Unveiling decaying mechanism through quantitative structure-activity relationship in electrolytes for lithium-ion batteries

Abstract Understanding the decaying mechanism in lithium-ion batteries (LIBs) is critical to establishing a stable electrolyte system. Despite the advent of various novel electrolyte solvents designated for high-voltage LIBs, their working principles are not fully understood. Currently, oxidative decomposition of electrolytes is believed to be the major cause of capacity fade, and tremendous effort has been devoted to discovering a new electrolyte with enhanced anodic stability. However, the oxidative decomposition process cannot solely explain the rapid decay of some electrolyte systems with intrinsic high anodic stability when used with a high-nickel layered oxide cathode such as LiNi0.6Mn0.2Co0.2O2 (NMC622). In this report, a study of the quantitative structure-activity relationship was conducted to deepen the mechanistic understanding of the decay in high-voltage LIBs. The results obtained from the newly introduced molecular pair analysis and linear free-energy relationship (LFER) studies were highly consistent with the solvation-involved decaying mechanism in a high-nickel layered oxide cathode cycling at high voltage (> 4.5 V vs. Li/Li+). There was no evidence correlating the solvation ability of electrolyte solvents with the decay of a high-nickel layered oxide cathode cycling at a relatively low voltage (