无溶剂法低温制备双碳包覆多孔硅碳负极材料及储锂性能研究

doi:10.15541/jim20250080

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1379-1386.DOI: 10.15541/jim20250080

无溶剂法低温制备双碳包覆多孔硅碳负极材料及储锂性能研究

易国刚¹^,²(), 吴耀应², 俎喜红²()

1.广东省南华节能和低碳发展研究院, 广州 510635
2.广东工业大学轻工化工学院, 广州 510006

收稿日期:2025-02-24 修回日期:2025-05-16 出版日期:2025-12-20 网络出版日期:2025-06-10
通讯作者: 俎喜红, 教授. E-mail: xhzu@gdut.edu.cn
作者简介:易国刚(1982-), 男, 正高级工程师. E-mail: tadd.yi@gdnhec.com
基金资助:
国家自然科学基金(22378075);广东省自然科学基金(2023A1515011851)

Non-solvent and Low-temperature Preparation of Porous Silicon-carbon Anodes for Enhanced Lithium Storage

YI Guogang¹^,²(), WU Yaoying², ZU Xihong²()

1. Guangdong Nanhua Energy Conservation and Low Carbon Development Institution, Guangzhou 510635, China
2. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China

Received:2025-02-24 Revised:2025-05-16 Published:2025-12-20 Online:2025-06-10
Contact: ZU Xihong, professor. E-mail: xhzu@gdut.edu.cn
About author:YI Guogang (1982-), male, professor. E-mail: tadd.yi@gdnhec.com
Supported by:
National Natural Science Foundation of China(22378075);Guangdong Provincial Natural Science Foundation(2023A1515011851)

摘要/Abstract

摘要： 针对锂离子电池硅碳负极体积膨胀大、循环稳定性差、导电性不佳、能耗高等问题, 本研究以纳米硅为活性物质、石墨为导电载体、沥青为碳前驱体、氯化钾为造孔模板剂, 采用绿色节能的无溶剂法在较低温度下制备了多孔硅碳负极材料P-Si@G@C, 并研究了其作为锂离子电池负极的性能, 对比分析了不同结构硅碳负极的性能差异, 阐明了构效关系。结果表明, 用石墨载体锚定硅纳米颗粒(Si@G), 有利于提高电极材料整体导电性, 加快电子传输速率, 并抑制纳米硅的体积膨胀; 在Si@G表面包覆多孔碳壳层, 大大减少了硅的体积膨胀, 并加快了锂离子和电子的传输速率。相比Si@G和未造孔的Si@G@C硅碳负极材料, P-Si@G@C负极材料所构建的电池呈现出更优异的电性能。电池的首次库仑效率高达85.8%; 在0.1、0.2、0.5、1.0、2.0、5.0 A·g^-1电流密度下, 电池比容量分别高达1403.6、1291.7、1206.1、1093.6、868.4和609.5 mAh·g^-1, 且比容量恢复率达98.3%, 倍率性能优异; 在1.0 A·g^-1下循环200圈仍具有770.7 mAh·g^-1的比容量, 表现出优异的长循环稳定性。

关键词: 锂离子电池, 硅碳负极, 双碳包覆, 多孔壳层, 储锂机制

Abstract:

To solve the problems of large volume expansion, poor cycling stability, low electrical conductivity and high energy consumption of silicon-anode materials, a porous silicon-carbon anode material (P-Si@G@C) was prepared by a non-solvent low-temperature method with nano-silicon as active substance, graphite as conductive carrier, asphalt as carbon precursor, and potassium chloride as pore-forming agent. Structure and performance of P-Si@G@C anode were systematically studied by comparing with a series of silicon-carbon anodes. The results showed that insertion of silica nanoparticles in graphite matrix (Si@G) could improve the electrical conductivity of the whole material which is beneficial for electron transport, and the graphite matrix could alleviate the volume expansion of silica nanoparticles. Then the porous carbon shell coated on the surface of Si@G greatly reduced the volume expansion of nano-silicon, and improved the diffusion rate of lithium ion and electron transport rate. Compared with Si@G and unperforated Si@G@C anodes, the P-Si@G@C anode presented the best electrical performance with initial Coulombic efficiency of 85.8%. At the current density of 0.1, 0.2, 0.5, 1.0, 2.0, and 5.0 A·g^-1, the specific capacities of P-Si@G@C anode were 1403.6, 1291.7, 1206.1, 1093.6, 868.4, and 609.5 mAh·g^-1, respectively. Its recovery rate of specific capacity reached 98.3%, displaying excellent rate performance. The specific capacity still remained 770.7 mAh·g^-1 after 200 cycles at 1.0 A·g^-1, showing good long-cycle stability.

Key words: lithium-ion battery, silicon-carbon anode, dual-carbon coating, porous shell, lithium storage mechanism

中图分类号:

O646

易国刚, 吴耀应, 俎喜红. 无溶剂法低温制备双碳包覆多孔硅碳负极材料及储锂性能研究[J]. 无机材料学报, 2025, 40(12): 1379-1386.

YI Guogang, WU Yaoying, ZU Xihong. Non-solvent and Low-temperature Preparation of Porous Silicon-carbon Anodes for Enhanced Lithium Storage[J]. Journal of Inorganic Materials, 2025, 40(12): 1379-1386.

图/表 6

图1 (a) P-Si@G@C复合材料的制备示意图; (b) Si@G@C和(c) P-Si@G@C复合材料的SEM照片

Fig. 1 (a) Schematic of preparation of P-Si@G@C composite; (b, c) SEM images of (b) Si@G@C and (c) P-Si@G@C

图2 P-Si@G@C的(a) TEM照片、(b) HRTEM照片、(c) SAED图像、(d~h) TEM照片及EDS元素分布图

Fig. 2 (a) TEM image, (b) HRTEM image, (c) SAED pattern, (d-h) TEM image and their corresponding EDS elemental maps of P-Si@G@C

图3 不同复合材料的结构表征

Fig. 3 Structure characterization of different composite materials (a) XRD patterns; (b) Raman spectra; (c) Thermogravimetric curves; (d) N2 adsorption-desorption isotherms

图4 P-Si@G@C的XPS谱图

Fig. 4 XPS spectra of P-Si@G@C (a) Total; (b) Si2p; (c) C1s; (d) O1s

图5 不同负极材料电池的电化学性能

Fig. 5 Electrochemical performance of batteries with different anode materials (a) CV curves of initial 4 cycles of P-Si@G@C battery; (b) Charging-discharging curves of initial 3 cycles of P-Si@G@C battery; (c) Rate performances and (d) EIS spectra of Si@G, Si@G@C and P-Si@G@C batteries

图6 (a) Si@G、Si@G@C和P-Si@G@C电池在1.0 A·g-1下循环100圈的循环性能; (b) P-Si@G@C电池在1.0 A·g-1下循环200圈的长循环性能

Fig. 6 (a) Cycling performances of Si@G, Si@G@C and P-Si@G@C batteries at 1.0 A·g-1 for 100 cycles; (b) Long cycling performance of P-Si@G@C battery at 1.0 A·g-1 for 200 cycles

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无溶剂法低温制备双碳包覆多孔硅碳负极材料及储锂性能研究

Non-solvent and Low-temperature Preparation of Porous Silicon-carbon Anodes for Enhanced Lithium Storage

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