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Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes
Name
s41467-019-11317-3.pdf
Description
Published version
Size
1.2 MB
Format
Adobe PDF
Checksum (MD5)
4950859d3ef819fec268560f79f2ac5b
Author(s)
Fadel, Eric R
Faglioni, Francesco
Samsonidze, Georgy
Molinari, Nicola
Merinov, Boris V
Goddard III, William A
Grossman, Jeffrey C
Mailoa, Jonathan P
Kozinsky, Boris
Date Issued
2019
Journal
Nature Communications
Publisher
Springer Science and Business Media LLC
Version
Final published version
Abstract
© 2019, The Author(s). Electrochemical stability windows of electrolytes largely determine the limitations of operating regimes of lithium-ion batteries, but the degradation mechanisms are difficult to characterize and poorly understood. Using computational quantum chemistry to investigate the oxidative decomposition that govern voltage stability of multi-component organic electrolytes, we find that electrolyte decomposition is a process involving the solvent and the salt anion and requires explicit treatment of their coupling. We find that the ionization potential of the solvent-anion system is often lower than that of the isolated solvent or the anion. This mutual weakening effect is explained by the formation of the anion-solvent charge-transfer complex, which we study for 16 anion-solvent combinations. This understanding of the oxidation mechanism allows the formulation of a simple predictive model that explains experimentally observed trends in the onset voltages of degradation of electrolytes near the cathode. This model opens opportunities for rapid rational design of stable electrolytes for high-energy batteries.
Terms of Use
Creative Commons Attribution 4.0 International license
Persistent DSpace Link
DOI of Published Version
10.1038/s41467-019-11317-3
