution of the molar fraction of the three components is visualized using contour plots calculated from intensities of the integrated areas. Environmental scanning electron microscopy was applied to qualitatively investigate the drying effects on the structure of investigated specimens.

Introduction process in a non-solvent bath (distilled water) for 72 hours and are kept moist until have been used for the The efficiency of alkaline electrolysis is highly influenced several characterisation methods. by the properties of the diaphragm, responsible for separating hydrogen and oxygen gases. Traditionally Results used asbestos diaphragms fulfill these requirements The Raman mapping of the diaphragms enables a better thanks to their hydrophilicity, fibrous structure and understanding of segregation effects between the specific porosity. This material is undesired because of individual compounds within the matrix. The preferred the health hazards caused by asbestos. Thus new types binding of the PSU/Olivine to the PPS matrix is reduced of porous materials are being developed to substitute by the infiltration with olivine water based slurry, leading asbestos fabrics, based on inorganic-organic composites. to a mechanical instable structure. A repeated Processing impregnation leads to stable samples, even though a Polyphenylene sulphide (PPS) felts with a thickness of 3 minor segregation is achieved. Environmental SEM mm were twice infiltrated and impregnated by a mixture imaging allows to qualitatively indicating the drying effect on the microstructure. The analysis revealed that upon of olivine (Mg,Fe)2SiO4 and (PSU) polysulfone, dissolved in an aprotic solvent N-methyl-2-pyrrolidone in the ratio of removal of water, structure deformation occurred as a 5:2:48. Subsequently they underwent the phase inversion result of the segregation of the olivine/polysulfone body packing within polyphenylene sulphide matrix.

Born 14. 11. 1982 in Levoca, Slovakia. 2001 – 2007, study of chemistry at the Comenius University in Bratislava. 2006 - 2007 Master Thesis "TiO2 surface modified ceramic foams for catalytic applications" at Empa, Dept. of High Performance Ceramics. In 2007 graduated as Master of Science in inorganic chemistry. 2007 - 2008 employee of Empa, at the Dept. of Internal Combustion Engines and High Performance Ceramics in Dübendorf, Switzerland. Research focused on production and development of ceramic foams as a support for catalytic materials. 2008 - 2011, PhD student at University of Fribourg and in the Laboratory "Hydrogen & Energy" at Empa, Dübendorf. Involved in the CTI project (NMAE2), BFE & SwissElectric project and EU project ELYGRID until Michal Gorbar present.

Corresponding author: Michal Gorbar, [email protected], Tel. (+41) (58) 765 4301

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

IMPROVED HYDROGEN SORPTION KINETICS IN SUPPORTED MG2CU NANO-PARTICLES

Yuen S. Au, Petra E. de Jongh

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitweg 99, P.O. Box 80083, 3508 TB Utrecht, The Netherlands

Supported nano-particles of Mg2Cu on different types of carbon were synthesized and the kinetic and thermodynamic properties for hydrogen sorption were investigated. Smaller crystallites (~50 nm) and better hydrogen desorption kinetics were observed by using porous carbon as support material. A temperature shift of 150 0C for hydrogen release was observed with temperature programmed desorption under Ar-flow. Results from cycling experiments performed gravimetrically showed that the improved desorption kinetics were maintained.

Introduction Material and hydrogen sorption properties Reversible hydrogen storage in metal hydrides is favorable with regard to safety and volumetric storage The smallest crystallites were obtained with porous density. The Mg2Cu-H system can reversibly store carbon (a) with an average size of 50 nm according to hydrogen following the reaction: XRD. SEM, performed in BSE mode, confirmed the 2 Mg2Cu + 3 H2 ↔ 3 MgH2 + MgCu2. The equilibrium 0 presence of the small crystallites. The sample prepared temperature for H2-sorption in this system is 240 C at 1 on graphite (b) yielded significant larger crystallites (>200 bar H2. Nano-sizing and confinement improve the kinetics nm). Sample a prepared on porous carbon released and reversibility of hydrogen sorption reactions in light hydrogen at much lower temperatures than the other metal hydrides [1]. We investigated the hydrogen release samples. This is likely due to the decrease in diffusion and reversibility for different carbon-Mg2Cu distance for hydrogen and/or increased specific surface nanocomposites. area of the Mg-Cu crystallites. Preparation Hydrogen Release Mg2Cu species were prepared on porous and non-porous (a) Mg Cu with porous carbon graphitic carbon supports. We first impregnated the 2 (b) Mg2Cu with non-porous graphite carbon with a Cu(NO3)2 solution. After decomposition of (c) Mg Cu physical mixture with porous carbon the nitrate and reduction, supported metallic Cu particles 2

were obtained. Mg2Cu was formed by adding MgH2 to the (ml/min.g) (b)

2 (a) Cu-carbon composition and heating the mixture to the (c)

melting temperature of Mg. Normalized Flow H

150 200 250 300 350 400 450 Temperature (0C) Fig. 2: Temperature programma desorption measured under 25 ml/min Ar-flow at 10 0C/min. Acknowledgements We acknowledge NWO (Vidi grant 016.072.316) for financial support.

Fig. 1: SEM image in BSE mode of Mg2Cu particles on porous References carbon (a) and non-porous graphite (b). [1] De Jongh, P.E., Adelhelm, P., ChemSusChem, 1332- 1348 (2010)

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Born in The Netherlands. 2007 Bachelor degree in Chemistry (Leiden University). 2009 Master degree in Chemistry (Leiden University). 2010-present PhD-student in the group of Inorganic Chemistry and Catalysis, Utrecht University.

Yuen Au

Corresponding author: Yuen Au, email: [email protected], Tel. (+31) (6) 22736385

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGENATION OF CARBON MONOXIDE OVER NANOSTRUCTURED SYSTEMS: MECHANOCHEMICAL APPROACH

Gabriele Mulas1, Renato Campesi2, Sebastiano Garroni1, Francesco Delogu3, Chiara Milanese4

1Department of Chemistry, University of Sassari and INSTM, via Vienna 2, I-07100 Sassari, Italy 2JRC-IET, westerduinweg 3, Petten 1755 ZG, The Netherlands 3Department of Chemical Engineering and Materials, University of Cagliari, piazza d’Armi, I-09123 Cagliari, Italy 4C.S.G.I & Department of Chemistry, Physical Chemistry Section, University of Pavia, Viale Taramelli 16, I-27100 Pavia, Italy

Abstract: In this study we investigated the mechanochemical hydrogenation of carbon monoxide over nanostructured FeCo- and Mg2Ni-based catalysts. To this aim, powdered materials prepared by mechanical alloying were subjected to mechanical treatment under CO/H2 (1:3) atmosphere. A methodology to evaluate the activity of the solid catalysts on an absolute basis was developed. Conversion data were, indeed, expressed as turnover frequency, TOF, and related to the occurrence of ball to powder collision events through the mechanochemical turnover frequency parameter, MTOF. Differences in the catalytic activity and selectivity were observed for the two FeCo-based studied systems, the solid solution Fe50Co50 and its dispersion on TiO2 support. As for the Mg2Ni system, we explored the possibility to estimate the speciﬁc role of hydrogen pre-activation step. The catalytic properties of the mechanically alloyed Mg2Ni system were compared with the conversion data shown by the same system pre-hydrogenated and subsequently milled under CO atmosphere

Introduction We propose a methodology to describe, displacement at 14.6 Hz. The conversion rate and the on a quantitative basis, chemical processes at the gas– selectivity of the CO hydrogenation were monitored by solid interface promoted by mechanical treatment. The gas-chromatography (GC). Hydrogen and carbon experimental set up, as well as the developed monoxide gases were detected using a Fisons 8000 procedures, were applied to the study of the apparatus equipped with a Hot Wire Detector, whereas hydrogenation process of carbon monoxide (CO), carried hydrocarbons were analyzed by a Perkin-Elmer 8600 out over multi-component metal alloys and hydrides. This apparatus equipped with a Flame Ionization Detector. process, well known as Fischer–Tropsch (FT) synthesis, Results The methodology presented in this work has had particular relevance in the industry in the post- allows to compare on an absolute basis war period [1], and nowadays it is receiving increasing mechanochemical conversion data with the results of attention for environmental issues and potential heterogeneous catalytic tests carried out under applicative purpose in a clean energy scenario. In a conventional thermal activation conditions. Results of CO classical scheme of the FT reaction activated by + H synthesis over FeCo based catalysts indicated that conventional thermal treatment, hydrogen and carbon 2 mechanochemical processes, characterized by mild monoxide react over supported transition metal catalysts conditions (room temperature, and near to atmospheric to yield saturated hydrocarbons, oleﬁns and oxidized pressure), displayed conversion data similar or better products. Such consideration prompted us to select, as than the corresponding thermally activated reactions, catalysts, the cited systems for which recent literature performed under severe conditions (400–800 K, 2–5 data are available [2]. MPa). Further improvement in conversion data and Experimental kinetics was observed in the CO conversion over The catalytic properties of different systems, i.e. hydrides. The quantiﬁcation of such effect allowed to gain some hints of the reaction mechanism, and may open Fe50Co50, FeCo supported on TiO2 (FeCo)/(TiO2) and some potential perspective for the application of the Mg2Ni were investigated. All the samples were synthesized by mechanical treatment: by using a studied process in a future hydrogen-based energy commercial Spex mixer/mill model 8000. scenario Mechanochemical carbon monoxide hydrogenation runs References were performed over 8 g of catalyst powders. [1] R.B. Anderson, The Fischer-Tropsch Synthesis, Experiments were carried out in batch, inside a stainless Academic Press, Orlando, 1984. steel cylindrical reactor, with two pressure valves allowing the inlet and outlet of gases. The reactor was connected [2] D.J. Duvenhage, N.J. Coville, Appl. Catal. A 153 with an external gas reservoir where the desired gaseous (1997) 43. mixture was prepared. In particular, the powders of all the systems were exposed to a CO:H2 gaseous mixture in the molar ratio 1:3. a. Moreover, the reactor temperature was kept at 300 K and the frequency of reactor 49

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Was born in Olbia, Sardegna, Italy on the 15-01-1981

Graduated in Chemistry at the Universita’ di Sassari in 2005

PhD in Engineering Science and Environment, Universite’ de Paris-Est in 2008

Currently working as a researcher at the JRC-IET in Petten, the Netherlands Renato Campesi

Corresponding author: Renato Campesi, [email protected], Tel. +31224565228

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

THE ENERGY DENSITY OF HYDROGEN STORAGE MATERIALS Andreas ZÜTTEL

EMPA Materials Science & Technology, Dübendorf, Switzerland Renewable energy occurs in energy fluxes while fossil fuels are energy carriers with an energy density of 13 kWh/kg and 10’000 kWh/m3. Therefore, a synthetic energy carrier has to be produced in order to store and transport the renewable energy, i.e. match the conversion with a typical intensity of 100 W/m2 and the demand 20 W/m2 (for heating) to MW/ capita for transport in an airplane. Hydrogen exhibits an energy density of 39 kWh/kg but a very low volumetric energy density. The goal is to develop a hydrogen storage system with a similar energy density as compared to fossil fuels, e.g. synthetic hydrocarbons produced from CO2 from the atmosphere and hydrogen from water and renewable energy.

Energy carriers Hydrides The economy in the industrialised world is mainly based The hydrogen density in hydrogen storage materials is on open materials cycles, i.e. mining the ore, produce a limited to <25 mass% and <150 kg/m3 [1]. The resulting product and deposit or burn the wast. This systems not energy density is therefore limited to 6 kWh/kg and 5’000 sustainable and needs to be converted into an economy kWh/m3 on a materials basis, without oxidation of the based on closed cycles. Especially the energy carriers host material. Furthermore, the application of hydrogen are produced from renewable energy and used in a storage materials requires a tank system, which reduces closed cycle, e.g. hydrogen is produced by electrolysis the hydrogen density to approx. 50% of the hydrogen from water and electricity, stored, used in a fuel cell, density in the host material itself. turbine or internal combustion engine and finally releases water to the atmosphere. Synthetic hydrocarbons Only few molecules exist in a significant concentration A system using the oxygen from the atmosphere and and are transported in the atmosphere without negative releasing the product of the combustion into the effects on the living matter, i.e. N2, O2, H2O and CO2. atmosphere exhibits a ten times greater energy density Therefore the only synthetic energy carriers, with an compared to a closed system e.g. battery. Considering energy density comparable to the fossil fuels are the Carnot efficiency of the combustion (<40%) hydrocarbons and ammonia as well as compounds of compared to the Gibbs free enthalpy of an electro- nitrogen, carbon and hydrogen. These materials lead to chemical system (>80%), the theoretical maximum water, carbon dioxide and nitrogen upon oxidation. The energy density of a combustion is still 5 times the energy main challenge is to efficiently synthesize the energy density of a battery (1 kWh/kg and 1000 kWh/m3). carriers from the products in the atmosphere by means of heat and electricity from renewable sources, i.e. sun, geothermal and tide. The extraction of CO2 from the atmosphere requires thermodynamically very little energy ( 0.2 kWh/kg CO2) but with todays technology consumes a significant amount of the energy stored in the form of carbon. Furthermore, the co-electrolysis of H2O and CO2 on the same electrode, the electrochemical synthesis of ammonia and the activation of CH4 would open new efficient pathways for the production of synthetic fuels.

References [1] A. Züttel, A. Remhof, A. Borgschulte and O. Friedrichs, “Hydrogen: the future energy carrier”, Phil. Trans. R. Soc. A 368 (2010), pp. 3329-3342 Fig. 1. Energy density of fossil fuels, hydrogen in various forms, hydrocarbons and batteries.

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf, Switzerland. Exchange student Dow Chemical in Terneuzen, Netherlands. 1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr. rer. nat. from the science faculty UniFR. 1994 Post doc AT&T Bell Labs in Murray Hill, New Jersey, USA. 1996 Head of the Metalhydride Group at the UniFR. 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 Andreas ZÜTTEL UniFR. 2009 Guest Professor at IMR, Tohoku University in Sendai, Japan

Corresponding author: Andreas ZÜTTEL, email: [email protected], Tel. +41 58 765 4038; m: +41 79 484 2553 51

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SORPTION ENHANCED METHANATION OF CO2

Riccardo Suter, Andreas Borgschulte, Shunsuke Kato, Benjamin Probst, Andreas Züttel

Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

The reduction of CO2 by hydrogen eventually forming hydrocarbons depends on the interaction of CO2 and H2 with a catalyst surface, i.e. ad- and desorption of hydrogen, CO2 and products [1]. A significant increase of the process efficiency is possible by the so-called sorption enhanced reaction. The desorption reaction is strongly enhanced by the removal of water by its absorption in the inner bulk of a sorption catalyst (see picture). As a proof-of-concept, an improvement of the reaction yield of more than 100% of the Sabatier was realized using Ni-zeolite sorption catalysts.

Sorption enhanced reaction reactor with a diameter of x cm and a length of x cm. At the outlet nitrogen is added to dissolve the gas to The Sabatier reaction optimize the signal to noise ratio in the coupled FTIR- CO2 + 4 H2 <=> 2 H2O + CH4 spectrometer. To avoid water condensation in the IR cell a cool trap with ice water was installed before the is strongly enhanced by the removal of water by its spectrometer. absorption in the inner bulk of a sorption catalyst. As a proof-of-concept, an improvement of the reaction yield of more than 100% of the Sabatier was realized using Ni- Cat Preparation and Characterization zeolite sorption catalysts [1].

Catalysts were prepared by ion exchange using different zeolite precursors with Nickel(II)nitrate. The calcination of the solids were carried out under a nitrogen flow at 450 °C for 16 h and further reduction of Nickel oxide with hydrogen at 650 °C for 4 h. The Nickel content was evaluated using EDX to 14 w%. SEM-EDX mapping showed homogeneously dispersed Nickel with a small excess on the border of the zeolite cores.

Sorption studies The pore diameters of the zeolites are highly dependent on the preparation of the zeolites and are commercially available. Interesting for our purposes were the 3A, 4A and 5A, who have different characteristics in the Figure 1: Sorption Enhanced Methanation adsorption of water and other small molecules such as H2, CH4, CO and CO2. Reactor design The reacting gases are lead into the reactor without References preheating or purification. The reactor is a stainless steel [1] B. T. Carvill, et al. , AIChE J. 1996, 42, 2765.

Riccardo Suter from Freienwil is born in 1988, in Baden Switzerland. 2011 Master in Science Chemistry ETH Zürich. 2010 Research project on the Synthesis of Tetramethyl-phosphinanone. 2011 Research project on Luminescent Lanthanide Complexes on Silica Nanoparticles. 2011 Master-Thesis in Bristol in the group of Ian Manners on the Heterogeneous Dehydrocoupling of Amine-Borane Adducts by Skeletal Nickel Catalysts. Since October 2011 working on the Sorption Enhanced Methanation of CO2 in the Hydrogen & Energy Laboratory at Empa, Dübendorf, Switzerland.

R. Suter

Corresponding author: Riccardo Suter: [email protected], Tel. +41 58 823 4729

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN-METAL COMPLEXES IN METAL-HYDROGEN INTERSTITIAL ALLOYS. DESCRIPTION OF HEAT CAPACITY ANOMALY Ioseb Ratishvili*, Natela Namoradze** *I.Javakhishvili Tbilisi State University, Andronikashvili Institute of Physics, Tbilisi, Georgia **Georgian Technical University, Chavchanidze Institute of Cybernetics, Tbilisi, Georgia

Abstract Basing on measurements [1] it was established [2] that the light rare-earth dihydrides LaH2 and CeH2 reveal a sufficiently remarkable qualitative difference in the heat capacity temperature dependence C(T) (see Fig.1, reproduced from [2]). Description of experimental dependences C(T)[LaH2] and C(T)[CeH2] using the traditional mathematical methods applicable to interstitial alloy lattices provides exclusively good coincidences of experimental and calculated C(T)-curves in both hydrides, except the temperature region 150-300K in LaH2 [2, 3]. In order to describe this anomaly we have elaborated a tentative model of metal-hydrogen compounds, based on the assumption that the given stoichiometric dihydrides can be considered as consisting of MH2- complexes having tetrahedral or octahedral configurations. Within the frames of this model additional heat capacity at 150-300K in lanthanum dihydride is ascribed to tetra-octa reorientations of MH2 complexes. 14 12

10 LaH2 8 CeH 6 2 4 (T) [cal / mole K]

C 2 0 0 100 200 300 400 T [K]

References 1. B.Stalinski, Z.Bieganski. Bull. Acad. Pol., Ser. Chem., v. 12, N 5, 331-334 (1964); Z.Bieganski, D.Gonzalez Alvarez, F.W.Klaijsen Physica (Utrecht), 37, 153-157 (1967)’ Z.Bieganski. Bull. Acad. Pol., Ser. Chem., v. 19, N 9, 581-586 (1971). 2. N.Namoradze, I.Ratishvili. Poster Presentation at GRC “Hydrogen-Metal Systems”, Stonehill, MA, USA (2011) 3. N.Namoradze, I.Ratishvili. Bullet. Georg. Nat. Acad. Scien., v. 5, N 3, (2011) [in press].

55 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Muons probe strong hydrogen interactions with defective graphene

Mauro Riccò¥,*, Daniele Pontiroli¥, Marcello Mazzani¥, Mohammad Choucair&, John A. Stride&,§, Oleg V. Yazyevç,,

¥Dipartimento di Fisica, Università di Parma, Via G.Usberti 7/a, 43100 Parma, Italy.

&School of Chemistry, University of New South Wales, Sydney 2052, Australia.

§Bragg Institute, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234, Australia.

çDepartment of Physics, University of California at Berkeley, Berkeley, CA 94720, USA

Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Institute of Theoretical Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

ABSTRACT: Here, we present the first SR investigation of graphene, focused on chemically- produced, gram-scale samples, appropriate to the large muon penetration depth. We have observed an evident muon spin precession, usually the fingerprint of magnetic order, but here demonstrated to originate from muon-hydrogen nuclear dipolar interactions. This is attributed to the formation CHMu (analogous to CH2) groups, stable up to 1250 K where the signal still persists. The relatively large signal amplitude demonstrates an extraordinary hydrogen capture cross-section of CH units. These results also rule out the formation of ferromagnetic or antiferromagnetic order in chemically synthesized graphene samples.

57 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

CATALYTIC DEHYDROGENATION OF MG(NH2)2-2LIH COMPOSITE MATERIAL

Jianhui Wang, Zhitao Xiong, Guotao Wu, Ping CHEN

Dalian Institute of Chemical Physics, Dalian, China 116023

Abstract The kinetics of hydrogen desorption from Mg(NH2)2-2LiH can be significantly improved by doping it with 3 mol% KH. Mechanistic investigation reveals that K keeps on changing bonding environment in the dehydrogenation.

