静电纺丝法制备TMO/C复合纳米纤维在锂离子电池负极材料中的应用进展

doi:10.19799/j.cnki.2095-4239.2021.0073

摘要/Abstract

摘要：

过渡金属氧化物(TMO)因其极高的理论比容量被认为是代替石墨成为锂离子电池负极材料的最佳选择之一，但是在充放电过程中的过度体积膨胀以及较差的导电性能限制了其进一步发展。将TMO材料与碳材料复合，既能满足储锂容量需求，又能避免充放电过程中过度体积膨胀。通过对近期相关文献的调研，对以静电纺丝技术为基础制备的TMO/C混合材料纳米纤维作为锂离子电池的负极材料的研究结果进行了总结。着重介绍了多孔、核壳、中空以及混合结构的TMO/C混合材料纳米纤维的制备过程，以及这些特殊结构对锂离子电池性能的影响情况。综合分析表明，具有较大比表面积和丰富孔洞结构的纳米纤维膜在充放电循环过程中为化学反应提供更多的活性点位，为锂离子的快速扩散和电荷转移建立了良好的导电通路，对于锂离子电池的电化学性能有着较大的改善作用。最后讨论了该领域目前存在的不足和挑战，并对TMO基锂离子电池负极材料未来的发展方向做了如下展望：简化制备工艺，降低制备成本，提高制备效率，实现量产；研究发掘出更适合与TMOs复合的材料，开发出结构更加合理、性能更加优异的锂离子电池。

关键词: 过渡金属氧化物, 静电纺丝法, 纳米纤维, 锂离子电池

Abstract:

Transition metal oxides (TMOs) are considered to be one of the best choices to replace graphite as a negative electrode material for Li ion batteries because of the extremely high theoretical specific capacity of TMOs. However, during charging and discharging, excessive volume expansion and poor electrical conductivity limit its further development. Combining TMO materials with carbon materials can meet the demand for Li storage capacity and avoid excessive volume expansion during charging and discharging. After an investigation of recent literature, research results are summarized regarding the preparation of TMO/C hybrid nanofibers using an electrospinning technology as anode materials for Li ion batteries. The preparation process of TMO/C hybrid nanofibers with porous, core-shell, hollow, and hybrid structures, and the influence of these special structures on the performance of Li ion batteries, are introduced. Comprehensive analysis shows that nanofiber membranes with larger specific surface areas and rich pore structures provide additional active sites for chemical reactions during the charge and discharge cycle and establish a good conductive path for the rapid diffusion and charge transfer of Li ions. This can considerably improve the electrochemical performance of Li ion batteries. Finally, the current limitations and challenges in this field are discussed, and future development directions of TMO-based Li-ion battery anode materials are suggested. Prospective research directions could include the simplification of the preparation process, reduction in the cost of preparation, increase in preparation efficiency, and improvement in mass production. It will be important to discover more suitable materials to combine with TMOs to develop Li ion batteries with a more reasonable structure and improved performance.

Key words: TMO, electrospinning, nanofibers, ithium-ion batteries

中图分类号:

TM 912

杨瑞, 汪丽莉, 宓一鸣, 刘烨, 吴建宝, 赵新新. 静电纺丝法制备TMO/C复合纳米纤维在锂离子电池负极材料中的应用进展[J]. 储能科学与技术, 2021, 10(4): 1253-1260.

Rui YANG, Lili WANG, Yiming MI, Ye LIU, Jianbao WU, Xinxin ZHAO. Research progress of transition metal oxides /C composite nanofibers fabricated by electrospinning in anode materials for lithium-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(4): 1253-1260.

图/表 5

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TMO	理论比容量/mA·h·g^-1	体积膨胀率/%
Fe₂O₃	1007	92.9
Fe₃O₄	924	74.4
Cr₂O₃	1058	102
MnO	756	69.7
ZnO	987	124
SnO2	1493	395
Co₃O₄	890	101.5
CuO	674	74.2
NiO	718	91.6

电极材料	电流密度/mA·g^-1	初始充/放电比容量/mA·h·g^-1	库仑效率 /%	参考文献
Porous SnO_x/C nanofibers	200	1057/1529	69.1	[17]
Porous γ-Fe₂O₃/C nanofibers	100	1057/1578	67	[18]
Core-shell rGO-C/ZnO nanofibers	50	815.25/1187.85	68.6	[19]
Core-shell MnO₂/C nanofibers	50	1163/1906	61.0	[20]
Hollow V₂O₃/C nanofibers	100	906.3/1383.6	65.5	[24]
Multi-wall Sn/SnO₂@C hollow nanofibers	1000	1121.5/1960.7	57.2	[25]
Co_xO_y/C coating porous CNF	100	1520/2297.8	66.2	[29]
Hollow Co₃O₄nanoball@porous CNF	100	1003/1824	55.0	[30]
Rice-panicle-like gamma-Fe₂O₃@C nanofibers	200	1414/1956	72.0	[32]
Pea-pod V₂O₃ yolk-shell microspheres@N, S co-doped carbon fiber	100	825.2/1025.6	80.5	[33]
Hollow bubble-nanord Fe₂O₃/C nanofibers	500	957/1385	69.1	[34]

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