First-Principles-Based Optimized Design of Fluoride Electrolytes for Sodium-Ion Batteries

Because of the abundance and low cost of sodium, sodium-ion batteries (SIBs) are next-generation energy storage mediums. Furthermore, SIBs have become an alternative option for large-scale energy storage systems. Because the electrolyte is a critical component of SIBs, fluorination is performed to improve the cycling performance of electrolytes. Based on the first-principles study, we investigated the effects of the type, quantity, and relative position relationships of three fluorinated units, namely -CF₁, -CF₂, and -CF₃, on the cyclic ester molecule ethylene carbonate (EC) and the linear ether molecule 1,2-dimethoxylethane (DME). The optimal fluorination was proposed for EC and DME by studying the bond length, highest occupied molecular orbital, lowest unoccupied lowest orbital, and other relevant parameters. The results revealed that for EC, the optimal fluorination is 4 F fluorination based on four -CF₁ units; for DME, CF₃CF₁CF₁-, CF₃CF₂CF₂-, CF₃CF₁CF₂CF₃, and CF₃CF₂CF₂CF₃, four combinations of three -CF₁, -CF₂, and -CF₃ units are optimal. The designed fluorinated EC and DME exhibited a wide electrochemical stability window and high ionic solvation ability, which overcomes the drawback of conventional solvents and can improve SIB cycling performance.