Introduction Hydrogen Storage is one of the challenging technical barriers in the implementation of hydrogen energy.1 Chemicals with high hydrogen content are potential hydrogen storage materials. A number of promising candidates have been identified and investigated over the past decades, among which amide-hydride complexes have attracted considerable attention.2-8 It has been demonstrated that ~ 10.5 wt.% and 5.5 wt.% of hydrogen can be stored in lithium amide-lithium hydride and magnesium amide-lithium hydride systems through reactions (1) and (2), respectively.2, 6 LiNH2 + LiH = Li2NH + H2 (1) Mg(NH2)2 + 2LiH = Li2Mg(NH)2 + 2 H2 (2) Figure 2 Pressure-Compositional isotherms of the Mg(NH ) -2LiH sample w/o K catalyst. However, relatively high operating temperatures due to 2 2 thermodynamic or kinetic reason place a serious XAFs analyses reveal that K in K-H state gradually restriction onto the application of those materials. transformed to the K in K-N environment in the dehydrogenation. Interestingly, there is kickpoint at a H content of ca. 3.5 showing a rapid enrichment of K-N content in the early stage of dehydrogenation revealing Pristine sample K-doped sample that a part of the KH takes the advantage to react with Mg(NH2)2 to form the K-N species. It is, therefore, that KH catalyzes the dehydrogenation through actively participation in the reactions with reactant(s) and/or intermediates, which is significant different from those of

Intensity (a. u.) (a. Intensity transition metal catalyzed dehydrogenation of metal hydrides and alanates. References

50 100 150 200 250 300 [1] Schlapbach L. & Zuttel A. Nature 2001, 414, 353 0 Temperature ( C) [2] Chen P, Xiong ZT, Luo, JZ, Lin JY, Tan K. L. Nature 2002, 420, 302. Figure 1 Hydrogen release from the Mg(NH2)2-LiH samples with/o K. [3] Luo WF. J Alloy Compd 2004, 381,284. Results and Discussions [4] Leng HY, Ichikawa T, Hino S, et al. J Phys Chem B 2004, 108, 8763. Among all variables that affect the kinetics of a heterogeneous solid state reaction, mass transport and [5] Nakamori Y, Orimo S. J Alloy Compd 2004, 370,,71. reaction at the surface or interface(s) are the two [6] Xiong ZT, Wu GT, Hu JJ, Chen P. Adv. Mater. 2004, common rate-determining processes. It was found that 16, 1522. the interface reactions between amide-imide and imide- hydride are slow steps in the reaction (2). Conventional [7] Pinkerton FE, Meisner GP, Meyer MS, Balogh MP, & transition metals have limited catalytic effect on the Kundrat MD J. Phys. Chem. B 2005, 109, 6. dehydrogenation of those amide-hydride composites. [8] Wang JH, Liu T, et al, Angew Chem Int Ed 2009, 19, Interestingly, KH of 3 mol% works well which can reduce 2141 the dehydrogenation temperature from ca. 180 C to 107

C (see Figs 1 and 2).8 59

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Ping Chen is a professor at the Dalian Institute of Chemical Physics (DICP, China). Chen received a BS degree in 1991 and a PhD degree in 1997 in chemistry from Xiamen University, China. She was a faculty member in the Faculty of Science at the National University of Singapore (NUS) before she joined DICP. Her primary research interest includes the development of chemical and complex hydrides for hydrogen storage, catalysis, and organic synthesis.

Ping Chen

Corresponding author: Ping Chen, [email protected], 86-411-84379905.

5th Hydrogen & Energy Symposium Stoos, Switzerland 2011

SUPERIONIC CONDUCTIVITY IN FULLERENE POLYMERS

Daniele Pontiroli, Matteo Aramini, Mattia Gaboardi, Marcello Mazzani and Mauro Riccò

Dipartimento di Fisica, Università degli Studi di Parma, Via G. Usberti 7/a, 43124 Parma, Italy

Abstract: The successful intercalation of lithium and magnesium in the fullerene C60 lattice leads to the formation of the isostructural two-dimensional polymers Li4C60 and Mg2C60, with an ordered crystalline structure. Here the small alkali and alkali-earth ions can easily diffuse, even at low temperature. These findings open to the possibility of employing these materials as electrodes in future ion batteries.

Li and Mg doped C60 polymers conductivity). Due to the low activation energy of the process (∆Ea≈200 meV), the Production of energy from renewable uncorrelated Li+ hopping among these sites sources also requires an effective and grows up already at 130 K. Then, following practical way to storage it. For this reason it an Arrenius law, conductivity reaches the is important designing new materials suitable exceptional value for the of 10-2 S/cm at for increasing the performance of current room temperature [2]. batteries. Preliminary DC measurements on Mg2C60 It is known that carbon nanomaterials like indicated a similar behaviour, with the onset fullerenes are able to intercalate small alkali of the Mg2+ diffusion at T=150 K and an even metals to form polymerised layered lower activation energy for the hopping structures. In particular, our previous study process (∆Ea≈105 meV); these analyses are on Li doped C showed that the charge 60 currently in progress. This material appears transfer of 4 electrons from the metal to the promising for the production of the future and fullerene stabilizes a peculiar two- still unexplored Mg ion batteries. dimensional polymer structure in the solid state [1]. Surprisingly, Li4C60 behaves also as References an extraordinary good ionic conductor (see below) [2]. More recently, we successfully intercalated also magnesium in the fullerene [1] S. Margadonna, D. Pontiroli, M. Belli, T. lattice and found that, interestingly, Mg2C60 Shiroka, M. Riccò and M. Brunelli, "Li4C60: A shows the same polymeric arrangement of Polymeric Fulleride with a Two-Dimensional Li C [3]. Architecture and Mixed Interfullerene Bonding 4 60 Motifs", Journal of the American Chemical Society, 2004 Volume 126 (46), 15032. Ionic conductivity [2] M. Riccò, M. Belli, M. Mazzani, D. Pontiroli, D. An extensive analysis with DC/AC Quintavalle, A. Jánossy and G. Csányi, conductivity and solid state 7Li NMR, "Superionic conductivity in the Li4C60 fullerene ab-initio polymer", Physical Review Letter, 2009, supported also by DFT calculations, Volume 102, 145901. clearly demonstrated that, in polymerised + [3] D. Pontiroli, M. Aramini, M. Gaboardi, M. fullerene Li4C60, Li ions diffuse with an Mazzani, A Gorreri, M. Riccò, I. Margiolaki and extremely high mobility, even at low T. This D. Sheptyakov, “Two-dimensional could be obtained thanks to the presence of polymerization with mixed bonding intrinsic unoccupied interstitial sites in the architecture observed in Mg2C60”, Journal of crystalline structure, connected by three- the American Chemical Society, submitted. dimensional channels (superionic

Corresponding author: Daniele Pontiroli, email: [email protected], Tel. (+39) 0521 905231

61 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

A first-principles study of defects in LiNH2 and nano-sized LiBH4 clusters E. Hazrati1, G. Brocks2, R. A. de Groot1 and G. A. de Wijs1 1Radboud University Nijmegen, Institute for Molecules and Materials, Electronic Structure of Materials, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands 2Computational Materials Science, Faculty of Science and Technology and MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands

Defects in LiNH2 clusters of LiH and LiB are more strongly destabilized than the LiBH4 clusters upon decreasing the cluster size. We present a first-principles study of native point defects As a result the desorption energies for LiBH4 clusters and dopants in LiNH2 using density functional theory. We + - increase as the cluster size decrease (see figure 2). find that Li-related defects (Lii and VLi ) are most Finally, we present some of our preliminary NMR abundant. Having diffusion barriers of 0.3–0.5 eV, they - chemical shift results for different LiBH4 surface diffuse rapidly at moderate temperatures. VH , which - terminations. corresponds to the [NH]2 ion, is the dominant species available for proton transport with a diffusion barrier of + 0.7 eV. The equilibrium concentration of Hi , which corresponds to the NH3 molecule, is negligible in bulk LiNH2. Dopants such as Ti and Sc do not affect the concentration of intrinsic defects, whereas Mg and Ca can alter it by a moderate amount [1].

Figure 2. Calculated desorption energies (without zero- Figure 1. The geometry of 12 formula units LiBH4 cluster. point energies) of LiBH4.

References

Nano-sized LiBH4 clusters [1] Intrinsic defects and dopants in LiNH2: A first- In the second part we discuss about the geometries (see principles study, E. Hazrati, G. Brocks, B. Buurman, R. A. Phys. Chem. Chem. Phys. figure 1), total energies and different decomposition de Groot and G. A. de Wijs; , 2011, 13, 6043-6052 pathways of LiBH4 clusters. The calculations show that 4 destabilization can only be achieved for very small LiBH clusters up to 12 formula units. We also find that small

Born 1983 in Iran. 2000-2004 B.Sc. in Physics, 2005-2007 M.Sc. in Condensed Matter Physics, Ebrahim Isfahan University of Technology, Isfahan, Iran. Since 2008 Ph.D. student in the Electronic Structure Hazrati of Materials group at the Radboud University Nijmegen, The Netherlands.

Corresponding author: Ebrahim Hazrati, [email protected], (+31) 24 36 52810. 63

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN PRESSURE DEPENDENCE OF LI2B12H12 FORMATION DURING DEHYDROGENATION OF LIBH4-MGH2 COMPOSITE

Hai-Wen Li1,2, Yigang Yan3, Hideki Maekawa4, Etsuo Akiba2,5, Shin-ichi Orimo6

1International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395, Japan 2International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka 819-0395, Japan 3Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland 4Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan 5Department of Mechanical Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan 6Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

2- Intermediate compound containing [B12H12] anion formed in the dehydrogenation is regarded to be responsible for the degradation of reversibility of metal borohydrides, whereas little is known about the formation of Li2B12H12 in the LiBH4- MgH2 composite. In this study, we investigated the dehydrogenation process of the LiBH4-MgH2 composite in a heating run under different hydrogen pressures. Our experimental results demonstrated that Li2B12H12 was formed during dehydrogenation, whereas depending on hydrogen pressures.

LiBH4-MgH2 Composite Formation of intermediate compound Li2B12H12 during the dehydrogenation of LiBH -MgH composite was LiBH -MgH composite attracted a great of attention due 4 2 4 2 investigated under hydrogen pressures of 0 - 2.0 MPa at to its good reversible de-/rehydrogenation performances a heating rate of 5 K/min. via reaction 1. Raman and NMR measurement results indicated that 2LiBH4 + MgH2 ↔ 2LiH + MgB2 + 4H2 (1) Li2B12H12 was formed from the individual decomposition of LiBH4 when hydrogen pressure below 2.0 MPa, The formation of MgB2, which is considered to be crucial whereas not formed under 2.0 MPa. Moreover, the for the reversibility of reaction 1, however, largely formation of Li2B12H12 was found to negatively depending depends on hydrogen pressures [1]. on the hydrogen pressure, and also influence subsequent formation of MgB2: the more Li2B12H12 formed, the less Li2B12H12 Formation MgB2 obtained (see Fig. 1) [2]. These findings indicate that suppression of the formation of intermediate compound Li2B12H12, such as by using adequate hydrogen pressures (e.g. 2.0 MPa), is of great importance for further improvement of hydrogen storage properties of LiBH4−MgH2 system.

References [1] J. J. Vajo, S. L. Skeith, F. Mertens, J. Phys. Chem. B, 109 (2005) 3719–3722.

Figure 1 Relationship between the formation of the intermediate [2] Y. Yan, H.-W. Li, H. Maekawa, K. Miwa, S. Towata, compound Li2B12H12 and final product of MgB2 under different S. Orimo, J. Phys. Chem. C, 115 (2011) 19419- pressure; He atmosphere is regarded as a hydrogen pressure of 19423. 0 MPa. The relative amounts of Li2B12H12 and MgB2 are roughly calculated from Raman spectra areas and diffraction peak areas, respectively.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Born 1976 in Zunhua, China. 1998 Bachelor in Chemical Engineering, Wuhan, China. 2000 Exchange student in Kitami, Japan. 2001 Master in Chemical Engineering from Wuhan University of Science and Technology, China. 2005 Ph.D in Materials Engineering from Kitami Institute of Technology. 2005 Post doc Orimo Lab in Institute for Materials Research (IMR), Tohoku University in Sendai, Japan. 2006 Japan Society for the Promotion of Science (JSPS) Post doc at IMR, Tohoku University. 2008 Assistant professor at IMR, Tohoku University. 2011 associate professor at Hai-Wen LI International Research Center for Hydrogen Energy, Kyushu University.

Corresponding author: Hai-Wen Li, Email: [email protected], Tel. (+81) (92) 802 3235

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

STUDY OF THE DECOMPOSITION PATH OF Al-Li-BOROHYDRIDE

Inge Lindemann1, Elsa Callini2, Andreas Borgschulte2, Andreas Züttel2, Ludwig Schultz1, Oliver Gutfleisch1

1Leibniz Institute for Solid State and Materials Research Dresden (IFW), 01069 Dresden, Germany 2Empa Materials Science & Technology , 8600 Dübendorf, Switzerland

The mixed metal borohydride Al3Li4(BH4)13 decomposes at moderate temperatures forming LiBH4 as a residual in the solid phase. In particular the desorbed species in the gas phase were under investigation using combined thermogravimetric and spectroscopic gas phase analysis. As a result the full decomposition pathway of Al3Li4(BH4)13 was revealed. It showed the formation of the single borohydrides LiBH4 and Al(BH4)3 upon decomposition.

Introduction Results The stability of borohydrides can be tuned by mixing The TG measurement confirmed the mass loss of 25 % different cations. Most conventional borohydrides are too after decomposition of Al3Li4(BH4)13. Due to the stable as e.g. LiBH4 which decomposes above 350°C. [1] metathesis process only 44 wt.% of the powder Whereas Al(BH4)3 decomposes at moderate correspond to the complex borohydride. LiCl is formed as temperatures but it is a volatile liquid at ambient a side product. The IR analysis of the desorbed gas conditions and therefore hard to handle. [2] The mixed showed strong vibrations of Al(BH4)3 and a small amount metal borohydride Al3Li4(BH4)13 shows decomposition at of B2H6. Therefore Al3Li4(BH4)13 decomposes into its moderate temperatures ~60°C. In-situ Raman component borohydrides LiBH4 and Al(BH4)3. Most of the measurements showed the formation of LiBH4 upon volatile Al(BH4)3 is evaporated. This can be reduced by decomposition accompanied by a mass loss of ~25 %. [3] the addition of porous carbon. The vapour pressure of The decomposition products in the gas phase are hard to Al(BH4)3 is smaller when adding carbon and therefore the identify and require a special experimental setup. overall weight loss is reduced by 6 wt.%.

Experimental Al3Li4(BH4)13 → 4 LiBH4 + 3 Al(BH4)3

Al3Li4(BH4)13 was prepared by metathesis reaction of References AlCl and LiBH (1:4.33) using high energy ball milling. 3 4 [1] Züttel et al., J. Power Sources 118 (2003) Another milling was carried out with 10 wt.% carbon addition. The decomposition behaviour was followed with [2] Schlesinger et al., J. Am. Chem. Soc. 62 (1940) a TG measurement using a magnetic suspension [3] Lindemann et al., Chem. Eur. J. 16 (2010) balance combined with FT-IR measurements of the desorbed gas. [4] [4] Borgschulte et al., J. Phys. Chem. C 115 (2011)

Born 8.4.1984 in Cottbus, Germany 2003-2009 Studies in Materials Science at the University of Technology in Dresden, Germany (Diploma 2009) 2006 Exchange student at Advanced Nanotechnology Ltd. in Perth, Australia Since 2009 PhD student at IFW Dresden in the group of Functional magnetic materials and hydrides, Germany

I. Lindemann

Corresponding author: Inge Lindemann, [email protected], Tel. (+49) (351) 4659 337

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

THEORETICAL AND EXPERIMENTAL INVESTIGATIONS OF KSIH3 AS A REVERSIBLE HYDROGEN STORAGE MATERIAL

Wan Si Tang1, Jean-Noël Chotard1, Pascal Raybaud2 and Raphaël Janot1

1Laboratoire de Réactivité et Chimie des Solides, UMR 6007 CNRS Université de Picardie Jules Verne 33 rue St Leu, 80039 Amiens (France) 2IFP Energies Nouvelles, Rond-point de l’échangeur de Solaize BP 3 - 69360 Solaize (France)

Abstract Potassium silicide (KSi) can absorb hydrogen to form the KSiH3 hydride. The full structure of KSiD3, solved using neutron powder diffraction (NPD), shows a short Si-D bond length of 1.47 Å. Through a combination of density functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of the KSi/KSiH3 system are determined. This system can store 4.3 wt.% of H2 reversibly within a good P–T window; a 0.1 MPa hydrogen equilibrium pressure is obtained at about 414 K. Owing to its relatively high hydrogen storage capacity and its good thermodynamic values, the KSi/KSiH3 system is a promising candidate for reversible hydrogen storage.

Introduction occupancy of 11.95% (refined composition KSiD2.87). The Si-D bond distance is 1.47 Å, close to that of gaseous KSiH3 exists as 2 allotropes: the high temperature silanes (dSi-H = 1.40 Å), a short distance very rarely seen  [1] phase with unknown hydrogen atomic positions and in solid state silicon hydrides. DFT calculations were then the low temperature phase that has a fully resolved re-made using the completely solved KSiH3 structure, structure.[2] Instead of using the wet chemistry synthesis [3] showing enthalpy and entropy values in very good route for KSiH3 , it was interesting to first form KSi and agreement with those found by experimental means then perform a direct hydrogenation on this alloy. The -1 -1 -1 (PCI/Van’t Hoff plot): 23 kJ.mol H2 and 54 J.K mol H2, theoretically calculated capacity for this KSi/KSiH3 respectively. The low entropy value in this system is system is 4.3 wt.%. Because progress in density caused by the huge disorder of the hydrogen atoms as functional theory (DFT) calculations has allowed for seen during NPD refinements (Biso = 5.19). Desorption of predicting the thermodynamic properties of hydrides, the [2] KSiH3 at 200 °C allowed the release of 4.3 wt.% of H2 completely solved KSiH3 structure was first used for with the re-formation of KSi. Several cycling tests were preliminary estimations for the KSi/KSiH3 system, giving -1 [4] made showing good capacity retention. an hydrogenation enthalpy value of -35 kJ.mol H2. Prompted by such encouraging values of capacity and Conclusion enthalpy, this system was looked into more closely as a A new synthetic route of preparing cubic KSiH3 by the hydrogen storage material, stated herein. direct hydrogenation of KSi is performed and its complete Results and Discussion structure was solved using NPD. Both DFT calculations and experimental methods show that the hydrogenation KSi was prepared by annealing its stoichiometric process is fully reversible at 373-473 K with a hydrogen elements under Ar atmosphere at 500 °C. It was then [5] storage capacity of 4.3 wt.%. This is, to the best of our successfully hydrogenated by 2 methods to form the knowledge, the first time that the hydrogen storage  Fm-3m rocksalt-type KSiH3 ( ): 1) volumetric absorption properties of this K-Si-H system have been investigated. at 100 °C for 20 hours, 2) ball-milling under H2 pressure for 90 min. A huge cell expansion occurs upon References absorption: ΔV/V ca. 50 % - the largest known value, to [1] M. A. Ring, D. M. Ritter, J. Phys. Chem. 1961, 65, 182 – 183. our knowledge, indicating a complete atomic [2] O. Mundt, G. Becker, H.-M. Hartmann, W. Schwarz, Z. Anorg. redistribution within the unit cell. A deuterated sample of Allg. Chem. 1989, 572, 75– 88. [3] M. A. Ring, D. M. Ritter, J. Am. Chem. Soc. 1961, 83, 802 – 805. KSiD3 was sent for neutron powder diffraction to solve [4] P. Raybaud, F. Ropital, US Patent No. US 2009/0302270, 2009. for its previously unknown hydrogen/deuterium atomic [5] J-N. Chotard, W. S. Tang, P. Raybaud, R. Janot, Chem. Eur. J., position: D atoms sit in the 96k Wyckoff site with an 2011, DOI: 10.1002/chem.201101865

2010 – present: Doctor of Philosophy; Laboratoire de Réactivité et Chimie des Solides, Université de Picardie Jules Verne, Amiens, France 2008 – 2010: Erasmus Mundus European Master, Materials for Energy Storage and Conversion; Université de Picardie Jules Verne (Amiens), Politechnika Warszawska (Warszaw), Université Paul Sabatier - Toulouse III, (Toulouse) 2003 – 2007: Bachelor of Applied Science (Honours); National University of Singapore (Singapore) Wan Si TANG Corresponding author: Raphaël Janot, [email protected], (+33) 322-82-79-01

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN STORAGE PROPERTIES OF LIBH4 DESTABILIZED BY IN- SITU FORMATION OF MGH2 AND LAH3

Yongfeng Liu, Yifan Zhou, Mingxia Gao, Hongge Pan

Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China.

