硅酸盐学报

碳材料改性SiOC负极在锂离子电池中的研究进展

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张军战 ¹^,² , 韩晴 ¹ , 陈红侠 ¹ , 石宗墨 ¹^,² , 刘永胜 ³ , 雷琬莹 ¹ , 魏剑 ¹^,² , 张颖 ¹

硅酸盐学报 | 综合评述 2024,52(10): 3327-3337

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硅酸盐学报 |综合评述 2024 , 52 (10) : 3327 -3337

碳材料改性SiOC负极在锂离子电池中的研究进展

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张军战¹^,², 韩晴¹, 陈红侠¹, 石宗墨¹^,², 刘永胜³, 雷琬莹¹, 魏剑¹^,², 张颖¹

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．陕西省纳米材料与技术重点实验室，西安 710055

^3．西北工业大学材料学院，西安 710072

通讯作者:

张颖（1972—），女，博士，副教授。

作者简介:

张军战（1972—），男，博士，副教授。

Research Progress on Carbon Materials Modified SiOC Anodes in Lithium-Ion Batteries

Junzhan ZHANG¹^,², Qing HAN¹, Hongxia CHEN¹, Zongmo SHI¹^,², Yongsheng LIU³, Wanying LEI¹, Jian WEI¹^,², Ying ZHANG¹

Affiliations

^1.College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

^2.Shaanxi Key Laboratory of Nano Materials and Technology, Xi'an 710055, China

^3.School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China

Corresponding Author:

ZHANG Ying (1972-), female, Ph.D., Associate Professor. E-mail: xayzhang@xauat.edu.cn

ZHANG Junzhan (1972-), male, Ph.D., Associate Professor. E-mail: xajzzhang@xauat.edu.cn

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240275

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摘要

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SiOC具有理论比容量高、机械柔性好、结构稳定和价格低等一系列优良性能，被认为是极具潜力的锂离子电池负极材料之一。然而，SiOC电导率低导致倍率性能和循环能力较差，从而制约了其在锂离子电池领域的发展与应用。纳米碳材料具有高比表面积、高机械稳定性以及优异的导电性等特点，与SiOC复合后作为负极材料可显著改善锂离子电池的电化学性能。本文综述了石墨、碳纳米管、石墨烯以及碳纳米纤维等与SiOC负极材料的复合工艺路线，探讨了基于不同碳材料的改性设计思路，以及电极微观结构与电化学性能之间的构效关系。最后，指出了SiOC/C复合负极材料存在的主要问题和发展方向，并展望了SiOC基负极材料的应用前景。

关键词

硅氧碳 / 碳材料 / 负极 / 电导率 / 锂离子电池

Abstract

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Lithium-ion batteries are considered as the most promising chemical power source due to their high energy density, good safety, and environmental friendliness. As a key component of batteries, anode material plays an important role on the electrochemical performance. Graphite, Li₄Ti₅O₁₂ and Si-based materials have attracted much attention as anode materials in lithium-ion batteries. Among these materials, graphite has good conductivity, small volume change, high initial coulombic efficiency, and low cost. As a conventional anode material for lithium-ion batteries, graphite is first commercially applied. However, its low theoretical capacity is the main factor restricting the development of high energy density lithium-ion batteries. Li₄Ti₅O₁₂ anode material is considered to have a great development potential due to its stable structure during lithiation and delithiation processes and good safety. However, its low theoretical capacity and high cost restrict its practical application. Si has a high theoretical capacity, but it has a disadvantage of large volume expansion during lithiation and delithiation processes, resulting in the poor safety of batteries. The composite of Si and carbon materials is considered as an effective strategy for stabilizing electrodes.

