Surface Chemical Disorder Engineering Enabled Superior Anion Redox for Li‐Rich Mn‐Based Cathode

ABSTRACT The Li‐rich Mn‐based oxides have attracted extensive attention due to the specific anion redox reaction to provide high capacity. However, the poor reversibility of anion redox leads to serious lattice oxygen loss and surface structure evolution. Here, we report an approach by integrating chemical disorder‐based crystallographic texture into the cathode surface to solve these questions, which involves the spatial rearrangement of lattice oxygen by supersaturated occupation of cations in the lattice. This makes the oxygen electronic structure delocalized and diversified, strengthens the metal‐oxygen orbital hybridization, and effectively improves the reversibility and kinetics of anion redox reactions. Meanwhile, the robust surface architecture effectively inhibits superficial detrimental phase evolution and electrode/electrolyte interface side reactions, maintaining the structural integrity of the electrochemical process. Accordingly, the as‐designed modified cathode delivered a promising capacity (291.8 mAh g −1 ), excellent long cycling stability, and voltage retention (90.5% capacity retention and 0.68 mV/cycle voltage fade with 300 cycles). This work highlights the role of surface chemical disorder and the strongly correlated chemical environment of transition metals with oxygen, which is expected to provide a new paradigm for the structural design of cathode materials.