Published August 1, 2025 | Published
Journal Article

Structure and ion diffusion of hexagonal Li₅(PS₄)Cl₂ superionic conductor from molecular dynamics simulations

  • 1. ROR icon California Institute of Technology
  • 2. Hong Kong Quantum AI Lab Limited, Pak Shek Kok, Hong Kong SAR China
  • 3. ROR icon University of Hong Kong

Abstract

All-solid-state battery technology is considered a promising candidate for next-generation batteries. Sulfide-based materials, particularly lithium thiophosphates, show great potential due to their Li-superionic conductivity at room temperature. We have performed a study of the structure and Li-ion diffusion in Li5(PS4)Cl2 using molecular dynamic simulations at various temperatures. Our research proposed a new hexagonal structure with space group P63mc for this material. We find that the Li sublattice is disordered over four crystallographic positions in this structure, which provides favorable conditions for fast Li-ion diffusion, ∼10−7 cm2/s, leading to a superionic conductivity of ∼2 × 10−2 S/cm with an activation energy of ∼0.3 eV at room temperature. Our simulations indicate that the Li-ion conductivity of Li5PS4Cl2 is almost isotropic. This predicted conductivity is among the highest reported for known solid electrolytes. Based on our computational findings, we proposed a mechanism for the Li-ion diffusion in the hexagonal Li5PS4Cl2 and discussed it in detail. This research shows the potential of computational tools to guide the rational design of next-generation solid-state electrolytes and how predictive modeling can accelerate innovation in materials development.

Acknowledgement

Financial support for this research from the Hong Kong Quantum AI Lab, AIR@InnoHK of the Hong Kong Government is gratefully acknowledged. We thank Dr. Sergey Zybin for the helpful discussions.

Copyright and License

Contributions

Tridip Das: Writing – original draft, Visualization, Software, Methodology, Investigation, Data curation. Boris V. Merinov: Writing – review & editing, Supervision, Investigation, Formal analysis, Conceptualization. Moon Young Yang: Software, Methodology, Formal analysis. Guanhua Chen: Validation, Supervision, Project administration, Funding acquisition. William A. Goddard III: Writing – review & editing, Supervision, Resources, Project administration, Funding acquisition, Conceptualization.

Conflict of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Supplemental Material

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Data Availability

The data supporting this article have been included as part of the Supplementary Information.

Additional details

Created:
July 23, 2025
Modified:
July 23, 2025