Insights into the Electrolyte Hydrolysis and Its Impacts on the Interfacial Chemistry of a Li+‐Intercalated Anode during High‐Temperature Calendar Aging

, HF and LiF are generated and assist formation of an inorganics-rich solid electrolyte interphase (SEI), improving anode stability against parasitic reactions. The LiFSI-based electrolyte does not involve hydrolysis, which facilities the formation of an organics-rich SEI. Nevertheless, the SEI does not passivate the anode surface and could induce severe corrosions via electron tunneling at a high temperature. Our work offers original insights into rational design of electrolyte and interface for high-energy, long-calendar-life LIBs.