Constructing Stable Anion-Tuned Electrode/Electrolyte Interphase on High-Voltage Na3 V2 (PO4 )2 F3 Cathode for Thermally-Modulated Fast-Charging Batteries

Angew Chem Int Ed Engl. 2022 Nov 25;61(48):e202213416. doi: 10.1002/anie.202213416. Epub 2022 Oct 25.

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 Na3 V2 (PO4 )2 F3 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 (Cx ClOy ), 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 Cx ClOy species. This work elucidates the role of tuning interphase in fast-charging batteries.

Keywords: Fast-Charging Batteries; Interfacial Kinetics; Interphase; Na3V2(PO4)2F3.