硅酸盐学报

煤系固废基硅/碳复合材料的结构设计与电化学储能

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赵赛丹 ¹ , 邢宝林 ¹^,² , 张亚超 ³ , 郭晖 ³ , 张传祥 ¹^,² , 曾会会 ¹ , 屈笑笑 ¹ , 程松 ¹^,²

硅酸盐学报 | 非金属矿清洁高效利用专题—研究论文 2025,53(12): 3585-3599

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硅酸盐学报 |非金属矿清洁高效利用专题—研究论文 2025 , 53 (12) : 3585 -3599

煤系固废基硅/碳复合材料的结构设计与电化学储能

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赵赛丹¹, 邢宝林¹^,², 张亚超³, 郭晖³, 张传祥¹^,², 曾会会¹, 屈笑笑¹, 程松¹^,²

作者信息

^1．河南理工大学化学化工学院，河南省煤炭绿色转化重点实验室，河南焦作 454003

^2．煤炭安全生产与清洁高效利用省部共建协同创新中心，河南焦作 454003

^3．河南理工大学材料科学与工程学院，河南焦作 454003

通讯作者:

邢宝林（1982—），男，博士，教授。

作者简介:

赵赛丹（1996—），女，博士研究生。

Structural Design of Coal-Based Solid Waste-Derived Silicon/Carbon Composites for Electrochemical Energy Storage

Saidan ZHAO¹, Baolin XING¹^,², Yachao ZHANG³, Hui GUO³, Chuanxiang ZHANG¹^,², Huihui ZENG¹, Xiaoxiao QU¹, Song CHENG¹^,²

Affiliations

^1.College of Chemistry and Chemical Engineering, Henan Polytechnic University, Henan Key Laboratory of Coal Green Conversion, Jiaozuo 454003, Henan, China

^2.State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454003, Henan, China

^3.School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, Henan, China

Corresponding Author:

XING Baolin (1982-), male, Ph.D., Professor. E-mail: baolinxing@hpu.edu.cn

ZHAO Saidan (1996-), female, Doctoral candidate. E-mail: saidan001@163.com

出版时间: 2025-12-20 doi: 10.14062/j.issn.0454-5648.20250449

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摘要

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煤系固废的高值化利用在推动绿色低碳发展和实现“双碳”目标中扮演着至关重要的角色。基于煤系固废资源粉煤灰和煤气化渣的富硅特性，分别以粉煤灰和煤气化渣为前驱体，通过熔盐辅助镁热还原工艺结合碳包覆策略和一步镁热还原工艺制备出具有“核壳结构”的粉煤灰基硅碳复合材料和具有“镶嵌结构”的煤气化渣基硅碳连生体复合材料。2种复合材料均具有较高的比表面积（215.7 m²·g^-1和274.8 m²·g^-1）和丰富的层次孔结构（微孔和介孔协同分布）；粉煤灰基硅碳复合材料中碳组分占比28.1%（质量分数），其丰富的sp³结构缺陷和边缘缺陷能够增加锂离子的吸附活性位点；煤气化渣基硅碳连生体复合材料中碳组分占比36.9%，其较高含量的sp²碳能够增强复合材料的结构稳定性且丰富的堆叠缺陷能够为锂离子提供传输路径。两种复合材料用作锂离子电池负极时在50 mA·g^-1电流密度下可逆容量分别为800 mA·h·g^-1和420 mA·h·g^-1，且在500 mA·g^-1电流密度下经300次循环后可逆容量仍可达348 mA·h·g^-1和334 mA·h·g^-1，展现出良好的倍率性能及循环稳定性，为煤系固废的高值化利用提供了新路径，有利于推动低成本、高性能储能材料的开发和应用。

关键词

煤系固废 / 粉煤灰 / 煤气化渣 / 硅/碳复合材料 / 锂离子电池 / 负极材料

Abstract

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Introduction

The large-scale mining and processing of coal resources inevitably result in the continuous generation and accumulation of solid wastes such as fly ash and coal gasification slag. However, their utilization rate remains low, with primary dependence on open-air stockpiling, leading to substantial resource depletion and ecological hazards. The existing resource utilization of fly ash and coal gasification slag is still confined to low-value-added fields like construction materials and agriculture. It is critically necessary to explore their inherent resource properties and develop high-value utilization pathways, thereby addressing environmental challenges, while enhancing economic benefits. Some researches reveal that fly ash and coal gasification slag both contain abundant silicon components in their phase compositions. This characteristic endows them with significant potential as precursors for synthesizing silicon anode materials. This study was to fabricate silicon/carbon composites with fly ash and coal gasification slag as precursors, provide novel insights into the high-value application of coal-based solid waste resources and expand the methodology for low-cost preparation of silicon-based materials for lithium-ion batteries.

