硅酸盐学报

卤化物基固态电池正极界面问题及其改性策略

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黄卿 ¹^,² , 王明坛 ² , 李峥 ¹^,² , 田传进 ¹ , 张雪 ²

硅酸盐学报 | 综合评述 2026,54(9): 3300-3314

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硅酸盐学报 |综合评述 2026 , 54 (9) : 3300 -3314

卤化物基固态电池正极界面问题及其改性策略

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黄卿¹^,², 王明坛², 李峥¹^,², 田传进¹, 张雪²

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333001

^2．清陶（昆山）能源发展集团股份有限公司，江苏昆山 215334

通讯作者:

李峥（1984—），男，博士，高级工程师；

田传进（1980—），男，博士，副教授；

张雪（1994—），女，博士，高级工程师。

作者简介:

黄卿（1999—），男，硕士研究生。

Cathode Interfacial Challenges and Mitigation Strategies in Halide-Based All-Solid-State Batteries

Qing HUANG¹^,², Mingtan WANG², Zheng LI¹^,², Chuanjing TIAN¹, Xue ZHANG²

Affiliations

^1.School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333001, Jiangxi, China

^2.Qingtao (KunShan) Energy Development Group Co., Ltd., Kunshan 215300, Jiangsu, China

Corresponding Author:

LI Zheng (1984-), male, Ph.D., Senior Engineer. E-mail: lizheng@jsqingtao.com;

TIAN Chuanjing (1980-) male, Ph.D., Associate Professor. tianchuanjin@jcu.edu.cn;

ZHANG Xue (1994-) female, Ph.D.,Senior Engineer. zhangxue@qingtao.pro

HUANG Qing (1999-), male, Master candidate. E-mail: hq990907@126.com

出版时间: 2026-01-30 doi: 10.14062/j.issn.0454-5648.20250843

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摘要

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卤化物固态电解质因兼具较高的离子电导率、优异的电化学稳定性及良好的可加工性，被视为制备高能量密度全固态电池的重要固态电解质材料。然而，在卤化物基固态电池复合正极中，固态电解质与正极材料颗粒的界面处仍存在显著的界面接触失效以及界面副反应等问题，从而恶化了固态电池的动力学性能及循环稳定性。本文系统综述了近年来关于卤化物复合正极中界面研究的相关报道，对卤化物固态电解质与活性材料间的界面问题进行了系统性的阐述，并对卤化物复合正极在材料优化、界面修饰等方面的未来发展方向进行了展望。本文旨在为构建高性能卤化物全固态电池提供系统性的科学参考与设计思路。

关键词

卤化物基固态电池 / 正极界面反应 / 失效机制 / 材料设计 / 结构优化

Abstract

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Conventional lithium-ion batteries have been widely used in consumer electronics, electric vehicles, and energy storage systems. However, safety concerns such as the flammability of liquid electrolytes and the melting of separators at high temperatures have become increasingly prominent, limiting their further development in high-energy-density energy storage applications. In contrast, all-solid-state batteries (ASSBs), which use non-flammable solid electrolytes and high-temperature-resistant solid electrolyte membranes, offer advantages such as high safety and high energy density, making them a promising direction for next-generation battery technology.

Solid-state electrolytes (SSEs) are broadly classified as polymer, oxide, sulfide, and halide. Among them, halide SSEs have attracted particular interest owing to their combination of high oxidative stability with excellent processability and high Li⁺conductivity, making them ideal for high-energy-density ASSBs. When integrated into composite cathodes, they markedly improve electrochemical and thermal stability, rendering halides a leading choice of solid electrolyte for cathode composites. However, in halide-based composite cathodes, interface failure remains a significant challenge. The volume changes in the active material during cycling cause loss of interfacial contact, leading to rising impedance. Additionally, halide SSEs tend to oxidize at high potentials, generating insulating byproducts that hinder lithium-ion transport. The misalignment of energy bands at the interface also forms space charge layers, suppressing ion migration, which degrades battery performance.

In this review, recent research on the interfaces of halide-based composite cathodes is summarized, highlighting the progress in this field. The failure mechanisms at the cathode interface in halide-based ASSBs are discussed in detail, and strategies for achieving stable interfaces through materials design, interface engineering, and structural optimization are elaborated. On one hand, electrolyte optimization, including cation doping, anion substitution, high-entropy strategies, and surface coatings, can enhance intrinsic oxidative resistance. On the other hand, surface modification of the cathode, such as LiNbO₃ coating or in-situ formation of LiF-rich electrolyte interface layers, can effectively block direct contact between the active material and electrolyte, thus suppressing interfacial side reactions. Moreover, the synergistic optimization of structural design and processing techniques (such as controlling component ratios, designing single-crystal cathodes, and employing dry pressing and solvent lamination) can further improve the ion/electron transport network and interfacial compactness of composite cathodes, significantly reducing interface impedance and extending cycling life. Through this systematic analysis, this review aims to provide a theoretical foundation and research direction for the optimization and industrialization of halide-based ASSBs materials, offering scientific guidance for the development of next-generation high-energy-density ASSBs systems.