Abstract decomposition of MgH2 first occurs to convert into Mg with hydrogen release, and subsequently catalyze the The safe and efficient storage of hydrogen is recognized reaction of LiBH and LaH to liberate additional as one of the key technological challenges for the 4 3 hydrogen and form LaB and LiH. The in situ formed widespread use of hydrogen as an energy carrier in the 6 MgH and LaH provide a synergetic thermodynamic and future. LiBH are attracting considerable attention as one 2 3 4 kinetic destabilization on the de-/hydrogenation of LiBH , of the most promising hydrogen storage media because 4 which is responsible for the distinct reduction in the of its high gravimetric (18.5 wt%) and volumetric -3 operating temperatures of the as-prepared LiBH - hydrogen density (121 kg m ). However, high 4 xLa Mg composites under 40 bar H . thermodynamic stability and large activation energy 2 17 2 barrier result in rather high operating temperatures, which References prevents it from practical applications for on-board hydrogen [1] A. Züttel, S. Rentsch, P. Fischer, P. Wenger, P. storage. The present work demonstrates a significant Sudan, Ph. Mauron, Ch. Emmenegger, J. Alloys improvement on the hydrogen storage reversibility and a Compd. 2003, 356-357, 515-520. distinct reduction on the operating temperatures of LiBH4 by introducing La2Mg17 reactive additive. The LiBH4- [2] J. J. Vajo, S. L. Skeith, F. Mertens, J. Phys. Chem. B xLa2Mg17 composite is prepared by means of 2005, 109, 3719-3722. mechanochemical reaction under 40 bar H . It is found 2 [3] D. M. Liu, Q. Q. Liu, T. Z. Si, Q. A. Zhang, F. Fang, D. that MgH and LaH are readily in situ formed during 2 3 L. Sun, L. Z. Ouyang, M. Zhu, Chem. Commun. 2011, high-pressure ball milling LiBH and La Mg . Hydrogen 4 2 17 47, 5741-5743. desorption examinations show a strong dependency of the dehydrogenation performances on the content of [4] T. Sun, H. Wang, Q. A. Zhang, D. L. Sun, X. D. Yao, La2Mg17. The as-prepared LiBH4-0.083La2Mg17 M. Zhu, J. Mater. Chem. 2011, 21, 9179-9184. composite under 40 bar H2 exhibits superior hydrogen storage properties as ~ 6.8 wt% of hydrogen can be reversibly desorbed and absorbed below 400 ºC with a two-step reaction. In dehydrogenation process, the self-

Yongfeng Liu received his PhD in Materials Science and Engineering from Zhejiang University in 2005. He then moved to National University of Singapore as a postdoctoral research fellow (working with Dr. Ping Chen). In 2007, he joined Zhejiang University as an associate professor. His research is focused on solid-state hydrogen storage materials and electrode materials of rechargeable batteries.

Yongfeng Liu

Corresponding author: Hongge Pan, [email protected], Tel: +86 571 87952615.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

THE DESTABILIZATION OF MG(BH4)2-2NAALH4 COMBINATION SYSTEM DOPED WITH TITANIUM FLUORIDES

Yanjing Yang, Mingxia Gao*, Jian Gu, Yongfeng Liu, Hongge Pan

Department of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, P.R. China

Abstract: A combination system of Mg(BH4)2-2NaAlH4 was ball-milled. The study of the structure, the hydrogen storage property of the ball-milled system and the destabilization ability of the system by addition of titanium fluorides shows that a new system of Mg(AlH4)2 and NaBH4 was formed after the ball-milling. The ball-milled system starts to desorb hydrogen at ca. 120 °C, which is from the decomposition of Mg(AlH4)2, and the total hydrogen desorbed is 9.24 wt.% up to 500 °C. The system is further destabilized by the addition of TiF3/TiF4 during the ball-milling process.

Introduction solely, which is supposed to be attributed to the in-situ formed medium product of Al decomposed from Mg(BH ) is a promising candidate for hydrogen storage 4 2 Mg(AlH ) . The effect of Al to the destabilization of NaBH materials1. However, its relatively high decomposition 4 2 4 and MgH was proved by the dehydrogenation process of temperature, poor dehydrogenation kinetic properties and 2 a ball-milled mixture of 2NaBH +MgH +2Al. harsh hydrogenation conditions cannot fulfill the 4 2 requirement for practical hydrogen storage systems. The destabilization to the system by doping Combining metal borohydride with metal alanate has TiF /TiF been proved to be an effective way to improve the 3 4 hydrogen storage properties of alkali metal Both TiF3 and TiF4 show superior destabilization to the borohydride2,3. In the present work, combination of Mg(AlH4)2, especially for TiF4. The in-situ formed Mg(AlH4)2 decomposes almost completely during ball- Mg(BH4)2 and NaAlH4 was performed by ball-milling. The structure and the hydrogen storage property of the ball- milling with the extra addition of TiF3/TiF4 in a weight fraction of 5 wt.% at room temperature. The hydrogen milled system were studied. Titanium fluorides of TiF3 desorbed from the ball-milled combination system with and TiF4 were added in the combination system during ball-milling in order to further destabilize the hydrogen TiF3/TiF4 extra added during heating was mostly from the storage system. decomposition of MgH2 and NaAlH4. The hydrogen desorbed for MgH2 and NaAlH4 was comparable to that The structure and the hydrogen storage without TiF3/TiF4 addition, being of 5.81 wt.% and 5.68 property of the ball-milled system wt.% respectively. However, the decomposition temperatures started for MgH and NaBH were further A metathesis reaction occurred during the ball-milling 2 4 reduced by the addition of TiF3/TiF4, showing close process with the transformation from Mg (BH ) to Mg o 4 2 reduced values of ca. 30 and 20 C, respectively. (AlH4)2, forming Mg(AlH4)2 and NaBH4 as the final products. The Mg(AlH4)2 in the combination product is References unstable even stored in the glove box at room 1. K. Chlopek, C. Frommen, A. Leon, O. Zabara, M. temperature. It can decompose gradually into MgH and 2 Fichtner, J. Mater. Chem. 2007, 17, 3496. Al in several months. From the dehydrogenation curves and the TPD (temperature-programmed desorption) 2. J.F. Mao, X.B.Yu, Z.P. Guo, C.K.Poh, H.K.Liu, Z. Wu, curves, it was found that three major dehydrogenation J. Ni, J. Phy. Chem. C 2009, 113, 10813. steps occurred for the ball-milled combination system 3. D.B. Ravnsbaek, T.R. Jensen, J. Phy. Chem. Solids upon heating up to 500 °C, corresponding to the 2010, 71, 1144. decomposition of Mg(AlH4)2, MgH2 and NaBH4, respectively, where MgH2 was decomposed from Mg(AlH4)2 in the first step. The hydrogen desorbed in the entire heating process is ca. 9.24 wt.%. The dehydrogenation temperatures of the latter two are lower than that of the corresponding hydride dehydrogenated

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

Mingxia Gao received her PhD in Materials Science and Engineering from Zhejiang University in 2004. She is currently an associate professor of Zhejiang University. Her research interests include advanced cathode and anode materials for lithium-ion batteries, hydrogen storage electrode alloys, hydrogen storage compounds of light metal hydrides, ceramic matrix composites.

Mingxia Gao

Corresponding author: Mingxia Gao, email: [email protected], Tel.:+86-571-87952615.

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

GRAPHENE COMPOSITES FOR NEXT GENERATION LITHIUM ION BATTERIES

Mohammad Choucaira*, John A. Stridea, Shi-Xue Doub, Shu-Lei Choub,c, Jia-Zhao Wangb,c, Hua-Kun Liub,c aSchool of Chemistry, University of New South Wales, Sydney 2052, Australia. bInstitute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, NSW 2522, Australia. cARC Centre of Excellence for Electromaterials Science, University of Wollongong, Wollongong, NSW 2522, Australia.

Abstract The facile synthesis of gram-scale quantities of graphene [1] has allowed us to develop composite anodic and cathodic materials that enhance the performance of lithium ion batteries. Such materials include nano-silicon/graphene and sulfur/graphene composites. Assessments on the materials’ electrochemical nature, structural stability, characteristics, and performance were conducted. The composites were shown to significantly improve the electrical conductivity, capacity, and cycle stability in a lithium cell compared with the bare electrodes.

Introduction were uniformly coated onto the surface of the graphene nanosheets. The S-GNS electrode contained 17.6 wt.% Rechargeable lithium-ion batteries are currently the sulfur. The materials utilization of sulfur is 96.35%. The predominant power sources for portable electronic initial discharge capacity of S-GNS composite was devices. Over the past decade, substantial efforts have −1 −1 1611mAhg at a current density of 50mAg . The initial been devoted to developing energy storage systems that capacity of the S-GNS electrode is higher than that of the can be coupled to renewable sources as a solution to pure sulfur electrode. The cycling stability of the sulfur emission and pollution challenges. More advanced graphene composite is also improved. The improvement lithium-ion batteries with high energy and high power in the capacity and cycling stability is due to graphene density still need to be achieved for the projected era of improving the conductivity of the electrode. hybrid electric vehicles [2]. Results Conclusion Lithium ion batteries are amongst the longest lasting Si/graphene composite was prepared by simply mixing of batteries available. Our work has the potential to commercially available nanosized Si and graphene. significantly improve the capabilities of emerging Electrochemical tests showed that the Si/graphene -1 consumer technologies and electronics, primarily those composite maintained a capacity of 1168 mAhg and an which need to have a reliable source of energy. average coulombic efficiency of 93% up to 30 cycles. EIS indicated that the Si/graphene composite electrode has less than 50% of the charge-transfer resistance References compared with nanosize Si electrode, evidencing the Nature enhanced ionic conductivity. The enhanced cycling [1] M. Choucair, P. Thordarson, J.A. Stride. Nanotechnology 4 stability is attributed to the fact that the Si/graphene (2009) 30. composite can accommodate a large volume charge of Si [2] J.M. Tarascon, M. Armand. Nature 414 (2001) 359. and maintain good electronic contact. Sulfur-graphene (S-GNS) composites were synthesized by heating a mixture of graphene and elemental sulfur. Sulfur particles

Short CV

PhD in Chemistry, University of New South Wales (2010).

Graduate Certificate in Research Management and Commercialisation, University of New South Wales (2009).

B Sc Nanotechnology (Honours Class 1), University of New South Wales (2007). Dr. Mohammad Choucair

*Corresponding author: Mohammad Choucair, [email protected], +61293854672. 75

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

CORROSION BEHAVIOUR OF STEEL INTERCONNECTS AND COATING MATERIALS IN SOLID OXIDE ELECTROLYSIS CELL (SOEC)

Ji Woo Kima, Cyril Radob, Aude Brevetb, Seul Cham Kimc, Yong Seok Choic, Karine Couturierb, Florence Lefebvre-Joudb, Kyu Hwan Ohc, Ulrich F. Vogta, Andreas Züttela a Div. Hydrogen & Energy, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland b CEA-Grenoble, LITEN, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France

C Dept. of Materials Science and Engineering, Seoul National University, Seoul 151-744, Republic of Korea

Introduction investigated at SOEC operating temperature (700°C) with severe anode atmosphere (pure oxygen). High temperature steam electrolysis (HTSE), which is the electrolysis of steam at high temperature, offers a Experimental promising way to produce hydrogen with high efficiency. LNF and LSMC coated stainless steel interconnects Compared with conventional water electrolysis, HTSE (Crofer 22APU, K41X) are pre-heated at 750°C for 1.5h reduces the electrical energy requirement for the and subsequently heat treated for 200h and 3000h at electrolysis and increases thermal efficiency of the power 700°C with pure oxygen flow. LNF and LSMC layers (~60 generating cycle. Among the various methods, SOEC m) were deposited through screen-printing. In this (Solid Oxide Electrolysis Cell) has been considered one configuration, especially for LNF/Crofer 22APU sample, of the efficient ways. One efficient way of reducing the Mn-Co oxide is additionally coated between LNF and raw material and fabrication cost is to lower the operating Crofer 22APU as a protective coating material. The heat temperature of the SOEC (from 1000°C to 600~700°C) treated interconnect/coating samples are analysed using thereby enabling the use of stainless steel interconnects. scanning electron microscopy (SEM) with energy Stainless steel interconnects in the SOEC stack connect dispersive spectroscopy (EDS) mapping and line each cell in series by conducting electricity, distribute scanning. For selected samples, focused ion beam (FIB) active gas to the cells and separate the hydrogen and and transmission electron microscopy (TEM) are used to oxygen between the cells. Although stainless steel investigate the corrosion mechanism of the stainless interconnects can reduce the stack cost, they also steel interconnect and the perovskite coating material. introduce several challenges that hinder commercialization of the technology. Chromium oxide- References forming alloys are preferred due to their high oxidation [1] G.Y. Lau et al., J Power Sources 195 (2010) 7540 resistance associated with low electrical resistance, thus minimizing the ohmic loss within the stacks. However, [2] R. Lacey et al., Solid State Ionics 181 (2910) 1294 chromium oxide scale can react with the anode materials [3] X. Montero et al., J Power Sources 188 (2009) 148 and form non-catalytic and/or resistive compounds. These compounds finally lead to the degradation of the SOEC performance. In order to reduce the reaction between interconnect and anode electrode and to improve electrical contact as well, LNF(La(NixFe1-x)O3), LSMC((La Sr )(Mn Co )O ) are proposed as a coating x 1-x y 1-y 3 material between anode and interconnect. In this study, material compatibility between the proposed coating materials and the commercialized interconnects is

Born Jan. 1980 in Suwon, Korea. 2004 B.S. in Advanced Materials Science & Engineering from Hong Ik University, Seoul, Korea. 2004-2011 M.S. and Ph.D. student at Dept. Materials Science & Engineering of Seoul National University, Korea. 2004-2011 Research student at Center for High Temperature Energy Materials of Korea Institute of Science and Technology, Seoul, Korea. Feb. 2011 Ph.D. in Materials Science and Engineering from Seoul National University, Seoul, Korea. Ph.D. Thesis; “A study on the correlation between hydrogen sorption behavior and microstructure of metal hydrides for hydrogen storage”. From April 2011 Post-Doc. working on solid oxide electrolysis cell, Div. of Hydrogen & Energy, EMPA, Dübendorf, Switzerland. Ji Woo Kim

Corresponding author: Ji Woo Kim, [email protected], +41 58 65 4153 77

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SOLVENT-FREE SYNTHESIS AND DECOMPOSITION OF Y(BH4)3

Arndt Remhof, Andreas Borgschulte, Oliver Friedrichs, Philippe Mauron, Yigang Yan, Andreas Züttel

Empa, Hydrogen and Energy, Dübendorf, Switzerland

The direct and solvent-free synthesis of yttrium borohydride was demonstrated by reactive ball milling of yttrium hydride in diborane/hydrogen atmosphere. The product contains only the solid elemental hydride as remaining contaminant. Yields above 75% were obtained. The product crystallizes in the cubic α-phase and releases hydrogen above 460 K. The decomposition was measured by in situ X-ray diffraction and the hydrogen release was monitored gravimetrically in conjunction with infrared gas analysis. Only traces of diborane were detected during the thermal decomposition.

Introduction The high hydrogen content of 9.1 wt%, the moderate hydrogen release temperature of about 460 K and the demonstrated partial reversibility make Y(BH4)3 an attractive candidate for hydrogen storage. In the present study we demonstrate the direct, solvent-free synthesis of Y(BH4)3 at room temperature by a gas–solid reaction of YH3 with B2H6 and H2. The thermal decomposition is measured gravimetrically and by in situ X-ray diffraction (XRD). The evolved gas is investigated via infrared (IR) spectroscopy. Results Figure 1 shows the XRD pattern of the product. All Bragg peaks can either be attributed to Y(BH4)3, YH3 or YH2. There are no unidentified reflections. The qualitative phase analysis yields 77 wt.% Y(BH4)3, 17 wt.% YH3 and Figure 1: XRD pattern of the as-prepared Y(BH4)3.

6 wt.% YH2. Given the hydrogen contents of 9.1 wt.% for Y(BH4)3, 3.3 wt.% for YH3 and 2.2 wt.% for YH2, The present study shows the applicability of reactive ball respectively, the sample contains 7.7 wt.% hydrogen. milling for the direct and solvent-free synthesis of borohydrides beyond alkaline and alkaline earth The onset of the hydrogen desorption lies at about 460 K, borohydrides. However, reactive ball milling is not in agreement with earlier reports. The maximum occurs generally applicable, as there are thermodynamic at 523 K, the integrated weight loss is 6.8%, which is well limitations. Obviously, the desired borohydride has to be below the theoretical value of 7.7 wt.%. Obviously, there stable under the milling conditions. Furthermore, the is still hydrogen contained in the residual phases. The synthesis reaction of the borohydride competes with the amount of released diborane is negligible. formation of the corresponding metal boride, as can be In-situ X-ray diffraction reveal the disappearance of the seen by the reaction of TiH2 with B2H6 to TiB2 structural Bragg reflections of Y(BH ) prior to the 4 3 Reference evolution of the reflections from the solid decomposition products, indicating that Y(BH4)3, like LiBH4, decomposes [1] A. Remhof, A. Borgschulte, O. Friedrichs, Ph. from the melt. Above 600 K the decomposition is Mauron, Y. Yan, A. Züttel, Scripta Mater, in press. completed and we observe no further change in doi:10.1016/j.scriptamat.2011.11.010. diffracted intensity until the transformation from YH3 to YH2 at 700 K.

Corresponding author: Arndt Remhof, [email protected] +41587654369 79

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HOW TO WATCH HYDROGEN DIFFUSE IN ANY ABSORBING MATERIAL Andreas Bliersbach, Gunnar K. Pálsson, Atieh Zamani and Björgvin Hjörvarsson

Department of Physics and Astronomy, Materials Physics Division, Uppsala University, Box 516, SE-75120, Uppsala, Sweden.

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.

Introduction In the 1970s Fukai et al. used soft x-ray emission spectroscopy, on hydrogenated vanadium, to observe a substantial change in the density of states located 7 eV below the Fermi energy [3]. They interpreted the observed changes as the hybridization of the 1s-state of hydrogen and one of the host lattices 3d-states. Accompanied by this hybridization is a change in the density of states in the d-band, leading to an increased Fermi level. The absorption of light by matter is strongly correlated to the available states the electrons of the absorbant can be excited to, the occupation and clearly the photon energy. As hydrogen changes the density of states within vanadium under absorption, it will induce Figure 1: Schematic illustration of the experimental approach. changes in the absorptance correspondingly. These Light at a specially chosen wavelength shines through the changes in the absorptance can be used as a gaugeable sample and is detected with a CCD camera. The sample is variable. From collected data and previous research [2] covered with Al2O3 to prevent hydrogen from going in and out we can deduce continuous and linear dependence except at a small opening at one end of the sample. between the hydrogen concentration and for a Conclusion certain wavelength. Where / stands for the transmitted intensity with and without hydrogen. A scaling for The experimental results are a spectacular realization of Fick's second law of diffusion. No other experiment with ∝ln can be estimated either by comparison with simultaneous measurement of concentration in space bulk data, if the assumption of comparable thicknesses and time is know to us at the moment. The method is in holds, or by measuring the concentration ex-situ. general applicable to all materials that absorb hydrogen Experiment and its extraordinary sensitivity enables investigations of hydrogen diffusion as a function of crystallographic To quantify hydrogen diffusion in thin films changes in the direction, strain, confinement, electronic proximity and transmitted intensity are measured with a position finite-size. sensitive camera (CCD) as a function of position and time. To ensure clearly defined and reproducible conditions, i.e. temperature, hydrogen pressure and surface cleanness, the sample is placed in a sample chamber which is bakeable up to 523 K and connected to an ultra high vacuum (UHV) system with a base pressure of 10 Pa. In addition to the mentioned features the UHV-system is used to minimize the amount of water surrounding the sample. Water, present in form of humidity, can condensate on the surface, at elevated temperatures deteriorate the sample through oxidation, block dissociation of H2 and is therefore undesirable. The Figure 2: Comparison of three different times during sample chamber is connected to the vacuum system via hydrogenation of a 50 nm vanadium sample. The initial a bellow, to reduce transport of vibrations from the rest of concentration, at 423 K, corresponds to the β-phase. The dotted the system. A schematic of the experimental setup can line marks the end of the palladium window. The H migration, be seen in Figure 1. visible as a darkening of the sample with increasing cocentration, is easily followed. 81

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

References [3] Y. Fukai et. al. Solid State Communications, 19(6):507 – 509, 1976. [1] A. Blomqvist et. al. Phys. Rev. Lett., 105(18):185901, Oct 2010. [4] A. M. Stoneham. J Phys FMet Phys, 2(3):417–420, 1972. [2] J. Prinz et. al. Applied Physics Letters, 97(25):251910, 2010.

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.

Bliersbach A,

Corresponding author: Bliersbach Andreas, [email protected], 0041 / 58 / 765 48 62.

Preparation, testing and scale-up of nanoscale, doped amide systems for hydrogen storage

Ulrich Ulmera, Jianjiang Hua, Matthias Franzrebb and Maximilian Fichtnera

a Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, D-76021 Karlsruhe, Germany

b Institute of Functional Interfaces, Karlsruhe Institute of Technology, P.O. Box 3640, D-76021 Karlsruhe, Germany

Abstract: The LiNH2 - MgH2 system has been intensively investigated as a hydrogen storage material due to its high hydrogen capacity and favourable thermodynamics1. The reversible hydrogen storage reaction has been shown to occur via the following reaction mechanism: (MgH2 + 2 LiNH2 →) Mg(NH2)2 + 2 LiH ↔ Li2Mg(NH)2 + 2 H2 5.6 wt % H2 Hydrogen sorption of the pristine system shows poor kinetics and the formation of undesirable by-products (e.g. ammonia). Therefore the effect of various additives has been studied in order to improve sorption kinetics and to minimize by-product formation. LiBH4, ZrCoH3 and KH have been reported to be effective additives to enhance the hydrogen sorption kinetics via various 2-4 mechanisms . We have found that KH and ZrCoH3 significantly improve the de-/rehydrogenation kinetics, however, the addition of LiBH4 does not improve absorption kinetics considerably. Furthermore, it was found that the addition of KH results in irreversible reactions. Testing of catalyst combinations revealed that a system composed of 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 shows excellent absorption/desorption kinetics and a reversible capacity of 4.2 wt. %. An optimal milling time of five hours was obtained by variation of ball-milling conditions, whereas too long milling durations resulted in a lower capacity and reduced reversibility. Based on optimized conditions, the system was scaled up on an industrial milling equipment in order to produce large quantity of material for testing in a tank coupled to a fuel cell.

