G.M. Hobold, C. Wang, K. J. Steinberg, Y. Li, and B. M. Gallant
Nature Energy, 2024, 9, 580-591
[publisher link]

Abstract

Current electrolyte design for Li metal anodes emphasizes fluorination as the pre-eminent guiding principle for high Coulombic efficiency (CE) based largely on perceived benefits of LiF in the solid–electrolyte interphase (SEI). However, the lack of experimental techniques that accurately quantify SEI compositional breakdown impedes rigorous scrutiny of other potentially key phases. Here we demonstrate a quantitative titration approach to reveal Li2O content in cycled Li anodes, enabling this previously titration-silent phase to be compared statistically with a wide range of other leading SEI constituents including LiF. Across diverse electrolytes, CE correlates most strongly with Li2O above other phases, reaching its highest values when Li2O particles order along the SEI, demonstrating integrated chemical–structural function. The beneficial role of Li2O was exploited to create entirely fluorine-free electrolytes that breach >99% CE, highlighting electrolyte/SEI oxygenation as an underexplored design strategy.