硅酸盐学报

固态锂/钠离子电解质膜制备技术进展

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苏航 ¹^,² , 唐函 ¹^,² , 苏韵 ³ , 容晓晖 ¹^,² , 胡勇胜 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1600-1623

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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) : 1600 -1623

固态锂/钠离子电解质膜制备技术进展

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苏航¹^,², 唐函¹^,², 苏韵³, 容晓晖¹^,², 胡勇胜¹^,²

作者信息

^1．中国科学院物理研究所，北京 100190

^2．长三角物理研究中心有限公司，江苏溧阳 213300

^3．军事科学院防化研究院，北京 102205

通讯作者:

容晓晖（1990—），男，博士，特聘研究员；

胡勇胜（1976—），男，博士，研究员。

作者简介:

苏航（2000—），女，硕士研究生。

Preparation Technology of Solid-State Lithium/Sodium Ion Electrolyte Membranes

Hang SU¹^,², Han TANG¹^,², Yun SU³, Xiaohui RONG¹^,², Yongsheng HU¹^,²

Affiliations

^1.Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

^2.Yangtze River Delta Physics Research Center Co. Ltd, Liyang 213300, Jiangsu, China

^3.Beijing Key Laboratory of Advanced Chemical Energy Storage Technology and Materials, Chemical Defense Institute, Academy of Military Sciences, Beijing 102205, China

Corresponding Author:

RONG Xiaohui (1990-), male, Ph.D., distinguished Research Fellow. E-mail: rong@iphy.ac.cn;

HU Yongsheng (1976-), male, Ph.D., Research Fellow. yshu@iphy.ac.cn

SU Hang (2000-), female, Master candidate. E-mail: suhang22@mails.ucas.ac.cn

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240775

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摘要

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全固态电池有望实现超越液态电池的能量密度，并提供更高的安全性，已成为当前研究的热点领域。作为全固态电池的核心组件之一，固体电解质膜的厚度、离子传输能力、机械性能、化学/电化学稳定性等性能对全固态电池的性能起着至关重要的作用。本文总结了现有固体电解质膜的加工方法，根据电解质膜加工技术对溶剂的使用情况，分为湿法制备、干法制备、干/湿法均可制备等3类加工技术，详细介绍了所制备的固态电解质膜的厚度、离子电导率、机械性能、电池性能、大规模加工潜力等关键技术指标，并对不同制备工艺面临的挑战和未来的发展方向进行了总结和展望。

关键词

固体电解质膜 / 干法制备 / 湿法制备 / 大规模生产

Abstract

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All-solid-state batteries are expected to achieve higher energy density and provide a higher safety rather than liquid batteries. As one of the core components of the all-solid-state battery, the thickness, ion transport capacity, mechanical properties, chemical/electrochemical stability and other properties of the solid electrolyte film play a crucial role in the performance of the all-solid-state battery. This review summarizes the processing methods of the existing solid electrolyte membrane. According to the solvent usage of the electrolyte membrane processing technology, it can be divided into three types of processing technologies, i.e., wet preparation, dry preparation and dry/wet preparation. The key technical indicators of the prepared solid electrolyte membrane, such as thickness, ionic conductivity, mechanical properties, battery properties and large-scale processing potential, are introduced. In addition, some challenges faced by different preparation processes and the future development direction are also summarized and prospected.

