Oxygen Vacancies Driven by Co in the Deeply Charged State Inducing Intragranular Cracking of Ni‐Rich Cathodes

Abstract Intragranular cracking within the material structure of Ni‐rich (LiNi x Co y Mn 1 ‐ x ‐ y , x ≥0.9) cathodes greatly threatens cathode integrity and causes capacity degradation, yet its atomic‐scale incubation mechanism is not completely elucidated. Notably, the physicochemical properties of component elements fundamentally determine the material structure of cathodes. Herein, a diffusion‐controlled incubation mechanism of intragranular cracking is unraveled, and an underlying correlation model with Co element is established. Multi‐dimensional analysis reveals that oxygen vacancies appear due to the charge compensation from highly oxidizing Co ions in the deeply charged state, driving the transition metal migration to Li layer and layered to rock‐salt phase transition. The local accumulation of two accompanying tensile strains collaborates to promote the nucleation and growth of intragranular cracks along the fragile rock‐salt phase domain on (003) plane. This study focuses on the potential risks posed by Co to the architectural and thermal stability of Ni‐rich cathodes and is dedicated to the compositional design and performance optimization of Ni‐rich cathodes.