Formation, Electronic Structure, and Defects of Ni Substituted Spinel Cobalt Oxide: a DFT+U Study

Abstract

Nickel substituted spinel cobalt oxide is a promising technological material with complex electronic and magnetic structures. Understanding these structures is important for improving the material’s performance in various applications. We have carried out first-principles calculations on the formation, electronic properties, and defects of bulk NiCo2O4 using density functional theory (DFT) with on-site Hubbard U terms on the transition metal d states. Analysis of the electronic structure of NixCo3-xO4 as a function of x = 0–1 shows that Ni acts as a p-type dopant in Co3O4, gradually transforming the minority spin channel from insulating to conducting. As a result, the inverse spinel NiCo2O4 (NCO) is found to have a ferrimagnetic half-metallic ground state with fractional valence on Ni and Co cations at tetrahedral sites (Td), in agreement with experimental observations. Projected densities of states confirm that the states around the Fermi energy originate from Ni and Co(Td) 3d states hybridized with oxyg...