Journal Article

FZJ-2026-04397

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Exploring the Possibility of Extrinsic Anion Vacancies in $Li_6PS_5Cl$

Helm, B. ; Saravanan, R. S. ; Lange, M. A.FZJ* ; Faka, V. ; Samanta, B. ; Kraft, M. A.FZJ* ; Suard, E. ; Francisco, B. E. ; Hansen, M. R. ; Mo, Y. ; Zeier, W. G. (Corresponding author)FZJ*

2026
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/acsaem.6c02127  doi:10.34734/FZJ-2026-04397

Abstract: The search for superionic conductors requires a deep understanding of the underlying crystal structure and local dynamic processes. Therefore, cationic and anionic substitutions are typically performed to monitor the resulting changes in the structure and ionic transport, ultimately drawing conclusions to find optimized $Li^+$ conductors. Within a substitution series, the anionic framework is generally assumed to be fully occupied in contrast to defective cationic substructures. This study addresses the question of whether the targeted introduction of extrinsic anion vacancies can be stabilized within a $Li^+$ argyrodite with the help of a targeted $Li_6(PS_4)S_{1+x/2}□_{x/2}Cl_{1−x}$ substitution series. Furthermore, by not changing the amount of $Li^+$ in the structure, there could be a possibility to decouple $Li^+$ carrier density effects from anion influence on $Li^+$ transport. Using diffraction and spectroscopic techniques, Monte Carlo simulations, as well as density functional theory calculations, changes in crystal structure and ionic and electronic transport are monitored, and the configurational stability is assessed. The structures with anion vacancies were found to have high formation energies, in agreement with the experimental observation. Instead, the phase formation of $Li_{6+x}PS_{5+x}Cl_{1−x}$ is observed, showing a decrease in $Li^+$ conductivity related to the anion ordering.

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Contributing Institute(s):

1. Helmholtz-Institut Münster Ionenleiter für Energiespeicher (IMD-4)

Research Program(s):

1. 1221 - Fundamentals and Materials (POF4-122) (POF4-122)

Appears in the scientific report 2026

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Engineering, Computing and Technology ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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