Elucidating Anisotropic Ionic Diffusion Mechanism in Li₃YCl₆ Using Molecular Dynamics Simulations

Halide-based solid electrolyte has emerged as promising materials for the development of solid-state batteries, due to their high ionic conductivity and excellent chemical properties. Li₃YCl₆ is a prototype halide-based superionic material that features anisotropic ionic diffusion. Elucidating the ionic transport and optimizing the conductivity in such anisotropic materials is crucial for enhancing the performance of solid-state batteries. In this work, by using molecular dynamics simulations with a machine learning force field, we systematically study the anisotropic ion diffusion behavior, including directional conductivity contribution, concerted migration, disorder-order transition in Li₃YCl₆. Our results prove that the fast <i>c</i>-direction is the major contributor to total diffusivity, especially under room temperature. The hcp anion arrangement leads to anisotropic diffusion mechanism. Lithium diffusion along the <i>c</i>-direction exhibit a highly concerted feature, which is absent in the <i>ab</i>-plane diffusion. A disorder-order transition of lithium sublattice can occur below a critical temperature. Our results show that the ordering occurs with a regular pattern of lithium ions. The lithium sublattice ordering is strongly influenced by yttrium cation arrangement and can be suppressed if a small amount of Li/Y anti-site defects are present. These understanding can help to provide guidance for the future development of anisotropic superionic materials.