Synergistic LiBO 2 /CeF 3 hybrid coating engineering for chemically stabilized cathode–electrolyte interphase in nickel‐rich cathodes

Abstract Nickel‐rich LiNi x Co y Mn 1− x − y O 2 (NCM) cathodes, pivotal for high‐energy–density lithium‐ion batteries, face severe challenges from surface residual lithium compounds and hydrofluoric acid (HF)‐induced degradation. These issues accelerate capacity fading, exacerbate interfacial polarization, and compromise safety. To address these issues, we proposed a scalable CeF 3 /H 3 BO 3 hybrid coating strategy for LiNi 0.82 Co 0.12 Mn 0.06 O 2 cathodes. The CeF 3 nanoparticles served as a robust physical barrier, effectively scavenging HF, while the LiBO 2 layer derived from H 3 BO 3 eliminated residual Li 2 CO 3 through chemical conversion and established rapid Li + transport pathways. Dynamic B‐O bond reorganization enabled self‐repair of coating defects, synergistically suppressing interfacial polarization and maintaining structural integrity. Electrochemical evaluations demonstrated that the hybrid‐coated cathode achieves 94% capacity retention after 200 cycles at 1C (2.8–4.3 V), significantly outperforming the pristine NCM (56.3%). Additionally, the modified cathode exhibits enhanced air stability, with suppressed H 2 O/CO 2 infiltration, and delivers 80% capacity retention after 1000 cycles in practical pouch cells. This work provides a cost‐effective and industrially viable solution to simultaneously mitigate HF corrosion, residual lithium accumulation, and cathode–electrolyte interphase instability, paving the way for durable high‐energy–density batteries.