硅酸盐学报

高电极相容性的氯化物基超离子导体

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杨张弛 ¹ , 姚宏斌 ¹^,² , 殷逸臣 ¹^,² , 罗锦达 ¹

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1751-1763

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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) : 1751 -1763

高电极相容性的氯化物基超离子导体

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杨张弛¹, 姚宏斌¹^,², 殷逸臣¹^,², 罗锦达¹

作者信息

^1．中国科学技术大学化学与材料科学学院，合肥 230026

^2．中国科学技术大学合肥微尺度物质科学国家研究中心，合肥 230026

通讯作者:

殷逸臣（1995—），男，博士，教授。

作者简介:

杨张弛（2004—），男，本科。

姚宏斌（1983—），男，博士，教授。

Chloride-Based Superionic Conductors with High Electrode Compatibility

Zhangchi YANG¹, Hongbin YAO¹^,², Yichen YIN¹^,², Jinda LUO¹

Affiliations

^1.School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China

^2.Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China

Corresponding Author:

YIN Yichen (1995-), male, Ph.D., Professor. E-mail: artist@ustc.edu.cn

YANG Zhangchi (2004-), male, Undergraduate. E-mail: yangzhangchi@mail.ustc.edu.cn

YAO Hongbin(1983-), male, Ph.D., Professor. yhb@ustc.edu.c

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20250783

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摘要

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相对于传统商用锂离子电池，使用不易燃无机固体电解质的全固态锂电池可在实现高电压和大容量的同时确保电池的安全性。为实现全固态锂电池在室温条件下的稳定循环，开发具有良好电极相容性的超离子导体作为无机固体电解质材料显得至关重要。2018年，采用Li₃YCl₆快离子导体作为电解质的InLi/LiCoO₂全固态锂电池在无需任何额外界面修饰情况下即可实现室温下的稳定循环，这使得氯化物基固体电解质材料重新引起关注，并在近几年得到飞速发展。本文首先强调了良好的正极相容性是氯化物基超离子导体最具吸引力的优势，同时指出传统氯化物基电解质在负极侧的界面不稳定性来源于易被还原的中心金属元素，并提出了通过非密堆积型阴离子亚晶格实现氯化物基超离子导体更快、更低势垒的离子传导设计思路。最后，总结了近几年氯化物基固体电解质材料的研究进展，并讨论了在其大规模应用之前仍需解决的问题。

关键词

氯化物基固体电解质 / 超离子导体 / 电极相容性 / 非密堆积结构

Abstract

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Compared to conventional commercial lithium-ion batteries, all-solid-state lithium batteries (ASSLBs) with inflammable inorganic solid electrolytes (SEs) can elevate energy density via choosing the combination of high output voltage and electrodes with a high capacity (i.e., high-nickel ternary cathode and lithium metal anode) and ensure safety. It is crucial to use solid electrolytes with a good electrode compatibility and a high ion conductivity to realize stable cycling at room temperature. Chloride SEs have been developed rapidly in recent years since their preparation in 2018 due to the success of Li₃YCl₆-based InLi/LiCoO₂ ASSLBs without extra interface modifications. This review highlights the excellent cathode compatibility of chloride SEs, which is the most attractive advantage of these SEs. This review also discusses that the easy reduction of central elements causes an unstable interface towards an anode. For the design of chloride SEs, the non-closed packing anion sublattice to enable faster ion transport with a lower migration barrier is described. Finally, this review summarizes the typical annual progress of chloride SEs in the past five years and discusses some challenges to be addressed for the future large-scale application of chloride SEs.

Summary and prospects

The advances and limitations of chloride SEs from electrode compatibility and ionic conductivity perspectives are analyzed. To better understand recent development of chloride SEs and inspire further explorations and improvements, a typical annual progress is summarized. Chloride SEs were brought back into the spotlight in 2018 due to the stable cycling of uncoated 4 V class cathode LiCoO₂ enabled by Li₃YCl₆ at room temperature. In 2019, a facile and scalable water-mediated synthetic route based on Li₃InCl₆ was developed to overcome the shortcomings of traditional time-consuming mechanical methods. AIMD simulations on LiScCl₃₊_x is carried out to systematically explore the influence of lithium content on the structure and Li⁺ diffusivity. Note that the above-mentioned chloride SEs (i.e., Li₃YCl₆, Li₃InCl₆ and Li_xScCl₃₊_x) all use expensive and low-abundance rare-earth elements, which cause high cost and sustainability concerns. Cost-effective Li₂ZrCl₆ with cheap Zr as a central element is developed. As a breakthrough to the close packing anion sublattice of conventional chloride SEs in 2023, a non-close packing style for superionic conduction was realized via selecting large central cation, i.e., LaCl₃-based SE, or employing partial anion replacement, i.e., LiNbOCl₄. The non-close packing anion sublattice with more distorted sites for a low ion migration barrier can theoretically or experimentally realize a high room-temperature ionic conductivity of over 10 mS/cm, compared to those sulfide superionic conductors.

Although a remarkable progress is made on chloride SEs, several crucial challenges have yet to be resolved. The first is still the insufficient interface stability towards the anode. LaCl₃-based SE and Li₃YBr_5.7F_0.3 can enable the cycling of all-solid-state lithium metal battery without extra interface modifications. The interface stabilization mechanisms are still not thoroughly identified. Meanwhile, the 100 cycles and capacity of around 1 mA·h/cm² are insufficient to meet the demand of practical applications. A deeper understanding of interface evolution, accompanied by an artificial interfacial layer to enhance anode interface stability, is needed. The second is that rare and expensive elements like In, Ta, and Sc are still mostly used for high-performance chloride SEs despite Zr-based chloride SEs. It is important for sustainability perspectives and large-scale production to apply cheap and high-abundance elements like Mg, Ca, Al to construct an ion conductive framework and ensure high ionic conductivity and electrode compatibility. The third is that the atmosphere tolerance of chloride SEs needs enhancement to restrain the ionic conductivity loss during ASSLB fabrication due to their easy reaction or combination with water. It is anticipated that chloride SEs can be pushed from laboratory study towards practical applications via taking the intrinsic advantages of chloride SEs and overcoming their shortcomings.

Key words

chloride solid electrolyte / super ionic conductor / electrode compatibility / non-close-packed structure

引用本文

杨张弛, 姚宏斌, 殷逸臣, 罗锦达. 高电极相容性的氯化物基超离子导体. 硅酸盐学报, 2025 , 53 (6) : 1751 -1763 . DOI: 10.14062/j.issn.0454-5648.20250783

Zhangchi YANG, Hongbin YAO, Yichen YIN, Jinda LUO. Chloride-Based Superionic Conductors with High Electrode Compatibility[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1751 -1763 . DOI: 10.14062/j.issn.0454-5648.20250783

基金

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国家自然科学基金(22475235; 22325505; 22305236)
安徽省科技创新攻坚计划项目(202423h08050005)

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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.0454-5648.20250783

接收时间：2024-12-07
首发时间：2026-10-23
出版时间：2025-06-20

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收稿日期：2024-12-07
修回日期：2025-02-02

基金

国家自然科学基金(22475235; 22325505; 22305236)

安徽省科技创新攻坚计划项目(202423h08050005)

作者信息

^1．中国科学技术大学化学与材料科学学院，合肥 230026

^2．中国科学技术大学合肥微尺度物质科学国家研究中心，合肥 230026

通讯作者:

殷逸臣（1995—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250783

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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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