Summary and prospects

Halide SSEs are regarded as ideal candidates for high-energy-density ASSBs owing to their high ionic conductivity, superior electrochemical stability, and good processability. Nevertheless, cathode interfacial instability remains a principal bottleneck in practical applications. Although notable advances have been achieved in materials optimization, interfacial engineering, and structural design, several scientific and engineering challenges remain unresolved.

1) Intrinsic materials stability. Under high-voltage operation, the chemical and electrochemical stability of halide SSEs are still limited. Anion substitution, cation doping, and high-entropy strategies can partially expand these windows, yet their action mechanisms and the governing rules for interfacial electronic-structure modulation are not fully elucidated. Future studies should integrate experiment and theory to establish quantitative links among chemical composition, electronic structure, and stability, considering density of states, space-charge layers, and band alignment at interfaces, to derive design principles for interfacial stabilization.

2) Construction and evolution of interfacial structures. Current efforts focus on electrolyte modification or cathode surface treatments, forming passivating layers from electrolyte decomposition or applying protective coatings to block direct contact between active materials and the electrolyte. Building on this, priority should be given to controllable synthesis that delivers nanoscale, uniform interfacial contact while avoiding byproducts and voids-key to enhancing electrochemical stability. Gradient architectures, core-shell designs, and in situ-formed interphases are promising, but their cycling evolution and mechanical matching require deeper investigation. In parallel, combining single-crystal cathodes with highly stable halide SSEs may offer a new balance between energy density and interfacial stability.

3) Processing and manufacturability. Halide-based ASSBs still face challenges in scalable fabrication and environmental sensitivity. Many halide electrolytes are extremely sensitive to moisture and polar solvents, limiting the direct use of conventional wet processes. Priority should be placed on developing coating, dry pressing, and lamination routes in low-polarity or non-solvent environments, and on mapping how processing parameters (pressure, temperature, atmosphere) affect interfacial structure and performance to unify electrochemical metrics with manufacturability.

In summary, halide SSEs present a compelling suite of advantages for ASSBs, yet cathode interfacial stability remains the key constraint on performance and deployment. Research on halide cathode interfaces is transitioning from mechanistic elucidation to controllable construction and engineering implementation. Future efforts should pursue coordinated advances in materials optimization, structural design, and process development to enable safe, high-energy-density storage. Through the integration of multiple strategies, halide ASSBs hold promise for achieving high energy density, long cycle stability, and industrial viability-advancing ASSBs technology and underpinning safer, more efficient energy-storage systems.

Key words

halide-based all-solid-state batteries / composite cathode / failure mechanisms / interface modification / solid-state electrolytes

引用本文

黄卿, 王明坛, 李峥, 田传进, 张雪. 卤化物基固态电池正极界面问题及其改性策略. 硅酸盐学报, 2026 , 54 (9) : 3300 -3314 . DOI: 10.14062/j.issn.0454-5648.20250843

Qing HUANG, Mingtan WANG, Zheng LI, Chuanjing TIAN, Xue ZHANG. Cathode Interfacial Challenges and Mitigation Strategies in Halide-Based All-Solid-State Batteries[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (9) : 3300 -3314 . DOI: 10.14062/j.issn.0454-5648.20250843

基金

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国家自然科学基金(52162028)
江西省科技厅自然科学基金(20232ACB204011; 20224BAB204001)
景德镇市陶瓷产业重大攻关项目(2023ZDGG001)
江苏省前沿技术研发项目(BF2024033)
苏州市科技计划项目(ZXL2023236)
低成本卤化物基全固态锂电池关键材料及界面研究(BK20250539)

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2026年第54卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250843

接收时间：2025-11-14
首发时间：2026-10-22
出版时间：2026-01-30

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出版历史

收稿日期：2025-11-14
修回日期：2025-11-26

基金

国家自然科学基金(52162028)

江西省科技厅自然科学基金(20232ACB204011; 20224BAB204001)

景德镇市陶瓷产业重大攻关项目(2023ZDGG001)

江苏省前沿技术研发项目(BF2024033)

苏州市科技计划项目(ZXL2023236)

低成本卤化物基全固态锂电池关键材料及界面研究(BK20250539)

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333001

^2．清陶（昆山）能源发展集团股份有限公司，江苏昆山 215334

通讯作者:

李峥（1984—），男，博士，高级工程师；

田传进（1980—），男，博士，副教授；

张雪（1994—），女，博士，高级工程师。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250843

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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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