The Origin of the Reduced Reductive Stability of Ion–Solvent Complexes on Alkali and Alkaline Earth Metal Anodes

Abstract

The intrinsic instability of organic electrolytes seriously impedes practical applications of high-capacity metal (Li, Na) anodes.I on-solvent complexes can even promote the decomposition of electrolytes on metal anodes. Herein, first-principles calculations were performed to investigate the origin of the reduced reductive stability of ionsolvent complexes.Both ester and ether electrolyte solvents are selected to interact with Li + ,N a + ,K + ,M g 2+ ,a nd Ca 2+ .T he LUMO energy levels of ion-ester complexes exhibit al inear relationship with the binding energy,r egulated by the ratio of carbon atomic orbital in the LUMO,w hile LUMOs of ionether complexes are composed by the metal atomic orbitals. This work shows why ion-solvent complexes can reduce the reductive stability of electrolytes,reveals different mechanisms for ester and ether electrolytes,a nd provides at heoretical understanding of the electrolyte-anode interfacial reactions and guidance to electrolyte and metal anode design.

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