Anion‐Adsorption Mediated Facet Engineering and Surface Phase Regulation for Boosting Kinetics of Li‐Rich Layered Oxides

ABSTRACT Li‐rich layered oxides (LLOs) are promising high‐energy‐density cathodes. However, they suffer from poor rate performance and severe capacity fading, primarily due to oxygen loss and structural degradation. Herein, an anion‐adsorption mediated surface structure dual‐regulation strategy based on Ostwald ripening principle is engineered to enhance Li + transport kinetics and oxygen redox stability. It is revealed that anion‐adsorption during the growth of single‐crystal LLOs (SC‐LLOs) directly impact the facet exposure and surface biphasic distribution, determining the Li + diffusion behavior and oxygen evolution. Specifically, SC‐LLOs with Li 2 SO 4 assisting preparation exhibit hexagonal‐plate morphology with orderly active (010) and stable (003) facets exposure, which significantly promotes Li + diffusion rate and reduces interfacial side reaction. Additionally, the formation of a specific LiTMO 2 ‐enriched and Li 2 MnO 3 ‐deficient surface prevents Li 2 MnO 3 surface enrichment to alleviate oxygen release and robust structural stability. As a result, the surface structure dual‐regulation effectively promotes anionic redox kinetics and alleviates the structural degradation, contributing to the achievement of exceptional rate performance (166.0 mAh g −1 at 5 C) and ultra‐stable cyclic stability (98.52% and 91.51% capacity retention after 300 cycles at 1 C and 5 C, representatively). These findings provide a vital reference for synthesizing high‐performance SC‐LLOs through anion‐adsorption mediated regulation.