Configurational Disorder, Strong Anharmonicity, and Coupled Host Dynamics Lead to Superionic Transport in Li3YCl6 (LYC)

Abstract

AbstractIn superionic crystals, liquid‐like ionic diffusivities often come hand‐in‐hand with ultra‐low thermal conductivity and soft vibrational dynamics. However, generalized relationships between ion transport and vibrational dynamics remain elusive due to the diversity of superionic materials and complex underlying mechanisms. Here, the links between vibrational dynamics and ion transport in close‐packed lithium halide ion conductor Li3YCl6 (LYC) are examined using a suite of atomistic first‐principles methods. It is shown that configurational disorder, lattice anharmonicity, and coupled host‐mobile ion vibrational dynamics together induce a transition to the superionic state. Statistical correlations between ionic hops and activation of the distribution of vibrational modes are found. However, typical phenomena associated with superionic conductors such as selective breakdown of zone‐boundary soft phonons, or long wavelength transverse acoustic modes as in the ‘phonon‐liquid‐electron crystal’ concept, are not present. Instead, anharmonic zone‐boundary modes aiding Li diffusion are found to broaden and soften selectively but persist across the superionic transition. These anharmonic modes couple Li ion motion with the vibrations of the flexible close‐packed anion framework, which remains stable and facilitates ionic hopping. The results provide insights into how configurational disorder and soft‐yet‐resilient vibrational modes enable ionic hopping, particularly in 3D close‐packed crystals.