Exploring the Relationship Between Halide Substitution, Structural Disorder, and Lithium Distribution in Lithium Argyrodites (Li(6–x)PS(5–x)Br(1+x))

[Image: see text] Lithium argyrodite superionic conductors have recently gained significant attention as potential solid electrolytes for all-solid-state batteries because of their high ionic conductivity and ease of processing. Promising aspects of these materials are the ability to introduce halides (Li(6–x)PS(5–x)Hal(1+x), Hal = Cl and Br) into the crystal structure, which can greatly impact the lithium distribution over the wide range of accessible sites and the structural disorder between the S(2–) and Hal(–) anion on the Wyckoff 4d site, both of which strongly influence the ionic conductivity. However, the complex relationship among halide substitution, structural disorder, and lithium distribution is not fully understood, impeding optimal material design. In this study, we investigate the effect of bromide substitution on lithium argyrodite (Li(6–x)PS(5–x)Br(1+x), in the range 0.0 ≤ x ≤ 0.5) and engineer structural disorder by changing the synthesis protocol. We reveal the correlation between the lithium substructure and ionic transport using neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and electrochemical impedance spectroscopy. We find that a higher ionic conductivity is correlated with a lower average negative charge on the 4d site, located in the center of the Li(+) “cage”, as a result of the partial replacement of S(2–) by Br(–). This leads to weaker interactions within the Li(+) “cage”, promoting Li-ion diffusivity across the unit cell. We also identify an additional T4 Li(+) site, which enables an alternative jump route (T5–T4–T5) with a lower migration energy barrier. The resulting expansion of the Li(+) cages and increased connections between cages lead to a maximum ionic conductivity of 8.55 mS/cm for quenched Li(5.5)PS(4.5)Br(1.5) having the highest degree of structural disorder, an 11-fold improvement compared to slow-cooled Li(6)PS(5)Br having the lowest degree of structural disorder. Thereby, this work advances the understanding of the structure–transport correlations in lithium argyrodites, specifically how structural disorder and halide substitution impact the lithium substructure and transport properties and how this can be realized effectively through the synthesis method and tuning of the composition.