硅酸盐学报

超薄硫化物固态电解质膜的研究与开发进展

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余灿文 ¹ , 刘心怡 ¹ , 张柏松 ¹ , 姜益栋 ¹ , 邓永红 ¹^,² , 许晓雄 ² , 池上森 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1577-1599

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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) : 1577 -1599

超薄硫化物固态电解质膜的研究与开发进展

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余灿文¹, 刘心怡¹, 张柏松¹, 姜益栋¹, 邓永红¹^,², 许晓雄², 池上森¹^,²

作者信息

^1．南方科技大学材料科学与工程系，广东深圳 518055

^2．南方科技大学创新创业学院，广东省电驱动力能源材料重点实验室，广东深圳 518055

通讯作者:

许晓雄（1979—），男，博士，教授。

池上森（1983—），男，博士，副教授。

作者简介:

余灿文（1998—），男，硕士研究生。

Development and Research Process of Ultra-Thin Sulfide Solid-State Electrolyte Film

Canwen YU¹, Xinyi LIU¹, Baisong ZHANG¹, Yidong JIANG¹, Yonghong DENG¹^,², Xiaoxiong XU², Shangsen CHI¹^,²

Affiliations

^1.Department of Materials and Engineering, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China

^2.School of Innovation and Entrepreneurship, Southern University of Science and Technology, Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China

Corresponding Author:

XU Xiaoxiong (1979-), male, Ph.D., Professor. E-mail: xuxx@sustech.edu.cn;

CHI Shangsen (1983-), male, Ph.D., associate Professor. chiss@sustech.edu.cn

YU Canwen (1998-), male, Master candidate. E-mail: yucw@mail.sustech.edu.cn

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240855

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摘要

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以固态电解质（SSEs）代替传统有机液态电解质的全固态锂电池（ASSLBs）具有优异的安全性和高的能量密度，是最有潜力的下一代储能电池。在SSEs中，硫化物电解质具有高离子导电性、低活化能和良好的机械性能而备受关注，开发超薄硫化物SSEs膜可以有效提升ASSLBs的能量密度。然而，硫化物粉末颗粒成膜后，薄膜强度低和力学性能差，限制了电解质超薄膜和ASSLBs的研究开发进展，使得制备具有一定力学性能的超薄硫化物SSEs膜成为挑战。本文介绍几种常见的硫化物SSEs合成方法及其应用进展，综述硫化物薄膜干法和湿法工艺合成，薄膜合成过程中黏结剂选择，薄膜致密化策略以及SSEs薄膜与正负极接触稳定性，探讨材料、制造工艺和系统集成相关的挑战并提出应对这些挑战的策略，强调硫化物SSEs薄膜在实现高比能ASSLBs的关键作用。

关键词

全固态锂电池 / 硫化物电解质 / 超薄膜制备 / 黏结剂 / 界面稳定性

Abstract

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Sulfide solid-state electrolytes (SSEs) emerge as a promising candidate for replacing conventional liquid electrolytes in all-solid-state lithium batteries (ASSLBs). With their inherent advantages of high ionic conductivity, low activation energy, and good mechanical properties, sulfide SSEs hold a great potential for achieving high safety and energy density in next-generation energy storage devices. Unfortunately, the electrolyte layers or solid-state films of sulfide-based ASSLBs typically require a thickness of greater than 100 μm to prevent lithium dendrite penetration and SSEs layer fracture, leading to short circuits during battery cycling. Ultra-thin sulfide SSEs films have attracted recent attention. Compared to conventional thick films, ultra-thin sulfide SSEs films can significantly reduce the non-active material content in batteries, thereby improving energy density. They can also enhance Li⁺ transport efficiency, lower electrolyte surface resistance and battery internal resistance, and improve battery cycling performance and rate performance. Some binders need to be added when the thickness of the sulfide SSEs layer is less than 100 μm, resulting in a conductivity of less than 1.0 mS/cm. Therefore, the development of ultra-thin SSEs films with high ionic conductivity, high strength, high toughness, and based on sulfide electrolytes is a key direction for high-energy-density sulfide ASSLBs. This review represents recent development on sulfide SSEs, focusing on material development, synthesis methods, film preparation, binder selection, densification strategies, and interface stability.

This review introduces the significant advancements of sulfide SSEs in recent years. Various types of sulfide SSEs with superior properties are developed, including glass, glass-ceramics, thio-LISICON, LGPS, and argyrodite-type materials. These materials exhibit diverse structures and properties, and the ion conductivity and stability of sulfide SSEs are continuously improved through various strategies, such as component optimization, element substitution, and crystal structure engineering. Several methods exist for synthesizing sulfide SSEs, each with its advantages and disadvantages. Solid-state synthesis, mechanochemical synthesis, and liquid-phase synthesis are the most commonly used methods.

