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 the 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: Li_5.5PS_4.5Cl_1.5 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 the 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.