Density Functional Theory Investigation of Mixed Transition Metals in Olivine and Tavorite Cathode Materials for Li-Ion Batteries.

Lithium-ion batteries (LIBs) are widely used in various electronic devices and have garnered a huge amount of attention. In addition, evaluation of the intrinsic properties of LIB cathode materials is of considerable interest for practical applications. Therefore, through first-principles calculations based on the density functional theory, we investigated the structural, electronic, electrochemical, and kinetic properties of mixed transition metals, that is, Ni-substituted LiMnPO4 (LMP) and LiMnPO4F (LMPF) cathode materials, that is, LiMn0.5Ni0.5PO4 (LMNP) and LiMn0.5Ni0.5PO4F (LMNPF), respectively, which have not been extensively studied. We also evaluated their delithiated phases, that is, Mn0.5Ni0.5PO4 (MNP) and Mn0.5Ni0.5PO4F (MNPF). Our calculations suggest that Ni substitution significantly affected the structural and electrochemical properties. After Li insertion, the MNPF unit-cell volume increased by about 8%, lower than that of pristine MnPO4F. The Li intercalation voltage also increased in LMNP (4.27 V) and LMNPF (5.23 V). In addition, the migration barrier was calculated to be 0.4 eV for LMNPF, lower than that of LMPF. This study may provide insights for developing LMNP and LMNPF cathode materials in LIB applications.