Comparison of Small Polaron Migration and Phase Separation in Olivine LiMnPO₄ and LiFePO₄ using Hybrid Density Functional Theory

Using hybrid density functional theory based on the Heyd-Scuseria-Ernzerhof (HSE06) functional, we compared polaron migration and phase separation in olivine LiMnPO4 to LiFePO4. The barriers for free hole and electron polaron migration in the Mn olivine system are calculated to be 303 and 196 meV, respectively, significantly higher than the corresponding barriers of 170 and 133 meV, respectively, for the Fe olivine system, in agreement with previous experimental findings. These results suggest that the electronic conductivities of LiMnPO4 and MnPO4 are about 177 and 11 times lower than their respective Fe analogs at room temperature. In the presence of lithium vacancies or ions, the barriers for both hole and electron polaron migration were found to be about 100‐120 meV higher in the Mn olivine. The HSE06 functional, with its more universal treatment of self-interaction error, was found to be essential to the proper localization of a polaron in the Mn olivine but predicted qualitatively incorrect phase separation behavior in the LixFePO4 system.

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