Summary and Prospects

The development of all-solid-state batteries puts forward new requirements and challenges for the processing and manufacturing of solid electrolytes. In this review, the processing technology of solid electrolyte in a relatively comprehensive and systematic way (i.e., dry preparation, wet preparation and dry/wet preparation) is introduced. Dry preparation mainly uses ball milling, roll pressing and other technologies, the processing process does not need to introduce solvents, avoid complex and cumbersome processing, efficient and environmentally friendly, and the prepared film thickness is easier to control. Wet preparation mainly uses magnetic stirring, ultrasonic and other methods to make the slurry mixed evenly, and then volatilizes the solvent through solution pouring, casting, freeze drying and other methods to form a film. The advantages of wet preparation are mainly that the prepared solid electrolyte film is more uniform and controllable. Dry/wet preparation mainly includes non-in-situ processing technologies such as 3D printing and electrospinning, as well as in-situ polymerization technologies such as photocuring and thermal curing. Among them, 3D printing technology has a high shapeability, which is easy to design the solid state battery structure. Electrospinning is convenient in the preparation of solid electrolyte film matrix. In-situ curing can achieve good interface properties and better integrate battery processing technology. Despite the existing solid electrolyte processing technologies, further research and attempts are still needed to achieve the large-scale production and landing of solid electrolyte membranes. The following aspects are concerned:

1) To achieve both film thickness and mechanical properties. Making the film thickness thin to achieve a high energy density is one of the important goals of all-solid-state batteries. However, the reduction in film thickness can make it easier for dendrites to Pierce, leading to short circuits. Therefore, the mechanical properties of the films should be improved via introducing high mechanical strength polymers, adding inorganic fillers and roller compaction.

2) To reduce production costs and improve preparation efficiency. Polymer synthesis usually involves relatively complex chemical reaction processes. In addition, the battery materials have generally high requirements for anhydrous and anaerobic environments. From raw materials to the production, the process steps need to be continuously optimized to reduce production costs and improve production efficiency.

3) To promote the process of film preparation from the laboratory to industrialization. A basic research in laboratory is relatively easy to achieve due to its small scale. The assembled button battery has a small area, so its consistency is relatively better controlled. However, it will inevitably encounter a variety of problems after enlarging it. Some problems in wet method such as slurry defoaming and viscosity control need to be solved. The uniformity problem in dry method as well as the adaptation of new materials to the existing processing equipment all need to be continuously verified.

4) Theoretical calculation and process production are closely integrated and mutually feedback, providing a more accurate and efficient path for the development of solid electrolytes.

In general, there is still a long way to go to obtain a solid electrolyte film with ultra-thin, excellent electrochemical performance, stable interface, low cost and easy mass production. The progress of the process is also inseparable from the development of novel materials and the update of production equipment. It is thus necessary to integrate material research and development, process design, production and processing interactive interconnection, and truly achieve the combination of production and learning to grasp the initiative of all-solid-state batteries as soon as possible.

Key words

solid electrolyte film / solvent-free dry-film technology / solvent wet-film technology / large-scale production

引用本文

苏航, 唐函, 苏韵, 容晓晖, 胡勇胜. 固态锂/钠离子电解质膜制备技术进展. 硅酸盐学报, 2025 , 53 (6) : 1600 -1623 . DOI: 10.14062/j.issn.0454-5648.20240775

Hang SU, Han TANG, Yun SU, Xiaohui RONG, Yongsheng HU. Preparation Technology of Solid-State Lithium/Sodium Ion Electrolyte Membranes[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1600 -1623 . DOI: 10.14062/j.issn.0454-5648.20240775

基金

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国家自然科学基金(92372116; 22422906; 52394170; 52394172; 52394174)
北京市自然科学基金(JQ24006)
中国科协青年人才托举工程(2022QNRC001)
中国博士后科学基金(2024T171193; 2024M764314)

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排序方式：

2025年第53卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240775

接收时间：2024-12-05
首发时间：2026-10-22
出版时间：2025-06-20

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出版历史

收稿日期：2024-12-05
修回日期：2025-01-08

基金

国家自然科学基金(92372116; 22422906; 52394170; 52394172; 52394174)

北京市自然科学基金(JQ24006)

中国科协青年人才托举工程(2022QNRC001)

中国博士后科学基金(2024T171193; 2024M764314)

作者信息

^1．中国科学院物理研究所，北京 100190

^2．长三角物理研究中心有限公司，江苏溧阳 213300

^3．军事科学院防化研究院，北京 102205

通讯作者:

容晓晖（1990—），男，博士，特聘研究员；

胡勇胜（1976—），男，博士，研究员。

参考文献

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240775

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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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