Impact of Structural Coherence and Disorder on the Ionic Transport and Lattice Dynamics in Li+-conducting Argyrodites

Solid-state batteries offer improved safety and higher energy density compared to conventional lithium-ion systems. Among candidate solid electrolytes, lithium argyrodites stand out for their exceptional ionic conductivity and compositional flexibility. Recent studies have revealed strongly anharmonic, liquid-like ion and lattice dynamics in these materials, including the collapse of soft phonons driven by Li⁺ diffusion, which impacts both local vibrations and thermal transport. Yet, the connection between local structure, phonon dynamics, and macroscopic heat transport remains unresolved. In this work, we employ post-synthesis processing to tune microstructural parameters—such as crystallite size, strain, and coherence length—in two model systems: Li5.5PS4.5Cl1.5 and Li6PS5Br,. We systematically examine how mechanical treatments influence structural coherence, ion and lattice dynamics, and thermal transport. To further probe the role of structural disorder, we investigate bromide substitution in Li6PS5I. Across all compounds, thermal transport above 100 K is dominated by diffusons. At lower temperatures, however, structural disorder is significantly more effective than reduced coherence length at suppressing phonon-gas-type transport, underscoring the crucial role of local structure. Together with a detailed analysis of lithium-ion dynamics, these results provide new insights into how structural coherence and disorder govern both transport and vibrational properties in fast ionic conductors.