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  • The Electrochemical Society  (7)
  • Winter, Martin  (7)
  • 1
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Meeting Abstracts Vol. MA2015-02, No. 5 ( 2015-07-07), p. 425-425
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-02, No. 5 ( 2015-07-07), p. 425-425
    Abstract: Ionic liquid (ILs) have received much attention next to traditional carbonates based electrolytes, due to their high oxidation potential (above 5V vs Li/Li + for typical pyrrolidinium based ILs) [1-2] , excellent thermal stability [3] , negligible vapor pressure and non-flammable nature [3] . Nevertheless, the high price of ILs represents a major drawback for the commercialization of these electrolyte materials. Furthermore, for the use of graphite anodes cells, severe reductive decomposition of ILs can be triggered by an intercalation of cation of the ILs into graphite layer [4] , which results in graphite exfoliation. As a result, less reversible capacity can be achieved during the charge/discharge process. In recent years, many approaches have been pursued to optimize (1-butyl-1-methylprrolidinium bis(trifluoromethane-sulfonyl)imide (Pyr 14 TFSI)) based electrolyte to obtain a suitable electrolyte formulation for application in lithium-ion batteries [4-5] . More attention has been paid to accommodate the incompatibility with carbon anodes, such as mixture use of ILs and organic solvents [1] , addition of certain amount of SEI additives (e.g. VC [6-7] ,  ClEC [7-8] , FEC and ES [6-7] ) and substitution of conductive salts [4-5] . The basic strategy is to form an ideal surface layer on graphite [4] , which can offer sufficient ability to prevent the intercalation of the cation of ILs and avoid a continuous electrolyte decomposition of electrolyte. In order to enrich the knowledge of the ionic liquid performance in lithium ion batteries, the concept of this work is set on IL with organic functional group modifications. The structure medication is considered to be an easy way for synthesis approaching and favorable for fast change of physical and chemical properties. In this work, we synthesized a series of ester group modified ILs from Pyr 14 TFSI, based on our computational screening results. The synthesized ILs methyl-methylcarboxymethyl prrolidinium bis(trifluoromethane-sulfonyl)imide (MMMPyrTFSI)) and   methyl-propylcarboxymethyl prrolidinium bis(trifluoromethane-sulfonyl)imide (MPMPyrTFSI)) show high oxidation stability (ca 5.4 V vs Li/Li + ). TGA measurements show that modified ILs are thermally stable above 300 o C. Moreover, electrolytes based either on MMMPyrTFSI or MPMPyrTFSI show excellent electrochemical performance in Li/LiFePO 4 cells, display a stable reversible capacity of 150 mAh/g at 1C and 110 mAh/g at higher rate of 5C. For the graphite anode, MPMPyrTFSI based electrolyte shows stable capacity of 330 mAh/g at 0.1C with an efficiency of 99% during the 100 cycles. These interesting results illustrate cation modification of ILs as an effective way for improved performance of ILs in lithium-ion batteries. References   [1]R. A. Di Leo, A. C. Marschilok, K. J. Takeuchi, E. S. Takeuchi, Electrochimica Acta 2013 , 109 , 27-32. [2]V. Borgel, E. Markevich, D. Aurbach, G. Semrau, M. Schmidt, Journal of Power Sources 2009 , 189 , 331-336. [3]S. F. Lux, M. Schmuck, G. B. Appetecchi, S. Passerini, M. Winter, A. Balducci, Journal of Power Sources  2009 , 192 , 606-611. [4]M. Nádherná, J. Reiter, J. Moškon, R. Dominko,  Journal of Power Sources 2011 , 196 , 7700-7706. [5]G. B. Appetecchi, M. Montanino, A. Balducci, S. F. Lux, M. Winterb, S. Passerini, Journal of Power  Sources 2009 , 192 , 599-605. [6]M. Holzapfel, C. Jost, A. Prodi-Schwab, F. Krumeich, A. Würsig, H. Buqa, P. Novák, Carbon 2005 , 43 , 1488-1498. [7]H. Zheng, K. Jiang, T. Abe, Z. Ogumi, Carbon 2006 ,  44 , 203-210. [8]H. Zheng, B. Li, Y. Fu, T. Abe, Z. Ogumi,  Electrochimica Acta 2006 , 52 , 1556-1562.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 2
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    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-04, No. 10 ( 2019-06-30), p. 0462-0462
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-04, No. 10 ( 2019-06-30), p. 0462-0462