Effect of single and combined catalysts on the de-/rehydrogenation properties

Two stoichiometric amide systems, the MgH2 + 2 LiNH2 and the 1.1 MgH2 + 2 LiNH2 systems, were prepared undoped and with the addition of 0.1 LiBH4, 0.1 KH and 3 wt.% ZrCoH3 under constant ball-milling conditions (20 h, 300 rpm). Sorption properties of the as- prepared materials were tested under constant de-/rehydrogenation conditions (desorption: 180 °C, 1 bar H2 – pressure; absorption: 150 °C, 100 bar H2 – pressure). It was shown that an excess of MgH2 (1.1 MgH2) has a positive effect on the dehydrogenation kinetics. Therefore, this system was chosen for a more thorough investigation. The effect of varying the amount of dopant was investigated. Combinations of catalysts were prepared and tested. A composition of 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 was found to exhibit the best kinetics and a good reversible capacity. The temperature effect on the rehydrogenation kinetics was investigated. A decrease of rehydrogenation time was observed, explicable by the temperature dependence of reaction kinetics (Arrhenius’s law).

Effect of ball-milling conditions on the de-/rehydrogenation properties

Ball-milling time of the 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 system was varied between 5 and 60 h. By FTIR it was observed that the conversion reaction MgH2 + 2 LiNH2 → Mg(NH2)2 + 2 LiH takes place within the first 10 milling hours. Sorption properties of the samples were investigated. Variation of milling time between 5 and 30 h does not have a significant effect on the sorption properties in terms of kinetics and capacity. However, ball-milling for 60 h leads to a decrease of capacity after cycling the material.

Scale-up of the milling process

Based on optimized stoichiometry and milling conditions, the system was scaled up in order to produce 200 g of material on an industrial vibrational ball mill. Total ball-milling time was 300 min; small samples were removed and tested after 90 and 180 min. De- and Absorption kinetics were found to have decreased as compared to the material prepared in the lab-scale. A decrease in capacity was measured during the first two cycles; the material received after 90 min was shown to have a constant capacity of 3.5 wt. %. No hydrogen was desorbed after ball-milling for 300 min. This indicates milling in a vibrational ball mill is a very high-energetic process.

References

1 Jianjiang Hu, Maximilian Fichtner, Chem. Mater., 2009, 21, 3485-3490 2 Jianjiang Hu, Maximilian Fichtner, Ping Chen, Chem. Mater., 2008, 20(22), 7089-7094 3 Xugang Zhang, Zhinian Li, Fang Lu, Hualing Li, Jing Mi, Shumao Wang, Xiaopeng Liu, Lijun Jiang, Int. J. of Hydrogen Energy 35, 2010, 7809-7814 4 G. Wu, Z. Xiong, P. Chen, Angew. Chem. Int. Ed. 2009, 48, 5828-5832

Short CV

Name: Ulrich Martin Ulmer Date of birth: May 29th, 1985 Nationality: German

Education:

Since 11/2011 Karlsruhe Institute of Technology, Institute of Nanotechnology, Karlsruhe, Germany: Research Associate in the “Energy Storage” group Research interest: Hydrogen storage, heat storage

04/2008 – 07/2011 Karlsruhe Institute of Technology, Karlsruhe, Germany: Studies of Chemical and Process Engineering (Final Grade: 2.0 good) Academic title: Diplom-Ingenieur (equivalent to Master of Science)

07/2009 – 11/2009 Indian Institute of Technology Madras, Chennai, India: Semester abroad at an Indian University

09/2004 – 02/2008 University of Applied Sciences Frankfurt, Frankfurt/Main, Germany: Studies of Biological Process Engineering (Final Grade: 1.4 very good) Academic title: Bachelor of Engineering

Work Experience:

03/2010 – 04/2010 E.ON Ruhrgas AG, Essen, Germany: Division of Natural Gas Dispatching Modelling of business contracts using various modelling tools

03/2009 – 04/2009 E.ON Ruhrgas AG, Essen, Germany: Division of Research and Development Comparing study of innovative processes to separate CO2 from raw biogas

09/2008 – 10/2008 E.ON Ruhrgas AG, Essen, Germany: Division of Energy Measurement Technology Development of a tool for the calculation of thermodynamic properties of natural gas

02/2007 – 03/2007 Dechema e.V., Frankfurt/Main, Germany: Division of Biological Process Engineering Build-up and evaluation of experiments for the biotechnological production of preservatives

08/2006 – 10/2006 The Scripps Research Institute, La Jolla, Ca, USA: Division of Arthritis Research Experiments for studying the influence of gene deletions on the bone formation in strains of mice

Scholarships:

07/2011 Ford Motor Company: Fee waiver for the participation at the Gordon Research Conference on Hydrogen-metal systems, Stonehill college, Easton, USA, July 17th – 22nd 2011

02/2008 – 02/2011 E.ON Ruhrgas AG, Essen, Germany: Participation at the program „E.ON Supports Engineering Students“(E.SIS)

Publications:

U. Ulmer, M. Franzreb, J. Hu, M. Fichtner: Preparation, testing and scale-up of doped, nanoscale amide systems for hydrogen storage The Gordon Research Conference on hydrogen-metal systems, July 17th - 22nd 2011, Easton MA, USA (Poster)

N. Taniguchi, B. Caramés, L. Ronfani, U. Ulmer, S. Komiya, M.E. Bianchi, and M. Lotz: Aging-related loss of the chromatin protein HMGB2 in articular cartilage is linked to reduced 84 cellularity and osteoarthritis Proceedings of the National Academy of Sciences, 2009, vol. 106 (4), 1181 - 1186 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

MELTING TEMPERATURE OF COMPLEX HYDRIDES

Marius van den Berg, Andreas Züttel

Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

Abstract:

To help narrowing down the selection of promising complex metal hydrides two models have been investigated. These models have been expanded in an attempt to predict key abilities of the complex metal hydrides. Especially the proposed relation between electronegativity and the melting seems promising. These results will be presented on the poster.

Hydrogen storage in Complex hydrides AlH4, NH2) the selection field narrows down to about 20- 25 possible cations. Lacking a complete, theoretical, Hydrogen is the ideal means of storage, transport and understanding of all the phenomena responsible for the conversion of energy for a comprehensive clean-energy physical abilities of these compounds only empirical concept. The availability of a safe and effective way to models and theoretical approximations are available for store hydrogen reversibly is one of the major issues for some physical abilities. Not being able to predict optimal, its large scale use as an energy carrier. Hydrogen or near optimal, atomic combinations based on those storage in solids offers a safe alternative to storage in theoretical predictions slows down the development of compressed or liquid form. However, at present, no complex hydrides. Using available data and expanding single material fulfilling all requirements is in sight. Metal existing models could lead to an enhanced model which borohydrides seem to be ideal candidates for this could predict essential abilities like melting temperature, purpose. Some preliminary studies have already shown enthalpy of fusion etc. If such a model could be found a in the past few years that this can be a promising way. next step towards finding a functional, reliable and Appealing is the high gravimetric capacity that these portable energy carrier would be completed. On this compounds can provide, storing up to 17 wt% of poster I compare various models to predict the melting of hydrogen, and the low temperature of hydrogen release, complex hydrides. close to the room temperature, a target for technological applications. Need for empirical modelling References The configuration and setup of complex hydrides allows  Buchter, F. Investigation of the existence and for an almost infinite amount of atomic combinations. the properties of liquid complex hydrides. 2006. While the complex hydride should still match the previously mentioned requirements of at least functioning  Über ein periodensystem der metallboranate. around room temperature and a good gravimetric- and Schrauzer, G.N. s.l. : Die Naturwissenschaften, volumetric density. Looking for the desired atomic 1955, Vol. 42, p. 438. configuration basically equals looking for a needle in a haystack. There are a few boundary conditions which do  F.R. de Boer, A.R. Miedema, R.Boom, allow for a narrowing of the search. As a rule of thumb it W.C.M.Mattens and A.K. Niessen. Cohesion in can be said that any metallic element beyond the 5th metals; transition metal alloys. s.l. : North period of the periodic table is too heavy to of interest. Holland Physics Publishing, 1988. Even the second half of the 5th period is actually already ISBN:0444870989. falling short of the required gravimetric density of hydrogen. With a few standard “complexes” used (BH4,

Marius van den Berg, Born: 25.06.1986, Veenendaal, Netherlands, Bachelor: Applied Physics at Fontys Universities, Eindhoven, Netherlands, 09.2005 – 03.2010, Internship : Lithography dep. at CNSE, Albany, NY, USA, 08.2007 – 01.2008, Bachelor thesis: In-situ neutron radiography of hydrogen absorption in zirconium alloys, KIT, Germany, 10.2009 – 03.2010, European Master in Material Science exploiting Large Scale facilities 09.2010 – 08.2012, 1st year: Université Rennes 1, Rennes, France, Internship: Melting Temperature of Complex hydrides, EMPA, Switzerland 04.2011 – 08.2011, 2nd year: LMU and TUM, München, Germany 09.2011 – Current

M. v.d.Berg

Corresponding author: Marius van den Berg, E-mail:[email protected] Tel. +31 6 4375 1990 85

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

MARKET POTENTIAL FOR HYDROGEN IN OFF-GRID ENERGY SYSTEMS

Michael Bielmann

Empa Materials Science and Technology, Hydrogen and Energy, Überlandstrasse 129, CH-8600 Dübendorf

Off-Grid energy systems relying on renewable sources have to solve demand – supply – mismatch. Batteries with low energy storage density do not qualify to store bulk energy over long periods of time. Hydrogen is an ideal energy carrier for long term storage. We present the cost metrics for battery storage as a function of initial cost and usage frequency. We present a model to assess the cost of energy for the hydrogen cycle. Cost of electrolysis is the mayor cost driver dominating cost of storage and fuel cell by a large margin. The solution has the potential for cheaper storage than batteries over periods of months even today.

The Off-Grid Energy Market defined by electrolyzer and fuel cell, while energy is freely scalable by the storage size. Assessing cost Off-Grid energy solutions are dominated today by Diesel competitively to other forms of system implementation generator solutions usually combined with batteries and therefore has to be abstracted from the individual size of some degree of renewable energy sources. The main the implementation to get a generalized estimate of the advantage of generators is the dispatchability of energy cost of energy through this pathway. on demand. Fuel cost and especially transport of fuel can increase the cost of energy well above 1$/kWh with Technology Limitations and Opportunities unsecure future trends. PV/Wind-Battery systems on the PEM electrolysis is available in the low to medium power other hand suffer from low production capacity usage due regime and allows for fast power modulation and part to limited battery capacity and capability of load load, a necessity for excess energy usage in renewable deference. Unused, excess production is the norm, with systems. High pressure electrolysis is a key technology sometimes as little as 20% of the total production used. to leverage on cheap storage. Currently, this technology is very expensive and with limited availability, but as caught strong attention in R&D [2]. Currently, it is the key cost driver in hydrogen hybrid systems and therefore offers opportunity for improvement. Fuel Cells today do not contribute substantially to the cost of energy in such a system, if stack life around 5000h are achieved. Current technology satisfies this criterion [3]. References [1] Bielmann, M., et al.,. Journal of Power Sources, 2011. 196(8): p. 4054-4060. [2] Clarke, R.E., S. Giddey, and S.P.S. Badwal, International Journal of Hydrogen Energy, 2010. 35(3): p. 928-935. Integrated Hydrogen Cycle for Energy [3] Kammerer, M., in Proceedings of the WHEC, D.G. By integrating the hydrogen cycle, excess energy can be Stolten, Thomas;, Editor 2010, Schriften des harvested, stored and made dispatchable over long Forschungszentrums Jülich: Jülich. periods of time[1]. The main difference to battery storage is the total decoupling of power and energy. Power is

1999 University Diploma in Solid State Physics, Fribourg, Switzerland 1999-2005 PhD student at nanotech@surfaces Labs, EMPA Thun and University of Fribourg, Switzerland From 2006 PostDoc and Project Leader, Hydrogen and Energy Labs, EMPA Dübendorf

Michael Bielmann Corresponding author: Michael Bielmann, [email protected], Tel. +41(0)587654342 87

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN SORPTION PROPERTIES OF THE MgB2 BASED CaH2 AND CaH2-CaF2 REACTIVE HYDRIDE COMPOSITES

C. Pistidda1, K. Suarez Alcantára2, F. Karimi1, C. Bonatto Minella1, L. Rude3, J. Bellosta von Colbe1, K. Taube1, T. R. Jensen3, T. Klassen1, M. Dornheim1

1 Helmholtz Zentrum Geesthacht, Max-Planck-Strasse 1, D-21502 Geesthacht, Germany, 2 MAX-Lab, Lund, Sweden. 3 University of Aarhus, Denmark

The hydrogen sorption properties of MgB2 based Reactive Hydride composites (RHC), prepared from mixtures of CaH and MgB2 and CaH, MgB2 and CaF2, were studied in detail. In order to understand the phase developments and reaction pathways, the two MgB2 based mixtures, were investigated by Powder X-ray diffraction (PXD), in situ Synchrotron Radiation Powder X-ray diffraction (SR-PXD), High Pressure titration (volumetric measurement), High Pressure Differential Scanning Calorimetric techniques (HP-DSC) and solid state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). It was found, that the enhancement of the formation of the borides CaB6 and MgB2 will be the key to develop a fully reversible hydrogen storage material with good kinetics and working temperatures.

Motivation that of the not fluorinated material (roughly 50 °C less). Upon cycling, the starting hydrogen desorption Compared to the pure borohydrides, the so called temperature decreases further. Ex situ and in situ XRD Reactive Hydride Composites exhibit full (mixtures of show the partially reversible formation of Ca(BH ) and LiBH + MgB [1.]) or partial reversibility (Ca(BH ) + 4 2 4 2 4 2 MgH , plus MgF and rests of CaF , the latter being MgB [2.]) at much more moderate conditions. The 2 2 2 2 stable during further cycling of the material. Results from reactive hydride composite Ca(BH ) + MgH is of high 4 2 2 the MAS NMR analysis indicate, that the formation of interest, as it combines a rather low hydrogenation CaB upon cycling is a key factor for the reversible enthalpy (expected to be below 50 kJ/(mol H ) [3.] with a 6 2 formation of the Ca(BH ) . theoretical gravimetric hydrogen capacity of 8.3 wt.%. 4 2 Addition of fluorine is expected to further reduce the Discussion reaction enthalpy, in case it substitutes for hydrogen in Addition of fluorine significantly enhances the formation the (BH )- groups. In addition, an enhancement of the 4 of Ca(BH ) in a CaH and MgB containing RHC. reaction kinetics is also expected [2.]. In order to fully 4 2 2 2 Furthermore, it lowers the hydrogen desorption exploit the potential of F substitution, the reaction temperature. So far the effect of F was found to be not pathways of CaH and CaH -CaF , respectively, + MgB 2 2 2 2 stable upon cycling. In this study, full reversibility was not based RHC were studied. achieved for any of the investigated systems. Experimental Results Further studies of the effects of reaction pressure and temperature have to take place, in order to find conditions to hinder the formation of the unwanted side and end products like MgF2, amorphous boron and other

-1 2 K min too stable boron compounds. New additives have to be -1 5 K min 10K min-1 found, in order to enhance the formation of the wanted boron compounds (CaB6 and MgB2).

Heat flow (exo. ) [a.u.] 3CaH2+4MgB2+CaF2 First hydrogen desorption References 100 200 300 400 [1.] U. Bösenberg et al., Acta Materialia 55 (2007) 3951- Temperature [°C] 3958 Fig. 1: DSC measurements of hydrogenated mixtures of [2.] C. Bonatto et al., Journal of Physical Chemistry (i) CaH2+MgB2 and (ii) 3CaH2+4MgB2+CaF2. C 115 (2011) 18010-18014 CaH2 and MgB2 were milled in a Spex 8000 ball mill, with a ball to powder ratio of 10:1. A fluorine containing [3.] D. J. Siegel, C. Wolverton, V. Ozolins, Phys. Rev. B compound was produced under the same conditions 76 (2007) 134102-1 – 134102-6 starting from CaH2, MgB2 and CaF2 [3.]. Zirconia balls [4.] K. Suarez Alcantára et al., J. Solid State Chem., in were used in order to reduce the contamination by Fe, press, DOI: 10.1016/j.jssc.2011.09.019 which is detrimental for MAS NMR measurements.

Fig. 1 shows the DSC traces of the two hydrogenated compounds. As can be seen, the hydrogen release from fluorinated compound starts at a temperature lower than 89

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

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 EU Collaborative Project "FLYHY" (2009 - 2011), Coordinator of the Marie Curie RTN COSY (2006 - 2010) Klaus Taube

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

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SELF IGNITING CATALYTIC HYDROGEN BURNER WITH ZERO IMMISSON

Ulrich F. Vogt1,2, Benjamin Fumey1, Noris Gallandat1 and Andreas Züttel1

1EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland 2Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

For the development of a catalytic hydrogen diffusion burner, a highly porous silicon carbide foam ceramics (SiC) with a platinum based catalytic coating has been utilized. Passive safety measures are achieved through the strict separation of hydrogen and air, feed to the reaction zone and the catalytic response of platinum for the hydrogen oxidation.

Set up of the catalytical H2 burner If hydrogen is available, the direct combustion of hydrogen for cooking and heating purposes is favorable before converting hydrogen to electricity and then to heat due to the higher efficiency and lower system complexity. For this purpose a novel catalytic hydrogen diffusion burner based on highly porous silicon carbide ceramic foams with platinum (Pt) coating has been Fig. 1: Principle of the burner setup with one catalytic coated SiC developed. The catalytic properties and the separated foam and overlying air supply system. supply of hydrogen and oxygen as air to the catalytic active area assures a high passive safety standard. Owing to the absence of hydrocarbon fuel and due to combustion temperatures just below 1000°C, no harmful exhaust gases such as CO, CO2 and NOx are emitted, achieving yet another decisive system safety benefit. The burner development has undergone two mayor steps. Initially one Pt coated porous SiC foam was used, whereby hydrogen is fed from below the SiC plate and air is supplied to the surface. A forced air stream is supplied through a web of perforated steel tubes overlaying the SiC plate as shown in figure 1. For an advancement development, a second Pt coated SiC foam was introduced above the air supply, as demonstrated in figure 2. Reaching the lower flammability limit outside of the reaction zone is so Fig. 2: Principle the advanced burner setup with primary and definitely prevented, the hydrogen slip above the secondary catalytic SiC foam and intermediate air supply reaction zone was measured to be below 100 ppm. For system. indoor applications and zero hazard emission combustion this is a decisive issue.

Dr. Ulrich Vogt is Senior Scientist at EMPA, Laboratory “Hydrogen & Energy” and leader of the group electrolysis & membranes. He received his PhD and his P.D at the Albert-Ludwig-University Freiburg, Germany. Topics of his research work are hydrogen production via “high temperature steam electrolysis”, “new membrane materials for low temperature alkaline water electrolysis” and “applying hydrogen for cooking and heating” by a novel developed catalytic hydrogen burner system. U. Vogt authored over 50 publications and he is lecturer at the University of Freiburg, with the topic “Materials for Energy Research”.

Dr. Ulrich Vogt

Corresponding author: [email protected], Tel. (+41) 58 765 4160 91

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

DYNAMICS IN SOLID AND LIQUID LIBH4

Pascal Martelli1,2, Arndt Remhof1, Andreas Borgschulte1, Philippe Mauron1, Dirk Wallacher3, Margarita Russina3, Andreas Züttel1,2

1 Empa Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland, 2 Physics Department, University of Fribourg, 1700 Fribourg, Switzerland, 3 Department Methods and Instruments, Helmholtz-Zentrum Berlin, Hahn-Meitner Platz 1, 14109 Berlin, Germany

The hydrogen dynamics of LiBH4 were studied by means of incoherent quasielastic neutron scattering (QENS). In the - solid phase, we observe rotational jump diffusion of the BH4 subunits. And we measured the diffusion coefficient in the liquid phase. This one shows an Arrhenius behavior.

