Interfacial Engineering With a Multifunctional LaPO 4 /LaF 3 Coating Enables Durable 4.65 V LiCoO 2 Cathodes With High‐Rate Capability

High‐power fast‐charging lithium‐ion batteries (LIBs) are indispensable energy sources for electric vehicles and consumer electronics. LiCoO 2 (LCO) offers remarkable energy density and high voltage but suffers from structural degradation and irreversible O3/H1‐3 phase transition at high voltage (e.g., 4.65 V), thus limiting its practical use. This study introduces a novel multifunctional LaPO 4 /LaF 3 coating to tackle the structural and interfacial engineering plaguing LCO at 4.65 V. The LaPO 4 /LaF 3 coating effectively reduces interfacial side reactions on LCO by inhibiting structural degradation and intergranular cracks, enables a more reversible O3/H1‐3 phase transition, and enhances rapid Li + transport at the electrode surface. The interfacial engineering of the LaPO 4 /LaF 3 coating also stabilizes the lattice oxygen of LCO by suppressing side reactions and Co dissolution. Specifically, the modified LCO exhibits a capacity retention rate of 79.3% after 1500 cycles when charged to 4.65 V at 5C, highlighting its exceptional electrochemical performance. Further, the assembled pouch cell shows a capacity retention of 89.9% after 200 cycles at 4.6 V with 1C. In particular, these findings offer critical insights into stabilizing LCO at elevated operating voltages, thereby opening new pathways for the development of high‐power fast‐charging LIBs.