    Abstract: Lithium metal constitutes a promising anode material, based on its high theoretical specific capacity (3 860 mAh g −1 ), and low electrochemical potential (−3.04 V vs . SHE). Non-homogeneous lithium deposition, however, may lead to the formation of reactive high surface area lithium (HSAL) upon cycling, eventually yielding losses of active material, safety risks, and insufficient cycling efficiency. HSAL with e.g. needle-like structure does not only cause higher capacity losses based on side reactions and solid electrolyte interface (SEI) formation, but also could result in internal short circuits by penetration of separator layers. In contrast, low surface area lithium (LSAL) such as nodule-like deposits[1] may reduce unwanted side reactions as well as safety risks. The actual microstructure of lithium deposits is governed by extrinsic factors including cell pressure, temperature, current densities, as well as surface properties of lithium metal electrodes but also the explicit choice of electrolyte constituents, and is therefore crucial for the overall cell performance.[2] In this work, highly concentrated electrolytes are exploited to achieve improved cycling stability and reduced HSAL formation, where the formation of a highly robust SEI, more uniform lithium deposits, fewer side reactions on the anode surface, as well as higher viscosity of the electrolytes were identified as key factors.[1, 3] Electrochemical in situ investigations, scanning electron microscopy (SEM) [4] and in situ 7 Li nuclear magnetic resonance (NMR) spectroscopy [5, 6] are applied to in detail elucidate lithium deposition phenomena in symmetrical Li/Li cells. In addition to SEM data, in situ 7 Li NMR constitutes an alternative, highly viable spectroscopic method that affords (semi-) quantitative and qualitative monitoring of lithium microstructure growth upon cycling, thereby unraveling critical processes during electrodeposition while delivering counterstrategies for unrestrained HSAL growth and options for achieving significantly improved electrochemical performance and life time of the considered cells. [1] J. Qian , et al. , Nature Communications, 6 (2015) 6362. [2] X.-B. Cheng , et al. , Chemical Reviews, 117 (2017) 10403-10473. [3] L. Suo , et al. , Nature Communications, 4 (2013) 1481. [4] G. Bieker , et al. , Physical Chemistry Chemical Physics, 17 (2015) 8670-8679. [5] H.J. Chang , et al. , The Journal of Physical Chemistry C, 119 (2015) 16443-16451. [6] R. Bhattacharyya , et al. , Nature Materials, 9 (2010) 504-510.
    Type of Medium: Online Resource
    ISSN: 2151-2043
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    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 3
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    Online Resource
    The Electrochemical Society ; 2020
    In:  ECS Meeting Abstracts Vol. MA2020-02, No. 4 ( 2020-11-23), p. 745-745
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2020-02, No. 4 ( 2020-11-23), p. 745-745
    Abstract: Lithium metal has the most negative deposition potential of all metals (-3.04 V vs. SHE) and a very high theoretical specific capacity of 3861 mA h g -1 , which makes it a promising anode material for next generation batteries. However, the commercialization of lithium metal anodes is still impaired by several drawbacks. 1 Lithium metal reacts with the electrolyte, forming a solid electrolyte interphase (SEI). Due to the inhomogeneity of this SEI, electrodissolution/-deposition of lithium is favored where the SEI is less resistive or cracked, leading to protrusions and dendrite growth. This does not only lower the coulombic efficiency (CE) and cell specific capacity but also raises the risk of short circuits and thermal runaway. 2-3 Therefore, an effective SEI is required to enable safe high energy batteries with lithium metal anodes by limiting lithium protrusions. An ideal SEI is electronically insulating and highly conductive for Li + but blocking for other ionic species in the electrolyte. Furthermore, it does not react with the electrolyte, is homogeneous in terms of Li + transport and mechanically stable. 4 To enable those characteristics, there are different approaches to grow an effective SEI, such as the use of electrolyte additives, mechanical methods (roll-pressing, micro-patterning) and chemical modification (immersion). 