- Introduction diffusion of the BH4 units is found. The measured diffusion coefficients are in the 10-5cm2/s range at The use of complex hydrides as hydrogen storage temperatures around 700 K, which is in the same order of materials is hindered by the slow sorption kinetic; magnitude as the self-diffusion of liquid lithium or the therefore it is more than welcome to study carefully the diffusion of ions in molten alkali halides. The temperature dynamical processes. The two phases of LiBH were 4 dependence of the diffusion coefficient shows an investigated by means of incoherent quasielastic neutron Arrhenius behaviour, with an activation energy of Ea=88 scattering. In the solid phase, experimental results -4 2 meV and a prefactor of D =3.1×10 cm /s [2]. reported in [1] were reproduced. The liquid phase was 0 stabilized by applying a hydrogen overpressure of 50 bar. Take-home message While there are rapid localized molecular motions of the The use of complex hydrides as hydrogen storage BH - anion, the lateral mobility of individual H atoms is 4 materials is hindered by the slow sorption kinetics. One orders of magnitude slower than that of Li+ cations. possible barrier is a slow diffusion of species. However, Thereby, the main mechanism of hydrogen transport is -5 the measured diffusion coefficient in the order of 10 cm2/s is relatively fast when compared to hydrogen diffusion in conventional metal hydrides with fast hydrogen sorption. Therefore the diffusion can be excluded as the rate limiting step for hydrogen sorption in molten LiBH4. The rate limiting step is thus yet due to other mechanisms, such as the formation or the breaking of the B-H bonds [3]. References [1] Remhof, A.; Łodziana, Z.; Martelli, P.; Friedrichs, O.; Züttel, A.; Skripov, A. V.; Embs, J. P.; Strässle, T., Phys. ReV. B, 2010, 81, 214304. [2] Martelli, P.; Remhof, A.; Borgschulte, A.; Mauron, Ph.; Wallacher, D.; Russina, M.; Züttel, A.; et Al., J. Phys. Chem. A, 2010, 114, 10117 - related to the diffusion of complete BH4 units. [3] Friedrichs, O.; Remhof, A.; Borgschulte, A.; Buchter, F.; Orimo, S. I.; Züttel, A., Phys. Chem. Chem. Phys. Left: Arrhenius plot of self-diffusivities of BH in liquid 4 2010, 12, 10919. LiBH4, Right: The right panel compares the Li diffusivities in elemental, liquid Li, and molten salts.

Results - Rotational jump diffusion of the BH4 subunits on the picosecond scale were observed in solid LiBH4. In the molten phase of LiBH4 above 553 K, translational

Born 12.05.1981 in Fribourg, Switzerland. 1998 language course in Germany. 2002 College in Math, Fribourg, Switzerland. 2007 Master in physics and math of University of Fribourg. 2011 PhD in Condensed Matter Physics from University of Fribourg, at A. Züttel lab "Hydrogen & Energy", EMPA

Dübendorf, Switzerland.

Corresponding author: Pascal Martelli, email: [email protected], Tel. (+41) (79) 354 60 44 93

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SOLID STATE ELECTROCHEMICAL CONVERSION OF CLEAN ELECTRONS TO FUELS

John TS Irvine

School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, Scotland, United Kingdom

Abstract

High temperature steam electrolysis (HTSE) is a highly efficient process for the production of pure hydrogen using a combination of electrical and thermal energy and is environmentally clean provided that the electricity used comes from a renewable source (e.g. solar, wind, wave, tidal).

Summary comparing oxygen-excess (La0.3Sr0.7TiO3+) and A-site High temperature steam electrolysis (HTSE) is a highly deficient (La0.2Sr0.7TiO3) compositions. La0.3Sr0.7TiO3+ is efficient process for the production of pure hydrogen part of the LaxSr1-xTiO3+ series (x = 0.3) and the parent using a combination of electrical and thermal energy and perovskite SrTiO3. is environmentally clean provided that the electricity used In a different approach, synthetic hydrocarbon comes from a renewable source (e.g. solar, wind, wave, fuels prepared from water and carbon dioxide are tidal). HTSE is carried out using a solid oxide electrolysis proposed as alternatives to hydrogen as an energy cell (SOEC), which is essentially a solid oxide fuel cell carrier to enable a carbon neutral energy cycle, given (SOFC) operated in reverse. That is, steam is their inherent advantages of high H/C ratio and electrochemically reduced to hydrogen gas and oxide convenience of storage and transportation. Here we ions at the hydrogen electrode (cathode), followed by demonstrate the successful synthesis of methane via oxide ion migration across the solid electrolyte to the air direct electrochemical reduction of carbon dioxide in a electrode (anode) where oxygen is evolved. This study proton conducting solid oxide electrolyzer based on considers (La,Sr)TiO3 perovskites as alternative BaCe0.5Zr0.3Y0.16Zn0.04O3-δ and composite Iron/Iron oxide electrolysis cell cathode materials to Ni/YSZ due to their cathode. chemical, dimensional, redox, thermal and mechanical stability. The influence of defect chemistry on steam electrolysis properties in particular is investigated by

John Irvine is Professor of Chemistry at the University of St Andrews. His research interests are in solid state ionics, new materials, ceramic processing, electrochemistry, fuel cell technology, hydrogen, photoelectrochemistry, electrochemical conversion and heterogeneous catalysis.

John TS Irvine

Corresponding author: John TS Irvine, Tel: +44 1334 463817, Email: [email protected]

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

SORPTION ENHANCED REACTIONS FOR RENEWABLE SYNFUELS

Andreas Borgschulte, Shunsuke Kato, Benjamin Probst, Riccardo Suter, Andreas Züttel,

Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

Starting from findings by Sabatier in 1902, it is known that CO2 can be reduced by H2 over a catalyst producing eventually methane and water. If the hydrogen is produced from renewable energy sources by electrolysis and the carbon dioxide is extracted from the atmosphere, the methane from such a process represents a CO2 neutral synthetic fuel. Apart from being a model system for the investigation of synfuels, a ready-to-go application is the upgrade of biogas using this process. Biogas produced by fermentation of biological materials contains approximately 60% CH4 and 40% CO2. Instead of separating the CO2 and releasing it into the atmosphere, it is converted into CH4 using the Sabatier process. In this talk I demonstrate the concept of the sorption enhanced reaction to improve the efficiency of process.

Sorption enhanced reaction

The reduction of CO2 by hydrogen eventually forming CO22 + 4H hydrocarbons depends on the interaction of CO2 and H2 with a catalyst surface, i.e. ad- and desorption of hydrogen, CO2 and products [1]. A significant increase of the process efficiency requires a novel concept to catalyze the complex chemical reactions. In this talk, we will utilize the link between surface and bulk to control the surface reaction. This will be done either by controlling the educts’ side, or by controlling the products’ side, both by using bulk sorption reactions (Sorption CH enhanced reaction) [2]. 4

Educts’ side Products’ side The golden rule of catalysis (Sabatier principle) is usually depicted by the volcano curve: an optimal catalyst The desorption reaction is strongly enhanced by the has intermediate binding energy to the adsorbent, removal of water by its absorption in the inner bulk of a because an enhanced bonding strength increases the sorption catalyst (see picture). As a proof-of-concept, an adsorption, but decreases the desorption reaction. Due to improvement of the reaction yield of more than 100% of the high mobility of hydrogen, it is most simple to control the Sabatier was realized using Ni-zeolite sorption the driving force of the Sabatier reaction by enhancing catalysts. the amount of chemisorbed hydrogen on the catalyst’s References surface. I will discuss the surface reactions of CO2 on various metal hydrides. [1] J. K. Nørskov, et al., Nature Chemistry 1, 37 (2009). [2] B. T. Carvill, et al. , AIChE J. 1996, 42, 2765.

Born 1973 in Lippstadt, Germany. 1998/2002 diploma and PhD in physics from Technical University Braunschweig, Germany. 2002-2005: PostDoc at the VU Amsterdam, The Netherlands, head Prof. R. Griessen, “Combinatorial Research for New Light Weight Complex Hydrides by Optical Spectroscopy.” 2005–2006: Project co-ordinator of the hydrogen storage project FuncHy, GKSS Research Centre Geesthacht, Germany, head Prof. R. Bormann, “Kinetics and Stability of magnesium hydride.” Since 2006 Group leader in the Laboratory Hydrogen & Energy at Empa, Dübendorf, Switzerland. A. Borgschulte

Corresponding author: Andreas Borgschulte: [email protected], Tel. +41 58 765 4639

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

HYDROGEN STORAGE AND DELIVERY

Gábor Laurenczy

EPFL, École Polytechnique Fédérale de Lausanne, ISIC, LCOM, Groupe de catalyse pour l’énergie et l’environnement – GCEE, CH-1015 Lausanne, Switzerland

Carbon dioxide and carbonates have been proven to be viable H2 vectors, as these widely available natural C1 sources can be easily hydrogenated to formic acid and formates in water. Although ruthenium(II) and other platinum group metal compounds are the predominant catalysts in these reactions, iron(II) can be also active, giving a new perspective to use abundant and inexpensive Fe based compounds in CO2 reduction. On the other hand, formic acid can be selectively decomposed into CO free (< 10 ppm) carbon dioxide and hydrogen. We have shown, that beside the ruthenium(II)- mTPPTS system, the iron(II) – hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex also catalyses with an exceptionally high rate and efficiency (turnover frequency, TOF= 9425 h-1mol-1; turnover number, TON= 92400) the formic acid cleavage, opening the way to use cheap, non-noble metal based catalysts for this reaction.

Introduction The same complex, formed by mixing Fe(BF4)2·6H2O and the ligand tris[(2-diphenylphosphino)ethyl]phosphine Hydrogen is one of the potential candidates to replace (P(CH CH PPh ) , PP ) has been proven very active in fossil fuels both for environmental and economic 2 2 2 3 3 formic acid decomposition: Applying 50 ppm of this reasons. H2 has the advantage to form only water when it catalyst precursor, H2 generation is carried out with is burned; and combined with fuel cell technology a very -1 outstanding turnover frequencies up to 9425 h ; and efficient conversion of the chemical energy into electricity turnover numbers as high as 92.000 were achieved. can be achieved. However, the delivery of H2 remains a challenge: conventional hydrogen storages like high Acknowledgment. Swiss National Science Foundation pressure gas containers and cryogenic liquid containers and EPFL are thanked for financial support. have weight and safety issues. Therefore a variety of new materials and methods are under development; the References H2 storage and generation currently are active areas of [1] C. Fellay, P. J. Dyson, G. Laurenczy*, A Viable research. Hydrogen-Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Results and discussion Catalyst, Angew. Chem. Int. Ed., 2008, 47, 3966.

For the first time, the reduction of CO2 and bicarbonates [2] C. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn, to formate/formic acid in the presence of an iron catalyst P. J. Dyson, R. Scopelliti, G. Laurenczy*, M. Beller*; (Fe(II)hydrido-tris[(2-diphenylphosphino)ethyl]phosphine) A Well-Defined Iron Catalyst for the Reduction of have been demonstrated. Bicarbonates and Carbon Dioxide to Formates, Alkyl Formates, and Formamides, Angew. Chem. Int. Ed., 2010, 49, 9777. [3] G. Papp, J. Csorba, G. Laurenczy, F. Joó, A Charge/Discharge Device for Chemical Hydrogen Storage and Generation, Angew. Chem. Int. Ed., 2011, in press, DOI: 10.1002/anie.201104951 [4] A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy*, R. Ludwig*, M. Beller*, Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst, Science, 2011, 333, 1733. Figure 1. View of the molecular structure of the catalyst [FeH(PP3)]BF4. Born in Békéscsaba, Hungary, 1954. Chemistry M.Sc. at the Univ. Debrecen, Hungary, 1978. PhD. in Physical Chemistry, Univ. Debrecen, Hungary, 1982. Habilitation in Inorganic Chemistry, Hungarian Academy of Sciences, 1991. Assistant professor, Dept. of Inorganic Chemistry, Univ. Debrecen, Hungary, 1984. Maître assistant, Université de Lausanne, 1991. Maître d’enseignement et de recherche, Univ. Lausanne, 1997. M.E.R., EPFL, École Polytechnique Fédérale de Lausanne, 2002. Chairman of the Management Committee of the European COST D10 Chemistry Action: Innovative Methods and Techniques for Chemical Transformation, 2001-2002. Chairman of the M. C. European COST D30: High Pressure Tuning of Chemical and Biochemical Processes, 2002- 2007. Visiting professor, Dept. of Chemistry, University of Bourgogne, France, 2007. Prof. EPFL, Gábor Laurenczy 2010. Head of Group of Catalysis for Energy and Environment – GCEE, 2010.

Corresponding author: Prof. Gábor Laurenczy, email: [email protected], Tel. (+41) (21) 693 9858 99

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

100

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

REVERSIBILITY OF H2 SORPTION IN NANOCONFINED SODIUM ALANATE

Jinbao Gao, Krijn P. de Jong, Petra E. de Jongh

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht, the Netherlands

Abstract: Nanoconfining NaAlH4 in porous materials improve the reversibility of desorption, but still capacity decay is observed during cycling. Present study showed that the large Al grains (>100 nm) formed after desorption could react with Na and H2 forming nanoconfined NaAlH4. With additional Na, almost full reversibility was obtained under mild conditions. These findings indicate that the solid state diffusion of large Al grains was not the limiting factor for hydrogen absorption; instead, it was the availability of Na that limits the reversibility of this nanoconfined NaAlH4 desorption.

Introduction nanoconfined NaAlH4/C system, large Al grains were also formed after full desorption, it is found that the solid Al Sodium alanate (NaAlH ) releases H in three steps with 4 2 has a remarkable mobility and can be reconverted into a total H content of 7.4 wt%. However, it shows slow 2 nanoconfined NaAlH under mild conditions. Further kinetics for H2 sorption, and only limited reversibility of 4 study shows that it is the availability of Na after first desorption can be achieved. In addition to the catalyst desorption hinder the rehydrogenation. With addition of doping, improved kinetics and reversibility were obtained extra Na, almost full reversibility of desorption was by confining NaAlH in nano-porous materials [1, 2]. 4 achieved (Figure 1, red curve). The unavailability of Na is However, only partial reversibility was achieved. In our mainly caused by the side reactions between Na- contribution, we discuss the factors that govern the H 2 containing species and impurity (especially O-groups) on absorption of fully desorbed nanoconfined NaAlH , and 4 the surface of carbon support. how full reversibility can be achieved. Materials and Methods

Nanoconfined 20 wt% NaAlH4 in porous carbon was desorption nanocomposited with 1.2 Al : Na = 1.3 synthesized by melt infiltration as described earlier [2]. st 1 nd Extra Na was introduced to the dehydrogenated sample 2 0.9 by desorbing physical mixture of melt infiltrated 20 wt% Al : Na = 0.8 st NaAlH4/C and NaH. Dehydrogenation was conducted in a 1 / g Sample

o 0.6 nd tubular oven at 325 C under Ar flow. Rehydrogenation 2 2 was conducted in an autoclave under 55 bar H and 150

2 wt% H o 0.3 C. H2 sorption properties were studied by temperature programmed desorption (TPD) and Sieverts apparatus. 0.0 60 120 180 240 300 360 420 Results and Discussion Temperature oC st nd Nanoconfined NaAlH4 shows improved reversibility Figure 1. 1 and 2 H2 release of nanocomposites with Al / Na molar ratios of 1.0 and 0.8 without a metal-based catalyst. However, only partial reversibility of desorption was observed (Figure 1, black curve). For bulk NaAlH4, high pressures and extended References charging times are needed to achieve partial reversibility, [1] B. Bogdanovic, M. Schwickardi, J. Alloys which has commonly be ascribed to the hypothesis that Compd., 1-9, 253 (1997) H2 absorption is limited by solid state diffusion of [2] J. Gao, P. Adelhelm, M. H.W. Verkuijlen et al., decomposition products, especially Al. Although in J. Phys. Chem. C, 114, 4675 (2010)

Born 08. 02. 1982 in Inner Mongolia, China. 2004 Science Degree in Chemistry, Shanghai, China. 2007 Master Degree in Physical Chemistry from the East China Normal University, China. 2008- now PhD student in the group of Inorganic Chemistry and Catalysis at Utrecht University, the Netherlands.

Jinbao Gao

Corresponding author: Jinbao Gao, email: mail to: [email protected], Tel. (+31) (30) 253 676 101

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

102

Development Of Alkylation Toluene With Methanol for fuel On Modified ZSM-5 Zeolites By Amphoteric surfactant

A.K.El Morsi* , A.M.A.Omar1

Nora Y Almehbad2

1 Egyptian Petroleum Research Institute. 2 University of Gizan, Kingdom Of Saudi Arabia . . * [email protected]

ABSTRACT:

Methylation of toluene over ZSM-5 zeolites modified by the introduction of Sr of 2.5 % , 5 % , 10 % by weight was studied. Experiments were performed in a fixed bed,reaction temperatures between 300-500o C and liquid hour space velocity of 4 g toluene / h.g catalyst and methanol to toluene ratio 4:1 and 0.01% of N-Octyl-N- benzyl- N-methylglycine as emulsifier . Microemulsion are stable emulsions of surfactants and co-surfactants. The wide spread interest in microemulsion and use in industrial applications are based mainly on their high solublization capacity for both hydrophilic and lipophilic compounds , large interfacial areas and on the ultra- low interfacial tensions achieved when they coexist with exess aqueous and oil phases Data for conversion of toluene and selectivity towards xylene isomers showed that 2.5 % Sr/ZSM-5 catalyst has the highest conversion of toluene at 500 o C , and the lowest p-xylene selectivity , while 10 % Sr/ZSM-5 catalyst has the highest selectivity for p-xylene production. Nevertheless , the catalyst 2.5 % Sr/ZSM-5 has the highest selectivity for m-xylene. The two catalysts 2.5% and 5% Sr/ZSM-5 give nearly the same selectivity for the three xylene isomers at all conversions obtained at the reaction conditions under study.

103 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

104

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

OPTICAL NANOANTENNAS SHINE LIGHT ON SINGLE NANOPARTICLES

Christoph Langhammer

Department of Applied Physics, Chalmers University of Technology and Insplorion AB, Göteborg, Sweden

Studying nanomaterials in situ in real time and relating details in structure and local chemistry to functionality is a key challenge in modern (nano)materials science. The exploitation of plasmonic optical nanoantennas as single particle sensing units opens up a completely unique avenue towards real time single particle in situ spectroscopy of functional nanomaterials operating in harsh environments typical for (photo-) catalysis as well as hydrogen storage.

New and more efficient implementation of nanomaterials study nanomaterials’ structure-functionality relations in requires the correlation of details in nanoparticle size, harsh environments. structure and local chemistry with the targeted Here particular focus will be put on the unique possibility functionality. Scrutinizing such systems and relating to use the INPS concept to study single functional details in their chemistry and geometry to functionality nanoparticles for hydrogen storage and hydrogen remains, however, a significant experimental challenge sensing applications3,4. The latter will be illustrated on a with two main aspects. study of the hydride formation thermodynamics of single The first one relates to the fact that the only fully Pd and Mg nanoparticles. Aspects relating to the long- satisfactory way to acquire such information is by the use standing question of the origin of slope on the equilibrium of real time in situ spectroscopy. The latter is, however, plateau will also be addressed together with a discussion experimentally very tough, in particular in harsh of the general potential of single particle optical antenna- environments (high temperatures, reactive gas based spectroscopy for materials science applications. atmospheres) such as those typical for heterogeneous catalysis or hydrogen storage applications and relates to the well-known material (structure) and pressure gaps. The second one relates to unwanted “artifacts” and averaged response as always present in ensembles of sample material and mainly caused by inhomogeneous size-distributions, and differences in the local chemistry and the local structure of (quasi-identical) nano-entities in the ensemble. Experiments aiming at the characterization of single functional nano-entities in situ have the potential to completely eliminate or significantly alleviate such problems by facilitating highly relevant systematic studies Figure 1: (a) Environmental SEM picture of truncated Au of correlations between details in nano-entity nanocone antennas functionalized with Ti/Mg/Ti/Pd “tips” for geometrical, physical and chemical properties, and single particle hydrogen storage experiments. (b) Dark-field scattering microscope image of a single nanocone antenna. functionality. Indirect Nanoplasmonic Sensing (INPS)1,2 exploits References plasmon excitations in gold nanoparticles (so-called [1] E.M. Larsson et al., Science 326, 1091-1094 (2009) optical nanoantennas) to scrutinize processes in adjacent [2] C. Langhammer et al., Nano Lett. 10, 3529–3538 complex nanomaterials in situ and in real time. Studies in (2010) gas and liquid environments are possible at high [3] T. Shegai and C. Langhammer Adv. Mater. 23, 4409- temperatures and pressures, which qualifies INPS as a 4414 (2011) valuable addition to the existing methodologies used to [4] N. Liu et al. Nat. Mater. 10, 631–63 (2011)

M.Sc. in Materials Science 2004, Swiss Federal Institute of Technology (ETH), Department of Materials, Zürich, Switzerland.

Ph.D. in Materials Science 2009, Chalmers University of Technology, Applied Physics, Göteborg, Sweden.

Current: Assistant professor, Department of Applied Physics, Chalmers University of Technology, Göteborg, Sweden C. Langhammer CTO at Insplorion AB, Göteborg, Sweden (www.insplorion.com).

Corresponding author: Christoph Langhammer, [email protected], Tel. +46 (0)31 772 3331 105

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

106

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

LONG-TERM STABILITY OF SOFC CATHODES

Werner Sitte, Edith Bucher and Andreas Egger

Chair of Physical Chemistry, Montanuniversität Leoben, 8700 Leoben, Austria

Abstract: Within this work the long-term stability of promising SOFC cathode materials with respect to the oxygen surface exchange kinetics in dry as well as in H2O- and CO2-containing atmospheres is reported: the chemical surface exchange coefficients kchem of oxygen of the perovskite oxide La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF) is compared to that of the K2NiF4-type oxide Nd2NiO4+δ (NNO) in long-term tests (t>1000 h) between 600 and 700°C in dry and humid atmospheres. Post-test XPS-depth profiles of LSCF and NNO samples, especially those which were kept in humid atmospheres show significant changes of the surface and near-surface cation compositions correlated with a strong decrease of kchem.

