Investigation on Structural and Electrochemical Properties of Olivine-Structured LiMn1−xFexPO4/C Cathode Materials Based on First-Principles Calculation

Abstract

Currently, LiMnPO4 is a highly prevalent cathode material in lithium-ion batteries. However, its low conductivity and Li+ diffusion rate limit its practical application. To overcome these inherent defect, we have modified its properties by doping Fe at the Mn site. In the LiMn1-xFexPO4 system, the total density of states of electrons near the Fermi level and the energy band of the Fermi surface are obtained by first-principles calculation. The adjustment of the energy band width immediately influences the electronic conductivity of LiMn1-xFexPO4 system, which is positively related to the electrochemical performance. According to the results of first-principles calculation, we speculated that x = 1/4 was the optimal doping concentration. Then, the LiMn1-xFexPO4/C systems were compounded by hydrothermal method to verify the first-principles’ hypothesis. The electrochemical tests show that the LiMn3/4Fe1/4PO4/C material has the best cycle performance and rate performance. At the condition of 0.05 C rate, this material possesses an initial discharge capacity of 142.5 mAh g−1. with the capacity retention maintained 93.9% after 100 cycles. The theoretical calculation in consistent with the experimental findings, which accounts for the fact that the first-principles strategy is very effective in the research and development of lithium-ion batteries.