Pentafluoro(phenoxy)cyclotriphosphazene Stabilizes Electrode/Electrolyte Interfaces for Sodium‐Ion Pouch Cells of 145 Wh Kg⁻¹

Abstract Sodium‐ion batteries are competitive candidates for large‐scale energy storage batteries due to the abundant sodium resource. However, the electrode interface in the conventional electrolyte is unstable, deteriorating the cycle life of the cells. Introducing functional electrolyte additives can generate stable electrode interfaces. Here, pentafluoro(phenoxy)cyclotriphosphazene (FPPN) serves as a functional electrolyte additive to stabilize the interfaces of the layered oxide cathode and the hard carbon anode. The fluorine substituting groups and the π–π conjugated ─PN─ structure decrease the lowest unoccupied molecular orbital and increase the highest occupied molecular orbital of FPPN, respectively, realizing the preferential reduction and oxidization of FPPN on the anode and cathode simultaneously, which results in the formation of a uniform, ultrathin, and inorganic‐rich solid electrolyte interlayer and cathode electrolyte interphase. The sodium‐ion pouch cells of 5 Ah capacity rather than coin cells are assembled to evaluate the effect of FPPN. It can retain a high capacity of 4.46 Ah after 1000 cycles, corresponding to a low decay ratio of 0.01% per cycle. The pouch cell also achieves a high energy density of 145 Wh kg⁻¹ and a wide operating temperature of −20–60 °C. This work can attract more attention to the rational electrolyte design for practical applications.