Overview atmosphere. XPS-depth profiles show that the decrease of k can be attributed to a change of the cation With the efforts to reduce the operating temperature of chem composition at and near the surface (La- and Sr- SOFCs to 600-750°C, the development of a number of enrichment within about 30 nm depth) together with an novel mixed conducting cathode materials has been increased oxygen content. Under comparable conditions stimulated. A main issue of these cathodes is the long- at 700°C, the chemical surface exchange coefficient of term-stability in ambient atmospheres. Within this work NNO remains perfectly stable. the long-term behaviour of the oxygen exchange kinetics of the two cathode materials La0.58Sr0.4Co0.2Fe0.8O3-δ In a humidified atmosphere at 600°C an additional strong (LSCF, perovskite structure) and Nd2NiO4+δ (NNO, decrease of kchem by a factor of 10 is observed with K2NiF4-structure) in H2O- and CO2-containing atmos- LSCF. XPS post-test analysis identifies severe Si- pheres is described. poisoning within a 10 nm thick Sr- and O-enriched surface zone as the origin of the degradation. It is Experimental assumed, in agreement with thermodynamic data, that Chemical surface exchange coefficients kchem of oxygen silicon is transported in humid atmospheres as Si(OH)4(g) are obtained from dc-conductivity relaxation experiments via the gas phase towards the surface of the sample. in long-term tests (t>1000h) in dry (Ar-O2) and humid Also for NNO a decrease in kchem by a factor of 10 is atmospheres (Ar-O2-H2O; 30% relative humidity) at 600- observed in humid atmospheres at 700°C. According to 700°C. Pre- and post-test analyses of the samples were XPS, the degradation of NNO can be interpreted by the carried out by X-ray photoelectron spectroscopy (XPS, formation of a 100 nm thick zone with significant changes Thermo MultiLab 2000, alpha 110 hemispherical in the Nd:Ni cation ratio. No indication of Si-poisoning analyzer, Thermo Electron). Elemental depth profiles was found for NNO. were obtained by Ar ion etching. The sputter rate was In this respect the use of dry air as an oxidant for IT- calibrated by use of a Ti layer. SOFCs operating at 600-700°C is recommended. Since Results and discussion Sr-containing cathodes such as LSCF seem to degrade to some extent even in a dry atmosphere, the use of The chemical surface exchange coefficient k of chem alternative Sr-free materials may be one way to increase oxygen of LSCF and NNO was monitored for t>1000h in the long-term stability of SOFCs. dry and humid atmospheres at 600-700°C. XPS-depth profiles of LSCF and NNO - especially those samples References which were kept in humid atmospheres - show significant [1] A. Egger, W. Sitte, F. Klauser, E. Bertel, changes of the surface and near-surface cation J. Electrochem. Soc., 157 (2010) B1537-B1541. compositions which are correlated with a decrease of kchem [1, 2]. [2] E. Bucher, W. Sitte, F. Klauser, E. Bertel, Solid State Ionics 191 (2011) 61-67. At 600°C, kchem of LSCF decreases at least by a factor of two within a time scale of 1000 h in a dry O2–Ar reference

Short CV Born in Salzburg (Austria); Studies of Technical Chemistry at Graz University of Technology 1990: Habilitation in the field of Physical Chemistry Since 2000: Full Professor of Physical Chemistry, Chair of Physical Chemistry, Montanuniversität Leoben Since 2004: Head of Department of General, Analytical and Physical Chemistry, Montanuniversität Leoben

Werner Sitte Corresponding author: Prof. Werner Sitte, [email protected], Tel.: +43 3842 402 4800 107

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

108

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

ELECTROCHEMICAL CHARACTERISATION OF A SMALL-SCALE ALKALINE ELECTROLYZER AND NOVEL MEMBRANES

Ivo Trajkovic1, Michal Gorbar1,2, Ulrich F. Vogt1,3, Andreas Züttel1,2

1EMPA, Materials Science & Technology, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland

2University of Fribourg, Dept. of Physics, Fribourg, Switzerland

3Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

Abstract In the industry, hydrogen is used for producing ammonia and fertilizers, refining metals, and as energy carrier. Electrolysis with alkaline electrolytes is established and proven to extract hydrogen from water. If the driving electricity is produced based on renewable resources, electrolysis can be clean and environment-friendly.

Traditionally, asbestos membranes separate the oxygen and hydrogen inside the electrolyser. The geometrical pore constitution in these membranes ensures high ion conductivity when the pores are filled with an electrolyte solution. In most industrialized countries, asbestos is declared to be dangerous to health, and hence its usage is prohibited. Thus, the overall aim is to replace asbestos by alternative materials which, in addition, work at higher temperatures and higher KOH concentrations and are not dangerous to health. Novel membranes made of these new materials shall be cheap, broadly available and be advantageous concerning ion conductivity and gas separability as well.

We present (i) a simple experimental setup with a previously built small-scale alkaline electrolyser for estimating the ion conductivity through the novel membranes, (ii) the estimated conductivity values for each novel membrane compared to asbestos, (iii) the measuring and data evaluation procedures and (iv) the measured potential drop values along the electrolyser.

Conclusively, our experimental setup has been successfully built up and used to electrochemically characterise novel membranes which will replace asbestos membranes in industrial electrolysers.

 Born on March 3, 1980 in Belgrade, Serbia

 2007, Dipl. El. Ing. / Master of Science ETH in the field of digital communications, ETH Zürich.

 2010, Dr. sc. ETH in the field of signal processing and biomedical engineering, ETH Zürich.

 2011, postdoctoral research fellow in the field of alkaline electrolysis, EMPA.

Ivo Trajkovic

Corresponding author: Ivo Trajkovic, [email protected], Tel. +41 44 823 4746 109

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

110

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

FAST IONIC CONDUCTION IN COMPLEX HYDRIDES

Motoaki Matsuo1, Arndt Remhof2, Andreas Züttel2, Shin-ichi Orimo1

1 Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan 2 Empa, Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

Complex hydrides exhibit various energy-related functions such as hydrogen storage, microwave absorption, and neutron shielding. Furthermore, we recently discovered another novel energy-related function, that is, lithium fast-ionic conduction, suggesting that complex hydrides can be a potential candidate for solid electrolytes for lithium ion batteries. A review of our recent progress in the development of lithium fast-ionic conductors of complex hydrides is presented.

Lithium Fast-Ion Conduction in LiBH4 K) after melting, respectively, suggesting the possible ionic liquids.4 The ion conductivity of LiBH4 increases by three orders of magnitude at 390 K due to its structural New Complex Hydride in LiNH2–LiI system transition from the orthorhombic low-temperature The new complex hydride, Li3(NH2)2I, with an (LT-)phase to the hexagonal high-temperature (HT- 5 unique double-layered structure was synthesized. )phase1. From the application point of view, it is Because of the characteristic structure, Li3(NH2)2I highly desirable to enhance the conductivity of exhibits fast-ion conductivity of 1 × 10–5 S/cm at LiBH4 at RT. 296 K with lithium ion transport number of almost Enhanced Conductivities in LiBH4–LiI and unity although the conductivities of the host –9 –8 LiBH4–LiNH2 systems materials LiNH2 (3 × 10 S/cm) and LiI (3 × 10 S/cm) are very low. The enhanced conductivities in LiBH4–LiX (X = Cl, 2 3 Br, and I) and LiBH4–LiNH2 have been demonstrated. In LiBH4–LiI, the HT-phase of LiBH4 This research was funded by KAKENHI (22760529) can be stabilized below 390 K by forming solid and the Integrated Project of ICC-IMR. solution phase with a wide range of compositions; as a result, the conductivity (4 × 10−5 S/cm) becomes three orders of magnitude higher than References that of pure LiBH (2 × 10−8 S/cm) at RT. In the 4 [1] M. Matsuo et al., Appl. Phys. Lett. 91, 224103 (2007). case of LiBH4–LiNH2, Li2(BH4)(NH2) and – [2] M. Matsuo et al., Appl. Phys. Lett. 94, 084103 (2009). Li4(BH4)(NH2)3 both with combinations of [BH4] and – [NH2] complex anions, show fast-ion conductivities [3] M. Matsuo et al., J. Am. Chem. Soc. 131, 16389 −4 of 1 × 10 S/cm at RT because of new occupation (2009). + sites available to Li ions. Furthermore, the total ion [4] M. Matsuo and S. Orimo, Adv. Energy Mater. 1, 161 conductivities of Li2(BH4)(NH2) and Li4(BH4)(NH2)3 (2011). reach 6×10–2 S/cm (378 K) and 2×10–1 S/cm (513 [5] M. Matsuo et al., Chem. Mater. 22, 2702 (2010).

Born 1977 in Kanazawa, Japan. 2008 Ph.D. degree in materials science Tohoku University. 2008 Postdoctoral Fellow, Institute for Materials Research, Tohoku University. 2010 Assistant Professor in Orimo group. Research interests: fundamental, physical, and chemical properties of lightweight hydrides; especially solid-state ionics and hydrogen storage.

http://www.hydrogen.imr.tohoku.ac.jp/

Motoaki Matsuo

Corresponding author: Motoaki Matsuo, Email: [email protected], Tel.: +81-22-215-2094

111

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

112

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

CONTROLING THE HYDROGEN DESORPTION OF LIBH4

1Yigang Yan, 1Arndt Remhof, 2Sonjong Hwang, 3, 4Hai-wen Li, 1Philippe Mauron, 5Shin-ich Orimo, 1Andreas Züttel 1EMPA, Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland 2Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA 3International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395, Japan 4International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka 819-0395, Japan 5Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

The dehydrogenation pathway is crucial for the applicability of LiBH4 as a hydrogen storage material. We discuss and compare the different dehydrogenation pathways of LiBH4 according to the thermodynamic parameters and show the experimental ways to realize them. Two dehydrogenation pathways of LiBH4, i.e. the direct decomposition into boron and the decomposition via Li2B12H12, were realized by choosing appropriate conditions, respectively.

Lithium borohydride bar at 873 K and 10 bar at 700 K, LiBH4 is forced to decompose into Li B H . In a lower pressure range of The results of PCT measurement by Ph. Mauron suggest 2 12 12 0.1 to 10 bar at 873 K and 800 K, both two a one-step direct decomposition of LiBH into boron [1], 4 dehydrogenation pathways are observed. Raman according to reaction (1). Based on the observation of 11 spectroscopy and B NMR MAS measurement confirm Li B H by Raman spectroscopy and 11B NMR 2 12 12 the formation of intermediate phase Li B H and measurements [2, 3], LiBH is considered to decompose 2 12 12 4 amorphous boron. according to reaction (2). The knowledge of the thermodynamic properties of the LiBH → LiH + B + 3/2H (eq.1) 4 2 hydride and its possible decomposition products and LiBH4 → 5/6LiH + 1/12Li2B12H12 + 13/12H2 (2) intermediates allows choosing the decomposition pathway by tuning the external parameters such as Thermodynamic consideration pressure and temperature. Therefore, unwanted by- The enthalpy change of the decomposition reaction into products or boron sinks that prevent reversibility can be

Li2B12H12 (reaction (2)) is predicted to be 56 kJ/mol H2 [4], circumvented. which is approximately 18 kJ/mol H2 lower than that of the direct decomposition (reaction (1)). This suggests References that by applying appropriate external pressures, the [1] Ph. Mauron, F. Buchter, O. Friedrichs, A. Remhof, reaction (1) can be supressed and the decomposition of M.Bielmann, C. N. Zwicky, A. Züttel, J. Phys. Chem. LiBH4 will be forced via Li2B12H12 according reaction (2). C 112, 906 (2008). [2] S. Orimo, Y. Nakamori, N. Ohba, K. Miwa, M. Aoki, S. The decomposition reactions of LiBH at 873 K in 4 Towata, A. Züttel, Appl. Phys. Lett. 89, 021920 different hydrogen external pressure of 50, 10, 2 and 0.1 (2006). bar were carried out. On the other hand, the temperature [3] S. J. Hwang, R. C. Bowman, J. W. Reiter, J. dependence of the decomposition was investigated by Rijssenbeek, G. L. Soloveichik, J.-C. Zhao, fixing the H pressure as 10 bar and adjusting 2 H.Kabbour, C. C. Ahn, J. Phys. Chem. C 112, 3164 temperature from 873 to 700 K. (2008). Dehydrogenation pathway [4] N. Ohba, K. Miwa, M. Aoki, T. Noritake, S. Towata, Y.Nakamori, S. Orimo, Phys. Rev. B 74, 075110 The two reaction pathways were realized at approximate (2006). conditions, respectively. By applying a H2 pressure of 50

Born 14. 2. 1980 in Hubei Province, China. 2001 Bachelor in Chemical Engineering, Chengdu, China. 2004 Master in Chemical Process Equipment from Sichuan University, China. 2007 Ph.D in Material Science from Sichuan University. 2008 Post doc Orimo Lab in Institute for Materials Research (IMR), Tohoku University in Sendai, Japan. 2009 Japanese Society for the Promotion of Science (JSPS) Post doc at IMR, Tohoku University. Research field: Fundamental properties and hydrogen storage functions of metal borohydrides. 2011 Post doc Züttel Lab in EMPA Swiss Federal Laboratories for Materials Science and Technology, Switzerland. YIGANG YAN

Corresponding author: Yigang Yan, email: [email protected], Tel. (+41) 58 765 4082 113

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

114

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

VERIFICATION OF THE ENTHALPY-ENTROPY COMPENSATION EFFECT IN METAL HYDRIDES C. Boelsma1, L.P.A. Mooij1, R. Griessen2, and B. Dam1

1DelftChemTech, Delft University of Technology, Julianalaan 136, 2600 GA Delft, The Netherlands 2Department of Physics and Astronomy, VU University Amsterdam, De Boelelaan 1801, 1081 HV Amsterdam, The Netherlands

The enthalpy-entropy compensation effect is extensively discussed in literature. Although it is observed in many experiments (e.g. in the analysis of reactions considering proteins or metal hydrides), it is not clear whether this effect has a physical or a statistical origin. For situations with a compensation temperature close to the harmonic mean measurement temperature, it is often impossible to distinguish a possible physical origin from a statistical one. We present and demonstrate a method to verify this kind of compensation in metal hydrides. We show, without using any statistical analysis, that it is possible to determine the compensation temperature with a much higher accuracy than the involved temperature range. This indicates a non-statistical origin of the effect.

Introduction sample compositions from one measurement [3]. This technique allows us to obtain PTIs at one temperature T The enthalpy-entropy compensation effect, characterized for many Mg Ti H compositions, all measured at the by the compensation temperature T , is known for y 1-y x comp same conditions. From these PTIs, the pressure plateaus more than a century. It is observed in the analysis of the with P can be obtained at different T. With use of the thermodynamics of many reactions, for example in the eq Van ‘t Hoff relation, we are able to obtain the (change of) (de)formation of metal hydrides [1]. Since in many of the enthalpy H and entropy S for each composition. These observed compensations the obtained T is close to Δ Δ comp parameters show a correlation, known as enthalpy- the harmonic mean temperature of the performed entropy compensation, which can be expressed as measurements, a statistical origin cannot be distinguished from a physical one. Therefore the true ∆! = !!"#$∆! + ! nature of the compensations is questioned [1,2]. where φ is constant. Inserting this expression in the Van ‘t Nevertheless, for compensations in metal hydride Hoff equation results in two situations. At T=Tcomp, Peq is systems we present a method to verify whether the the same for all y. At T≠Tcomp, Peq is different for each y; compensation has a statistical origin or not. We there is a spread in Peq and this spread increases when demonstrate this method with use of MgyTi1-yHx, that increasing the difference between T and Tcomp. shows a compensation for 0.6 < y < 0.8 with Tcomp close the harmonic mean temperature of the performed We investigate this temperature dependence of the measurements. pressure plateau spread in the PTIs of MgyTi1-yHx, which are obtained without applying any statistics on them. This The Method allows us to determine Tcomp with a precision much higher To determine the thermodynamics of each fraction y in than our measurement temperature range. From our MgyTi1-yHx, we need two ingredients: 1) pressure-optical analysis we conclude that there exist a non-statistical transmission-isotherms (PTIs) and 2) the Van ‘t Hoff origin of the compensation effect. relation given by: References !!" ∆! ∆! !" = − [1] Andreassen et al., J. Phys. Chem. B, 2005, 109, !! !" ! 3340-3344 The PTIs, identical to pressure-composition-isotherms [2] Cornish-Bowden, J. Biosci., 2002, 27, 121-126 (PCIs), are obtained with hydrogenography, an optical technique that can produce PTIs of thousands different [3] Gremaud et al., Adv. Mat. 2007, 19, 2813

2004 – 2008: Bachelor Physics and Astronomy, VU University Amsterdam; 2008 – 2011: Master Physics, Spec. 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], 0031-152782676 115

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

116

6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

FUNCTIONALIZED METAL-ORGANIC FRAMEWORKS FOR CHEMICAL HYDROGEN STORAGE

Samir Barman,a Arndt Remhof,b Oliver Friedrichs,b Thomas Fox,a Philippe Mauron,b Olivier Blacque,a Andreas Züttel,b Heinz Berkea aUniversity of Zurich, Institute of Inorganic Chemistry, CH-8057 Zurich, Switzerland. bEmpa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div.Hydrogen & Energy, CH-8600 Dübendorf, Switzerland.

A strategy for incorporating the ammonia borane (AB) derivatives as functional spacers of the framework materials namely DMOF-1-NH2 and IRMOF-3 following gas solid phase reactions were investigated.[1] From the hydrogen desorption experiments of the AB functionalized MOFs, it was evidenced that in some special circumstances room temperature hydrogen release from AB derivatives could be achieved.

Introduction using FTIR spectroscopy, ICP-AES analysis and solid state 11B, 15N, 2H NMR spectroscopic The extraordinary high gravimetric H2 content analysis. (19.6 wt %) and moderate operating temperature of ammonia borane (NH3BH3) stimulated research Hydrogen desorption efforts to change it into a practical H storage 2 As expected both the AB functionalized MOFs material.[2] Among the several strategies known showed onset of hydrogen release at below 50 °C. to improve hydrogen desorption kinetics, Our investigation supports the fact that strong nanoconfinement is of special interest. Hydrogen confinement effect should permit to achieve release is supported by decreasing the pore size lowered onset temperature even with relative in combination with a metal catalyst or ligand large pore size materials. More interestingly, one deficient metal sites. The increased confinement of these AB functionalizes MOFs show room effect of the reduced pore size is exploited. temperature hydrogen release. It is hypothesized Incorporation of ammonia borane that in addition to the confinement, a special structural effect are thought to play an important derivatives in MOFs role for such an abnormal behaviour. Room temperature in situ PXRD measurements were carried out to investigate the structural References responses of the dry MOFs under diborane (B2H6) [1] Z. Wang, K. K. Tanabe, S. M. Cohen, Inorg. atmosphere. Which further allowed us to Chem. 2009, 48, 296; J. L. C. Rowsell, O. M. standardize a precise reaction condition where AB Yaghi, J. Am. Chem. Soc. 2006, 128, 1304. functionalized materials could be prepared. Further evidence of the incorporation of covalently [2] F. H. Stephens, V. Pon, R. T. Baker, Dalton bound AB derivatives in MOFs were corroborated Trans. 2007, 25, 2613.

Born 24. 02. 1983 in Dubrajpore, India. 2001-2005 B.Sc. (Hons.) in Chemistry, Vidyasagar University, India. 2005-2007 M.Sc in Chemistry, Indian Institute of Technology, Bombay, India. Since 2008 PhD student in the group of Prof. Dr. Heinz Berke, at the University of Zurich, Switzerland.

Samir Barman

Corresponding author: Samir Barman, email: [email protected], Tel. (+41) (44) 635 4696

117 6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

118

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

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 system, which can facilitate efficient utilization of unevenly distributed renewable energy. A major challenge in a future ‘hydrogen economy’ is the development of a safe and efficient means of hydrogen storage, in particular for mobile applications. Here we report an overview of our recent results within different experimental approaches for (i) synthesis of novel metal borohydrides and studies of their properties, (ii) tailoring materials properties by anion substitution or nano-confinement, and (iii) in situ powder X-ray diffraction for studies of hydrogen release and uptake reactions.

