Impact of the Local Environment on Li Ion Transport in Inorganic Components of Solid Electrolyte Interphases

The spontaneously formed passivation layer, the solid electrolyte interphase (SEI) between the electrode and electrolyte, is crucial to the performance and durability of Li ion batteries. However, the Li ion transport mechanism in the major inorganic components of the SEI (Li2CO3 and LiF) is still unclear. Particularly, whether introducing an amorphous environment is beneficial for improving the Li ion diffusivity is under debate. Here, we investigate the Li ion diffusion mechanism in amorphous LiF and Li2CO3 via machine-learning-potential-assisted molecular dynamics simulations. Our results show that the Li ion diffusivity in LiF at room temperature cannot be accurately captured by the Arrhenius extrapolation from the high temperature (>600 K) diffusivities (difference of ∼2 orders of magnitude). We reveal that the spontaneous formation of Li–F regular tetrahedrons at low temperatures (<500 K) leads to an extremely low Li ion diffusivity, suggesting that designing an amorphous bulk LiF-based SEI cannot help with the Li ion transport. We further show the critical role of Li2CO3 in suppressing the Li–F regular tetrahedron formation when these two components of SEIs are mixed. Overall, our work provides atomic insights into the impact of the local environment on Li ion diffusion in the major SEI components and suggests that suppressing the formation of large-sized bulk-phase LiF might be critical to improve battery performance.