Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li(6+x)P(1–x)Ge(x)S(5)I as Probed by Neutron Diffraction and NMR

[Image: see text] Solid electrolytes are at the heart of future energy storage systems. Li-bearing argyrodites are frontrunners in terms of Li(+) ion conductivity. Although many studies have investigated the effect of elemental substitution on ionic conductivity, we still do not fully understand the various origins leading to improved ion dynamics. Here, Li(6+x)P(1–x)Ge(x)S(5)I served as an application-oriented model system to study the effect of cation substitution (P(5+) vs Ge(4+)) on Li(+) ion dynamics. While Li(6)PS(5)I is a rather poor ionic conductor (10(–6) S cm(–1), 298 K), the Ge-containing samples show specific conductivities on the order of 10(–2) S cm(–1) (330 K). Replacing P(5+) with Ge(4+) not only causes S(2–)/I(–) anion site disorder but also reveals via neutron diffraction that the Li(+) ions do occupy several originally empty sites between the Li rich cages in the argyrodite framework. Here, we used (7)Li and (31)P NMR to show that this Li(+) site disorder has a tremendous effect on both local ion dynamics and long-range Li(+) transport. For the Ge-rich samples, NMR revealed several new Li(+) exchange processes, which are to be characterized by rather low activation barriers (0.1–0.3 eV). Consequently, in samples with high Ge-contents, the Li(+) ions have access to an interconnected network of pathways allowing for rapid exchange processes between the Li cages. By (i) relating the changes of the crystal structure and (ii) measuring the dynamic features as a function of length scale, we were able to rationalize the microscopic origins of fast, long-range ion transport in this class of electrolytes.