5-7 Herein, we present a novel approach to form an effective SEI on the lithium metal surface by combining mechanical (roll-pressing) and chemical modification utilizing various ionic liquids (ILs) and salts prior to cell assembly for application in high voltage, low temperature lithium metal batteries with liquid electrolytes. Applying this mechanochemical method leads to significantly decreased impedance and low overvoltage during electrodissolution/-deposition, even at high current densities of 10 mA cm -2 . In addition to electrochemical tests, X-Ray photoelectron spectroscopy (XPS) was utilized to shed light on the correlation between improved electrochemical performance and the composition of the artificial SEI layer. Acknowledgements: The research presented is part of the ‘VIDICAT’ project funded by the European Union's Horizon 2020 research and innovation program under grant agreement n° 829145. The authors would like to thank Dr. Uta Rodehorst for conducting the XPS measurements. References: Manthiram, A.; Fu, Y.; Chung, S.-H.; Zu, C.; Su, Y.-S., Chemical Reviews 2014, 114 (23), 11751-11787. Peled, E.; Menkin, S., Journal of The Electrochemical Society 2017, 164 (7), A1703-A1719. Bieker, G.; Winter, M.; Bieker, P., Physical Chemistry Chemical Physics 2015, 17 (14), 8670-8679. Peled, E., Journal of The Electrochemical Society 1979, 126 (12), 2047-2051. Josef, E.; Yan, Y.; Stan, M. C.; Wellmann, J.; Vizintin, A.; Winter, M.; Johansson, P.; Dominko, R.; Guterman, R., Israel Journal of Chemistry 2019 . Basile, A.; Bhatt, A. I.; O’Mullane, A. P., Nature Communications 2016, 7 , 11794. Becking, J.; Gröbmeyer, A.; Kolek, M.; Rodehorst, U.; Schulze, S.; Winter, M.; Bieker, P.; Stan, M. C., Advanced Materials Interfaces 2017, 4 (16), 1700166.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2020
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  • 4
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2023-01, No. 1 ( 2023-08-28), p. 400-400
    Abstract: The energy density of traditional lithium ion batteries (LIB) based on graphite intercalation compounds as negative active material is approaching the theoretical limit and are restricting the increasing demand of high energy battery systems for various mobile and stationary applications. [1] Consequently, the implementation of active materials with high specific energies became prerequisite for future battery technologies. Therein, lithium metal is one of the most promising anode active materials to replace state-of-the-art graphite active materials, due to its high theoretical capacity and low electrode potential. [2] However, poor cycling performance, low Coulombic efficiency, and the uncontrollable Li dendrite growth during lithium electrodeposition/dissolution processes remain as predominant challenges. [3] Several approaches were proposed to eliminate dendrite formation by implementing a mechanically and electrochemically stable artificial solid electrolyte interphase or artificial protective coatings ( a PC) by in-situ or ex-situ surface modifications. [4] These designed a PCs should feature an increased and uniform Li-ion flux, mechanical robustness and/or protection against electrolyte decomposition, during substantial volume changes upon electrodeposition/dissolution. However, a PCs fail to support long term cycling stability in lithium metal batteries since they cannot cover all requirements. [5] Therefore, it is crucial to design and understand dual- and multilayer system that address multiple aforementioned requisites. [6] In this contribution, a dual-protective artificial layer is constructed on Li metal by physical vapor deposition consisting of an intermetallic LiZn-layer, providing a uniform Li-ion flux, and an inorganic Li 3 N-layer, which is electron-blocking, thus reveal surface protective properties. In addition to electrochemical characterization, the Li electrodeposition/dissolution behavior was investigated by cryo-FIB/SEM analysis to unravel the mechanism behind the enhanced cycling stability in symmetrical Li||Li cells and cells with a layered oxide-based positive electrode. [1] R. Schmuch, R. Wagner, G. Hörpel, T. Placke, M. Winter, Nature Energy 2018 , 3, 267. [2] J. Liu, Z. Bao, Y. Cui, E. J. Dufek, J. B. Goodenough, P. Khalifah, Q. Li, B. Y. Liaw, P. Liu, A. Manthiram, Y. S. Meng, V. R. Subramanian, M. F. Toney, V. V. Viswanathan, M. S. Whittingham, J. Xiao, W. Xu, J. Yang, X.-Q. Yang, J.-G. Zhang, Nature Energy 2019 , 4, 180. [3] T. Placke, R. Kloepsch, S. Dühnen, M. Winter, Journal of Solid State Electrochemistry 2017 , 21, 1939. [4] N. Delaporte, Y. Wang, K. Zaghib, Frontiers in Materials 2019 , 6. [5] D. Lin, Y. Liu, Y. Cui, Nature Nanotechnology 2017 , 12, 194. [6] S. Lee, K.-s. Lee, S. Kim, K. Yoon, S. Han, M. H. Lee, Y. Ko, J. H. Noh, W. Kim, K. Kang, Science Advances 2022 , 8, 1.