Developing thin and flexible sulfide SSEs films is crucial for achieving high energy density in ASSLBs. Wet processes such as slurry casting, spin coating, and dip coating are commonly used, but can be limited by solvent compatibility and film uniformity. Dry processes like powder pressing, powder spraying, and binder fiberization offer advantages in terms of film quality and process efficiency, but require further development for large-scale production. These dry methods offer a potential for minimizing solvent effects and improving film performance via directly depositing the SSEs powder onto the substrate without solvents. The choice of binder plays a vital role in film properties. Inert binders like ethylcellulose and SBR provide good mechanical strength, but can hinder Li⁺ transport. Li⁺ conducting binders like LiTFSI and PVDF offer an improved ion conductivity, but require careful optimization of processing conditions. PTFE is a popular option for dry film fabrication due to its low percolation threshold and good mechanical properties. The selection of binder depends on the specific application requirements and the desired trade-off among ion conductivity, mechanical strength, and interface stability.

Densification techniques like hot pressing and cold pressing are essential for achieving high ion conductivity and mechanical strength in sulfide SSEs films. These techniques improve the packing density and reduce the porosity of the films, leading to enhanced ion transport and mechanical properties. Also, innovative approaches like solvent-free synthesis and the use of reinforcing structures like fibers are explored to further enhance film properties and address the challenges associated with conventional wet processes. Ensuring interface stability between sulfide SSEs films and electrode materials is crucial for the battery performance. Sulfide SSEs can react with both cathode materials and lithium metal, leading to interface issues such as decreased ion conductivity, increased interface resistance, and battery capacity degradation. Strategies to address these challenges include surface modification of electrode materials, component optimization, and the use of interlayer materials like precursors of solid electrolyte interface (SEI). These approaches can improve the compatibility between sulfide SSEs and electrode materials and reduce the occurrence of interface reactions.

Summary and Prospects

While significant progress is made in sulfide SSEs research, some challenges are related to film properties, interface stability, and large-scale production remain. Future efforts should focus on several key areas, i.e., developing new sulfide SSEs materials with higher ionic conductivity, lower activation energy, and better chemical stability through material engineering and structure optimization; optimizing particle size and morphology to achieve optimal film properties and Li⁺ transport efficiency, which can be achieved through controlled synthesis and particle size engineering techniques; exploring new techniques like solvent-free synthesis, solution processing, and additive manufacturing to improve film performance, uniformity, and scalability; developing strategies to improve interface stability between sulfide SSEs films and electrode materials, including the use of interlayer materials, surface modification, and SEI engineering techniques; and implementing efficient and cost-effective production processes to enable commercialization of sulfide SSEs for ASSLBs, which requires the development of automation, high-throughput equipment, and optimization of production parameters. ASSLBs have a potential to revolutionize the energy storage landscape via addressing these challenges and continuously advancing sulfide SSEs technology, paving a way for a sustainable future with cleaner and more efficient energy storage solutions. The development of high-performance sulfide SSEs films is crucial for achieving this vision and unlocking the full potential of ASSLBs in various applications, including electric vehicles, grid-scale energy storage and portable electronics.

Key words

all-solid-state lithium batteries / sulfide electrolyte / ultra-thin film fabrication / binder / interface stability

引用本文

余灿文, 刘心怡, 张柏松, 姜益栋, 邓永红, 许晓雄, 池上森. 超薄硫化物固态电解质膜的研究与开发进展. 硅酸盐学报, 2025 , 53 (6) : 1577 -1599 . DOI: 10.14062/j.issn.0454-5648.20240855

Canwen YU, Xinyi LIU, Baisong ZHANG, Yidong JIANG, Yonghong DENG, Xiaoxiong XU, Shangsen CHI. Development and Research Process of Ultra-Thin Sulfide Solid-State Electrolyte Film[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1577 -1599 . DOI: 10.14062/j.issn.0454-5648.20240855

基金

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国家自然科学基金(22279051)
国家重点研发计划(2022YFB3807700)

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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.0454-5648.20240855

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：2025-01-20

基金

国家自然科学基金(22279051)

国家重点研发计划(2022YFB3807700)

作者信息

^1．南方科技大学材料科学与工程系，广东深圳 518055

^2．南方科技大学创新创业学院，广东省电驱动力能源材料重点实验室，广东深圳 518055

通讯作者:

许晓雄（1979—），男，博士，教授。

池上森（1983—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240855

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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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