Temperature-dependent dynamic disproportionation in LiNiO2

Abstract

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 . 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. Our 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 material properties of LiNiO 2 is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.