Constructing Stable Anion‐Tuned Electrode/Electrolyte Interphase on High‐Voltage Na3V2(PO4)2F3 Cathode for Thermally‐Modulated Fast‐Charging Batteries

Abstract Constructing stable electrode/electrolyte interphase with fast interfacial kinetics is vital for fast‐charging batteries. Herein, we investigate the interphase that forms between a high‐voltage Na3V2(PO4)2F3 cathode and the electrolytes consisting of 3.0, 1.0, or 0.3 M NaClO4 in an organic carbonate solvent (47.5 : 47.5 : 5 mixture of EC: PC: FEC) during charging up to 4.5 V at 55 °C. It is found that a higher anion/solvent ratio in electrolyte solvation structure induces anion‐dominated interphase containing more inorganic species and more anion derivatives (CxClOy), which leads to a larger interfacial Na+ transport resistance and more unfavorable gas evolution. In comparison, a low anion/solvent ratio derives stable anion‐tuned interphase that enables better interfacial kinetics and cycle ability. Importantly, the performance of a failed cathode is restored by triggering the decomposition of CxClOy species. This work elucidates the role of tuning interphase in fast‐charging batteries.