    Type of Medium: Online Resource
    ISSN: 2151-2043
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    Publisher: The Electrochemical Society
    Publication Date: 2023
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  • 5
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    Online Resource
    The Electrochemical Society ; 2022
    In:  ECS Meeting Abstracts Vol. MA2022-01, No. 2 ( 2022-07-07), p. 250-250
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2022-01, No. 2 ( 2022-07-07), p. 250-250
    Abstract: Apart from particle-type inorganic solid electrolytes, organic, i.e. solid polymer electrolytes (SPEs), are of high potential interest for the realization of next generation Li metal batteries, given their abundance, low cost, electrochemical stability and wetting ability.(1, 2) Nevertheless, the poor ion transport in SPEs limits the battery operation to elevated temperature and/or lower rates only and remains main focus of R & D.(3) Besides the internal-resistance induced polarizations (overpotentials), it is the onset of concentration polarization, which determines the operation limit in terms of e.g. temperature and current density. This work aims to practically unravel the mystery of concentration polarization by means of simple electrochemical experiments in Li||Li cells and mathematical descriptions via the well-known Sand and diffusion equations.(4, 5) The conformity of theory and experiments allows valuable mathematical determinations and predictions of parameter and operation limits. For example, these equations can predict the practical onset of concentration polarization. Also, parameter can be obtained, e.g. diffusion coefficients, based on the experimentally observed polarization onsets. The relevance of concentration polarization including its impact on the cell performance even in high voltage LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)||Li cells is demonstrated by experimentally varying the applied current, the salt concentration, the temperature as well as the cell set-up ( e.g. electrolyte thickness and electrode area-oversizing).(6) The validity of these relations is additionally confirmed in state-of-the-art liquid, i.e. LiPF 6 /carbonate-based, electrolytes and the special case of single-ion conducting electrolytes is discussed. L. Stolz, S. Röser, G. Homann, M. Winter and J. Kasnatscheew, The Journal of Physical Chemistry C , 125 , 18089 (2021). J. Mindemark, M. J. Lacey, T. Bowden and D. Brandell, Prog. Polym. Sci. , 81 , 114 (2018). J. Janek and W. G. Zeier, Nature Energy , 1 , 16141 (2016). L. Stolz, G. Homann, M. Winter and J. Kasnatscheew, Data in Brief , 34 , 106688 (2021). L. Stolz, G. Homann, M. Winter and J. Kasnatscheew, Materials Today , 44 , 9 (2021). L. Stolz, G. Homann, M. Winter and J. Kasnatscheew, ChemSusChem , 14 , 2163 (2021). Figure 1
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    ISSN: 2151-2043
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    Publisher: The Electrochemical Society
    Publication Date: 2022
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  • 6
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    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-03, No. 2 ( 2019-02-01), p. 142-142
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-03, No. 2 ( 2019-02-01), p. 142-142
    Abstract: Active cathode materials in lithium ion batteries are often based on transition metals like cobalt or nickel. High cost and toxicity as well as the mining and fabrication under ethically questionable conditions are serious drawbacks of these metals used in state-of-the-art materials. On the route towards a “greener” and more sustainable lithium ion technology, alternatives such as organic and hybrid inorganic/organic active materials obtained increasing attraction in the last years. [1] One promising hybrid material class are metal-organic frameworks (MOFs). Due to their high surface area and well-defined porosity as well as their flexible and designable structure MOFs have received increasing attention over the last decades for different potential applications like gas storage or catalysis. More recently, this promising class of materials has also been investigated for energy storage devices as electrode active material. [2] MOFs consist of inorganic metal-oxo clusters (called secondary building unit, SBU in short) coordinated to multivalent rigid organic molecules (often referred as “linker”), which can be modified with a variety of functional groups forming a crystalline porous structure. The well-defined pore size is tailorable by the length of the linker molecules leading to a high flexibility accessible for reversible insertion and removal of guest molecules. The highly porous crystalline structure, especially their large pore size, make them interesting for reversible cation or anion storage, e.g. in the dual-ion battery concept. [3] Furthermore, multivalent metal ions in the SBU as well as organic linker molecules can act as redox-activ e sites, leading to a promising active material. [4] Porphyrin-based organic derivates, which occur. e.g. in human blood and vitamin B12, are well known for their catalytic- and redox-activity. In the present work, we synthesize various porphyrin-based MOFs with different coordinated metals, which are successfully applied as an energy storage material in a lithium metal cell and characterized with respect to the structural and surface properties. Combining the redox-active porphyrin derivate, Tetrakis(4-carboxyphenyl)porphyrin (TCPP), and a redox-active metal(oxo-)cluster, a non-toxic and environmentally friendly cathode material was achieved. Constant current cycling and cyclic voltammetry studies reveal a high and reversible redox activity. Using suitable methods such as X-ray diffraction (XRD), the redox reaction behavior of the metal-organic framework and the structural properties of the MOFs were investigated upon charge/discharge operation. Furthermore, the influence of different conductive salts and solvents on the electrochemical performance were analyzed. References: [1] D. Larcher; J.-M. Tarascon; Towards greener and more sustainable batteries for electrical energy storage. Nature Chemistry 2015; 7; 19-29. [2] Wang, L.; Han, Y.; Feng, X.; Zhou, J.; Qi, P.; Wang, B., Metal–organic frameworks for energy storage: Batteries and supercapacitors. Coordination Chemistry Reviews 2016, 307, 361-381. [3] Aubrey, M. L.; Long, J. R., A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework. Journal of the American Chemical Society 2015, 137 (42), 13594-13602. [4] D'Alessandro, D. M., Exploiting redox activity in metal-organic frameworks: concepts, trends and perspectives. Chemical Communications 2016, 52, 8957-8971.
