A Critical Analysis of Chemical and Electrochemical Oxidation Mechanisms in Li-Ion Batteries.

Autor: Spotte-Smith EWC; Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California 94720, United States.; Materials Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States., Vijay S; Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California 94720, United States., Petrocelli TB; Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California 94720, United States., Rinkel BLD; Department of Chemical and Biomolecular Engineering, University of California, Berkeley, 201 Gilman Hall, Berkeley, California 94720, United States.; Energy Storage and Distributed Resources, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States., McCloskey BD; Department of Chemical and Biomolecular Engineering, University of California, Berkeley, 201 Gilman Hall, Berkeley, California 94720, United States.; Energy Storage and Distributed Resources, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States., Persson KA; Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California 94720, United States.; Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2024 Jan 18; Vol. 15 (2), pp. 391-400. Date of Electronic Publication: 2024 Jan 04.
DOI: 10.1021/acs.jpclett.3c03279
Abstrakt: Electrolyte decomposition limits the lifetime of commercial lithium-ion batteries (LIBs) and slows the adoption of next-generation energy storage technologies. A fundamental understanding of electrolyte degradation is critical to rationally design stable and energy-dense LIBs. To date, most explanations for electrolyte decomposition at LIB positive electrodes have relied on ethylene carbonate (EC) being chemically oxidized by evolved singlet oxygen ( 1 O 2 ) or electrochemically oxidized. In this work, we apply density functional theory to assess the feasibility of these mechanisms. We find that electrochemical oxidation is unfavorable at any potential reached during normal LIB operation, and we predict that previously reported reactions between the EC and 1 O 2 are kinetically limited at room temperature. Our calculations suggest an alternative mechanism in which EC reacts with superoxide (O 2 - ) and/or peroxide (O 2 2- ) anions. This work provides a new perspective on LIB electrolyte decomposition and motivates further studies to understand the reactivity at positive electrodes.
Databáze: MEDLINE
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