Published May 26, 2026 | Version v1
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Polymorphism in K3SbS4 and the role of tungsten-substitution on structure and potassium-ion conductivity

  • 1. Universität Münster, Fachbereich 12 Chemie und Pharmazie, Institut für Anorganische und Analytische Chemie
  • 2. International Graduate School of Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), University of Münster, Germany
  • 3. College of Engineering and Computer Science, VinUniversity, Vietnam
  • 4. Center for Environmental Intelligence (CEI), VinUniversity, Vietnam
  • 5. Forschungszentrum Jülich GmbH, Institute of Energy Materials and Devices (IMD-4): Helmholtz Institute Münster (HI MS), Germany
  • 6. Institute of Physical Chemistry, Justus-Liebig- University Giessen, Germany
  • 7. Center for Materials Research (ZfM/LaMa), Justus-Liebig-University Giessen, Germany
  • 8. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, UK
  • 9. Department of Chemistry–Ångström Laboratory, Uppsala University, Sweden
  • 1. Institute of Inorganic and Analytical Chemistry, University of Münster, Germany
  • 2. International Graduate School of Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), University of Münster, Germany
  • 3. Center for Environmental Intelligence (CEI), VinUniversity, Vietnam
  • 4. College of Engineering and Computer Science (CECS), VinUniversity, Vietnam
  • 5. Forschungszentrum Jülich GmbH, Institute of Energy Materials and Devices (IMD-4): Helmholtz Institute Münster (HI MS), Germany
  • 6. Institute of Physical Chemistry, Justus-Liebig- University Giessen, Germany
  • 7. Center for Materials Research (ZfM/LaMa), Justus-Liebig-University Giessen, Germany
  • 8. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, U.K.
  • 9. Department of Chemistry– Ångström Laboratory, Uppsala University, Sweden

Description

This work revisits the K+-ion conducting K3−xSb1−xWxS4 (0 ≤ x ≤ 0.10) system and finds a more complex structural scenario than previously reported. K3SbS4 does not only crystallize in the reported  space group, but also in a structure best described in the  space group. Both polymorphs are found present at room temperature, whereas variable temperature synchrotron X-ray diffraction shows that only the  phase persists at elevated temperatures. Similarly, the substitution of Sb(+V) with W(+VI) stabilizes the high temperature  polymorph. K3SbS4 further shows similar diffusion pathways for both polymorphs. It matches the measured transport properties dominated by W(+VI) substitution increasing ionic conductivity up to 0.64 mS∙cm−1 at 298 K for nominal K2.92Sb0.92W0.08S4 with an activation energy of 0.29 eV. This work emphasizes the need for a complementary understanding of atomic arrangement and microstructure in potassium-ion conductors.

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Additional details

Related works

Is published in
Dataset: 10.1021/acsaem.6c01758 (DOI)

Funding

Ministerium für Kultur und Wissenschaft des Landes Nordrhein-Westfalen
Bundesministerium für Forschung, Technologie und Raumfahrt
KAFEBAR 13XP0565A

Dates

Issued
2026-08-06