Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes

Eric R. Fadel, Francesco Faglioni, Georgy Samsonidze, Nicola Molinari, Boris V. Merinov, William A. Goddard, Jeffrey C. Grossman, Jonathan P. Mailoa and Boris Kozinsky ()
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Eric R. Fadel: Harvard University
Francesco Faglioni: University of Modena and Reggio Emilia
Georgy Samsonidze: Research and Technology Center
Nicola Molinari: Harvard University
Boris V. Merinov: California Institute of Technology
William A. Goddard: California Institute of Technology
Jeffrey C. Grossman: Massachusetts Institute of Technology
Jonathan P. Mailoa: Research and Technology Center
Boris Kozinsky: Harvard University

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract 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.

Date: 2019
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DOI: 10.1038/s41467-019-11317-3

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