硅酸盐学报

聚合物基固态电解质材料研究进展

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符军俊 ¹ , 郝锦锦 ¹ , 谢晓新 ² , 周伟东 ¹

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1520-1560

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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) : 1520 -1560

聚合物基固态电解质材料研究进展

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符军俊¹, 郝锦锦¹, 谢晓新², 周伟东¹

作者信息

^1．北京化工大学化学工程学院，北京 100029

^2．华南理工大学材料科学与工程学院前沿弹性体研究院，广州 510640

通讯作者:

谢晓新（1994—），女，博士。

周伟东（1981—），男，博士，教授。

作者简介:

符军俊（2000—），男，硕士研究生。

郝锦锦（1999—），女，硕士研究生。

Research Progress on Polymer-Based Solid-State Electrolyte Materials

Junjun FU¹, Jinjin HAO¹, Xiaoxin XIE², Weidong ZHOU¹

Affiliations

^1.College of Chemical Engineering, Beijing University of hemical Technology, Beijing 100029, China

^2.Institute of Frontier Elastomers, School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China

Corresponding Author:

XIE Xiaoxin (1994-), female, Ph.D. E-mail: xiexiaoxin1225@163.com;

ZHOU Weidong (1981-), male, Ph.D., Professor. zhouwd@mail.buct.edu.cn

FU Junjun (2000-), male, Master. E-mail: 2022210111@buct.edu.cn;

HAO Jinjin (1999-), female, Master. 2022210112@buct.edu.cn

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240854

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摘要

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与无机固态电解质相比，固态聚合物电解质（SPEs）具有柔韧性高、界面接触性好、成本低等特点，被认为是最先应用的固态电解质。根据SPEs电压稳定性的区别，本文综述了低电压稳定的聚醚基和高电压稳定的聚酯基2类典型SPEs体系的研究进展：1）聚醚类电解质，与锂金属的兼容性较好，但抗氧化性差，室温离子电导率偏低，主要概述了聚环氧乙烷（PEO）、聚—聚乙二醇甲基丙烯酸酯（pPEGMEA）、聚二氧环戊烷（PDOL）和聚甲醛（POM）等4类聚醚基SPEs面临的问题和解决策略；2）聚酯基电解质与高电压正极材料匹配较好，但其容易被锂金属还原，主要概述了聚己内酯（PCL）、聚碳酸三亚甲酯（PTMC）、聚碳酸丙烯酯（PPC）、聚草酸酯（POE）等4类聚酯的挑战和解决策略；3）原位聚合解决了固态电池产线与现行电池产线兼容性的问题，同时改善了SPEs与电极界面的接触性，概述了几类典型原位聚合SPEs的研究进展，包括：聚乙烯基碳酸酯（PVCA）、聚碳酸乙烯亚乙酯（poly（PVEC）和聚甲基丙烯酸甲酯（PMMA）。最后，简要阐述了未来SPEs的发展方向和策略，为实现高能量密度和长寿命固态锂电池提供解决思路。

关键词

聚醚基电解质 / 聚酯基电解质 / 原位聚合 / 固态锂电池

Abstract

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Compared with inorganic solid-state electrolyte, solid polymer electrolyte (SPEs) is an ideal electrolyte material for solid-state lithium metal batteries due to its high flexibility, excellent processability and good interfacial contact. The ionic conductivity, electrochemical window and interface stability of SPEs with electrodes play a crucial role in the overall performance of solid-state lithium batteries. According to the different electrochemical stability windows, this review represents research progress on two types of typical SPEs systems, i.e., low-voltage stable polyethers and high-voltage stable polyesters. Polyether-based electrolytes, which mainly outlines the problems and challenges faced by four types of polyether, such as poly(ethylene oxide) (PEO), poly(ethylene glycol monomethyl ether acrylate) (pPEGMEA), poly(1,3-oxolane) (PDOL), and polyoxymethylene (POM)-based SPEs. These electrolytes have a better compatibility with lithium metal, but a poor oxidation resistance and a low ionic conductivity at room temperature. The molecular structure design of polymers and the introduction of functional groups (—F, —CN, —C=O) can reduce the HOMO value of SPEs and improve the antioxidant ability of electrolytes. The crystallinity of PEO-SPEs can be reduced via compounding, blending and cross-linking with inorganic fillers to improve the ionic conductivity. In addition, the balanced interactions between Li⁺, lithium salts, ether groups, anions and polymer matrix structure also need to be considered to achieve high ionic mobility and ionic conductivity. Polyester electrolytes mainly outline the challenges and solution strategies of four types of polyester, i.e., poly(ε-caprolactone) (PCL), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC) and polyoxalate (POE). This type of electrolyte is a good match for high-voltage cathode materials, but is easily reduced by lithium metal. The construction of a stable solid electrolyte interface membrane (SEI) layer can improve the stability with lithium metal via introducing multifunctional groups. In addition, the development of in-situ polymerisation processes is also reviewed, considering that solid-state electrolytes suffer from a poor electrode-electrolyte interfacial contact, a low ionic conductivity and complex manufacturing processes. Therefore, this review outlines the advantages and disadvantages of the two types of polyether-based and polyester-based SPEs, and analyzes their key scientific issues as well as recent research progress of the modification methods to provide a reference for future research and practical applications.

