Comparative Analysis of LiMPO4 (M = Fe, Co, Cr, Mn, V) as Cathode Materials for Lithium-Ion Battery Applications—A First-Principle-Based Theoretical Approach

The rapidly increasing demand for energy storage has been consistently driving the exploration of different materials for Li-ion batteries, where the olivine lithium-metal phosphates (LiMPO4) are considered one of the most potential candidates for cathode-electrode design. In this context, the work presents an extensive comparative theoretical study of the electrochemical and electrical properties of iron (Fe)-, cobalt (Co)-, manganese (Mn)-, chromium (Cr)-, and vanadium (V)-based LiMPO4 materials for cathode design in lithium (Li)-ion battery applications, using the density-functional-theory (DFT)-based first-principle-calculation approach. The work emphasized different material and performance aspects of the cathode design, including the cohesive energy of the material, Li-intercalation energy in olivine structure, and intrinsic diffusion coefficient across the Li channel, as well as equilibrium potential and open-circuit potential at different charge-states of Li-ion batteries. The results indicate the specification of the metal atom significantly influences the Li diffusion across the olivine structure and the overall energetics of different LiMPO4. In this context, a clear correlation between the structural and electrochemical properties has been demonstrated in different LiMPO4. The key findings offer significant theoretical and design-level insight for estimating the performance of studied LiMPO4-based Li-ion batteries while interfacing with different application areas.