Metal borohydrides Nanoconfinement We have recently explored mechano-chemical and Nanoconfined chemical reactions has a high degree of solvent based methods for synthesis of new hydrides and reversibility and stability and possibly also improved have discovered new series of metal borohydrides thermodynamic properties as compared to bulk MM’BH4, typically containing an alkali metal, M, and a conditions. This new scheme of nanoconfined chemistry di- or tri-positive cation, M’. Apparently, the structural may have a wide range of interesting applications in the complexity increase with the increasing size of the alkali future, e.g. within the merging area of chemical storage metal and also the tendency to form mixed chloride- of renewable energy. Reversible chemical reactions can borohydride compounds and ternary chlorides. The latter take place at the nano-scale, e.g. LiBH4-MgH2 system or illustrate a fundamental drawback for mechano-chemical NaAlH4 in Ti-nano-particle functionalised nano-porous synthesis method [1,2], which, on the other hand, has carbon aerogels. Systematic studies where pore size and lead to the discovery of a new type of combined fast Li- scaffold surface area are varied will be presented. ion conductors and H2-storage materials based on heavy In this talk, we will also illustrate that in situ powder X-ray metals. Systematic ball-milling synthesis experiments will diffraction is a unique, sensitive and informative also be presented, which reveal new information on the technique for probing gas-solid reactions. We conclude, wide parameter space for this synthesis technique. Both that the chemistry of hydrogen is divers and a lot still synthesis and hydrogen release and uptake reactions remain to be discovered with a hope to discover the often occur via several coupled chemical reactions, which ‘magic’ hydride that may become the successor of can be utilized to stabilize boron in the solid state. gasoline. A fascinating structural chemistry is discovered within metal borohydrides, e.g. interpenetrated ‘MOF-like’ References networks or zeolite-type structures with up to 30% ‘empty’ [1] Rude, et al, Physica Status Solidi 2011, 208(8) 1754. space in the porous structures with chemical bonding [2] Ravnsbæk, et al, Z. Kristallogr. 2010, 225, 557–569. ranging from ionic to more covalent and containing composite polynuclear complex anions in the solid state [3] Filinchuk, et al, Angew. Chem. Int. Ed. 2011, DOI: [2]. Magnesium borohydrides form the most open- 10.1002/anie.201100675. 3 structured material ( = 0.55 g/cm ), which is the first [4] Nielsen, et al, Nanoscale, 2011, 3, 2086 (review). hydride storing both chemically bonded hydrogen (14.9 wt% H2) and additionally physisorped molecular [5] Nielsen, et al, ACS Nano, 2011, 5, 4056–4064. hydrogen, i.e. Mg(BH4)20.80H2, m = 17.4 wt% H2 [3].

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 and a Carlsberg research stipend (2005) form the Carlsberg Foundation. His research interests are focused on synthesis, structural, physical and chemical properties of inorganic materials and utilisation of synchrotron X-ray radiation for materials characterization. Corresponding author: Torben R. Jensen, [email protected], +45 8942 3894

119

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

120

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

MECHANOCHEMICAL REACTION OF SODIUM BOROHYDRIDE WITH TRANSITION METAL FLUORIDES

Georgios N. Kalantzopoulos, Stefano Deledda, Bjørn C. Hauback

Department of Physics, Institute for Energy Technology, Instituttveien 18, NO-2007, Kjeller, Norway

Abstract

In this study we are exploring the effect of the mechano-chemical reaction between NaBH4 and transition metal fluorides. Pressure and temperature evolution have been monitored during the mixing of the materials. The compounds have been examined by TPD and DSC studying the gas release temperature and melting temperature respectively. The structure of the ball milled compounds in elevated temperatures was investigated by In-situ PXD.

Introduction detection analysis. Measurements were carried out in vacuum (10-5 mbar) between RT and 600 oC. High Ball milling techniques are widely used as a synthesis temperature powder x-ray patterns were collected using technique of potential hydrogen storage materials. The an imaging plate system (MAR345) with an exposure grain-size reduction process that takes place during time of 30 s. continuous and vigorous fracturing occurs from mixing of powder particles enhancing the possibility of interaction between them [1]. The produced compounds can exhibit Results altered thermodynamic properties. The energy offered Results for 4 NaBH4 + TMF3 (TM = Fe, Mn, Ti) will be due to the mechanochemical reaction can favour the presented. Data from diffraction analysis will be formation of new phases [2]. Borohydrides are materials discussed with respect to phase selection processes that that recently have attracted lot of attention as potential occur during ball-milling and during in-situ heating of the hydrogen storage materials. The mixture of borohydrides as-milled powders. DSC and TPD show changes in the with other compounds can lead to the formation of thermal stability of the milling products, depending on the phases with attractive thermodynamic properties [3]. TMF3 used as a starting material. The effect of the different TMF on the selective release of H instead of 3 2 B2H6 which is investigated by residual gas analysis will Experimental be also discussed.

Powder mixtures of NaBH4 and transition metal fluorides with 4:1 ratio were ball-milled in Ar using a Fritsch P6 planetary ball mill. The ball-to-powder ratio was 100:1. References Differential Scanning Calorimetry (DSC) measurements [1] Zaluska, et al., J. Alloys Compounds, 288, (1999), were performed with a SensysDSC from Setaram. 217. Samples were placed in high-pressure capable stainless o [2] Zhang, et al., J. Alloys Compounds, 393, (2005), 147. steel crucible (pmax = 500 bar; Tmax = 600 C) and data were collected upon heating and cooling in Ar flow (15 [3] Hai-Wen Li, et al., Energies, 4, (2011), 185-214. ml/min) using a constant rate of 2 oC/min. Gas release was examined using a home-made apparatus for Thermal Programmed Desorption (TPD) coupled with a MULTIVISION IP detector system for residual gas

121

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

24.11.2006 Graduation from Materials Science & Engineering, University of Ioannina, Greece

20.02.2009 – 15.05.2009 Visiting Researcher, Max Planck Institute for Metals Research, Stuttgart, Germany, Dr. Michael Hirscher group Ph.D in Physics, University of Calabria, Italy, ph.D Dissertation in 09.12.2009 “Hydrogen Physisorption Processes on Porous Solids”. Georgios Supervisor: Prof. Raffaele G. Agostino Kalantzopoulos 10.12.2009 – 01.10.2010 Post-Doctoral fellow, University of Calabria, Italy

02.10.2010 till present Post-Doctoral fellow, Institute for Energy Technology (IFE), Department of Physics, Kjeller, Norway under the supervision of Prof. Bjørn C. Hauback.

Member of the EU project: SSH2S.

Corresponding author: Georgios Kalantzopoulos, [email protected], Tel.: +47 6380-6181

122

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

METAL HYDRIDE BASED PREHEATER FOR HT-PEM FUEL CELLS

Marc Linder, Inga Utz, Niko Schmidt, Christian Brack, Antje Wörner German Aerospace Center – DLR e.V., Institute of Technical Thermodynamics, Stuttgart Pfaffenwaldring 38-40, 70569 Stuttgart, Germany

This work focuses on the application of thermochemical energy storage for the start-up process of high temperature PEM fuel cells in order to avoid additional external measures such as electrical heater or catalytic burners.

Thermochemical Heat Storage additional benefit of this technology is its lossless storage of heat as long as the reactants are separated. The dissociation of a compound (AB) into two phases (A and B) by means of thermal energy can be used as heat storage if the products of the reaction are stored separately. The heat is released again if the two reaction Operation Principle partners are brought together: In Figure 1 the operation principle of the thermochemical preheater is shown. During start-up (left) hydrogen is endothermic supplied by the available supply connection of the fuel AB A + B ⇌ cell with its nominal operation pressure (pFC). According exothermic to the chemical equilibrium, the metal hydride heats up This general principle is investigated at DLR with various and releases heat at the respective start-up temperature gas-solid reactions operating at different temperature (Tmin). levels ranging from 100 °C to around 1000 °C for industrial waste heat utilization as well as solar ln p ln p MeH QWaste Heat (FC) applications. In case of oxygen or water vapour as reaction partner an open process can be realized, H2 H2 p Q p whereas for hydrogen a closed system is necessary. FC Preheating FC

MeH Application for HT-PEM Fuel Cells T RT 1/T T T 1/T High Temperature PEM fuel cells operating at min nom min temperatures between 120-180°C offer several Figure 1: Operation Principle of TC preheater advantages such as improved CO tolerance, reduced system complexity (no humidification) and simplified Since the nominal operation temperature (Tnom) of the waste heat removal due to higher operation temperatures HT-PEM fuel cell is higher than the necessary start-up in comparison to PEM fuel cells. However, in order to temperature, waste heat can be used to charge the avoid liquid water in the fuel cell preheating is required thermochemical heat storage. Thereby the desorbed which is in most cases based on electrical heaters and hydrogen can be released to the hydrogen supply consequently demands additional battery packs, connection of the FC (pFC, Figure 1, right). A proof of compare [1]. Therefore, this work focuses on the principle of this preheating concept will be shown application of a thermal energy storage that is charged including thermodynamic and kinetic analysis of suitable during fuel cell operation and discharged during the metal hydrides. preheating process. Due to the available hydrogen References supply for the fuel cell, a thermochemical heat storage (TC) based on metal hydrides seems promising. An [1] S. J. Andreasen, S. K. Kaer, Int. J. Hydrogen Energy 33, 4644-4664 (2008)

Dr.-Ing. Marc Linder graduated in Energy Engineering at the University of Stuttgart in 2006. During his PhD work at the Institute of Nuclear Technology and Energy Systems (IKE, University of Stuttgart) he was working with closed and open sorption systems based on metal hydrides. As postdoctoral research fellow at IKE he was responsible for the metal hydride laboratory and the laboratory for thermophysical properties of solids at high temperatures. In 2010, he joined the Institute of Technical Thermodynamics at the German Aerospace Center (DLR e.V.) where he is managing the research area Chemical Energy Storage with core activities on chemical hydrogen storage and the thermochemical storage of heat at different temperature ranges for solar applications as well as industrial waste heat utilization. Marc Linder

Corresponding author: Marc Linder, [email protected], + 49 (0) 711 6862 8034 123

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

124

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

TOWARDS UNDERSTANDING THE MOLECULAR REARRANGEMENTS IN COMPLEX HYDRIDES

Dr. Michael Felderhoff

Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany

Abstract After more than a decade of intense research on NaAlH4 doped with transition metals as hydrogen storage material, the actual mechanism of the decomposition and rehydrogenation reaction is still unclear. Early on, monomeric AlH3 was named as a possible transport shuttle for aluminium, but never observed experimentally. Trapping of volatile AlH3 produced during the decomposition of undoped NaAlH4 by an adduct of sodium alanate and crown ether is 27 reported. The resulting Al2H7 anion was identified by solid-state Al NMR spectroscopy. Based on this indirect evidence of volatile alane, a simple description of the processes occurring during the reversible dehydrogenation of NaAlH4 and related compounds is presented.

Crown ether adducts of complex hydrides

The crown ether adduct Na(18C6)AlH4 can be produced by ball milling of a mixture of both educts. This complex is completely transformed into Na(18C6)Al2H7 by trapping 27 AlH3 which can be observed with Al NMR-spectroscopy not exceeding 343K. This trapping is regarded as strong evidence of volatile alane on pristine NaAlH4. Based on this experimental evidence a simple description of the catalysed dehydrogenation and hydrogenation of sodium alanate is proposed. In this mechanism volatile

AlH3 plays the central role as transport species for Simplified mechanism of the decomposition of NaAlH4 aluminium. based on volatile AlH3 as transport species. The role of the catalyst in doped NaAlH4 is limited to facilitating the decomposition and formation of alane during the dehydrogenation and rehydrogenation. References [1] Michael Felderhoff, Bodo Zibrowius, Formation of

Al2H7 anions - indirect evidence of volatile AlH3 on sodium alanate using solid-state NMR spectroscopy; Phys.Chem.Chem.Phys. 2011, 13, 17234.

born 1960 PhD 1993 University Essen 1993-96 scientific co-worker, University Essen 1996-97 scientific co-worker, Eberhard Karls University, Tübingen 1997-98 scientific co-worker, University Osnabrück since1999 scientific co-worker, Max-Planck-Institut für Kohlenforschung, Department of Heterogeneous CatalysisAbteilung

Michael Felderhoff [email protected], +(49 (0)208 306 2448

125

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

126

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

FIRST AND SECOND UNIVERSALITIES – PHENOMENA AND MODEL- LING

Klaus Funke

University of Muenster, Institute of Physical Chemistry

Abstract

Ion-conducting materials with quite different kinds of disordered structures have been found to show an unexpected degree of similarity in their broadband conductivity spectra. In particular, two surprising “universalities” have been detected. One of them, the “first universality”, is a fingerprint of activated hopping along interconnected sites, while the other, the “second universality”, reflects non-activated, strictly localised movements of the ions. The former is observed at sufficiently high temperatures, while the other is found at sufficiently low ones, e.g., in the cryogenic temperature regime. In either case, rate equations have been found that reproduce the relevant time dependence of the ion dynamics as well as the spectra themselves. Therefore, these equations may be regarded as manifestations of the underlying common laws. At the same time, they also form a sound basis for understanding and visualising the phenomena in terms of simple physical pictures.

Reference:

See, e.g., K. Funke, R.D. Banhatti, D.M. Laughman, L.G. Badr, M. Mutke, A. Šantić, W. Wrobel, E.M. Fellberg, C. Bier- mann, “First and Second Universalities: Expeditions Towards and Beyond”, p. 459 – 518 in: Progress in Physical Chem- istry Vol. 4, “Ionic Motion in Materials with Disordered Structures – From Elementary Steps to Macroscopic Transport”, Klaus Funke, Ed., Oldenbourg, München, 2011

Klaus Funke, short CV:

Ph.D. with Wilhelm Jost, University of Göttingen (1970); Professor, Institute of Physical Chemistry and Electrochemistry, University of Hannover (1979 - 1985); Founding Editor of SOLID STATE IONICS (since 1979); Walter Schottky Award of Deutsche Physikalische Gesellschaft (1980); Successor to Ewald Wicke, Institute of Physical Chemistry, University of Münster (1985, retired 2010); Wilhelm Jost Memorial Lecture (1996); Chairman of SFB 458 (Collaborative Research Center), “Ionic motion in materials with disordered structures”, (Jan. 2000 - Dec. 2009); Chairman, Association of Ger- man Chemistry Professors (2001 - 2003); President, Deutsche Bunsen-Gesellschaft für Physikalische Chemie (2003 and 2004); President, International Society of Solid State Ionics (2007 – 2009)

Corresponding author: Prof. Dr. Klaus Funke, [email protected], phone ++ 49 – 251 - 8323418

127

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

128

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

VIBRATIONAL AND STRUCTURAL CHARACATERIZATION OF BOROHYDRIDES

Hans Hagemann, Vincenza D’Anna, Juan Carlos Fallas, Latevi Max Lawson Daku

Département de Chimie Physique, Université de Genève, 30, quai E. Ansermet, CH 1211 Geneva 4 Switzerland

Abstract The bending modes of borohydrides are compared in several crystalline surroundings. Experimental and y- theoretical spectra of complex M(BH4)x ions allow clearly to distinguish between tridentate and bidentate binding. The new compound K2Mg(BH4)2 was studied by powder x-ray diffraction, periodic DFT calculations and vibrational spectroscopy. Isotope exchange reactions of Ca(BH4)2 were monitored using IR spectroscopy.

- Bending modes of BH4 powder X-ray diffraction. K2Mg(BH4)4 crystallizes in space group P2 /n with a unit cell volume around 1000 Å3. In alkali and alkaline earth borohydrides the individual 1 Periodic DFT calculations for this compound converged borohydride groups can be considered as isolated ions, only very slowly, as a combined result of many degrees i.e. they do not form a complex with the metal ion. Thus, of freedom and possibly a relatively flat potential energy the vibrational infrared spectrum can be analyzed in surface. The calculations showed that locally the BH terms of its symmetry: for the tetrahedron (as in MBH 4 4 ions show bidentate bonding towards the central Mg ion, with M = Na, K, Rb,Cs), only one deformation mode in agreement with the X-ray refinement and the IR (triply degenerate) is IR-active. Upon lowering the spectra. An analogous Mn compound presents similar symmetry (as in LiBH ), this band is split and the 4 structural and vibrational properties. previously inactive mode becomes also active. Some trends are shown for different compounds. Isotope exchange reactions y- Complex ions M(BH4)x can present either tridendate or We have performed a series of deuterium exchange bidentate binding towards the central metal atom. Both reactions (at 40 and 80 bars) and achieved an almost situations show characteristic patterns of the bending complete replacement of hydrogen by deuterium at 170 mode region. Bidentate binding is reflected by a relatively °C in Mg(BH4)2 [2]. The isotope exchange takes place at -1 strong IR band around 1400 -1450 cm , which is shifted even lower temperatures in Ca(BH4)2: after 6h at ca to even higher values (1530 cm-1) for neutral molecules 130°C, about 75% of hydrogen was replaced by such as Al(BH4)3 [1]. deuterium (deuterium pressure 40 bar). However, DFT calculations show that partial substitution of borohydride by chloride (as observed for samples This work is supported by the Swiss National Science prepared by ball milling reactions) does not lead to - Foundation. significant spectral changes in the BH4 bending mode region. References

K2Mg(BH4)2 [1] J.O. Jensen, Spectrochim Acta A59 (2003) 1565- 1578. We have prepared the two new compounds K2Mg(BH4)4 and K3Mg(BH4)5 by ball milling of mixtures of KBH4 and [2] H. Hagemann, V. D'Anna, J.-P. Rapin and K. Yvon, Mg(BH4)2 in different ratios. In parallel, similar mixtures Journal of Physical Chemistry C, 114 (21) (2010), based on KBH4 and MgCl2 or MnCl2 were prepared. All p10045-10047. compounds were studied using FTIR spectroscopy and

Hans Hagemann is born in Wuppertal, Germany. 1979 Diploma thesis, Univ. of Geneva, 1984 PhD thesis Univ. of Geneva, 1985-1986 postdoctoral stay at UC Berkeley with H.L. Strauss and R.G. Snyder, since 1987 at University of Geneva. The research interests cover solid state chemistry, vibrational spectroscopy (IR and Raman), luminescence of rare earth ions in solids, and more recently high pressure techniques and DFT calculations, both on isolated ions as well as on periodic structures. Hans Hagemann teaches thermodynamics, statistical thermodynamics, vibrational spectroscopy and a seminar on spectroscopy of rare earth ions. Hans Hagemann

Corresponding author: Hans Hagemann, [email protected], +41 22 3796539 129

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

130

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

"NEW CATALYTIC APPROACH FOR THE DEHYDROGENATION OF AMINE BORANES AND RELATED COMPOUNDS”

Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich Switzerland.

Nowadays hydrogen generation from renewable sources and storage in a safe and reversible manner remain challenging. Amine boranes and related compounds have become promising storage materials in this regard. Here, we present a highly active nickel catalyst system for the liberation of H2 from organoamine, ammonia and amido boranes. Specifically, catalyst loading as low as 0.3 mol% of a diolefine nickel (I) complex is enough for the efficient dihydrogen releasing in few minutes and at room temperature. The isolation and characterization of diverse nickel hydride species has allow us to explain possible reaction mechanisms involved in the process.

Introduction While the Rh based complex A shows only limited activity in the DHC reaction of dimethyl amine borane (Me2HN– Amino olefin ligands, specifically the bis(5 H I BH3), the Ni complex 2 is highly active promoting the dibenzo[a,d]cyclohepten-5-yl)amine = bistropylidenyl catalytic DHC of (Me2HN-BH3) to the cyclic dimer (Me2N– amine = trop2NH, give rise to rhodium amido complexes BH2)2. Ammonia borane (H3N-BH3) and related metal (B), which serve as superb transfer hydrogenation amido boranes have been also tested. catalysts.[1] Complex B, which is simply derived through deprotonation of the very stable amine complex [Rh(trop2NH)(PPh3)]OTf A is a highly active catalyst in the dehydrogenative coupling (DHC) of primary alcohols to carboxylic derivatives.[2]

HB N N BH HB N H H H [Ni] B NH B NHH N B HN B N B H H H BN B NH >2H2 BN HN B HBNH x

Scheme 1. Synthesis of rhodium(I), nickel(I) and nickel(0) Scheme 3. Dehydrogenative coupling of (Me2NH–BH3) and H3N- complexes B, 2 and 3. BH3 mediated by complex 2 / [KMe2N–BH3].

References We were able to isolate and fully characterize two rare [1] Trincado, M.; Gruetzmacher, H.; Vizza, F.; Bianchini, examples of amino-olefin complexes of Ni in the I C. Chem. Eur. J. 2010, 16, 2751 oxidation state +I and 0: [Ni (trop2NH)(OOCCF3)] 2 and 0 [Ni (trop2NH)(PPh3)] 3, respectively. [2] Trincado, M.; Kuehlein, K.; Gruetzmacher, H. Chem. Eur. J. 2011, 17, 11905 [3] Vogt, M.; de Bruin, B.; Berke, H.; Trincado, M.; Gruetzmacher, H. Chem. Sci. 2011, 2, 723

Scheme 2. Molecular structure of complex 2.

131

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

M. Trincado received her PhD degree from the University of Oviedo, working with Prof. J. Barluenga and with Prof. B. M. Trost at Stanford University. This was followed by a Fulbright postdoctoral fellowship with Prof. J. A. Ellman at UC Berkeley. In 2008, she joined the research group of Prof. H. Gützmacher at ETH Zürich and currently is pursuing her Habilitation. Research interests span from the study of a variety of metal complexes in catalyzed processes, especially those involved in the transformation of biomass for the simultaneous production of energy and useful organic compounds and development of new strategies for the efficient and reversible hydrogen storage in main group- based compounds.

Corresponding author: Dr. Monica Trincado, [email protected], 044 633 48 15

132

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

REVERSIBLE HYDROGEN RELEASE AND UPTAKE IN NABH4 CONFINED IN NANOPOROUS CARBON MATERIAL

Peter Ngene, Roy van den Berg, Krijn P. de Jong, Petra E. de Jongh

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitweg 99, P.O. Box 80083, 3508 TB Utrecht, The Netherlands

NaBH4 is a promising material for on-board hydrogen storage in cars due to its high gravimetric hydrogen content( 10.8wt %). However the elevated temperatures (above 530 °C) [1] required to release the hydrogen and non reversibility of the hydrogen release render it unfit for practical application. Nanoconfinement in porous materials has been shown to be an effective strategy to improve the H2 sorption kinetics of light metal hydrides [2]. In this study, we investigate the thermal hydrogen release from NaBH4, and the effect of nanoconfinement in porous carbon material on the kinetics, reversibility and thermodynamics of hydrogen release and uptake from NaBH4.

