A First-Principles Study of Anion Doping in LiFePO4 Cathode Materials for Li-Ion Batteries

Chemphyschem. 2024 Feb 1;25(3):e202300756. doi: 10.1002/cphc.202300756. Epub 2023 Dec 13.

Abstract

Doping anions into LiFePO4 can improve the electrochemical performance of lithium-ion batteries. In this study, structures, electronic properties and Li-ion migration of anion (F- , Cl- , and S2- ) doping into LiFePO4 were systematically investigated by means of density functional theory calculations. Anion substitution for oxygen atoms leads to an expansion of the LiFePO4 lattice, significantly facilitating Li-ion diffusion. For Cl- and F- anion doped into LiFePO4 , the energy barrier of Li-ion migration gets lowered to 0.209 eV and 0.283 eV from 0.572 eV. The introduction of anions narrows the forbidden band of LiFePO4 , enhancing its electronic conductivity. This work pays a way towards the rational design of high-performance lithium-ion batteries.

Keywords: Li-ion batteries; anion doping; cathode materials; electronic structure; first-principles calculations.