MOF衍生多孔碳基材料的制备及其在锂离子电容器负极中的应用进展

doi:10.19799/j.cnki.2095-4239.2024.0050

摘要/Abstract

摘要：

锂离子电容器是一种兼具锂离子电池和超级电容器两者特点的新型功率型储能器件。然而，锂离子电容器电池型负极的动力学要慢于电容器型正极，导致其功率密度低、循环稳定性差等问题。金属有机骨架(metal-organic frameworks，MOF)衍生多孔碳基材料以其大比表面积的多孔结构，以及出色的化学稳定性等优点，成为电化学储能领域的研究热点。本文首先分析了锂离子电容器电极材料面对的挑战，阐述了锂离子电容器的储能机制。随后分析了碳化温度、热处理时间等碳化工艺对MOF衍生多孔碳基材料理化性质的影响，并着重讨论了受碳化工艺影响制备得到的不同产物组分类型。随后总结了MOF衍生多孔碳基材料在锂离子电容器中的应用进展，提出了与其他碳材料进行复合或掺杂改性是实现高功率密度、高能量密度的锂离子电容器负极材料的重要途径，最后对MOF衍生碳基电极材料的发展前景予以展望。

关键词: 锂离子电容器, 负极材料, 金属有机框架, 多孔碳

Abstract:

Lithium-ion capacitors represent novel power storage devices amalgamating the features of both lithium-ion batteries and supercapacitors. However, the sluggish dynamics of the lithium-ion capacitor's battery-type negative electrode, compared to the capacitor-type positive electrode, lead to a diminished power density and compromised cycle stability. Notably, porous carbon-based materials derived from metal-organic frameworks (MOFs) have emerged as a focal point in electrochemical energy storage research owing to their expansive specific surface area, porous structure, and exceptional chemical stability. This study analyzes the challenges associated with electrode materials of lithium-ion capacitors and elucidates the energy storage mechanism of lithium-ion capacitors. Subsequently, the influence of carbonization temperature and heat treatment time on the physicochemical properties of MOF-derived porous carbon-based materials is examined. Moreover, diverse products generated through the carbonization process are discussed. Furthermore, the advancements in utilizing MOF-derived porous carbon-based materials in lithium-ion capacitors are reviewed. Finally, the crucial role of composite or doping modifications with other carbon materials in improving the power and energy densities for anode materials of lithium-ion capacitors is emphasized.

Key words: lithium-ion capacitors, anode materials, metal-organic framework, porous carbon materials

中图分类号:

TM 911

孔妍妍, 张熊, 安亚斌, 李晨, 孙现众, 王凯, 马衍伟. MOF衍生多孔碳基材料的制备及其在锂离子电容器负极中的应用进展[J]. 储能科学与技术, 2024, 13(8): 2665-2678.

Yanyan KONG, Xiong ZHANG, Yabin AN, Chen LI, Xianzhong SUN, Kai WANG, Yanwei MA. Recent advances in preparation of MOF-derived porous carbon-based materials and their applications in anodes of lithium-ion capacitors[J]. Energy Storage Science and Technology, 2024, 13(8): 2665-2678.

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类型	MOF 前驱体	衍生负极材料	正极材料	电压窗口/V	最高能量密度/(Wh/kg) @对应功率密度/(kW/kg)	最高功率密度/(kW/kg) @对应能量密度/Wh/kg	电流密度/(A/g) @循环次数	循环容量保持率	参考文献
类型一	Fe-BTC	OLC	AC	2.2～3.8	195@0.138	17.717@92	1@4000	61.5%	[49]
	Zn-MOF	Z-T-PC	PC	1.5～4	95.8@0.2644	46@54.6	2@5000	83.67%	[51]
	ZIF-8	HCF-2	a-HCF-2	1～4.5	162@0.48	15.8@114.5	5@15000	76%	[52]

类型二	ZIF-67	Co@N-C	HPC	0～4	125.28@0.2	10@38.33	1@1000	91.74%	[60]
	Mn-MOF	MnO₂ @C-NS	NPCs	0.01～4	166@0.55	3.9@49.3	1@5000	91%	[53]
	CoZn-MOF	Co₃ZnC@NC	MPC	1.0～4.5	141.4@0.275	10.3@15.2	1@1000	80%	[14]
	CoZn-MOF	Co₃ZnC@NC	预锂化石墨	1～3	67.1@0.12	4.1@1.48	0.1@1000	—	[61]

类型三	Mn-MOF	Mn₂SnO₄@C	CSBC	1.5～4.5	217.9@0.21	21@25	2@5000	79%	[58]
	ZIF-67	CoTe₂@N-C	HPC	0～4	144.5@0.2	10@38.89	1@1000	90.95%	[59]
	ZIF-67	CoSn _x @CPAN	PDPC	1.5～4.2	143@0.285	22.8@41	2@5000	82.9%	[57]
	钼基MOF	MoO₂@rGO	PANI@rGO	1.25～4.5	241.7@0.2875	28.75@117.8	5@10000	96%	[56]

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