Feeling the strain: Enhancing the electrochemical performance of olivine LiMnPO[formula omitted] as cathode materials for Li-ion batteries through strain effects

Abstract

Currently, the improvement of Li-ion batteries (LIBs) is more important than ever, especially due to the increasing spread and rapid progress of electric vehicles and high-tech applications. Materials used for positive electrodes are one of the main constituents of batteries, which typically determine their electrochemical efficiency. Phospho-olivine LiMnPO4 (LMP) material has been regarded as a potential positive electrode material for LIBs due to its outstanding properties. However, it suffers from low electronic and ionic conductivity. Therefore, this work aims to overcome these drawbacks by applying a biaxial strain to LMP. In this regard, we used density functional theory calculations to investigate the effect of biaxial strain on the dynamic and thermal stabilities, structural, electronic, ionic diffusion, electrochemical potential, and defect properties of LiMnPO4 (LMP) structure, as well as on the Average (Mn–O, Li–O and P–O) bond lengths, electrical conductivity, and charge transfer. Moreover, the influence of anti-site defects on the ionic conductivity of LMP compound was evaluated. Our findings suggest that the biaxial tensile strain has a remarkable effect on the rate performance of LMP cathode material. A biaxial tensile strain of +2% reduces the band gap of LMP from 3.51 to 3.41 eV, and ameliorates the diffusion coefficient by 100 times. Furthermore, the migration barrier was calculated to be 0.37 eV for strained (+2%) defective MP, lower than 1.12 eV for unstrained defective MP, indicating that biaxial tensile strain can mitigate the negative effect of anti-site defects on Li-ion migration. These results can prompt us to suggest biaxial tensile strain as a good strategy for improving the electrochemical performance of LMP as cathode material for LIBs. Furthermore, this study may supply insights to cathode material designers and engineers on the importance of an appropriate biaxial strain value to improve the rate performance of LiMnPO4 as cathode materials for LIB batteries.