Fast 3D-lithium-ion diffusion and high electronic conductivity of LiMnSiO surfaces for rechargeable lithium-ion batteries.

High theoretical capacity, high thermal stability, the low cost of production, abundance, and environmental friendliness are among the potential attractiveness of LiMnSiO as a positive electrode (cathode) material for rechargeable lithium-ion batteries. However, the experimental results indicated poor electrochemical performance in its bulk phase due to high intrinsic charge transfer resistance and capacity fading during cycling, which limit its large-scale commercial applications. Herein, we explore the surface stability and various lithium-ion diffusion pathways of LiMnSiO surfaces using the density functional theory (DFT) framework. Results revealed that the stability of selected surfaces is in the following order: (210) > (001) > (010) > (100). Moreover, the Wulff-constructed equilibrium shape revealed that the LiMnSiO (001) surface is the most predominant facet, and thus, preferentially exposed to electrochemical activities. The Hubbard-corrected DFT (DFT + , with = 3 eV) results indicated that the bulk insulator with a wide band gap ( = 3.42 eV) changed into narrow electronic ( = 0.6 eV) when it comes to the LiMnSiO (001) surface. Moreover, the nudged elastic band analysis shows that surface diffusion along the (001) channel was found to be unlimited and fast in all three dimensions with more than 12-order-of-magnitude enhancements compared with the bulk system. These findings suggest that the capacity limitation and poor electrochemical performance that arise from limited electronic and ionic conductivity in the bulk system could be remarkably improved on the surfaces of the LiMnSiO cathode material for rechargeable lithium-ion batteries.