Enhanced Cycling Stability of High-Voltage Sodium-Ion Batteries via DFEC-Driven Fluorinated Interface Engineering

With their considerable capacity and structurally favorable characteristics, layered transition metal oxides have become strong contenders for cathode use in sodium-ion batteries (SIBs). Nevertheless, their practical deployment is challenged by pronounced capacity loss, predominantly induced by unstable cathode–electrolyte interphase (CEI) at elevated voltages. In this study, difluoroethylene carbonate (DFEC) is introduced as a functional electrolyte additive to engineer a robust and uniform CEI. The fluorine-enriched CEI effectively suppresses parasitic reactions, mitigates continuous electrolyte decomposition, and facilitates stable Na+ transport. Consequently, Na/NaNi1/3Fe1/3Mn1/3O2 (Na/NFM) cells with 2 wt.% DFEC retain 78.36% of their initial capacity after 200 cycles at 1 C and 4.2 V, demonstrating excellent long-term stability. Density functional theory (DFT) calculations confirm the higher oxidative stability of DFEC compared to conventional solvents, further supporting its interfacial protection role. This work offers valuable insights into electrolyte additive design for high-voltage SIBs and provides a practical route to significantly improve long-term electrochemical performance.