On the Lithium Distribution in Halide Superionic Argyrodites by Halide Incorporation in Li7−xPS6−xClx

Superionic lithium argyrodites are attractive as solid electrolytes for all-solid-state-batteries. These materials of composition Li 6 PS 5 X (X = Cl, Br, and I) exhibit structural disorder between the X − /S 2− positions, with higher disorder realizing better Li + transport. Further replacement of the sulfide by chloride anions (for the series Li 7 −x PS 6 −x Cl x ) has been shown to increase the ionic conductivity. However, the underlying changes to the lithium substructure are still relatively unknown. Here we explore a larger range of nominal halide compositions in this material from x = 0.25 to x = 1.5 and explore the changes with neutron diffraction and impedance spectroscopy. The replacement of S 2− by Cl − causes a lowered average charge in the center of the prevalent Li + “cages”, which in turn causes weaker interactions with Li + ions. Analysis of neutron diffraction data reveals that the increased Cl − content causes these clustered Li + “cages” to become more interconnected, thereby increasing Li + conductivity through the structure. This study explores the understanding of the fundamental structure–transport correlations in the argyrodites, specifically structural changes withinthe Li + ion substructure upon changing anionic charge distribution.