Mechanochemical Transformation From Zigzag‐Type Layered/Phenakite to Disordered Rocksalt in Mn‐Rich Cathodes for Li‐Ion Batteries

ABSTRACT Understanding how cation disorder develops in Mn‐rich disordered rocksalt (DRX) systems—particularly under mechanochemical activation—has been hindered by limited insight into the underlying transformation pathways. Here, we uncover a distinct transformation route in Li _1.2 Mn _(2+x)/3 Mo _(0.4‐x)/3 O _2‐x F _x (LMMOFx), in which Mo and F co‐doping drives the material toward a zigzag‐type layered/phenakite‐mixed structure. This layered/phenakite‐mixed phase undergoes pronounced local structural reconstruction, which promotes DRX formation and induces a transition from a two‐phase Mn and O redox mechanism to a stable single‐phase process, delivering a high reversible capacity of 297.9 mAh g ⁻¹ . Systematic structural and electrochemical comparisons across the LMMOF series further reveal how progressive disorder and phase mixing reshape Li‐ion transport pathways. Together, these results establish a mechanistic framework for leveraging dopant‐ and structure‐controlled precursor chemistry to direct mechanochemical DRX formation, and they offer a design principle for earth‐abundant, Mn‐rich DRX cathodes with tunable disorder.