Temperature-Dependent Dynamic Disproportionation in LiNiO$_2$ (2211.09047v3)

Abstract: Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO$2$) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO$_2$. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L${3,2}$-edge. Charge-transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO$_2$, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO$_2$ is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.