Achieving Synergistic Kinetics and Stability in Li‐Rich Mn‐Based Oxides via AlPO 4 ‐Assisted Multi‐Scale Regulation

ABSTRACT Realizing the full potential of Li‐rich Mn‐based oxides (LRMOs) is contingent upon overcoming the intrinsic conflict between sluggish anionic redox kinetics and structural instability. Conventional modification approaches often fail to harmonize kinetic enhancement with cycling longevity. Herein, we report an AlPO 4 ‐assisted high‐temperature lithiation strategy to achieve multi‐scale synergistic regulation of LRMOs. This innovative approach simultaneously optimizes particle morphology, stabilizes the surface/interface chemistry, and reinforces the bulk lattice integrity: The well‐controlled moderate‐sized primary particles effectively shorten the Li + diffusion path to boost kinetics; the Al‐rich near‐surface barrier and in situ formed Li 3 PO 4 coating synergistically construct a highly stable interface against electrolyte corrosion; the bulk Al/P co‐doping optimizes the electronic structure and stabilizes the lattice oxygen framework; meanwhile, the quasi‐ordered superlattice enables precise tailoring of interlayer stacking and mitigates cycling‐induced lattice strain. Benefiting from this synergistic modification, the optimized LRMO delivers a high capacity of ∼ 240 mAh g −1 at 1 C with 82.5% retention over 500 cycles at 25°C. It also exhibits robust high‐temperature performance (∼ 270 mAh g −1 , 82.3% retention after 200 cycles at 50°C). Notably, a 1 Ah pouch cell maintains 68.4% capacity after 1000 cycles, validating the practical feasibility of this strategy for advanced high‐energy batteries.