Invoking Interfacial Engineering Boosts Structural Stability Empowering Exceptional Cyclability of Ni‐Rich Cathode

Abstract The cycling stability of LiNi_0.8Co_0.1Mn_0.1O₂ under high voltages is hindered by the occurrence of hybrid anion‐ and cation‐redox processes, leading to oxygen escape and uncontrolled phase collapse. In this study, an interfacial engineering strategy involving a straightforward mechanical ball milling and low‐temperature calcination, employing a Se‐doped and FeSe₂&Fe₂O₃‐modified approach is proposed to design a stable Ni‐rich cathode. Se²⁻ are selectively adsorbed within oxygen vacancies to form O─TM─Se bond, effectively stabilizing lattice oxygen, and preventing structural distortion. Simultaneously, the Se‐NCM811//FeSe₂//Fe₂O₃ self‐assembled electric field is activated, improving interfacial charge transfer and coupling. Furthermore, FeSe₂ accelerates Li⁺ diffusion and reacts with oxygen to form Fe₂O₃ and SeO₂. The Fe₂O₃ coating mitigates hydrofluoric acid erosion and acts as an electrostatic shield layer, limiting the outward migration of oxygen anions. Impressively, the modified materials exhibit significantly improved electrochemical performance, with a capacity retention of 79.7% after 500 cycles at 1C under 4.5 V. Furthermore, it provides an extraordinary capacity retention of 94.6% in 3–4.25 V after 550 cycles in pouch‐type full battery. This dual‐modification approach demonstrates its feasibility and opens new perspective for the development of stable lithium‐ion batteries operating at high voltages.