Summary and prospects

Despite important advances in solid polymer electrolytes (SPEs), polyether and polyester electrolytes and in-situ polymerisation technologies still face several challenges before they can be applied commercially. Improving ionic conductivity and electrochemical stability while maintaining good mechanical properties and interfacial compatibility are key issues in the development of SPEs. In addition, the economics and scale-up of preparation are important considerations for commercial applications, and greener and more efficient preparation processes also need to be explored. The development of SPEs in solid-state lithium-ion batteries focuses on the following aspects, i.e., 1) designing new molecular structures, exploring the constitutive relationship between molecular structure and properties, and improving the ionic conductivity and antioxidant properties of electrolytes, 2) since all electrochemical reactions occur at the interface, constructing a stable cathode-electrolyte (CEI) and SEI membrane between SPEs and cathode and anode to improve the interfacial stability and inhibit the interfacial reactions, 3) improving the ionic conductivity of SPEs through strategies such as grafting, copolymerisation and organic-inorganic composites, and 4) exploring the recycling methods of lithium salts and polymers to further reduce the manufacturing cost of SPEs.

For quasi-solid state electrolytes (QSSEs) with a high ionic conductivity, it is necessary to solve the following problems, i.e., 1) to improve the molecular stability of polymers for high-voltage cathode materials and low-voltage anode materials, 2) to enhance the liquid-locking ability of polymer molecules, inhibit the interfacial side reactions and improve the safety of the battery, 3) to regulate the interactions among the components of polymer, solvent and lithium salt to optimize the solvation structure of Li⁺ and achieve the rapid migration of Li⁺, and 4) the electrolyte film thickness and electrode active substance loading must be as close as possible to or exceed the targets of commercial liquid batteries. In addition, the production of large capacity energy storage batteries (i.e., >200 A·h) , results in local inhomogeneities within the cell due to the inhomogeneous heating within the cell. The influence of various factors (i.e., initiator activity, initiator dosage, and polymerisation temperature) on the polymerisation process should be investigated. The "step-by-step in-situ curing" route should be adopted, so that the polymer is cured in the battery separator, cathode and anode, and the polymer is cured in a step-by-step process. The polymer is in-situ cured at the battery diaphragm, positive electrode and negative electrode, and then laminated to assemble the solid-state battery. In summary, the synergistic development of polyether electrolyte, polyester electrolyte and in-situ polymerisation technology has an important foundation for the commercial application of lithium solid-state batteries. In the future, high-performance, low-cost SPEs, especially the development of in-situ curing, are expected to be applied in a large scale, becoming the first practical solid-state battery system.

Key words

polyether-based electrolyte / polyester-based electrolyte / in situ polymerization / solid-state lithium batteries

引用本文

符军俊, 郝锦锦, 谢晓新, 周伟东. 聚合物基固态电解质材料研究进展. 硅酸盐学报, 2025 , 53 (6) : 1520 -1560 . DOI: 10.14062/j.issn.0454-5648.20240854

Junjun FU, Jinjin HAO, Xiaoxin XIE, Weidong ZHOU. Research Progress on Polymer-Based Solid-State Electrolyte Materials[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1520 -1560 . DOI: 10.14062/j.issn.0454-5648.20240854

基金

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国家重点研究计划(2022YFA1204501; 2022YFE0202400)
国家自然科学基金(22261160570; 22179004; 52403267)
中国博士后科学基金(2024M750944)

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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.0454-5648.20240854

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：2025-02-14

基金

国家重点研究计划(2022YFA1204501; 2022YFE0202400)

国家自然科学基金(22261160570; 22179004; 52403267)

中国博士后科学基金(2024M750944)

作者信息

^1．北京化工大学化学工程学院，北京 100029

^2．华南理工大学材料科学与工程学院前沿弹性体研究院，广州 510640

通讯作者:

谢晓新（1994—），女，博士。

周伟东（1981—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240854

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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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