Mechanistic Origin of Superionic Lithium Diffusion in Anion-Disordered Li₆PS₅X Argyrodites

The rational development of fast–ion-conducting solid electrolytes for all-solid-state lithium-ion batteries requires understanding the key structural and chemical principles that give some materials their exceptional ionic conductivities. For the lithium argyrodites Li₆PS₅X (X = Cl, Br, I), the choice of the halide, X, strongly affects the ionic conductivity, with room-temperature ionic conductivities for X = {Cl,Br} ×10³ higher than for X = I. This variation has been attributed to differing degrees of S/X anion disorder. For X = {Cl, Br} the S/X anions are substitutionally disordered, while for X = I the anion substructure is fully ordered. To better understand the role of substitutional anion disorder in enabling fast lithium-ion transport, we have performed a first-principles molecular dynamics study of Li₆PS₅I and Li₆PS₅Cl, with varying amounts of S/X anion-site disorder. Considering the S/X anions in terms a tetrahedrally close-packed substructure, we identify three partially occupied lithium sites that form a contiguous three-dimensional network of face-sharing tetrahedra. The active lithium-ion diffusion pathways within this network, however, depend on the S/X anion configuration. For anion-disordered systems, the active site–site path- ways give a percolating three-dimensional diffusion network; whereas for anion-ordered systems, critical site–site pathways are inactive, giving a disconnected diffusion network with lithium motion restricted to local orbits around S positions. Analysis of the lithium substructure and dynamics in terms of the lithium coordination around each sulfur site shows a mechanistic link between substitutional anion disorder and lithium disorder, which enables fast lithium diffusion. In anion- ordered systems the Li-ions are pseudo-ordered, with preferential 6-fold coordination of sulfur sites. Long-ranged lithium diffusion disrupts this SLi₆ pseudo-ordering, and is therefore disfavoured. In anion-disordered systems, a uniform 6-fold S–Li coordination is frustrated due to Li–Li Coulombic repulsion. Lithium positions become disordered, giving a range of S–Li coordination environments. Long-ranged Li diffusion is now possible with no net change in S–Li coordination numbers. This gives rise to superionic lithium transport in the anion-disordered systems, which is effected by a concerted string-like diffusion mechanism.