Modulating local structural disorder in layered cathodes with alternating edge- and face-sharing octahedra for enhanced high-rate performance

O2-type LiCoO$_2$ (O2-LCO), characterized by its alternating edge- and face-sharing octahedral framework, has emerged as a promising high-capacity cathode material. However, rapid capacity fading due to the collapse and sliding of Co–O slabs during electrochemical cycling has hindered the operation under larger working current. In this work, an exceptional cycling stability material (O2-LCMO) at high rate is obtained by introducing Mn into O2-LCO. This regulation enables the Li/TM intrinsic local structural disorder in a crystalline lattice through partial migration of transition-metal (TM) ions into the Li layers. The migrated TM ions serve as pillars to stabilize the deep de-intercalation structure. Furthermore, the tailored local disorder modulates the electronic structure to facilitate Li$^+$ migration, while the accompanying local Co–O–TM configuration improves the reversibility of the local CoO$_6$ octahedral structure during cycling. As a result, the modified cathode delivers markedly improved capacity retention and structural integrity under harsh electrochemical conditions. When cycled at a high rate of 10C up to a 4.65 V cut-off voltage, O2-LCMO delivers an extremely high discharge capacity of 238 mAh g$^{−1}$ and demonstrates superior stability, achieving a capacity retention of 77% after 100 cycles, whereas pristine O2-LCO retains only 10%. ... mehrOur work provides a novel design principle for achieving high-energy, long-cycle-life oxide cathodes through the engineering of intrinsic local structural disorder.