Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation
Chemistry of Materials
American Chemical Society
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Michan, A., Parimalam, B., Leskes, M., Kerber, R., Yoon, T., Grey, C., & Lucht, B. (2016). Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation. Chemistry of Materials, 28 (22), 8149-8159. https://doi.org/10.1021/acs.chemmater.6b02282
We have synthesized the products of fluoroethylene carbonate (FEC) and vinylene carbonate (VC) via lithium naphthalenide reduction. By analyzing the resulting solid precipitates and gas evolution, our results confirm that both FEC and VC decomposition products include HCO$_2$Li, Li$_2$C$_2$O$_4$, Li$_2$CO$_3$, and polymerized VC. For FEC, our experimental data supports a reduction mechanism where FEC reduces to form VC and LiF, followed by subsequent VC reduction. In the FEC reduction product, HCO$_2$Li, Li$_2$C$_2$O$_4$, and Li$_2$CO$_3$ were found in smaller quantities than in the VC reduction product, with no additional fluorine environments being detected by solid-state nuclear magnetic resonance or X-ray photoelectron spectroscopy analysis. With these additives being practically used in higher (FEC) and lower (VC) concentrations in the base electrolytes of lithium-ion batteries, our results suggest that the different relative ratios of the inorganic and organic reduction products formed by their decomposition may be relevant to the chemical composition and morphology of the solid electrolyte interphase formed in their presence.
This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154. This work was partially supported by the U.S. Department of Energy EPSCoR Implementation Award Grant DE-SC0007074 for B.L.L., B.S.P., and T.Y. A.L.M. is an awardee of a Schiff Foundation Studentship and a nanoDTC Associate. M.L. is an awardee of the Weizmann Institute of Science - National Postdoctoral Award for Advancing Women in Science and thanks the EU Marie Curie intra-European fellowship for funding.
External DOI: https://doi.org/10.1021/acs.chemmater.6b02282
This record's URL: https://www.repository.cam.ac.uk/handle/1810/261739