Anion-Induced Uniform and Robust Cathode–Electrolyte Interphase for Layered Metal Oxide Cathodes of Sodium Ion Batteries

Layer metal oxides demonstrate great commercial application potential in sodium-ion batteries, while their commercialization is extremely hampered by the unsatisfactory cycling performance caused by the irreversible phase transition and interfacial side reaction. Herein, trimethoxymethylsilane (TMSI) is introduced into electrolytes to construct an advanced cathode/electrolyte interphase by tuning the solvation structure of anions. It is found that due to the stronger interaction between ClO 4 – and TMSI than that of ClO 4 – and PC/FEC, the ClO 4 – –TMSI complexes tend to accumulate on the surface of the cathode during the charging process, leading to the formation of a stable cathode/electrolyte interface (CEI). In addition, the Si species with excellent electronic insulation ability are distributed in the TMSI-derived CEI film, which is conducive to inhibiting the continuous side reaction of solvents and the growth of the CEI film. As a result, under a current density of 250 mA g –1, the capacity retention of the NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NFM) cathode after 200 cycles in the TMSI-modified electrolyte is 74.4% in comparison to 51.5% of the bare electrolyte (1 M NaClO 4 /PC/5% FEC). Moreover, the NFM cathode shows better kinetics, with the specific discharge capacity increasing from 22 to 67 mAh g –1 at 300 mA g –1 . It also demonstrates greatly improved rate capability, cycling stability, and Coulombic efficiency under various operating conditions, including high temperature (55 °C) and high cutoff voltage (2.0–4.3 V vs Na + /Na).