硅酸盐学报

全固态锂金属电池的体积膨胀效应与调控

PDF下载

王子轩 ¹^,² , 赵辰孜 ³ , 张睿 ²^,⁴ , 黄佳琦 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1638-1654

收起

硅酸盐学报 |全固态电池发展专刊—综合评述 2025 , 53 (6) : 1638 -1654

全固态锂金属电池的体积膨胀效应与调控

全屏

王子轩¹^,², 赵辰孜³, 张睿²^,⁴, 黄佳琦¹^,²

作者信息

^1．北京理工大学材料学院，北京 100081

^2．北京理工大学前沿交叉科学研究院，北京 100081

^3．清华大学化学工程系，北京 100084

^4．北京怀柔实验室，北京 101400

通讯作者:

赵辰孜（1994—），女，博士，助理研究员；

黄佳琦（1984—），男，博士，教授。

作者简介:

王子轩（2000—），男，博士研究生。

Volume Expansion Effects and Mitigation in All-Solid-State Lithium Metal Batteries

Zixuan WANG¹^,², Chenzi ZHAO³, Rui ZHANG²^,⁴, Jiaqi HUANG¹^,²

Affiliations

^1.School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China

^2.Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China

^3.Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

^4.Beijing Huairou Laboratory, Beijing 101400, China

Corresponding Author:

ZHAO Chenzi (1994-), Ph.D., Assistant Researcher. E-mail: zcz@mail.tsinghua.edu.cn;

HUANG Jiaqi (1984-), Ph.D., Professor. jqhuang@bit.edu.cn

WANG Zixuan (2000-), male, Doctoral candidate. E-mail: 976326109@qq.com

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20240847

文章导航

摘要

收起

全固态锂金属电池（ASSLMB）因其高能量密度和安全性等优势，成为下一代电池技术的研究热点。然而，尽管全固态锂金属电池在理论上展现了巨大的潜力，实际应用中仍面临诸多挑战，尤其是由体积膨胀引发的力-电化学耦合效应。在充放电过程中，活性材料的体积变化导致电芯整体体积变化，不仅对电池模组设计带来挑战。同时，还会引发高达GPa级的应力响应。由此导致的界面失效及离子传输路径阻塞等问题，严重影响电池的性能和循环寿命。此外，随着能量密度的提高，该问题将愈发突出。因此，深入理解全固态锂金属电池中体积膨胀行为及其缓解策略，对于推动全固态电池实用化进程至关重要。本文综述了全固态锂金属电池中力-电化学耦合原理，并从多个视角深入探讨电池循环过程中体积膨胀效应及其对电化学性能的影响。随后，总结了缓解体积膨胀效应的最新研究进展，包括材料设计、界面调控和结构优化等。最后，展望了未来研究方向，分析当前技术挑战及解决方案，旨在为研究人员和工程师提供理论支持和实践指导，推动全固态锂金属电池技术的发展与应用。

关键词

全固态锂金属电池 / 体积膨胀 / 应力响应 / 力-电化学

Abstract

收起

The global energy transition toward sustainable and green energy systems have intensified a demand for advanced electrochemical energy storage technologies. Lithium-ion batteries (LIBs), while being dominant in portable electronics and electric vehicles, face some challenges, including safety risks from flammable liquid electrolytes and limited energy density. These limitations hinder their application in emerging fields such as electric aviation, high-performance drones, and long-range electric vehicles. Recent incidents of LIB thermal runaway and combustion further highlight an urgency for safe and high-energy-density alternatives. In this context, all-solid-state lithium metal batteries (ASSLMBs) emerge as a promising next-generation energy storage solution, offering enhanced safety and superior energy density.

ASSLMBs replace volatile liquid electrolytes with solid-state electrolytes (SSEs), thereby eliminating combustion risks and improving thermal stability. Also, the use of lithium metal anodes with an ultrahigh theoretical capacity (i.e., 3860 mA·h/g) and a minimum electrochemical potential (i.e., −3.04 V vs. SHE) significantly boosts energy density, compared to conventional graphite anodes. These advantages make ASSLMBs a focal point of research and development. However, despite their theoretical potential, ASSLMBs face some practical challenges, particularly the electrochemo-mechanical issues induced by volume expansion during charge and discharge cycles.

Volume changes in ASSLMBs stem from the expansion and contraction of electrode materials during lithium (de)intercalation. Cathode materials, such as lithium-rich manganese-based oxides, typically exhibit volume changes of 2%-10%. In contrast, lithium metal anodes can experience extreme volume expansion of up to 1000% when operating at a low negative-to-positive capacity ratio (i.e., N/P=1.1). In high-energy-density configurations, such as ASSLMBs targeting about 600 W·h/kg, the overall cell-level volume change can reach 18%. Unlike conventional LIBs that use liquid electrolytes to accommodate strain, the rigid solid-solid interfaces in ASSLMBs cannot self-adjust to such deformations. This rigidity leads to significant mechanical stresses, including stack-level stresses in the MPa range and localized stress concentrations in the GPa range, caused by heterogeneous current distribution, lithium dendrite growth, and particle cracking. These stresses can result in interfacial delamination, active material fracture, and ion transport blockages, severely degrading the battery performance and cycle life.

