硅酸盐学报

锂硫催化：缘起与展望

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江欣 ¹^,² , 张辰 ²^,³ , 吕伟 ⁴ , 张炳森 ⁵ , 杨全红 ¹^,²

硅酸盐学报 | 国家自然科学基金重点项目中期成果专题—综合评述 2024,52(2): 428-441

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硅酸盐学报 |国家自然科学基金重点项目中期成果专题—综合评述 2024 , 52 (2) : 428 -441

锂硫催化：缘起与展望

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江欣¹^,², 张辰²^,³, 吕伟⁴, 张炳森⁵, 杨全红¹^,²

作者信息

^1．天津大学化工学院，天津 300350

^2．天津市先进碳与电化学储能重点实验室，天津 300350

^3．天津大学海洋科学与技术学院，天津 300072

^4．清华大学深圳国际研究生院，广东深圳 518055

^5．中国科学院金属研究所，沈阳 110016

通讯作者:

杨全红（1972—），男，博士，教授；

张辰（1988—），男，博士，副教授。

作者简介:

江欣（2000—），女，硕士研究生。

Catalysis in Lithium-Sulfur Batteries: Origin and Prospect

Xin JIANG¹^,², Chen ZHANG²^,³, Wei LV⁴, Bingsen ZHANG⁵, Quan-Hong YANG¹^,²

Affiliations

^1.School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

^2.Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage, Tianjin 300350, China

^3.School of Marine Science and Technology, Tianjin University, Tianjin 300072, China

^4.Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong, China

^5.Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

Corresponding Author:

YANG Quan-Hong (1972-), male, Ph.D., Professor. E-mail: qhyangcn@tju.edu.cn;

ZHANG Chen (1988-), male, Ph.D., Associate Professor. zhangc@tju.edu.cn

JIANG Xin (2000-), female, Master candidate. E-mail: xjiang@tju.edu.cn

出版时间: 2024-02-20 doi: 10.14062/j.issn.0454-5648.20230450

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摘要

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锂硫电池因具有高理论能量密度（2600 W·h/kg）、低成本、环境友好等优点成为最具有应用前景的储能系统之一，但多硫化物的穿梭效应阻碍了其实用化进程。在锂硫电池中引入催化作用，被认为是加快硫转化反应动力学，抑制穿梭效应最有效的策略之一。本文从锂硫电池化学角度出发，系统梳理了“锂硫催化”研究方向的缘起、催化机制及催化剂研究进展，提出了指导锂硫催化剂理性设计的活性描述符，最后对锂硫电池实用化进程进行了展望。

关键词

锂硫电池 / 催化 / 穿梭效应 / 功能催化剂 / 活性描述符

Abstract

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Lithium-sulfur (Li-S) battery is considered as a next generation energy storage system with a great application prospect because of its high theoretical energy density (i.e., 2 600 W·h/kg), low cost and environmental friendliness. However, the shuttling of lithium polysulfides (LiPSs) is considered as one of the main bottlenecks hindering the commercial application of Li-S batteries. Conventional physical confinement and chemisorption are proved to be important strategies to solve a problem of shuttle effect, but they are still "passive" solutions and cannot solve the problem from the source. The shuttle effect is due to the slow transformation of the liquid intermediate LiPSs (i.e., Li₂S_n, 4≤n≤8) to the solid product Li₂S₂/Li₂S, which accumulates continuously in the electrolyte and diffuses to the negative electrode driven in the concentration gradient and electric field. The introduction of high-efficiency catalysts can reduce the energy barrier of sulfur conversion, accelerate a "solid-liquid-solid" conversion process, improve the utilization of sulfur, and inhibit the shuttle effect, playing a key role in improving the capacity and cycling performance of the battery. Therefore, a further understanding the sulfur conversion process in Li-S battery chemistry and putting forward the fundamental method to promote the rapid conversion of LiPSs and the uniform deposition of solid products from the perspective of electrocatalytic reaction kinetics can have important theoretical value and practical significance for promoting the practical development of Li-S battery.