SiOC is considered as one of the high potential anode materials for lithium-ion batteries due to its excellent properties such as high theoretical specific capacity, good mechanical flexibility and structural stability, and facile structure regulation. However, the low conductivity of SiOC leads to its poor rate performance and cycling ability, thus restricting its development and application in the field of lithium-ion batteries. The composition of SiOC materials can be controlled through optimizing the composition, structure, and pyrolysis conditions of polymer precursors. Carbon material has high specific surface area, high mechanical stability, and excellent electrical conductivity. Composite with SiOC anode materials, the conductivity of SiOC can be improved, accelerating the transfer rate of lithium ions during lithiation and delithiation processes. Carbon material can act as an inert layer to reduce the volume effect of SiOC. SiOC/C composites can improve the conductivity effectively, thereby significantly improving the electrochemical performance of lithium-ion batteries as anode materials.

For elucidating the structure of SiOC, this review analyzes the mechanism of lithium ions storage on SiOC anodes. To address the poor conductivity of SiOC, the composite process of graphite, carbon nanotubes, graphene and carbon nanofibers with SiOC anode materials are reviewed. The design of modification based on different carbon materials and between the anode microstructure and electrochemical performance are discussed. The selection of carbon materials is particularly important for the electrochemical performance of SiOC/C composites. Nanocarbon is beneficial to constructing conductive networks, and after composite with SiOC, there are many micro-/meso-pores inside, which enhances the capacitance effect and further improves the electrochemical performance. Therefore, the electrochemical performance of SiOC/nanocarbon composite materials is better than that of SiOC/traditional carbon composite materials. The rate capability and cycling stability of SiOC-based lithium-ions batteries are improved.

Summary and prospects

SiOC-based anode materials have a great potential for lithium-ion batteries, but the poor conductivity is the main problem that make it difficult to commercialize. The SiOC/C anode materials combine the high conductivity of carbon materials with some advantages of high capacity, stability, and mechanical flexibility of SiOC. Among them, SiOC/nanocarbon composite materials are developed due to their superior electrochemical performance. Although some progresses are achieved in the design of SiOC/C anode for the lithium-ion batteries, some challenges still remain in practical application. The main problems existing in SiOC/C anode materials are that the size of SiOC is larger, resulting in a lower utilization of active sites. The preliminary research conducted on nitrogen-doped carbon indicate that more active sites can be obtained via utilizing the defects. However, it is still necessary to explore the effect of other doping elements or through multi-component composites. To further enhance the feasibility of electrochemical performance, the lithium ions storage mechanism of SiOC anode materials still needs a further research. The detailed structure evolution of SiOC can be revealed during lithium ions storage process through some advanced in-situ characterization techniques. The lithium ions storage mechanisms can be further clarified, and, the electrochemical performance of SiOC-based anode materials can be improved more effectively. Improving the electrochemical performance and safety of lithium-ion batteries is a goal pursued by many researchers. Overcoming the above problems can lead to the widespread application of SiOC-based anode materials in high energy lithium-ion batteries, even in areas such as lithium sulfur batteries, sodium ion batteries, and potassium ion batteries.

Key words

silicon oxycarbide / carbon materials / anode / conductivity / lithium-ion battery

引用本文

张军战, 韩晴, 陈红侠, 石宗墨, 刘永胜, 雷琬莹, 魏剑, 张颖. 碳材料改性SiOC负极在锂离子电池中的研究进展. 硅酸盐学报, 2024 , 52 (10) : 3327 -3337 . DOI: 10.14062/j.issn.0454-5648.20240275

Junzhan ZHANG, Qing HAN, Hongxia CHEN, Zongmo SHI, Yongsheng LIU, Wanying LEI, Jian WEI, Ying ZHANG. Research Progress on Carbon Materials Modified SiOC Anodes in Lithium-Ion Batteries[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3327 -3337 . DOI: 10.14062/j.issn.0454-5648.20240275

基金

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国家自然科学基金(52202113)
中国博士后科学基金(2021M702550)

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240275

接收时间：2024-04-12
首发时间：2026-10-22
出版时间：2024-10-20

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出版历史

收稿日期：2024-04-12
修回日期：2024-05-05

基金

国家自然科学基金(52202113)

中国博士后科学基金(2021M702550)

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．陕西省纳米材料与技术重点实验室，西安 710055

^3．西北工业大学材料学院，西安 710072

通讯作者:

张颖（1972—），女，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240275

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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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