Preparation The equilibrium decomposition temperature of NaBH4 is ~540 °C in 1 bar H [1], however for the nanoconfined NaBH /C nanocomposites were successfully prepared 2 4 NaBH hydrogen release started around 280 °C under via pore volume impregnation of nanoporous carbon 4 1.1 bar H2. material with an aqueous alkaline NaBH4 solution, and also by melt infiltration under hydrogen pressure. Hydrogen sorption properties XRD, solid-state NMR and hydrogen release measurements revealed that NaBH4 decomposes into elemental Na and Na2B12H12 when heated to 600 °C under Ar, with a release of 8.1 wt % H2. Nanosizing and confinement of NaBH4 in a nanoporous carbon material resulted in much faster hydrogen desorption kinetics as shown in figure 1(A). The onset of hydrogen release was reduced from 470 °C for the bulk to below 250 °C for the Figure.1 H2 release from (A): bulk NaBH4, solution impregnated nanoconfined NaBH4. Remarkably, reversible formation (SI) and melt infiltrated (MI) NaBH4/C nanocomposites. (B): of NaBH4 from its dehydrogenation products was Dehydrogenated samples of A after rehydrogenation at 325 C, demonstrated for the first time; the dehydrogenated 50 and bar H2 for 5h. NaBH4/C nanocomposites released about 3.4 wt% H2 References after rehydrogenation at relatively mild condition ( 325 °C and 60 bar H2), while a negligible amount of hydrogen [1] Martelli, et al. J. Phys. Chem. C (2010), 114, 7173 was released from the dehydrogenated bulk after [2] Gross et al. J.Phys. Chem. C. (2008), 112, 5651 rehydrogenation under similar conditions. Reversibility of the system is limited by loss of Na at high temperatures [3] Ngene, de Jongh et al., Energy Environ. Sci, (2011), during hydrogen release. Compensation of Na loss by 4, 4108 extra Na resulted in almost full rehydrogenation of the dehydrogenated products to NaBH4.[3]

Petra de Jongh received her PhD in photoelectrochemistry in 1999, and worked 5 years as a senior

scientist at Philips Research. She is now associate professor at Utrecht University, where she (co)- supervises researchers working on supported nanoparticles, especially for applications in catalysis and energy storage and conversion.

Petra de Jongh

Corresponding author: Petra E. de Jongh, email: mail to: p.e [email protected], Tel +31 6 22736345

133

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

134

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

PERSPECTIVES OF H STORAGE AND ELECTROCHEMICAL STORAGE METHODS

M. Fichtnera, S. Büschel, R. Prakash, M. Anji Reddy a Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany

The perspectives are outlined and discussed of materials for energy storage based on solid storage materials for hydrogen, and for batteries. Whereas there are already established systems on the market which are based on intercalation type materials, conversion type systems seem to be the only option at the moment for reaching high storage capacities for hydrogen or electrons. Perspectives, principle disadvantages, and scientific and technical challenges are associated with each of these principles. Selected examples will be discussed in the contribution.

The contribution will start with an introduction to the problem of energy storage. Chemical methods offer the highest energy density for storing energy; they are the most interesting option for high energy and high power applications such as automobiles and for seasonal storage of electric energy from renewables. Each storage method has its own perspectives, limits of its physical potential, technical limitations, associated with cost and safety issues.

For storage of hydrogen or lithium, today´s systems are based on intercalation materials which have the advantage of being well reversible and available on the market. However, as the energy density shall be improved by a factor of two (H storage materials) or five (battery materials), a paradigm change is necessary in A new type of secondary battery which might fit in this the materials development in order to be able to reach category is based on fluoride ion shuttle and has the these goals. From the current knowledge, only systems potential to meeting these demands. The reaction of based on the conversion principle offer such high energy highly electronegative fluorine with metal leads to the densities [1]. formation of metal fluorides which are accompanied by Conversion materials are based on solid state chemical large change in free energy and thus high electromotoric reactions where several reaction partners may be force [2]. By choosing appropriate metal/metal fluoride involved depending on whether the material is charged or combinations, electrochemical cells can be built with discharged. The systems undergo a massive theoretical gravimetric and volumetric energy densities reconstruction of their structures, which is different in which exceed the theoretical potential of current Li ion intercalation based systems. Examples from H storage batteries by an order of magnitude. materials and battery research will be presented and discussed, and current directions of research in these fields will be outlined. References There is a growing interest for electrochemical storage [1] M. Fichtner, Conversion materials for hydrogen systems with higher storage densities and better safety. storage and electrochemical applications - concepts and Novel sustainable battery systems have to be developed similarities, J. ALLOYS COMPD. 509S, S529-S534 with storage densities which exceed those of current Li- (2011) ion systems considerably. This can only be achieved if new principles are applied where the chemical [2] M. Anji Reddy and M. Fichtner, Novel batteries based conversion of nanocomposites is utilized. on fluoride shuttle, J. MATER. CHEM. 21, 17059 (2011)

Maximilian Fichtner is Group Leader for “Energy Storage Systems” at KIT, Institute of Nanotechnology. His research interests include solid state chemistry on nanoscale systems for hydrogen storage and for batteries.

Corresponding author: M. Fichtner, [email protected], +49 721 6082 5340 135

6th Int. Symposium Hydrogen & Energy Stoos, Switzerland 2012

136

6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 137 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 138 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 139 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 140 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 141 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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

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.

PROCEEDINGS 142 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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 aword Prof. Rex Harris with the Science of Hydrogen & Energy prize 2010.

PROCEEDINGS 143 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 144 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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.

PROCEEDINGS 145 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

SCIENCE OF HYDROGEN & ENERGY AWARD 2012

Mogens Mogensen 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 39 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 MOGENSEN

Mogens Mogensen from the Department of Energy Conversion and Storage, Technical University of Denmark (which contains what previously was Fuel Cells and Solid State Chemistry, Risø National Laboratory for Sustainable Energy) was involved 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 latest 25 years (and in electrochemistry for 39 years). His topics include the material development for electrodes, electrolytes as well as interconnects, coatings and sealings. Mogens is known for his broad knowledge and understanding of the total systems and especially the deep knowledge of the cells thermodynamics and electrochemical behavior. His research activities are the principle understanding of the mechanisms including the aging in SOEC and SOFC systems, the electrochemical behavior, and 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 further 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. With 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%/1000 h) and an outstanding mechanical strength and flexibility. Mogens was also involved 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, methanol, DME or many other hydrocarbons, which are a more suitable energy carrier. These catalytic processes may take place inside the cell if the temperature is lowered compared to normal SOEC, or inside the electrolyser system, so the reaction heat can be utilized.

We award Prof. Mogens Mogensen for his outstanding work on the electrochemistry of electrolysers and fuel cells with the Science of Hydrogen & Energy prize 2011.

PROCEEDINGS 146 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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

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.

PROCEEDINGS 147 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PARTICIPANTS

PROCEEDINGS 148 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

ARAMINI Matteo, Mr University of Parma Tel: +39 0521 906067 Department of Physics email: [email protected] Via G. Usberti 7/A IT-43100 Parma

AU Yuen, Mr Utrecht University Tel: +31 622 736385 Inorganic Chemistry & email: [email protected] Catalysis Universiteitsweg 99 NL-3584 CG Utrecht

BARMAN Samir, Mr University of Zurich Tel: +41 44 635 4696 email: [email protected] Winterthurerstrasse 190 CH-8057 Zurich

BERKE Heinz, Prof. University of Zurich Tel: +41 44 635 4680 Anorganisch-Chemisches Fax: +41 44 635 6802 Institut email: [email protected] Winterthurerstrasse 190 CH-8057 Zurich

BIELMANN Michael, Dr. EMPA Materials Science & Tel: +41 58 765 4342 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

BLIERSBACH Andreas, Mr EMPA Materials Science & Tel: +41 58 765 4862 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

BOELSMA Christiaan, Mr email: [email protected]

Granaat 8 NL-1703 BC Heerhugowaard

BORGSCHULTE Andreas, Mr EMPA Materials Science & Tel: +41 58 765 4639 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Ueberlandstrasse 129 CH-8600 Dübendorf

PROCEEDINGS 149 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

CALLINI Elsa, Dr. EMPA Materials Science & Tel: +41 58 765 4933 Technology Fax: +41 58 765 4022 Hydrogen and Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

CAMPESI Renato, Mr

CHEN Ping, Prof. Dr. Dalian Institute of Chemical Tel: +86 411 84379905 Physics email: [email protected]

457 Zhongshan Road CN-116023 Dalian

CHOUCAIR MOHAMMAD, Dr. UNIVERSITY OF PARMA email: [email protected] PHYSICS VIA G.P. USBERTI NO. 7/A IT-43124 PARMA

DE JONGH Petra, Prof. Utrecht University email: [email protected] Inorganic Chemistry and Catalysis Universiteitsweg 99 NL-3584 CG Utrecht

FELDERHOFF Michael, Dr. MPI für Kohlenforschung Tel: +49 208 306 2248 Heterogeneous Catalysis email: felderhoff@mpi- Kaiser-Wilhelm-Platz 1 muelheim.mpg.de DE-45470 Mülheim/Ruhr

FICHTNER Maximilian, Dr. KIT email: [email protected] INT P.O. Box 3640 DE-76021 Karlsruhe

FRISCHKNECHT Urs, Mr EMPA Materials Science & email: [email protected] Technology Hydrogen & Energy Überlandstrasse 129 CH-8600 Dübendorf

FUNKE Klaus, Prof. University of Muenster Tel: +49 251 8323418 Physical Chemistry Fax: +49 251 8329138 Corrensstrasse 30 email: [email protected] DE-48149 Muenster

PROCEEDINGS 150 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

GABOARDI Mattia, Mr Università degli Studi di Tel: +39 052 1906067 Parma email: Physics [email protected] Viale G.P. Usberti n.7/A (Parco Area delle Scienze IT-43124 Parma

GAO Jinbao, Ms utrecht university email: [email protected]

Universiteitweg 99 NL-3584 CG UTRECHT

GAO Mingxia, Dr. Zhejiang University Tel: +86 571 87952615 Department of Materials Fax: +86 571 87952615 Science and Engineering email: [email protected] Zheda Road, No.38 CN-310027 Hangzhou

GIANOLA Corinne, Ms EMPA Materials Science & Tel: +41 58 765 4692 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

GORBAR Michal, Mr EMPA Materials Science & Tel: +41 58 765 4301 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

GRINBERGA Liga, Dr. Institute of Solid State email: [email protected] Physics Hydrogen storage materials 8 Kengaraga Street LV-LV-1063 Riga

HAGEMANN Hans, Dr. Univ. of Geneva email: hans- Dept. Physical Chemistry [email protected] 30, quai E. Ansermet CH-1211 Geneva

HAZRATI Ebrahim, Mr Tel: +31 243 652810 Electronic Structure of email: [email protected] Materials Heyendaalseweg 135 NL-6525 AJ Nijmegen

PROCEEDINGS 151 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

IRVINE John, Prof. University of St Andrews email: [email protected] School of Chemistry North Haugh GB-KY16 9ST St Andrews

JENSEN Torben R., Prof. Dr. Aarhus University Tel: +45 2272 1486 iNANO, Department of email: [email protected] Chemistry Langelandsgade 140 DK-8000 Aarhus

KALANTZOPOULOS Institute for Energy Tel: +47 6380 6181 Georgios, Dr. Technology (IFE) Fax: +47 6381 0920 Physics Department email: [email protected] P.O. Box 40 NO-NO-2027 Kjeller

KATO Shunsuke, Mr EMPA Materials Science & Tel: +41 58 765 4327 Technology Materials Fax: +41 58 765 4022 Science and Technology email: [email protected] Dept. Environment, Energy and Mobility Überlandstrasse 129 CH-8600 Dübendorf

KIM Ji Woo, Dr. EMPA Tel: +41 58 765 4153 Hydrogen & Energy Fax: +41 58 765 4022 ÜBERLANDSTRASEE 129 email: [email protected] CH-8600 Dübendorf

LANGHAMMER Christoph, Chalmers University of email: [email protected] Prof. Technology Applied Physics Fysikgränd 3 SE-41296 Göteborg

LAURENCZY Gabor, Prof. EPFL Tel: +41 21 693 9858 ISIC LCOM GCEE Fax: +41 21 693 9780 BCH 2405 email: [email protected] CH-1015 Lausanne

LI Haiwen, Dr. Kyushu University email: [email protected] International Research Center for Hydrogen Energy 744 Motooka, Nishi-ku JP-819-0395 Fukuoka

LINDEMANN Inge, Ms email: [email protected]

Helmholtzstr. 20 DE-01069 Dresden

PROCEEDINGS 152 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

LINDER Marc, Dr. German Aerospace Center email: [email protected] - DLR Institute of Technical Thermodynamics Pfaffenwaldring 38-40 DE-70569 Stuttgart

LIU Yongfeng, Prof. Dr. Zhejiang University Tel: +86 571 87952615 Department of Materials Fax: +86 571 87952615 Science and Engineering email: [email protected] 38# Zheda Road CN-310027 Hangzhou

LOHSTROH Wiebke, Dr. Technische Universität Tel: +49 89 289 14735 München Fax: +49 89 289 14989 FRM 2 email: [email protected] Lichtenbergstr. 1 DE-85747 Garching

MARTELLI Pascal, Mr EMPA Materials Science & email: [email protected] Technology Hydrogen & Energy Überlandstrasse 129 CH-8600 Dübendorf

MATSUO Motoaki, Dr. Tohoku Universtiy Tel: +81 22 215 2094 Institute for Materials Fax: +81 22 215 2091 Research email: [email protected] 2-1-1 Katahira, Aoba-ku JP-980-8577 Sendai

MAURON Philippe, Dr. EMPA Materials Science & Tel: +41 58 765 4099 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Ueberlandstrasse 129 CH-8600 Dübendorf

MOGENSEN Mogens Bjerg, Technical University of Tel: +45 2132 6622 Prof. Dr. Denmark DTU email: [email protected] Fuel Cells and Solid State Chemistry Frederiksborgvej 399 DK-4000 Roskilde

MULLER Jiri, Dr. IFE email: [email protected]

Kjeller NO-2027 Kjeller

OMAR Abdelazim, Prof. EGYPTIAN PETROLEUM email: [email protected] RESEARCH INSTITUTE Processes desigin and development depart. cairo nasr city EG-11727 nasr city

PROCEEDINGS 153 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

ORIMO Shin-ichi, Prof. Dr. Tohoku University Tel: +81 22 215 2093 Institute for Materials Fax: +81 22 215 2091 Research email: [email protected] 2-1-1, Katahira JP-980-8577 Sendai

PAN Hongge, Prof. Dr. Zhejiang University Tel: +86-571-87952615 Department of Materials email: [email protected] Science and Engineering

CN-310027 Hangzhou

PONTIROLI Daniele, Dr. Università di Parma Tel: +39 0521 90 5231 Dipartimento di Fisica Fax: +39 0521 90 5223 Via G. Usberti 7/a email: [email protected] IT-43124 Parma

RAMIREZ-CUESTA Timmy, STFC Tel: +44 7787 105335 Dr. ISIS Facility email: timmy.ramirez- Room 1-51 [email protected] GB-OX11 0QX Chilton

RATISHVILI Ioseb, Prof. Dr. Javakhishvili St. Univ., Tel: +99 532 2290798 Andronikashvili Ins.Phys. email: [email protected] Dep. Cond. Matter Physics 6 Tamarashvili str. GE-GE_0177 Tbilisi

REMHOF Arndt, Dr. EMPA Materials Science & Tel: +41 58 765 4369 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] ÜberlandstrASSE 129 CH-8600 Dübendorf

RICCÒ Mauro, Prof. Dr. Parma University Tel: +39 349 96609300 Physics Department Fax: +39 052 1905223 Via G. Usberti 7/a email: [email protected] IT-43124 Parma

SHEPTYAKOV Denis, Mr Laboratory for Neutron email: [email protected] Scattering

Paul Scherrer institut CH-5232 Villigen

PROCEEDINGS 154 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

SITTE Werner, Prof. Montanuniversitaet Leoben Tel: +43 384 24024800 Physical Chemistry Fax: +43 384 24024802 Franz-Josef-Strasse 18 email: [email protected] AT-A 8700 Leoben

SIVARS Andris, Mr Institute of Solid State Tel: +371 67262145 Physics email: [email protected]

Kengaraga iela 8 LV-LV-1063 Riga

STADIE Nicholas, Mr California Institute of Tel: +1 602 363 8883 Technology Fax: +1 626 795 6132 Materials Science email: [email protected] 1200 E California Blvd, MC 138-78 US-91125 Pasadena

SUTER Riccardo, Mr EMPA Materials Science & Tel: +41 58 765 4729 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

TANG Wan Si, Ms LRCS UMR 6007 UPJV Tel: +33 3 22 82 75 92 Material Chemistry Fax: +33 3 22 82 75 90 33 Rue St Leu email: [email protected] FR-80000 Amiens

TAUBE Klaus, Dr. Helmholtz-Zentrum Tel: +49 4152 87 25 41 Geesthacht Fax: +49 4152 87 4 25 41 Nanotechnology email: [email protected] Max-Planck-Strasse 1 DE-21502 Geesthacht

TORRES Alondra, Ms TU Delft email: [email protected] Department of Process & Energy Leeghwaterstraat 44 NL-2628 CA Delft

TRAJKOVIC Ivo, Dr. EMPA Materials Science & Tel: +41 58 765 4746 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

TRINCADO Monica, Dr. ETH Zurich Tel: +41 76 238 8779 LAC, Chemistry email: [email protected] Wolfgang-Pauli-Str. 10 CH-8093 Zurich

PROCEEDINGS 155 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

ULMER Ulrich, Mr KIT email: [email protected]

Hermann-von-Helmholtz- Platz 1 DE-76344 Eggenstein- Leopoldshafen

VAN DEN BERG Marius, Mr Tel: +31 643751990 email: [email protected] Friedenheimer strasse 139 DE-80686 Muenich

VOGT Ulrich, Dr. EMPA Materials Science & Tel: +41 58 765 4160 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Ueberlandstr. 129 CH-8600 Dübndorf

WU Chaoling, Prof. Dr. Sichuan Universtiy Tel: +86 28 85466916 Materials Science and Fax: +86 28 85466916 Engineering email: [email protected] Wangjiang Road 29# CN-610064 Chengdu

YAN Yigang, Dr. EMPA Materials Science & Tel: +41 58 765 4082 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

YUAN Peipei, Ms Zhejiang University Tel: +86 13567138396 (Yuquan Campus) email: [email protected] CN-310027 Hongzhou

ZHAO-KARGER Zhirong, Dr. Karlsruhe Institute of Tel: +49 72160828908 Technology email: [email protected] Institute of Nanotechnology Hermann-von-Helmholtz- Platz 1 DE-76344 Eggenstein- Leopoldshafen

ZHU Min , Prof. Dr. South China University of Tel: +86-20-87113924 Technology email: [email protected] School of Materials Science and Engineering

CN-510640 Guangzhou

PROCEEDINGS 156 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

ZÜTTEL Andreas, Prof. Dr. EMPA Materials Science & Tel: +41 58 765 4038 Technology Fax: +41 58 765 4022 Hydrogen & Energy email: [email protected] Überlandstrasse 129 CH-8600 Dübendorf

PROCEEDINGS 157 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 158 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

Information

PROCEEDINGS 159 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

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

Map of the region Schwyz-Stoos

PROCEEDINGS 160 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

Travel to Stoos from Zürich airport:

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

So, 23.01.11 Zürich Flughafen ab 14:13 3 IC 726, InterCity BZ RZ Zürich HB an 14:23 17 walk from track 17 to track 4 Zürich HB ab 14:35 4 IR 2345, InterRegio Zug an 15:01 4 change to train on opposite side of platform Zug ab 15:05 3 S2 21247, S-Bahn Linie 2 Schwyz an 15:33 2 the bus is parked in front of the station Schwyz, Bahnhof ab 15:36 Bus 1, Richtung: Muotathal, Hölloch Schwyz, Schlattli an 15:54 the bus stops in front of the cable car station, show your ticket at the counter Schlattli SSSF ab 16:10 FUN 19, Standseilbahn Stoos an 16:18 Time for trip: 2:05 http://www.sbb.ch

EMERGENCY TELEPHONE NUMBERS country code for Switzerland +41...

POLICE 117

FIRE FIGHTERS 118

AMBULANCE 144

RESCUE HELICOPTER 1414

Corinne Gianola 076 398 9985 Andreas Züttel 079 484 2553 Hotel Stoos, Reception 041 817 4444

Seminar- und Wellnesshotel Stoos (AG Sporthotel Stoos) Ringstrasse 10 CH-6433 Stoos [email protected] http://www.hotel-stoos.ch

PROCEEDINGS 161 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

STOOS Region

PROCEEDINGS 162 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 163 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

TIMETABLE

PROCEEDINGS 164 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

NOTES

PROCEEDINGS 165 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 166 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 167 6th Hydrogen & Energy Symposium Stoos, Switzerland 2012

PROCEEDINGS 168