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

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. Se^2- 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.