February 13, 2020
Auditorium LAVO 51 (Lavoisier Building)
Electrolyte, solvation shell and interphase for Ca metal anode based batteries
J. D. Forero-Saboya,1 E. Marchante,1 R. B. Araujo,2 D. Monti,1 P. Johansson,2 A. Ponrouch 1*
1 Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Catalonia (Spain).
2 Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg (Sweden).
Various metals have been used as battery anodes in electrochemical cells ever since the birth of the batteries with Volta’s pile and in the first commercialized primary (Zn/MnO2, Leclanché 1866) and secondary (Pb/acid, Planté 1859) batteries. Li-MoS2 cells, employing Li metal anodes, with specific energies two to three times higher than both Ni/Cd and Pb/acid cells, were withdrawn from the market due to safety issues related to dendrites growth. Instead, electrodeposition of Mg and Ca appears to be less prone to dendrite formation.[1,2] Pioneering work by Aurbach et al. in the early 1990’s showed a surface-film controlled electrochemical behavior of Ca and Mg metal anodes in electrolytes with conventional organic solvents.[3,4] The lack of metal plating was attributed to the poor divalent cation migration through the passivation layer.
Nevertheless, recent demonstration of Ca plating and stripping in the presence of a passivation layer or an artificial interphase [2,5] has paved the way for assessment of new electrolyte formulations with high resilience towards oxidation. However, several challenges remain to be tackled for the development of Ca based batteries.[6,7] Among these, the need for reliable electrochemical test protocols, mass transport limitations and high desolvation energies (due to strong cation-solvent and cation–anion interactions) are implied.[8,9] Here, a systematic investigation on the impact of the electrolyte formulation on the cation solvation structure and transport is presented. Finally, characterization of the SEI formed on the Ca metal anode in various electrolyte formulations using complementary techniques allowed for the identification of the most suitable SEI compounds in terms of divalent cation mobility.
Fig. 1 Scheme of a Ca metal anode-based battery with the main problems/ requirements outlined..
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- A. Ponrouch, C. Frontera, F. Bardé, M.R. Palacín, Nat. Mater., 15 (2016) 169
- D. Aurbach, R. Skaletsky, Y. Gofer, J. Electrochem. Soc.138 (1991) 3536
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- A. Ponrouch, M.R. Palacín, Current Opinion in Electrochemistry 9 (2018) 1
- M. Elena Arroyo-de Dompablo, A. Ponrouch, P. Johansson, M.R. Palacin, Chem. Rev. doi.org/10.1021/acs.chemrev.9b00339.
- D. S. Tchitchekova, D. Monti, P. Johansson, F. Bardé, A. Randon-Vitanova, M. R. Palacı́n, A. Ponrouch, J. Electrochem. Soc., 164 (2017) A1384
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- J. D. Forero-Saboya, E. Marchante, R. B. Araujo, D. Monti, P. Johansson, A. Ponrouch, J. Phys. Chem. C. 123 (2019) 29524.
Dr Alexandre Ponrouch received his Master Degree in Electrochemistry from Paul Sabatier University (Toulouse, France) and his PhD from the Institut National de la Recherche Scientifique (INRS-EMT, Canada) in 2010, where he worked on electrodeposition of metals, alloys and oxides for application in fuel cells and supercapacitors. Then he moved to the Institut de Cíencia de Materials de Barcelona (ICMAB-CSIC, Spain) as a postdoctoral fellow, studying electrodes and electrolyte formulations for Li and Na-ion batteries. In 2017, in the framework of an ERC starting grant, he set up a new laboratory in the ICMAB, dedicated to development of multivalent cation (Ca and Mg) based rechargeable and focusing on fundamental electrochemistry.