# Rigidity‐Driven Structural Isomers in the NaCl–Ga<sub>2</sub>S<sub>3</sub> System: Implications for Energy Storage

https://mdr.nims.go.jp/datasets/70eab2c1-ba5c-47c6-8b9e-5a2ff5aff8ec

## File

- [CompletemanuscriptNaCl-Ga2S3andSupporting.pdf](https://mdr.nims.go.jp/filesets/c39afb28-f1e8-4215-8cb6-d39a8b6c2f66/download) ([Detail](https://mdr.nims.go.jp/filesets/c39afb28-f1e8-4215-8cb6-d39a8b6c2f66.md))

## Id

70eab2c1-ba5c-47c6-8b9e-5a2ff5aff8ec

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2024-10-24T04:05:33.962794Z

## Updated at

2024-10-25T07:30:19.580128Z

## Published at

2024-10-25T07:30:20.890752Z

## Doi

https://doi.org/10.48505/nims.4891

## First published url

https://doi.org/10.1002/smsc.202400371

## Date published

2024-10-01

## Recorded date published

2025-1

## Resource type

journal_article

## Manuscript type

accepted_manuscript

## Collection



## Title

- title: 'Rigidity‐Driven Structural Isomers in the NaCl–Ga<sub>2</sub>S<sub>3</sub>
    System: Implications for Energy Storage'
  title_type: original
  lang: en

## Description

- description: "Alternative energy sources and energy storage, including all-solid-state
    batteries, require the search for innovative materials with promising functionalities.
    Systems with unusual chemical properties represent an insufficiently explored
    domain, concealing unexpected features. In particular, solids in eutectic systems
    typically undergo melting while preserving their chemical identity. Nevertheless,
    using diffraction and Raman spectroscopy over a wide temperature range, supported
    by first principles simulations, we unveil a rare phenomenon: phase-dependent
    chemical interactions between binary components in the NaCl-Ga2S3 system. In this
    unique occurrence, previously intact binary crystalline species transform upon
    melting into mixed liquid structural isomers, forming bonds with new partners.
    The chemical combinatorics, Na-Cl + Ga-S ⇄ Na-S + Ga-Cl, appears to be fully reversible
    for stable crystals and liquids. Despite this, rapidly frozen glasses out of thermodynamic
    equilibrium remain in a metastable isomeric state, offering remarkable properties,
    particularly a high room-temperature Na+ ion conductivity of 2.1 mS cm-1 with
    an activation energy of 0.249 eV, comparable to the best sodium halide superionic
    conductors and therefore encouraging for sodium solid-state batteries and energy
    applications. A rigidity paradigm is responsible for the observed phenomenon,
    as the extremely constrained Ga2S3 crystal lattice (with an average coordination
    〈\U0001D45F〉 = 3.2) does not survive viscous flow, breaking up at a short-range
    level. The removal of rigidity constraints and dense packing, approaching the
    optimally constrained disordered network with 〈\U0001D45F〉 = 2.4, leads to a significant
    increase in empty space, as calculated using Dirichlet-Voronoi tessellation, which
    is the origin of high sodium diffusivity. Broadly, the rigidity-driven structural
    isomerism opens up an inspiring path to the discovery of atypical materials."
  description_type: abstract
  lang: und

## Creator

- name: Maria Bokova
  role: author
  orcid: https://orcid.org/0000-0002-2419-1644
- name: Mohammad Kassem
  role: author
  orcid: https://orcid.org/0000-0003-0512-0004
- name: Takeshi Usuki
  role: author
- name: Andrey Tverjanovich
  role: author
  orcid: https://orcid.org/0000-0002-0795-8188
- name: Anton Sokolov
  role: author
- name: Daniele Fontanari
  role: author
- name: Alex C. Hannon
  role: author
  orcid: https://orcid.org/0000-0001-5914-1295
- name: Chris J. Benmore
  role: author
  orcid: https://orcid.org/0000-0001-7007-7749
- name: Igor Alekseev
  role: author
- name: Shinji Kohara
  role: author
  orcid: https://orcid.org/0000-0001-9596-2680
- name: Pascal Roussel
  role: author
  orcid: https://orcid.org/0000-0001-7243-7293
- name: Maxim Khomenko
  role: author
- name: Koji Ohara
  role: author
  orcid: https://orcid.org/0000-0002-3134-512X
- name: Yohei Onodera
  role: author
  orcid: https://orcid.org/0000-0002-3080-6991
- name: Arnaud Cuisset
  role: author
  orcid: https://orcid.org/0000-0002-4358-2819
- name: Eugene Bychkov
  role: author
  orcid: https://orcid.org/0000-0002-3292-1205

## Contact agent



## Publisher

organization: Wiley

## Managing organization



## Keyword

- subject: all-solid-state batteries
  schema: not_defined
- subject: neutron diffraction
  schema: not_defined
- subject: X-ray diffraction
  schema: not_defined

## Rights

- identifier: https://creativecommons.org/licenses/by/4.0/

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo



## Journal

- title: Small Science
  issn: '26884046'
  article_number: '2400371'

## Conference



## Related item



## Funding

- identifier: CPER ECRIN
  funder_name: Campus France
- identifier: 2017A1067
  funder_name: Foundation for Promotion of Material Science and Technology of Japan
- identifier: 2017B1771 and 2021B1197
  funder_name: Foundation for Promotion of Material Science and Technology of Japan
- identifier: DEAC02‐06CH11357
  funder_name: U.S. Department of Energy

## Instrument



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## Specimen



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## Structure for specimen



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## Fileset

- id: c39afb28-f1e8-4215-8cb6-d39a8b6c2f66
  filename: CompletemanuscriptNaCl-Ga2S3andSupporting.pdf
  content_type: application/pdf
  size: 6304129
  md5: 7ebc147e16726217b2ee0b6090e04df7

## Thumbnail

fileset_id: c39afb28-f1e8-4215-8cb6-d39a8b6c2f66
filename: CompletemanuscriptNaCl-Ga2S3andSupporting.pdf