Analysis of diffusion in solid state electrolytes through MD-simulations, improvement of the Li-ion conductivity in β-Li3PS4 as an example

Molecular dynamics simulations are a powerful tool to study diffusion processes in battery electrolyte and electrode materials. From a single molecular dynamics simulation many properties relevant to diffusion can be obtained, including the diffusion path, attempt frequency, activation energies, and collective diffusion processes. These detailed diffusion properties provide a thorough understanding of diffusion in solid electrolytes, and provides direction for the design of improved solid electrolyte materials. Here a thorough analysis methodology is developed, and applied to DFT MD simulations of Li-ion diffusion in \beta-Li3PS4. The methodology presented is generally applicable to crystalline materials and facilitates the analysis of molecular dynamics simulations. The code used for the analysis is freely available at: https://bitbucket.org/niekdeklerk/md-analysis-with-matlab. The results on \beta-Li3PS4 demonstrate that jumps between bc-planes limit the conductivity of this important class of solid electrolyte materials. The simulations indicate that by adding Li-interstitials or Li-vacancies the rate limiting jump process can be accelerated significantly, which induces three dimensional diffusion, resulting in an increased Li-ion diffusivity. Li-vacancies can be introduced through Br-doping, which is predicted to result in an order of magnitude larger Li-ion conductivity in \beta-Li3PS4. Furthermore, the present simulations rationalise the improved Li-ion diffusivity upon O-doping through the creation of local Li-interstitials.