Superionic lithium argyrodites are attractive as solid electrolytes for all-solid-state-batteries. These materials of composition Li6PS5X (X = Cl, Br, and I) exhibit structural disorder between the X−/S2− positions, with higher disorder realizing better Li+ transport. Further replacement of the sulfide by chloride anions (for the series Li7−xPS6−xClx) 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 S2− 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.
Wolfgang Zeier University of Münster
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