Long‐Range Cationic Disordering Induces two Distinct Degradation Pathways in Co‐Free Ni‐Rich Layered Cathodes

Abstract Ni‐rich layered oxides are one of the most attractive cathode materials in high‐energy‐density lithium‐ion batteries, their degradation mechanisms are still not completely elucidated. Herein, we report a strong dependence of degradation pathways on the long‐range cationic disordering of Co‐free Ni‐rich Li 1− m (Ni 0.94 Al 0.06 ) 1+ m O 2 (NA). Interestingly, a disordered layered phase with lattice mismatch can be easily formed in the near‐surface region of NA particles with very low cation disorder (NA‐LCD, m ≤0.06) over electrochemical cycling, while the layered structure is basically maintained in the core of particles forming a “core–shell” structure. Such surface reconstruction triggers a rapid capacity decay during the first 100 cycles between 2.7 and 4.3 V at 1 C or 3 C. On the contrary, the local lattice distortions are gradually accumulated throughout the whole NA particles with higher degrees of cation disorder (NA‐HCD, 0.06≤ m ≤0.15) that lead to a slow capacity decay upon cycling.