Inducing Favorable Cation Antisite by Doping Halogen in Ni‐Rich Layered Cathode with Ultrahigh Stability

Abstract The cation antisite is the most recognizable intrinsic defect type in nickel‐rich layered and olivine‐type cathode materials for lithium‐ion batteries, and important for electrochemical/thermal performance. While how to generate the favorable antisite has not been put forward, herein, by combining first‐principles calculation with neutron powder diffraction (NPD) study, a defect inducing the favorable antisite mechanism is proposed to improve cathode stability, that is, halogen substitution facilitates the neighboring Li and Ni atoms to exchange their sites, forming a more stable local octahedron of halide (LOSH). According to the mechanism, it is demonstrated by NPD that F‐doping not only induces the antisite formation in layered LiNi 0.85 Co 0.075 Mn 0.075 O 2 (LNCM), but also increases the antisite concentration linearly. F substitution (1%) induces 5.7% antisite, and it displays an excellent capacity retention of 94% at 1 C for 200 cycles under 25 °C, outstanding high temperature cyclability (153.4 mAh·g –1 at 1 C for 120 cycles under 55 °C). The onset decomposition temperature increases by 48 °C. The ultrahigh cycling/thermal stability is attributed to the stronger LOSH, and it keeps the structural integrity after long cycling and develops an electrostatic repulsion force between oxygen layers to increase the lattice parameter c , which benefits Li‐ion migration.