Conference Documents Workshop „Lithium-Sulfur-Batteries Vi“ November 6 - 7, 2017
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Einband_LiS_2017_Layout 1 20.10.2017 13:24 Seite 1 FRAUNHOFER-INSTITUT FÜR WERKSTOFF- UND STRAHLTECHNIK IWS 6th WORKSHOP »LITHIUM-SULFUR BATTERIES« November 6 – 7, 2017 Fraunhofer IWS Dresden, Germany CONFERENCE DOCUMENTS WORKSHOP „LITHIUM-SULFUR-BATTERIES VI“ NOVEMBER 6 - 7, 2017 Fraunhofer-Institut für Werkstoff- und Strahltechnik IWS Winterbergstraße 28, 01277 Dresden November 6, 2017 10:00 Registration Session I Trends in material development Chair: Prof. Dr. Stefan Kaskel, Fraunhofer IWS, TU Dresden 11:00 Welcome and opening Prof. Dr. Eckhard Beyer Fraunhofer IWS, TU Dresden 11:15 Solvate ionic liquids for lithium‐sulfur batteries Prof. Masayoshi Watanabe, Yokohama National University, Japan 12:00 Importance of carbon materials in positive electrodes of the lithium-sulfur batteries Dr. Elena Karaseva, Ufa Institute of Chemistry of Russian Academy of Sciences, Russia 12:30 Chemical engineering science of lithium metal anode in lithium-sulfur batteries Prof. Qiang Zhang, Tsinghua University, China 13:00 Lunch break Session II Lithium metal anodes Chair: Prof. Dr. Stefan Kaskel, Fraunhofer IWS, TU Dresden 14:15 Lithium/electrolyte interfaces Prof. Jürgen Janek, Justus-Liebig-Universität Gießen, Germany 14:45 Suitability of sulfide based solid state electrolytes for use in lithium metal secondary batteries Dr. Yuichi Aihara, Samsung R&D Institute Japan 15:15 Lithium metal anodes for lithium-sulfur batteries Stephen Lawes, OXIS Energy Limited, UK 15:45 Coffee break 16:15 Lithium-metal film deposition for Li-S-cells with high volumetric energy density Dr. Benjamin Schumm, Fraunhofer IWS 16:45 Handling and processing of metallic lithium in the production of next generation battery cells Anna Kollenda, Technische Universität München, Germany 17:15 Short poster introduction (Short presentation of some selected posters in preparation of the poster session) 17:45 Poster session and dinner at Fraunhofer IWS WORKSHOP „LITHIUM-SULFUR-BATTERIES VI“ NOVEMBER 6 - 7, 2017 Fraunhofer-Institut für Werkstoff- und Strahltechnik IWS Winterbergstraße 28, 01277 Dresden November 7, 2017 Session III Cathode chemistry and new electrolytes Chair: Dr. Holger Althues, Fraunhofer IWS 09:00 Is lithium-sulfur ready for commercial uptake? Market demand and competition Gleb Ivanov, Sigma Lithium Ltd 09:30 Stabilizing sulfur carbon cathodes - a biotechnology approach Mark Griffiths, EndLiS Energy, USA 10:00 On the factors affecting the capacity depletion of lithium-sulfur batteries at the cycling and storage Dr. Elena Kuzmina, Ufa Institute of Chemistry of Russian Academy of Sciences, Russia 10:30 Coffee break 11:00 Impact of adapted nitrate-free electrolytes on pouch cell performance Dr. Susanne Dörfler, Fraunhofer IWS 11:30 Sparingly solvating electrolytes design for high energy density lithium-sulfur batteries Dr. Kevin R. Zavadil, Sandia National Laboratories, USA 12:00 Effects of Li-anion interactions on solubility of lithium polysulfides in ionic liquids Dr. Seiji Tsuzuki, National Institute of Advanced Industrial Science and Technology (AIST), Japan 12:30 Lunch break 13:45 Characterization of reaction intermediates in lithium-sulfur battery via operando transmittance UV/Vis spectroscopy Qi He, TU München, Germany 14:15 Operando characterization of a lithium-sulfur battery by coupling X-ray absorption tomography and X-ray diffraction Guillaume Tonin, CEA Grenoble, France 14:45 Thermal effects and diagnosis tools in multilayer cells for real applications Dr. Monica Marinescu, Imperial College, UK 15:15 Concluding remarks Prof. Dr. Stefan Kaskel, Fraunhofer IWS, TU Dresden 15:30 Tour through the labs of the Fraunhofer IWS (optional 1h) With my registration I agree with the potential publication of photographs taken during the event and with the electronic storage of my address (incl. the use of my address for future invitations). LECTURE Solvate ionic liquids for lithium‐sulfur batteries Masayoshi Watanabe Department of Chemistry and Biotechnology, Yokohama National University 79‐5 Tokiwadai, Hodogaya‐ku, Yokohama 240‐8501, Japan Innovation in the design of electrolyte materials is crucial for realizing next‐generation electrochemical energy storage devices such as Li–S batteries. The theoretical capacity of the S cathode is 10 times higher than that of conventional cathode materials used in current Li– ion batteries. However, Li–S batteries suffer from the dissolution of lithium polysulfides, which are formed by the redox reaction at the S cathode. Herein, we present simple solvate ionic liquids, glyme–Li salt molten complexes [1], as excellent electrolyte candidates because they greatly suppress the dissolution of lithium polysulfides [2]. Certain concentrated mixtures of