硅酸盐学报

卤氧化物固态电解质及其全固态电池研究进展

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脱凯用 ¹^,²^,³ , 卢普顺 ¹^,²^,³ , 周志民 ¹^,² , 梁苏哲 ¹^,²^,³ , 张加旭 ¹^,²^,³ , 胡观泰 ¹^,²^,³ , 王超 ¹^,²^,³ , 刘婷婷 ¹^,²^,³ , 孙一芃 ¹^,² , 王长虹 ¹^,² , 孙学良 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1435-1455

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硅酸盐学报 |全固态电池发展专刊—综合评述 2025 , 53 (6) : 1435 -1455

卤氧化物固态电解质及其全固态电池研究进展

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脱凯用¹^,²^,³, 卢普顺¹^,²^,³, 周志民¹^,², 梁苏哲¹^,²^,³, 张加旭¹^,²^,³, 胡观泰¹^,²^,³, 王超¹^,²^,³, 刘婷婷¹^,²^,³, 孙一芃¹^,², 王长虹¹^,², 孙学良¹^,²

作者信息

^1．宁波东方理工大学（暂名），浙江宁波 315200

^2．宁波东方理工高等研究院，浙江宁波 315200

^3．中国科学技术大学，合肥 230026

通讯作者:

王长虹（1989—），男，博士，副研究员；

孙学良（1963—），男，博士，教授。

作者简介:

脱凯用（1994—），男，博士。

Recent Development on Oxyhalide Electrolytes for All-Solid-State Batteries

Kaiyong TUO¹^,²^,³, Pushun LU¹^,²^,³, Zhimin ZHOU¹^,², Suzhe LIANG¹^,²^,³, Jiaxu ZHANG¹^,²^,³, Guantai HU¹^,²^,³, Chao WANG¹^,²^,³, tingting LIU¹^,²^,³, Yipeng SUN¹^,², Changhong WANG¹^,², Xueliang SUN¹^,²

Affiliations

^1.Eastern Institute of Technology, Ningbo 315200, Zhejiang, China

^2.Eastern Institute for Advanced Study, Ningbo 315200, Zhejiang, China

^3.University of Science and Technology of China, Hefei 230026, China

Corresponding Author:

WANG Changhong (1989-), male, Ph.D., Associate Professor. E-mail: cwang@eitech.edu.cn;

SUN Xueliang (1963-), male, Ph.D., Professor. xsun@eitech.edu.cn

TUO Kaiyong (1994-), male, Ph.D. E-mail: tuokaiyong@163.com

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240844

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摘要

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全固态电池因其高能量密度、高安全性和长循环寿命等优势被视为下一代电化学储能系统的关键发展方向。设计开发超快离子传导、宽电化学窗口和适宜杨氏模量的固态电解质材料是实现全固态电池实际应用的关键。卤氧化物电解质凭借其高电压正极兼容性、优异机械变形性以及超高室温离子电导率，成为实现全固态电池实际应用最有希望的固态电解质之一。本文全面综述了用于全固态电池的卤氧化物固态电解质的最新进展，回顾了卤氧化物电解质的发展历程，概述了卤氧化物电解质的不同合成路线。特别地，分析了不同类型卤氧化物电解质的骨架结构，阐明了金属离子在晶态和非晶卤氧化物中的输运机制。此外，概述了卤氧化物电解质对锂金属负极和不同正极材料的界面相容性，并综述了卤氧化物电解质用于低温全固态电池的研究进展。最后，展望了高性能卤氧化物电解质的设计准则以及其在全固态电池实际应用中的发展方向，旨在为卤氧化物基全固态电池在能量转换和储存领域的发展提供重要指导。

关键词

卤氧化物电解质 / 合成方法 / 离子传导机制 / 界面相容性 / 全固态电池

Abstract

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The advancement of the global new energy revolution has placed stringent demands on energy storage technologies, emphasizing the need for high-energy-density and high-power electrochemical devices to enable the grid-scale and public infrastructure energy storage. All-solid-state batteries (ASSBs) exploiting solid ionic conductors as electrolytes offer advantages of high-energy-density, enhanced safety performance and long cycle life, which are considered as a crucial direction for the development of next-generation electrochemical energy storage. Designing and synthesizing solid-state electrolytes (SSEs) with ultrafast ionic conductivity, wide electrochemical windows and excellent mechanical deformability plays a crucial role to realizing the practical application of ASSBs.

To date, various types of inorganic solid electrolytes including oxides and sulfides are extensively investigated, but none of them are successfully combined the advantages of excellent interfacial wettability and outstanding oxidation stability. Oxyhalide SSEs are among the most promising solid electrolytes for the commercialization of ASSBs due to their advantages like good compatibility with high-voltage cathodes, excellent mechanical deformability and remarkable ionic conductivity compared to that of liquid electrolytes. Despite oxyhalide electrolytes use in ASSBs, challenges remain in their practical application, including the scalable preparation, enhancement of humid tolerance and improved compatibility with electrode materials.

In this review, a critical overview of the development, synthesis, ionic conduction mechanisms and challenges of oxyhalide electrolytes is given. Different synthesis routes of oxyhalide electrolytes including the promising hydrate-assisted synthesis method are summarized in detail. Furthermore, the framework structures of various types of oxyhalide electrolytes are analyzed, and the ionic conduction mechanisms in crystalline and amorphous oxyhalide electrolytes are elucidated. The interfacial compatibility of oxyhalide electrolytes with lithium metal anodes and various cathode materials is highlighted, and the latest progress of oxyhalide electrolytes in low-temperature ASSBs is also represented. Finally, future perspectives on designing high-performance oxyhalide electrolytes and their practical applications in ASSBs are provided, aiming to offer guidance for the advancement of oxyhalide-based ASSBs in energy conversion and storage.

