Abstract LiFePO$_{4}$ has normal olivine-structured ($\alpha $-LFP) and high pressure ($\beta $-LFP) phases, with the former being one of the cathode materials for commercial Li-ion batteries. Despite extensive focus on the respective electrochemical properties of the two phases, there is a lack of comparative studies on their electronic and magnetic properties, and the origin of the structural phase transition remains unclear. By combining first-principles calculations with molecular dynamics simulations, we find that the anisotropic compression of Li-O bonds drives the structural phase transition from $\alpha $-LFP to $\beta $-LFP at a critical pressure of 20 GPa, while $\beta $-LFP undergoes a transition from semiconductor to metal due to Fe$^{3+}$ generated during delithiation. Their antiferromagnetic (AFM) ground states are predicted to arise from the negative magnetic exchange interactions between nearest and next-nearest neighbor sites, with the corresponding Néel temperature showing significant enhancement under pressure. Furthermore, compared with $\alpha $-LFP, $\beta $-LFP shows increases in bulk, shear, and Young's moduli of 8%, 13%, and 12%, respectively. These findings enrich the physical property data of LiFePO$_{4}$ phase compounds, providing knowledge for expanding the application scenarios of the $\alpha $-LFP phase under special operating conditions such as high pressure.
Received: 16 July 2025
Revised: 15 September 2025
Accepted manuscript online: 26 September 2025
Fund: Project supported by the National Natural Science Foundation of China (Grant No. 12304089) and the start-up foundation from Shanghai University. Calculations were partially performed on computers at the Shanghai Technical Service Center for Scientific and Engineering Computing, Shanghai University.
Corresponding Authors:
Jie Li, Siqi Shi
E-mail: lij@shu.edu.cn;sqshi@shu.edu.cn
Cite this article:
Peiru Yang(杨佩如), Xinchun Du(杜新春), Jie Li(李杰), and Siqi Shi(施思齐) Comparative study on electronic structures of two phases compounds and origin of the structural phase transition in LiFePO4 2025 Chin. Phys. B 34 118201
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