Role of Solvent-anion Charge Transfer in Oxidative Degradation of Battery Electrolytes

Overview

Journal Nat Commun

Specialty Biology

Date 2019 Jul 28

PMID 31350394

Citations 4

Authors

Eric R Fadel

Francesco Faglioni

Georgy Samsonidze

Nicola Molinari

Boris V Merinov

William A Goddard Iii

Jeffrey C Grossman

Jonathan P Mailoa

Boris Kozinsky

Affiliations

Soon will be listed here.

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.

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