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| Hauptseite > Publikationsdatenbank > Influence of Halide Substitution on Local and Average Structure, Lattice Dynamics, and Transport Properties in $Cu_6PS_5X$ Argyrodites |
| Hauptseite > Publikationsdatenbank > Influence of Halide Substitution on Local and Average Structure, Lattice Dynamics, and Transport Properties in $Cu_6PS_5X$ Argyrodites |
| Journal Article | FZJ-2026-03528 |
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2026
ACS Publications
Washington, DC
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Please use a persistent id in citations: doi:10.1021/jacs.6c09122 doi:10.34734/FZJ-2026-03528
Abstract: Halide-substituted argyrodite materials have attracted increasing attention for energy applications since compositional tuning provides an effective strategy to modulate their structure and transport characteristics. While $Li^+$-based halide argyrodites have been extensively studied, a unified composition-resolved understanding of $Cu^+$-based halide argyrodites that integrates phase evolution, local structure, lattice dynamics, and electronic and ionic transport remain limited. In this work, we investigate $Cu_6PS_5X$ ($X$ = $Cl$, $Br$, $I$, $Cl_{0.5}Br_{0.5}$, $Cl_{0.5}I_{0.5}$, and $Br_{0.5}I_{0.5}$) within a combined experimental and computational framework. All compositions adopt an average cubic $F4̅3m$ structure at room temperature, while local structural analysis reveals deviations from cubic symmetry consistent with a monoclinic $Cc$ model involving $PS_4^{3–}$ tetrahedral tilting. $^{31}$P MAS NMR spectroscopy corroborates this local symmetry breaking through multiple distinct phosphorus environments arising from relative tetrahedral orientation rather than $S^{2–}/X^–$ site disorder. Halide substitution modifies the $Cu^+$ conductivity through changes in the activation energy and the Arrhenius pre-exponential factor, following the Meyer–Neldel behavior, with additional contributions from variations in jump distances and migration pathways. Direction-projected phonon density of states analysis identifies low-frequency $Cu^+$ vibrational components along the crystallographic migration pathways. Analysis of the Meyer–Neldel slope further suggests phonon assisted ion hopping involving multiphonon excitation of low-frequency $Cu^+$ vibrational modes. Together, these findings offer insight into structure–property relationships in $Cu_6PS_5X$ and suggest that, alongside the migration energy landscape, the vibrational energy scale, thermal population, and directionality of mobile ion modes should be considered when interpreting ion transport, thereby providing a vibrational perspective for the design of solid-state ion conductors.
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