Planar Gliding and Vacancy Condensation: The Role of Dislocations in the Chemomechanical Degradation of Layered Transition-Metal Oxides

Stacking faults driven by dislocations have been observed in layered transition-metal oxide cathodes both in cycled and uncycled materials. The reversibility of stacking-sequence changes directly impacts the material performance. Irreversible glide due to lattice invariance or local compositional changes can initiate a catastrophic sequence of degradation mechanisms. In this study we compare the chemomechanical properties of LiCoO2 and LiNiO2 by combining density functional theory and anisotropic linear elasticity theory. We calculate stacking fault energies as a function of Li content and quantify the extent to which excess Ni hinders stacking-sequence changes. We then characterize screw dislocations, which mediate stacking-sequence changes, and find a peculiarly compliant behavior of LiNiO2 due to the interaction of Jahn–Teller distortions with the dislocation strain field. Finally, we analyze the tendency of vacancies to segregate along dislocation lines. This study represents the first instance of explicit ab initio atomistic dislocation models in layered oxides and paves the way for the understanding and optimization of the chemomechanical behavior of cathode active materials during battery operation.