Methods

In the fabrication of distinct silicon-carbon composites, a fly ash-derived silicon material was prepared via uniformly grinding a mixture with 1 g of fly ash, 1 g of magnesium powder and 2 g of sodium chloride. Afterwards, the ground mixture was heated in argon atmosphere by magnesiothermic reduction at 750 ℃ for 8 h. A purified silicon material was obtained after sequential washing with hydrochloric acid and hydrofluoric acid. For the fly ash-derived silicon-carbon composite, this silicon material was dispersed with phenolic resin at an equal mass ratio, modified via cetyltrimethylammonium bromide assistance, and carbonized at 800 ℃ for 2 h to form a carbon-coated structure. In contrast, the coal gasification slag-derived composite was synthesized in a single step via subjecting 1 g of coal gasification slag, 0.6 g of magnesium powder, and 2 g of sodium chloride to identical magnesiothermic reduction conditions, thereby retaining inherent carbon to generate an interconnected silicon-carbon architecture.

The morphologies and microcrystalline structures of all the obtained samples were analyzed by X-ray diffraction, Raman spectroscopy, X-ray energy dispersive spectroscopy, scanning electron microscopy, and transmission electron microscopy. The thermal behavior was evaluated by thermogravimetric analysis, and the microstructures were characterized via BET specific surface area and pore size distribution measurements. The two composite materials were assembled into lithium-ion half-cells for charge-discharge cycling, cyclic voltammetry, and impedance testing to evaluate their lithium storage performance.

Results and discussion

Silicon materials obtained via the magnesiothermic reduction process with fly ash as a precursor exhibit a high crystallinity, primarily composed of densely packed crystalline particles. The corresponding fly ash-based silicon-carbon composite fabricated via a carbon-coating strategy exhibits a "core-shell structure" with a carbon content of 28.1%. This carbon layer predominantly consists of amorphous carbon enriched with abundant sp³-hybridized structural defects and edge disorders, significantly affecting the interfacial charge transfer dynamics. In contrast, the coal gasification slag-derived composite synthesized via one-step magnesiothermic reduction demonstrates a distinctive mosaic architecture incorporating 36.9% carbon with substantially enhanced sp²-hybridized carbon domains, thus facilitating a superior electrical conductivity.

Fly ash-based silicon-carbon composite and coal gasification slag-derived composite both have high specific surface areas (i.e., 215.7 and 274.8 m²·g^-1) and rich hierarchical pore structures (i.e., synergistic distribution of microporous and mesoporous pores). As lithium-ion battery anodes, fly ash-derived silicon-carbon composite and coal gasification slag-derived silicon-carbon composite exhibit reversible capacities of 800 and 420 mA·h·g^-1 at 50 mA·g^-1, respectively. These composites maintain reversible capacities of 348 and 334 mA·h·g^-1 after 300 cycles at 500 mA·g^-1, respectively, showing superior rate capability and cycling stability. This study demonstrates that silicon-carbon composites with high-performance lithium storage characteristics can be prepared by using low-cost coal-based solid waste-fly ash and coal gasification slag as precursors, which is helpful for promoting the development and application of low-cost, high-performance energy storage materials.

Conclusions

A silicon-carbon composite with a "core-shell structure" was synthesized by using fly ash as a precursor through a magnesia-based reduction process combined with a carbon coating strategy. Also, a silicon-carbon intergrown composite exhibiting an "mosaic architecture" was prepared by using coal gasification slag as a precursor by a one-step magnesia-based reduction process. The abundant sp³ structural defects and edge defects in fly ash-based silicon-carbon composite could enhance its lithium storage capacity, while the significant sp² carbon in the coal gasification slag-based composite could improve its structural stability. Consequently, the composites both exhibited excellent rate performance and cycling stability when used as anodes in lithium-ion batteries. This study could provide some insights for the high-value utilization of coal-based solid waste resources and expand avenues for low-cost preparation of silicon-based materials for lithium-ion batteries.

Key words

coal-based solid waste / fly ash / coal gasification slag / silicon/carbon composites / lithium-ion batteries / anode materials

引用本文

赵赛丹, 邢宝林, 张亚超, 郭晖, 张传祥, 曾会会, 屈笑笑, 程松. 煤系固废基硅/碳复合材料的结构设计与电化学储能. 硅酸盐学报, 2025 , 53 (12) : 3585 -3599 . DOI: 10.14062/j.issn.0454-5648.20250449

Saidan ZHAO, Baolin XING, Yachao ZHANG, Hui GUO, Chuanxiang ZHANG, Huihui ZENG, Xiaoxiao QU, Song CHENG. Structural Design of Coal-Based Solid Waste-Derived Silicon/Carbon Composites for Electrochemical Energy Storage[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (12) : 3585 -3599 . DOI: 10.14062/j.issn.0454-5648.20250449

基金

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国家自然科学基金(52274261; 52304284; 52474290)
河南省重点科技项目(252102231063)

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2025年第53卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250449

接收时间：2025-06-09
首发时间：2026-10-21
出版时间：2025-12-20

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出版历史

收稿日期：2025-06-09
修回日期：2025-07-22

基金

国家自然科学基金(52274261; 52304284; 52474290)

河南省重点科技项目(252102231063)

作者信息

^1．河南理工大学化学化工学院，河南省煤炭绿色转化重点实验室，河南焦作 454003

^2．煤炭安全生产与清洁高效利用省部共建协同创新中心，河南焦作 454003

^3．河南理工大学材料科学与工程学院，河南焦作 454003

通讯作者:

邢宝林（1982—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250449

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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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