A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries

Abstract Halides are promising solid electrolytes due to their high ionic conductivity and high oxidation potential. Here we report a superionic chloride material, NaTaCl6, which exhibits a high ionic conductivity of 3.3 mS cm−1 at 27 °C, being two-orders of magnitude higher than that of NaNbCl6 (0....

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Main Authors: Rui Li, Kaiqi Xu, Shenhao Wen, Xiaohan Tang, Zheyu Lin, Xia Guo, Maxim Avdeev, Zhizhen Zhang, Yong-Sheng Hu
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-61738-6
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author Rui Li
Kaiqi Xu
Shenhao Wen
Xiaohan Tang
Zheyu Lin
Xia Guo
Maxim Avdeev
Zhizhen Zhang
Yong-Sheng Hu
author_facet Rui Li
Kaiqi Xu
Shenhao Wen
Xiaohan Tang
Zheyu Lin
Xia Guo
Maxim Avdeev
Zhizhen Zhang
Yong-Sheng Hu
author_sort Rui Li
collection DOAJ
description Abstract Halides are promising solid electrolytes due to their high ionic conductivity and high oxidation potential. Here we report a superionic chloride material, NaTaCl6, which exhibits a high ionic conductivity of 3.3 mS cm−1 at 27 °C, being two-orders of magnitude higher than that of NaNbCl6 (0.01 mS cm−1). The considerably higher conductivity exhibited by NaTaCl6 vs. NaNbCl6 arises from the more facile rotational/reorientational dynamics of the [TaCl6] polyanions in comparison to the [NbCl6] anions. [TaCl6] polyanion rotation is readily activated while [NbCl6] polyanion reorientation is hindered at room temperature but can be turned on as the temperature increases or under prolonged mechanical milling. The higher degree of structural disorder exhibited by NaTaCl6 compared to NaNbCl6—likely attributed to its greater mechanical and phonon softness—is found to contribute to the more pronounced [TaCl6] anion rotation. Anion rotation is coupled with, and facilitates, macroscopic Na+-ion diffusion. As a result, enhanced rotational dynamics are directly correlated with the higher Na+-ion conductivity observed in NaTaCl6. The high ionic conductivity, combined with its electrochemical stability against positive electrode materials, enables good rate capability and long-term cycling performance in solid-state cells. These findings provide insights into ion transport mechanism in the newly emerging halide solid electrolytes.
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issn 2041-1723
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publishDate 2025-07-01
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spelling doaj-art-0d0486809e3b41fdb41f3bc9c553551e2025-08-20T03:46:15ZengNature PortfolioNature Communications2041-17232025-07-0116111810.1038/s41467-025-61738-6A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteriesRui Li0Kaiqi Xu1Shenhao Wen2Xiaohan Tang3Zheyu Lin4Xia Guo5Maxim Avdeev6Zhizhen Zhang7Yong-Sheng Hu8Shenzhen Campus of Sun Yat-sen UniversityGuangdong Engineering Technology Research Center of Energy Storage and Renewable Energy, China Southern Power Grid Technology Co., LtdShenzhen Campus of Sun Yat-sen UniversityKey Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of SciencesShenzhen Campus of Sun Yat-sen UniversityShenzhen Campus of Sun Yat-sen UniversityAustralian Centre for Neutron Scattering, Australian Nuclear Science and Technology OrganisationShenzhen Campus of Sun Yat-sen UniversityKey Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of SciencesAbstract Halides are promising solid electrolytes due to their high ionic conductivity and high oxidation potential. Here we report a superionic chloride material, NaTaCl6, which exhibits a high ionic conductivity of 3.3 mS cm−1 at 27 °C, being two-orders of magnitude higher than that of NaNbCl6 (0.01 mS cm−1). The considerably higher conductivity exhibited by NaTaCl6 vs. NaNbCl6 arises from the more facile rotational/reorientational dynamics of the [TaCl6] polyanions in comparison to the [NbCl6] anions. [TaCl6] polyanion rotation is readily activated while [NbCl6] polyanion reorientation is hindered at room temperature but can be turned on as the temperature increases or under prolonged mechanical milling. The higher degree of structural disorder exhibited by NaTaCl6 compared to NaNbCl6—likely attributed to its greater mechanical and phonon softness—is found to contribute to the more pronounced [TaCl6] anion rotation. Anion rotation is coupled with, and facilitates, macroscopic Na+-ion diffusion. As a result, enhanced rotational dynamics are directly correlated with the higher Na+-ion conductivity observed in NaTaCl6. The high ionic conductivity, combined with its electrochemical stability against positive electrode materials, enables good rate capability and long-term cycling performance in solid-state cells. These findings provide insights into ion transport mechanism in the newly emerging halide solid electrolytes.https://doi.org/10.1038/s41467-025-61738-6
spellingShingle Rui Li
Kaiqi Xu
Shenhao Wen
Xiaohan Tang
Zheyu Lin
Xia Guo
Maxim Avdeev
Zhizhen Zhang
Yong-Sheng Hu
A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
Nature Communications
title A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
title_full A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
title_fullStr A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
title_full_unstemmed A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
title_short A sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
title_sort sodium superionic chloride electrolyte driven by paddle wheel mechanism for solid state batteries
url https://doi.org/10.1038/s41467-025-61738-6
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