    Type of Medium: Online Resource
    ISSN: 2151-2043
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    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 7
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    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Meeting Abstracts Vol. MA2015-02, No. 1 ( 2015-07-07), p. 140-140
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-02, No. 1 ( 2015-07-07), p. 140-140
    Abstract: Introduction - CuO as a transition metal oxide has been used as Li-CuO primary battery for more than 30 years and the discharge reaction mechanism has been investigated ever since 1 . However, debates still exist as regarding to whether intermediate composites would be formed during the electrochemical discharge. Nowadays, CuO has become a powerful electrode candidate in the lithium-ion battery field because of its high theoretical capacity and nontoxic nature 2 . As the anode material for lithium-ion batteries, traditional graphitic carbon such as mesocarbon microbeads (MCMB) and natural graphite are under challenge of CuO due to their limited specific capacities, which cannot satisfy the demand for future energy storage, especially for electric vehicle application 3 . Experimental - With a commercial available CuO as raw material, a high capacity retaining CuO anode electrode has been fabricated with modifying/varying electrode preparation parameters. Among them, particle size and binder usage, as well as tableting pressure have proved to have great influence on the electrochemical performance of the cell. When matched with a commercial NMC cathode, the corresponding full pouch bag cell shows a specific capacity of 655.8mAh/g (capacity calculated based on CuO, Figure 1) within the voltage range of 0.7-4.0 V at room temperature. To understand the beneficial effect of the preparation method, the reaction mechanism of the modified CuO electrode is investigated. With the help of different characterization methods such as in-situ X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), electrochemical characterization (Cyclic Volatammerty, CCCV), a detailed picture can be obtained. In-situ XRD reveals phase changes at different voltages. Hence, the reaction between CuO and Li can be distinguished. Besides, the corresponding TEM images and X-ray Photoelectron Spectroscopy (XPS) analysis at different voltages allow to determine the thickness change of the electrolyte decomposition layer, which covers the active material and has been speculated to contribute to the capacity of the cell as well 4 . Furthermore, the catalytic activity of divided metallic copper is well known in organic chemistry when dealing with hydrogenation of olefin or carboxyl compounds5. To better understand the catalytic mechanism between metallic copper and the commonly used organic electrolytes, storage tests have been conducted to investigate if the electrolyte decomposition will be facilitated in LP30 electrolyte (EC:DMC 3:7, 1M LiPF6) with the appearance of pure copper particles. In addition, electrolytes are collected after charging the cells to different voltages to investigate whether a specific copper oxide which forms at that voltage has a particular effect on the electrolyte degradation. All the aged electrolytes are studied by means of Ion Chromatography (IC) and Gas chromatography–Mass Spectrometry (GC-MS). Acknowledgment – The authors would like to thank the German Research Foundation (DFG) for funding this work within the joint Priority Program 1473 “Materials with New Design for Improved Lithium Ion Batteries – WeNDeLIB”. References 1. H. Ikeda and S. Narukawa, J. Power Sources 9 (1983) 2. J.Y.Xiang, J.P.Tu, J. Zhang, J. Zhong, D.Zhang, J.P.Cheng, Electrochem. Commun. 12 (2010). 3. Z.C.Bai, Y.W.Zhang, Y.H.Zhang, C.L.Guo, B.Tang, Electrochimica Acta 159 (2015) 4. S.Grugeon, S. Laruelle, R. Herrera-Urbina, L. Dupont, P.Poizot, J-M.Tarascon,  Journal of The Electrochemical Society 148 (2001). 5. V. Grignard, Traite´ de Chimie Organique, Tome II, Masson & Cie, Paris (1949). Figure 1
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    ISSN: 2151-2043
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    Publisher: The Electrochemical Society
    Publication Date: 2015
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