硅酸盐学报

卤化物固态电解质研究进展

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齐绩 ¹ , 钟国彬 ² , 杨国威 ¹ , 刘昊 ² , 王昱杰 ² , 怡勇 ¹

硅酸盐学报 | 综合评述 2026,54(5): 1869-1880

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硅酸盐学报 |综合评述 2026 , 54 (5) : 1869 -1880

卤化物固态电解质研究进展

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齐绩¹, 钟国彬², 杨国威¹, 刘昊², 王昱杰², 怡勇¹

作者信息

^1．深圳供电局有限公司，广东省源网荷储互动协同技术重点实验室，广东深圳 518000

^2．广东新型储能国家研究院有限公司，广州 510080

通讯作者:

怡勇（1984—），男，博士，正高级工程师。

作者简介:

齐绩（1987—），男，学士，工程师。

Research Progress on Halide Solid Electrolytes

Ji QI¹, Guobin ZHONG², Guowei YANG¹, Hao LIU², Yujie WANG², Yong YI¹

Affiliations

^1.Shenzhen Power Supply Co., Ltd, Guangdong Provincial Key Laboratory of Source-Grid-Load-Storage Interactive Collaborative Technology, Shenzhen 518000, Guangdong, China

^2.National Institute of Guangdong Advanced Energy Storage, Guangzhou 510080, China

Corresponding Author:

YI Yong (1984-), male, Ph.D., Professorate Senior Engineer. E-mail: yiyongshanxi@126.com

QI Ji (1987-), male, Bachelor, Engineer. E-mail: qiji9064@126.com

出版时间: 2026-04-23 doi: 10.14062/j.issn.0454-5648.20250405

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摘要

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全固态锂电池（ASSLB）凭借其优异的安全性和高能量密度，正在成为大规模储能系统和电动汽车应用中的关键技术。固态电解质的研究是推动这一技术发展的核心，尤其是卤化物电解质，因其出色的离子导电性、优异的电化学稳定性及良好的机械性能而受到广泛关注。本文详细概述了卤化物电解质的分类，探讨了其离子传导机制以及合成方法，较为深入地阐述了一些改进策略。最后，展望了未来卤化物电解质材料在全固态锂电池应用中的发展前景，并为后续研究提供了方向性指导。

关键词

卤化物固态电解质 / 结构 / 传输机制 / 合成路径 / 改性

Abstract

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With the growing demand for large-scale energy storage systems, electric vehicles, and smart devices, the development of rechargeable batteries with a high energy density, a fast-charging capability, and a long cycle life becomes critically important. Although the existing lithium-ion batteries dominate the market, the organic liquid electrolytes used are flammable and pose a risk of thermal runaway, restricting their further application. In contrast, all-solid-state lithium batteries offer a highly promising solution to this challenge. To replace flammable liquid electrolytes with solid-state electrolytes (SSEs), all-solid-state lithium batteries significantly enhance thermal stability and enable the use of high-voltage cathode materials to increase energy density due to the wider electrochemical stability window of SSEs. Among the various solid-state electrolyte materials, halide solid-state electrolytes (HSSEs) have attracted much attention due to their unique combination of properties. They typically exhibit a high ionic conductivity, reaching 10^-3 S·cm^-1 to 10^-4 S·cm^-1 at room temperature, which is comparable to some liquid electrolytes and sulfides. Furthermore, they possess a wide electrochemical window (i.e., 3.0-5.0 V vs. Li⁺/Li), making them compatible with high-voltage cathode materials, and demonstrate a good mechanical deformability, which facilitates an intimate solid-solid interfacial contact. This review summarizes the key progress in understanding HSSEs, focusing on their classification, ion transport mechanisms, synthesis methods, and performance optimization strategies, while also outlining the current challenges and future directions.

