Li21Ge8P3S34: New Lithium Superionic Conductor with Unprecedented Structural Type

Jihun Roh; Saleh Gholam; Namgyu Do; Alicia Manjón-Sanz; Joke Hadermann; Seung Tae Hong

doi:10.1002/anie.202500732

Li₂₁Ge₈P₃S₃₄: New Lithium Superionic Conductor with Unprecedented Structural Type

Jihun Roh
, Saleh Gholam
, Namgyu Do
, Alicia Manjón-Sanz
, Joke Hadermann
, Seung Tae Hong

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Lithium superionic conductors are pivotal for enabling all-solid-state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li₂₁Ge₈P₃S₃₄, featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm⁻¹ at 303 K with a low activation energy of 0.20(1) eV. It's unique crystal structure was elucidated using three-dimensional electron diffraction (3D ED) and further refined through combined powder X-ray and neutron diffraction analyses. The structure consists of alternating two-dimensional slabs: one of corner-sharing GeS₄ tetrahedra and the other of isolated PS₄ tetrahedra, enabling efficient lithium-ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next-generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li₂₁Ge₈P₃S₃₄ could contribute to the development of high-performance all-solid-state batteries.

Original language	English
Article number	e202500732
Journal	Angewandte Chemie - International Edition
Volume	64
Issue number	22
DOIs	https://doi.org/10.1002/anie.202500732
State	Published - May 26 2025

Funding

This research was supported by the Nano & Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (RS-2024–00446825). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS – 32524 for POWGEN experiment). The authors acknowledge funding from the Research Foundation Flanders (FWO, Belgium) project SBO S000121N. Saleh Gholam acknowledges Amirhossein Hajizadeh and Hrushikesh Chintakindi for fruitful discussions on the structure solution. This research was supported by the Nano & Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (RS‐2024–00446825). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS – 32524 for POWGEN experiment). The authors acknowledge funding from the Research Foundation Flanders (FWO, Belgium) project SBO S000121N. Saleh Gholam acknowledges Amirhossein Hajizadeh and Hrushikesh Chintakindi for fruitful discussions on the structure solution.

Keywords

All-solid-state batteries
Conducting materials
Inorganic chemistry
Solid-state structures
Thio-LISICONs

Access to Document

10.1002/anie.202500732

Cite this

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title = "Li21Ge8P3S34: New Lithium Superionic Conductor with Unprecedented Structural Type",

abstract = "Lithium superionic conductors are pivotal for enabling all-solid-state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li21Ge8P3S34, featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm−1 at 303 K with a low activation energy of 0.20(1) eV. It's unique crystal structure was elucidated using three-dimensional electron diffraction (3D ED) and further refined through combined powder X-ray and neutron diffraction analyses. The structure consists of alternating two-dimensional slabs: one of corner-sharing GeS4 tetrahedra and the other of isolated PS4 tetrahedra, enabling efficient lithium-ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next-generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li21Ge8P3S34 could contribute to the development of high-performance all-solid-state batteries.",

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author = "Jihun Roh and Saleh Gholam and Namgyu Do and Alicia Manj{\'o}n-Sanz and Joke Hadermann and Hong, \{Seung Tae\}",

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