salts and solvents are not simply "solutions" anymore, but they may be described as "solvate ionic liquids", in which the solvents strongly coordinate the cation and/or the anion of the salts to form stable “solvate ions”. All of the solvents interact with the cation and/or anion, so that the liquids can be classified into “solvate ionic liquids” [3, 4]. Equimolar molten mixtures of glymes (triglyme (G3) or tetraglyme (G4)) and lithium bis(trifluoromethane sulfonyl)amide (Li[TFSA]) are typical examples that we propose [1]. The equimolar complexes [Li(G3 or G4)][TFSA] are stable + ‐ liquids consisting of [Li(glyme)1] complex cation and [TFSA] anion, both of which are extremely low coordinating ions with low Lewis acidity and basicity, respectively [3]. The [Li(G3 or G4)][TFSA] molten complexes do not readily dissolve other ionic solutes due to the low coordinating nature of the cation and anion, which leads to the stable operation of the Li–S battery over more than 400 cycles with discharge capacities higher than 700 mAh g‐sulfur‐1 and with coulombic efficiencies higher than 98% throughout the cycles [2]. Furthermore, the addition of a nonflammable fluorinated solvent, which does not break the solvate structure of the glyme–Li salt molten complexes, greatly enhances the power density of the Li–S battery [2]. It is also interesting to note that the [Li(G3 or G4)][TFSA] molten complexes are compatible with Si and graphite anodes [5], which makes it possible to construct Si‐Li2S and graphite‐Li2S batteries [6] on the basis of the fabrication of high performance Li2S/C cathode [7]. This paper deals with fundamental properties of solvate ionic liquids, and how characteristics of the solvate ionic liquids can be utilized in advanced Li‐S batteries. References: [1] K. Yoshida, M. Nakamura, Y. Kazue, N. Tachikawa, S. Tsuzuki, S. Seki, K. Dokko, M, Watanabe, J. Am. Chem. Soc. 2011, 133, 13121‐13129. [2] K. Dokko, N. Tachikawa, K. Yamauchi, M. Tsuchiya, A. Yamazaki, E. Takashima, J.‐W. Park, K. Ueno, S. Seki, N. Serizawa, M. Watanabe, J. Electrochem. Soc. 2013, 160, A1304‐A1310. [3] K. Ueno, K. Yoshida, N. Tachikawa, K. Dokko, M. Watanabe, J. Phys. Chem. B 2012, 116, 11323‐11331. [4] T. Mandai, K. Yoshida, K. Ueno, K. Dokko, M. Watanabe, Phys. Chem. Chem. Phys. 2014. 16, 8761‐8772. [5] H. Moon, R. Tatara, T. Mandai, K. Ueno, K. Yoshida, N. Tachikawa, T. Yasuda, K. Dokko, M. Watanabe, J. Phys. Chem. C 2014, 118, 20246‐20256. [6] Z. Li, S. Zhang, S. Terada, X. Ma, K. Ikeda, Y. Kamei, C. Zhang, K. Dokko, M. Watanabe, ACS Appl. Mater. Interfaces, 2016, 8, 16053‐16062. [7] Z. Li, S. Zhang, C. Zhang, K. Ueno, R. Tatara, K. Dokko, M. Watanabe, Nanoscale, 2015, 7, 14385‐14392. Importance of carbon materials into positive electrodes of the lithium-sulfur batteries Vladimir Kolosnitsyn, Elena Karaseva, Elena Kuzmina Ufa Institute of Chemistry of the Russian Academy of Sciences, Laboratory of Electrochemistry, Prospect Oktyabrya 71, Ufa, 450054, Russia Lithium-sulfur batteries belong to the batteries with a liquid depolarizer, since during their charge and discharge the solid-phase substances (sulfur and lithium sulfide) are converted into compounds - lithium polysulfides (Li2Sn), which are highly soluble in electrolytes. Mechanisms of electrochemical processes occurring in lithium-sulfur and lithium-ion batteries are significantly different. The active materials of the positive electrode in charged (sulfur) and discharged (lithium sulfide) states are dielectrics and don’t have electrochemical activity in solid state. However, sulfur is soluble into electrolyte systems of the lithium-sulfur batteries, and lithium sulfide is able to dissolve in electrolytes as lithium polysulfides. These properties of active materials also allow to involve both elemental sulfur and lithium sulfide into electrochemical conversions. The electrochemical reduction of sulfur during discharge of the lithium-sulfur batteries includes several stages - dissolution of elemental sulfur, diffusion transfer to the surface of the carbon current collector, sorption on the surface of the carbon current collector, electrochemical reduction, desorption of the reduced products from the surface of the carbon current collector. Similar processes occur also when lithium- sulfur cells are charged. Electrochemical processes which occur in the lithium-sulfur cells during charge and discharge are heterogeneous and are carried out at the interface between ionic and electronic conductors. The ionic conductor is an electrolyte saturated with active materials (sulfur or lithium polysulfides), and the electronic conductor is various types of carbon materials (carbon black, carbon nanotubes, graphenes, etc.). The depth and speed of electrochemical reactions during charge and discharge of the lithium-sulfur batteries are determined by the properties