Insight into the diffusion mechanism of sodium ion–polaron complexes in orthorhombic P2 layered cathode oxide NaxMnO2

Using the density functional theory, we investigated the geometric, electronic structure, phase stability and electrochemical properties of a potential P2 layer orthorhombic cathode material NaxMnO2 (0 ≤ x ≤ 1) applied for sodium ion batteries. Herein, we shed the light on the undeniable effect of the polaron formation and polaron migration on the diffusion of Na+ ions in the orthorhombic P2 layered oxides. Both GGA+U and HSE06 methods agree that, when Na+ ions are removed from the fully charged state of NaMnO2, the accompanying polaron preferably forms at the third nearest Mn (3NN) to the Na vacancy, implying the oxidization of the Mn3+ ion at one of these 3NN sites to Mn4+. The positive polaron migrates simultaneously with the Na vacancy and would hinder the diffusion of Na ions. Two kinds of elementary diffusion processes, named parallel and crossing, have been explored which required an almost same activation energy of about 423 meV (518 meV) by GGA+U (HSE06). In the fully discharged state, GGA+U and HSE06 methods indicate that the negative polaron forms at the second nearest Mn neighbour (2NN). The activation energy of 273 meV (327 meV) is needed for diffusion in a structure with a low Na concentration, which is much lower than that required for diffusion in the Na-rich regime. Consequently, Na+ ions can diffuse easier at lower Na concentrations. With the overall activation energy of 423 meV (518 meV), this material exhibits a faster ion diffusion in comparison with the prevailing lithium-based materials such as olivine phosphate.