Key Messages

In this study, we explain the electro chemical performance of the select materials on the basis of Bader charge analysis, partial density of states and calculated oxidation states.For evaluation of various electrochemical properties of these materials, we carried out topological analysis of charge density by Badermethod and partial density of states for O and substituents to study charge distribution phenomenon during lithiation. We observed significant correlation between Li charge transfer to oxygen and voltage across thesystems studied. In this series, Zn substitution gives the highest and Mn substitution gives the lowest electrochemical potential. The high electrochemical potential of the Zn composition is on account of maximum charge transfer to O orbitals located at Fermi energy as the frontier orbital. This is due to the filled d orbitals of Zn in the lithiated material. However in the case of Mn, lower charge gets transferred to O due to the unfilled   eg:↑ orbital of Mn sharing some chargeA first principle based study of the electrochemical properties of LiCoBO3 has been carried out. The theoretical energy density of LiMBO3 (M= Mn, Fe, Co) is comparable with the corresponding olivine phosphate Low volume change during cycling gives it structural stability during full charging and discharging, hence making it a promising battery material.

Effect of cation substitution on the electrochemical potential of LiCoBO3: An ab initio study