Deciphering Interphase Instability of Lithium Metal Batteries with Localized High-Concentration Electrolytes at Elevated Temperatures

Abstract: Lithium metal batteries (LMBs), when coupled with a localized high-concentration electrolyte and a high-voltage nickel-rich cathode, offer a solution to the increasing demand for high energy density and long cycle life. However, the aggressive electrode chemistry poses safety risks to LMBs at higher temperatures and cutoff voltages. Here, we decipher the interphase instability in LHCE-based LMBs with a Ni0.8Co0.1Mn0.1O2 cathode at elevated temperatures. Our findings reveal that the generation of fluorine radicals in the electrolyte induces the solvent decomposition and consequent chain reactions, thereby reconstructing the cathode electrolyte interphase (CEI) and degrading battery cyclability. As further evidenced, introducing an acid scavenger of dimethoxydimethylsilane (DODSi) significantly boosts CEI stability with suppressed microcracking. A Ni0.8Co0.1Mn0.1O2||Li cell with this DODSi-functionalized LHCE achieves an unprecedented capacity retention of 93.0% after 100 cycles at 80 {\deg}C. This research provides insights into electrolyte engineering for practical LMBs with high safety under extreme temperatures.