Oxychloride Polyanion Clustered Solid‐State Electrolytes via Hydrate‐Assisted Synthesis for All‐Solid‐State Batteries

Guanzhi Wang; Simeng Zhang; Han Wu; Matthew Zheng; Changtai Zhao; Jianwen Liang; Liyu Zhou; Junyi Yue; Xiangzhen Zhu; Yang Xu; Nian Zhang; Tianlu Pang; Jiamin Fu; Weihan Li; Yuanguang Xia; Wen Yin; Xueliang Sun; Xiaona Li

doi:10.1002/adma.202410402

journal article·2025-01Open access

Oxychloride Polyanion Clustered Solid‐State Electrolytes via Hydrate‐Assisted Synthesis for All‐Solid‐State Batteries

Guanzhi Wang, Simeng Zhang, Han Wu, Matthew Zheng, Changtai Zhao, Jianwen Liang, Liyu Zhou, Junyi Yue, Xiangzhen Zhu, Yang Xu, Nian Zhang, Tianlu Pang, Jiamin Fu, Weihan Li, Yuanguang Xia, Wen Yin, Xueliang Sun, Xiaona Li

Advanced Materials· Volume 37· Issue 4

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Source abstract

Abstract

Abstract Solid‐state electrolytes (SSEs) play a vital role in the development of high‐energy all‐solid‐state batteries. However, most adopted mechanical ball milling and/or high‐temperature annealing are ineffective approaches for large‐scale synthesis. Herein, a universal and scalable hydrate‐assisted strategy for the synthesis of oxychloride SSEs is developed based on the chemical reaction among alkali chlorides, AlCl₃, and AlCl₃·6H₂O. The synthesized aluminum‐based oxychloride SSEs possess a high Li⁺ conductivity over 1 mS cm⁻¹ at 30 °C. The final aluminum‐based oxychloride SSEs are structurally heterogeneous with nm‐sized LiCl‐like and LiAlCl₄ crystallites and large amounts of amorphous [Al_aO_bCl_c]⁽²^b⁺^c⁻³^a⁾⁻ components. Faster local mobility of Li⁺ ions in amorphous structures is verified and is attributable to weakened Li⁺‐X⁻ interactions ensured by the [Al_aO_bCl_c]⁽²^b⁺^c⁻³^a⁾⁻ polyanions. The potential applications for this synthesis technique are further demonstrated by kilogram‐scale reactions and synthesis of other oxychloride SSEs including zirconium‐based and tantalum‐based analogs. These findings not only provide a new simple, scalable, and energy‐efficient synthesis route for oxychloride SSEs but also further promote their application in all‐solid‐state batteries.

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Research context

Energy storage Materials processing

OpenAlex topics: Advanced Battery Materials and Technologies · Thermal Expansion and Ionic Conductivity · Layered Double Hydroxides Synthesis and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Eastern Institute for Advanced Study Eastern Institute of Technology Ningbo Zhejiang 315200 P. R. China

Eastern Institute for Advanced Study Ningbo Key Laboratory of All‐Solid‐State Battery Ningbo Zhejiang 315200 P. R. China

Department of Mechanical and Materials Engineering University of Western Ontario London ON N6A 5B9 Canada

Solid State Batteries Research Center GRINM (Guangdong) Institute for Advanced Materials and Technology Foshan Guangdong 528051 P. R. China

Shanghai Synchrotron Radiation Facility Shanghai Advanced Research Institute Chinese Academy of Sciences Shanghai 201204 P. R. China

National Key Laboratory of Materials for Integrated Circuits Shanghai Institute of Microsystem and Information Technology Chinese Academy of Sciences Shanghai 200050 P. R. China

Institute of High Energy Physics Chinese Academy of Sciences (CAS) Beijing 100049 China

Funding

National Natural Science Foundation of China · China Postdoctoral Science Foundation

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