This review provides a comprehensive analysis of the electrochemo-mechanical challenges in all-solid-state lithium metal batteries (ASSLMBs) and explores some strategies to mitigate these issues. First, we examine the fundamental mechanisms of mechanical-electrochemical coupling, emphasizing a relationship between material properties (i.e., modulus, fracture toughness), operational parameters (i.e., current density, pressure), and stress generation. Advanced characterization techniques, such as in-situ stress sensors, X-ray computed tomography, and finite element modeling, are employed to reveal multi-scale stress evolution and its impact on the battery performance. These tools enable to visualize and quantify stress distribution in micro- and macro-scale, providing insights into the dynamic interplay between mechanical and electrochemical processes. Second, we analyze the consequences of volumetric strain on key performance metrics, including interface stability, lithium deposition behavior, and cathode degradation.

To address these challenges, we evaluate strategic approaches such as material innovation, interface engineering, and structural optimization. Material innovation focuses on designing SSEs with balanced ionic conductivity and mechanical compliance. Strain-tolerant cathode architectures, including single-crystal particles and composite electrodes with buffer matrices, are also explored to mitigate volume changes. Interface engineering involves introducing functional interlayers, such as Li₃N coatings, to enhance adhesion and redistribute interfacial stresses. Artificial solid-electrolyte interphases (SEI) with self-healing properties are highlighted for stabilizing lithium anodes and preventing dendrite formation. Structural optimization explores cell-level designs, including pre-stress mechanisms and gradient porosity electrodes, to mitigate strain accumulation and improve the overall battery performance. Pressure management strategies for stack assemblies are also discussed to balance contact maintenance with stress relaxation. ASSLMBs with enhanced mechanical stability, improved electrochemical performance and extended cycle life are developed via integrating these approaches, paving a way for their practical application in next-generation energy storage systems.

Finally, we outline future research directions, emphasizing a need for multi-physics models that integrate electrochemical, thermal, and mechanical dynamics across scales. Advanced manufacturing techniques and novel diagnostic tools for real-time stress monitoring are identified as critical enablers for advancing ASSLMB technology. In addition, we also analyze the existing technical challenges and potential solutions, which can provide theoretical support and practical guidance.

Summary and prospects

One of the core challenges faced by all-solid-state lithium metal batteries during their development is a mechanical-electrochemical coupling effect caused by volumetric changes. The volumetric changes of active materials during charge and discharge, especially under high energy density conditions, can significantly negatively impact the structural stability and electrochemical performance of the battery, leading to some problems such as interface delamination and crack formation. These problems severely limit the cycle life and high-rate performance of all-solid-state lithium metal batteries, becoming a major obstacle to their practical application. To address these challenges, some strategies such as optimizing cell module structures, material modification, and structural regulation have been proposed. Future research should focus on four key directions, i.e., exploring the mechanical-electrochemical coupling mechanism using advanced experimental techniques and multiscale modeling to better understand the interactions between stress, ion transport, and electrochemical reactions, developing advanced characterization and testing methods to cope with the complexity of mechanical-electrochemical coupling mechanism, developing volumetric expansion suppression strategies for practical applications (i.e., the development of zero-strain electrode materials and interface engineering designs) to mitigate the adverse effects of volumetric changes during cell cycling while reducing the high stack pressure demands of all-solid-state lithium metal batteries, and leveraging machine learning and artificial intelligence to accelerate the discovery of high-performance materials and optimize the battery structure design.

Key words

all-solid-state lithium metal battery / volume expansion / stress responses / mechanical-electrochemical

引用本文

王子轩, 赵辰孜, 张睿, 黄佳琦. 全固态锂金属电池的体积膨胀效应与调控. 硅酸盐学报, 2025 , 53 (6) : 1638 -1654 . DOI: 10.14062/j.issn.0454-5648.20240847

Zixuan WANG, Chenzi ZHAO, Rui ZHANG, Jiaqi HUANG. Volume Expansion Effects and Mitigation in All-Solid-State Lithium Metal Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1638 -1654 . DOI: 10.14062/j.issn.0454-5648.20240847

基金

收起

国家自然科学基金(22425901)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2025年第53卷第6期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240847

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

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-12-31
修回日期：2025-02-06

基金

国家自然科学基金(22425901)

作者信息

^1．北京理工大学材料学院，北京 100081

^2．北京理工大学前沿交叉科学研究院，北京 100081

^3．清华大学化学工程系，北京 100084

^4．北京怀柔实验室，北京 101400

通讯作者:

赵辰孜（1994—），女，博士，助理研究员；

黄佳琦（1984—），男，博士，教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240847

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

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

关闭全屏

BibTeX
EndNote
RefWorks
TxT