Firstly, for material systems, researchers propose a classification system based on the valence state of the central metal ion, dividing halide electrolytes into three categories, i.e., 1) divalent metal-based electrolytes (e.g., Li₂MX₄), which typically exhibit spinel-type structures but generally suffer from low ionic conductivity (<10^-4 S·cm^-1), 2) trivalent metal-based electrolytes (e.g., Li₃MX₆), the most widely studied class, whose conductivity is highly sensitive to crystal structure and lithium-ion/vacancy distribution, and 3) tetravalent metal-based electrolytes (e.g., Li₂MCl₆, M = Zr, Hf), represented by Li₂ZrCl₆ (0.81×10^-3 S·cm^-1), which combine good stability and cost-effectiveness, showing a great potential for practical application. In terms of ion transport mechanisms, research reveals the decisive influence of the anion framework on lithium-ion diffusion behavior. Cation doping (e.g., introducing Zr⁴⁺, In³⁺) introduces additional lithium sites and vacancies, thereby reducing migration barriers and constructing interconnected three-dimensional diffusion networks. Anion doping also proves highly effective, i.e., oxygen doping can induce amorphization, creating a more disordered local structure that facilitates rapid lithium-ion hopping, as seen in the superionic amorphous xLi₂O-TaCl₅ system, which achieves an ionic conductivity of 6.6×10^-3 S·cm^-1; fluorine doping can form stable, passivating interfacial layers, thereby enhancing high-voltage stability. The existing research on amorphous halide electrolytes emerges as a new frontier. These materials can possess lower activation energies and more efficient percolative ion transport due to their lack of long-range order. To further enhance the comprehensive performance of halide electrolytes, researchers also develop various modification strategies. Chemical doping, which modulates the lattice structure and defect chemistry by introducing heteroatoms, becomes a primary approach of improving ionic conductivity. Composite electrolyte design achieves synergistic effects via combining halide electrolytes with other materials.

Summary and Prospects

HSSEs emerge as a highly promising material for next-generation all-solid-state lithium batteries. Their unique combination of high ionic conductivity, wide electrochemical window, and good mechanical properties makes them key materials for achieving high energy density and safe energy storage. Significant progress is made in understanding the classification of crystalline and amorphous halide materials, elucidating their ion transport mechanisms, and developing diverse synthesis and modification strategies to tailor their properties.

Despite this significant progress, several challenges are addressed to fully realize their potential. 1) Improving the ionic conductivity of fluoride-based electrolytes: Although fluorides offer the advantage of high-voltage stability, their ionic conductivity remains rather low. Future research must focus on overcoming this bottleneck through novel structural design, doping strategies, or the development of amorphous fluoride phases; 2) Enhancing electrochemical stability against lithium metal anodes: When halide solid-state electrolytes come into contact with lithium metal anodes, their metal cations are susceptible to reduction, leading to interfacial instability and capacity decay. Therefore, the rational design of stable artificial solid-electrolyte interphase layers that can both protect the electrolyte from reduction and ensure smooth lithium-ion transport is crucial; 3) Deepening the understanding of amorphous transport mechanisms: Although amorphous halides exhibit a superior conductivity, the fundamental principles governing ion transport in these disordered structures are not yet fully understood. Advanced characterization techniques and theoretical simulations are needed to elucidate the roles of dynamic structural relaxation and local chemical environments; and 4) Developing scalable and sustainable synthesis methods: Moving beyond laboratory-scale synthesis to develop cost-effective, environmentally friendly, and scalable production methods is key to commercialization. This includes exploring and optimizing water-based or solvent-based synthesis routes for a wider range of materials. The focused research will pave a way for the practical application of halide solid-state electrolytes. Their successful integration into all-solid-state lithium batteries holds a potential to revolutionize energy storage, providing safer, more powerful, and longer-lasting batteries for a wide range of applications, from consumer electronics to electric vehicles and grid-scale energy storage.

Key words

halide solid electrolyte / structure / transmission mechanism / synthesis path / modification

引用本文

齐绩, 钟国彬, 杨国威, 刘昊, 王昱杰, 怡勇. 卤化物固态电解质研究进展. 硅酸盐学报, 2026 , 54 (5) : 1869 -1880 . DOI: 10.14062/j.issn.0454-5648.20250405

Ji QI, Guobin ZHONG, Guowei YANG, Hao LIU, Yujie WANG, Yong YI. Research Progress on Halide Solid Electrolytes[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (5) : 1869 -1880 . DOI: 10.14062/j.issn.0454-5648.20250405

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中国南方电网有限责任公司科技项目(090000KC23090018)

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2026年第54卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250405

接收时间：2025-05-27
首发时间：2026-09-20
出版时间：2026-04-23

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收稿日期：2025-05-27
修回日期：2025-06-28

基金

中国南方电网有限责任公司科技项目(090000KC23090018)

作者信息

^1．深圳供电局有限公司，广东省源网荷储互动协同技术重点实验室，广东深圳 518000

^2．广东新型储能国家研究院有限公司，广州 510080

通讯作者:

怡勇（1984—），男，博士，正高级工程师。

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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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