Ionic conduction and cathodic properties of CaMO3 (M=Fe and Mn) electrode materials via molecular dynamics and first-principles simulations

Calcium-ion(Ca-ion) batteries are gaining ever-increasing attention for next-generation energy storage systems due to affordability, highly abundant, high energy density, high theoretical capacity, and low redox potential close to Li-ion. In this work, we deployed the first-principles and classical molecular dynamics simulations to investigate the electronic and diffusive properties of isostructural ternary perovskite CaMO₃ (M = Fe and Mn). The transport properties at various temperatures from ion dynamics and electronic properties of CaMO₃ perovskites are examined using classical molecular dynamics and quantum mechanical simulations, respectively. We present the microscopic origin of the diffusion of multivalent ions like Ca²⁺ within the crystal structure of perovskite material and the effects of two transition metals, manganese and iron. Dynamic studies of Ca-ions were performed using molecular dynamic simulation, which depicts the diffusivity and conductivity of Ca-ion in CaMO₃ material. We find that the diffusivity in both the crystals increases with temperature; as a result, conductivity increases. Among both the crystals, CaFeO₃ requires less activation energy for diffusion and ionic conduction than CaMnO₃. Using density functional theory, we calculated specific capacity, electronic density of states, phase stability and equilibrium cell voltage, and charge transfer process during intercalation-deintercalation from first-principles calculations. The electronic behavior of these materials show that CaFeO₃ has better electronic and transport properties than CaMnO₃.