Armoring LiNi_1/3Co_1/3Mn_1/3O₂ Cathode with Reliable Fluorinated Organic–Inorganic Hybrid Interphase Layer toward Durable High Rate Battery

Abstract Ternary layered oxide materials have attracted extensive attention as a promising cathode candidate for high‐energy‐density lithium‐ion batteries. However, the undesirable electrochemical degradation at the electrode–electrolyte interface definitively shortens the battery service life. An effective and viable approach is proposed for improving the cycling stability of the LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode using lithium difluorophosphate (LiPO 2 F 2 ) paired with fuoroethylene carbonate (FEC) as co‐additives into conventional electrolytes. It is found that the co‐additives can greatly reduce the interface charge transfer impedance and significantly extend the life span of LiNi 1/3 Co 1/3 Mn 1/3 O 2 //Li (NMC//Li) batteries. The developed cathode demonstrates exceptional capacity retention of 88.7% and remains structural integrity at a high current of 5C after 500 cycles. Fundamental mechanism study indicates a dense, stable fluorinated organic–inorganic hybrid cathode‐electrolyte interphase (CEI) film derived from LiPO 2 F 2 in conjunction with FEC additives on the surface of NMC cathode material, which significantly suppresses the decomposition of electrolyte and mitigates the dissolution of transition metal ions. The interfacial engineering of the electrode materials stabilized by the additives manipulation provides valuable guidance for the development of advanced cathode materials.