Summary and prospects

Metal oxyhalides ionic conductors represent a highly promising class of inorganic solid electrolytes for realizing the commercialization of high-performance ASSBs due to their outstanding electrochemical stability, excellent mechanical deformability, low-cost preparation and high ionic conductivity, compared to that of liquid electrolytes. Despite certain progress is made for the oxyhalide electrolytes in improving ionic conductivity, hydrate-assisted synthesis and low temperature application in ASSBs, some challenges remain for their practical application, including large-scale preparation, improving of moisture instability and enhancing compatibility with electrode materials. The attractive future research directions and prospects are outlined as follows, i.e., (1) Scale-up preparation: The wet-chemistry synthesis offers several advantages for the preparation of oxyhalide electrolytes, including scalable production, effective size control and shortened reaction time. However, reports on synthesizing oxyhalide electrolytes employing the wet-chemistry method remain scarce. By introducing auxiliary agents into the aqueous solution as a coordination agent to preferentially react with metal halides to form stable intermediates, offering a crucial guidance for the development of wet-chemistry synthesis of oxyhalide electrolytes, (2) Revealing ion-conduction mechanism: Advanced characterization techniques, such as synchrotron X-ray diffraction (SXRD), neutron powder diffraction (NPD), X-ray absorption near-edge structure (XANES) and solid-state nuclear magnetic resonance (SSNMR), can be preferentially utilized to deeply analyze the local structure of oxyhalide electrolytes, and combined with simulation and computational modeling to establish the structure-performance relationships of oxyhalide electrolytes, effectively promoting the design and synthesis of next-generation ultrafast ionic conductive oxyhalide electrolytes, (3) Enhancement of chemical stability: The chemical stability of oxyhalide electrolytes exerts a crucial influence on the implementation in their entire life from preparation, storage and transportation to application. An in-depth understanding of the degradation mechanisms of oxyhalide electrolytes when exposed to humid air and polar solvents can provide a significant theoretical guidance for the development of highly moisture-resistant oxyhalides and solvents with a good compatibility towards oxyhalide electrolytes, (4) Improving electrode-electrolyte interface compatibility. The development of highly ionically conductive oxyhalides with a superior reduction stability that are compatible with alkali metal anodes, and the construction of stable passivation layers at cathode-oxyhalide interfaces to suppress side reactions can offer crucial pathways for achieving high-energy-density ASSBs with oxyhalide electrolytes, and (5) Fabrication of electrolyte/electrode film: Tape casting is considered as a scalable strategy for the preparation of ultra-thin electrolyte membrane and electrode sheet. The screening of solvents and binders compatible with oxyhalides and the optimization of slurry component content can be the promising research directions in future due to the limited compatibility of oxyhalides with conventional polar solvents that are similar to those used in halide electrolytes. In addition, the solvent-free process for preparing self-supporting oxyhalide electrolyte membranes and sheet electrodes presents advantages such as simplified processes and reduced environmental pollution, providing a viable pathway for large-scale applications of oxyhalide electrolytes. The unique dual-anion chemistry of oxyhalide electrolytes grants them outstanding comprehensive performance, positioning them as one of the most promising solid electrolytes for the commercialization of ASSBs. It is foreseeable that ASSBs utilizing oxyhalide electrolytes will unlock new opportunities for the storage and conversion of renewable energy in future.

Key words

oxyhalide electrolytes / synthesis methods / ionic conduction mechanism / interfacial compatibility / all-solid-state batteries

引用本文

脱凯用, 卢普顺, 周志民, 梁苏哲, 张加旭, 胡观泰, 王超, 刘婷婷, 孙一芃, 王长虹, 孙学良. 卤氧化物固态电解质及其全固态电池研究进展. 硅酸盐学报, 2025 , 53 (6) : 1435 -1455 . DOI: 10.14062/j.issn.0454-5648.20240844

Kaiyong TUO, Pushun LU, Zhimin ZHOU, Suzhe LIANG, Jiaxu ZHANG, Guantai HU, Chao WANG, tingting LIU, Yipeng SUN, Changhong WANG, Xueliang SUN. Recent Development on Oxyhalide Electrolytes for All-Solid-State Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1435 -1455 . DOI: 10.14062/j.issn.0454-5648.20240844

基金

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国家自然科学基金委青年基金(22409103)
中国博士后科学基金第75批面上资助(2024M751548)
中国博士后科学基金第17批特别资助(2024T170442)
宁波市科技局科创甬江2035(2024Z040)
合作创新研究团队(W2441017)

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2025年第53卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240844

接收时间：2024-12-31
首发时间：2026-10-22
出版时间：2025-06-20

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收稿日期：2024-12-31
修回日期：2025-01-16

基金

国家自然科学基金委青年基金(22409103)

中国博士后科学基金第75批面上资助(2024M751548)

中国博士后科学基金第17批特别资助(2024T170442)

宁波市科技局科创甬江2035(2024Z040)

合作创新研究团队(W2441017)

作者信息

^1．宁波东方理工大学（暂名），浙江宁波 315200

^2．宁波东方理工高等研究院，浙江宁波 315200

^3．中国科学技术大学，合肥 230026

通讯作者:

王长虹（1989—），男，博士，副研究员；

孙学良（1963—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240844

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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