In the chemical industry, catalysts can reduce the activation energy of chemical reactions and increase the reaction rate. The desulfurization technology in conventional sulfur chemistry gives inspirations for the catalysis in Li-S battery. The key to this technology is that the C—S bond in petroleum distillate is broken by multi-step catalytic hydrogenation, and sulfur is gradually removed in the form of H₂S. The charge-discharge process of Li-S battery involves the conversion of solid phase S₈, liquid phase polysulfide (i.e., Li₂S_n, 4≤n≤8) and solid phase Li₂S₂/Li₂S. The reaction process is similar to the industrial step-by-step desulfurization process.

In this review, from the perspective of battery chemistry for Li-S batteries, the origin of the catalysis for Li-S batteries, catalytic mechanism and research progress of catalysts were summarized, and the activity descriptors guiding the rational design of catalysts for Li-S batteries were proposed. Finally, the future development of Li-S batteries was prospected. The idea of industrial desulfurization was introduced into Li-S battery to realize the combination of conventional chemical engineering and Li-S battery chemistry. The "lithium-sulfur catalysis" strategy is demonstrated as a "proactive" solution to the problem of shuttle effect of Li-S batteries, accelerating the transformation of polysulfides and reducing their accumulation in electrolyte, which is expected to fundamentally inhibit the shuttle effect. Since 2014, transition metal oxides, sulfides, nitrides and carbides have been developed as effective catalysts for Li-S battery. In addition, heterostructure catalysts with different functions have been also developed with multi-functions. With the comprehensive understanding of the sulfur redox process, selective catalysis, bidirectional catalysis and homogeneous catalysis have been proposed. Recent development on quantum chemistry and AI technology provides a novel research method for reasonable prediction and analysis of the properties and reaction process of catalysts. Several key activity descriptors, such as the lattice matching, orbital hybridization and p charge density are developed to guide the rational design of catalysts. However, there are some differences in the performance of different types of catalysts, the relevant internal reasons still need to be further revealed, and the universality of descriptors also need to be further explored.

Summary and prospects

"Lithium-sulfur catalysis" is considered as an important strategy to solve the bottleneck of practical application of Li-S batteries. Although a variety of catalytic material systems are developed, the catalytic mechanism still remains unclear, and advanced theories need to guide the rational design of high-efficiency catalysts. Therefore, it is extremely urgent to develop a novel lithium-sulfur battery system and explore an effective research paradigm of Li-S catalysis for the conversion reaction process of Li-S battery. Future research directions focus on three aspects: 1) The failure mechanism and stability of catalysts should be investigated; 2) The structure-activity relationship between the electronic structure and catalytic performance of the catalyst should be deeply explored by AI technology; and 3) The conversion mechanism of solid-state Li-S battery should be clarified, and a novel practical solid-state Li-S battery system should be constructed for some future extreme applications.

Key words

lithium-sulfur batteries / catalysis / shuttle effect / functional catalysts / activity descriptor

引用本文

江欣, 张辰, 吕伟, 张炳森, 杨全红. 锂硫催化：缘起与展望. 硅酸盐学报, 2024 , 52 (2) : 428 -441 . DOI: 10.14062/j.issn.0454-5648.20230450

Xin JIANG, Chen ZHANG, Wei LV, Bingsen ZHANG, Quan-Hong YANG. Catalysis in Lithium-Sulfur Batteries: Origin and Prospect[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (2) : 428 -441 . DOI: 10.14062/j.issn.0454-5648.20230450

基金

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国家自然科学基金(51932005)
国家重点研发计划(2021YFF0500600)

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排序方式：

2024年第52卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230450

接收时间：2023-06-29
首发时间：2026-10-22
出版时间：2024-02-20

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出版历史

收稿日期：2023-06-29
修回日期：2023-07-10

基金

国家自然科学基金(51932005)

国家重点研发计划(2021YFF0500600)

作者信息

^1．天津大学化工学院，天津 300350

^2．天津市先进碳与电化学储能重点实验室，天津 300350

^3．天津大学海洋科学与技术学院，天津 300072

^4．清华大学深圳国际研究生院，广东深圳 518055

^5．中国科学院金属研究所，沈阳 110016

通讯作者:

杨全红（1972—），男，博士，教授；

张辰（1988—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230450

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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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