Citation: SONG Jian-Jun, SHAO Guang-Jie, ZHAO Jian-Wei, MA Zhi-Peng, SONG Wei, LIU Shuang, WANG Cai-Xia. First-Principle Calculation of LiFe_1-xMo_xPO₄ as Cathode Material for Rechargeable Lithium Batteries[J]. Chinese Journal of Inorganic Chemistry, ;2014, 30(3): 615-620. doi: 10.11862/CJIC.2014.104 shu

First-Principle Calculation of LiFe_1-xMo_xPO₄ as Cathode Material for Rechargeable Lithium Batteries

1.
1 Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, Hebei 066004, China;

Received Date: 3 May 2013
Available Online: 8 November 2013
Fund Project: 河北省大学自然科学关键研究项目基金(No.ZH2011228)/河北省自然科学基金[No.B201220369]资助项目。 (No.ZH2011228)

The electronic structure and diffusion barriers of lithium ions in pure LiFePO₄ and doped LiFe_1-xMo_xPO₄(x=0.005, 0.01, 0.015, 0.02, and 0.025) have been calculated based on the first-principle density functional theory (DFT). The calculated results show that the LiFe_0.99Mo_0.01PO₄ has the largest interplanar distance of (101) crystal plane, suggesting the widest Li ion diffusion pathway in [010] direction. Pure LiFePO₄ has diffusion energy barrier of 4.289 eV for lithium ions, while the LiFe_0.99Mo_0.01PO₄ has lower diffusion energy barrier of 4.274 eV. The calculated diffusion coefficient of LiFe_0.99Mo_0.01PO₄ is 1.79 times as large as that of pure LiFePO₄, indicating that Mo doping is beneficial to lithium ion diffusivity of LiFePO₄. The intensity of the partial density of states (PDOS) near the bottom of conduction bands (CBs) becomes stronger after doping with Mo. According to the analysis above, Mo doping is beneficial to improve the electronic conductivity and lithium ion diffusivity of LiFePO₄. Lithium ion diffusivity plays more important roles than electronic conductivity on improving the electrochemical performance of LiFePO₄ by doping with Mo.
- density functional theory;electronic structure;diffusion barrier;doping
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First-Principle Calculation of LiFe1-xMoxPO4 as Cathode Material for Rechargeable Lithium Batteries

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First-Principle Calculation of LiFe_1-xMo_xPO₄ as Cathode Material for Rechargeable Lithium Batteries