金属有机框架衍生的0维材料在超级电容器中的应用

doi:10.11949/0438-1157.20200103

摘要/Abstract

摘要：

金属-有机框架( metal-organic frameworks，MOFs)衍生的0维材料，具有比表面积大、孔隙率高、孔径可调等特点，近年来广泛用于锂离子电池、燃料电池和超级电容器等储能器件中。电极材料是决定超级电容器电化学性能的关键因素。MOFs衍生的0维材料在超级电容器中的应用具有广阔的前景。综述了MOFs衍生的0维材料在超级电容器中的研究进展，探讨了目前在该领域中存在的问题，并对其未来的发展前景进行了展望。

关键词: 超级电容器, 电极材料, MOFs, 0维材料

Abstract:

Zero-dimensional (0D) materials derived from metal-organic frameworks (MOFs) are characterized by large specific surface area, high porosity and adjustable aperture. In recent years, they are widely used in lithium ion batteries, fuel cells, supercapacitors and other energy storage devices. Electrode material is a key factor in determining the electrochemical performance of supercapacitors. The application of zero-dimensional materials derived from MOFs in supercapacitors has broad prospects. In this paper, we reviewed the research progress of 0D materials derived from MOFs in supercapacitors. We summarized the current problems in this field, finally we look into the prospects of the future research trends.

Key words: supercapacitors, electrode materials, MOFs, zero-dimensional materials

中图分类号:

TM 531.1

宗爽, 刘歆颖, 陈爱兵. 金属有机框架衍生的0维材料在超级电容器中的应用[J]. 化工学报, 2020, 71(6): 2612-2627.

Shuang ZONG, Xinying LIU, Aibing CHEN. Metal-organic frameworks-derived zero-dimensional materials for supercapacitors[J]. CIESC Journal, 2020, 71(6): 2612-2627.

图/表 13

图1 ZIF-8衍生的纳米六面体多孔碳的合成(a); 纳米六面体多孔碳的结构表征[(b)~(e)]; 纳米六面体多孔碳的电化学性能(f) [46]

Fig.1 The preparation procedure of nano-hexahedron porous carbon (a); structural characterization of the nano-hexahedron porous carbon[(b)—(e)]; electrochemical performance of the nano-hexahedron porous carbon electrode (f) [46]

图2 双壳Zn-Co-S RDCs形成示意图(a); 双壳Zn-Co-S RDCs的结构表征[(b)~(e)];单壳及双壳Zn-Co-S RDCs的电化学性能[(f)~(h)][47]

Fig.2 Schematic illustration of the formation process of double-shelled Zn-Co-S RDCs (a); structural characterization of the single-shelled Zn-Co-S RDCs[(b)—(e)]; electrochemical performance of the double-shelled and single-shelled Zn-Co-S RDCs [(f)—(h)][47]

图3 NixSy@CoS双壳纳米笼的合成示意图(a)； NixSy@CoS双壳纳米笼的结构表征[(b)~(d)]; NixSy@CoS双壳纳米笼的电化学性能[(e)、(f)] [48]

Fig.3 Schematic illustration of the formation process of NixSy@CoS double-shelled nanocages (a)； structural characterization of the NixSy@CoS double-shelled nanocages[(b)—(d)]； electrochemical performance of the NixSy@CoS double-shelled nanocages[(e),(f)] [48]

图4 FeCo2O4电化学性能[(a)~(c)]；纯ZIF-67、铁-钴-ZIF-67 (d)、FeCo2O4的结构表征(e) [49]

Fig.4 Electrochemical performance of the FeCo2O4 samples[(a)—(c)]； structural characterization of the pure ZIF-67, Fe-Co-ZIF-67(d) and FeCo2O4 (e) samples[49]

图5 Co3O4-CeO2中空多面体的扫描电镜图(a)和透射电镜图(b)； Co3O4-CeO2中空多面体的恒流充放电曲线(c)； Co3O4-CeO2中空多面体的Ragone曲线(d) [50]

Fig.5 SEM (a) and TEM (b) images of the hybrid porous Co3O4-CeO2 hollow polyhedrons； GCD curves (c) and Ragone plots (d) of the hybrid porous Co3O4-CeO2 hollow polyhedrons [50]

图6 N,S-共掺杂的中空多孔碳纳米胶囊(h-CNST)制备路线 (a)； h-CNS900的扫描电镜图(b)； h-CNS900的透射电镜图(c)； h-CNS900的场发射高倍扫描电镜图(d)； 1 mol·L-1 H2SO4电解液中h-CNS900, CNS900, C900 电容随电流密度的变化曲线(e)； h-CNS900在离子液体电解液中电容随电流密度变化的曲线(900代表900℃下得到的产物)(f) [55]

Fig.6 Schematic diagram of the formation of the N and S co-doped hollow cellular carbon nanocapsules (h-CNST) (a)； SEM images of the h-CNS900 hollow cellular carbon nanocapsules (b)； TEM images of the h-CNS900 hollow cellular carbon nanocapsules (c)； HAADF-STEM images of the h-CNS900 hollow cellular carbon nanocapsules (d)； variation of specific capacitance as a function of current density for h-CNS900, CNS900 and C900 at 1 mol·L-1 H2SO4 electrolyte (e)； variation of specific capacitance as a function of current densities at IL electrolyte (f) [55]

图7 多孔中空氧化钴的结构表征[(a)~(c)]；多孔中空氧化钴的电化学性能[(d)、(e)] [56]

Fig.7 Structural characterization of the porous hollow Co3O4 structure(a—c)； electrochemical performance of the porous hollow Co3O4[(d),(e)][56]

图8 海星状中空多孔Co3O4/ZnFe2O4合成示意图(a); 海星状中空多孔Co3O4/ZnFe2O4的透射电镜图(b); Co3O4纳米笼的透射电镜图(c); Co3O4、ZnFe2O4、Co3O4/ZnFe2O4的电化学性能[(d)~(g)] [57]

Fig.8 Schematic illustration of the synthesis procedure of the starfish-shaped porous Co3O4/ZnFe2O4 hollow nanocomposite (a); TEM image of Co3O4/ZnFe2O4 hollow nanocomposites (b); TEM images of Co3O4 nanocages (c); electrochemical performance of Co3O4, ZnFe2O4, Co3O4/ZnFe2O4 [(d)—(g)] [57]

图9 硫化镍中空立方体的合成(a); 硫化镍中空立方体透射电镜图(b); 硫化镍中空立方体的电化学性能[(c)~(e)] [64]

Fig.9 Schematic illustration of the fabrication processes of NiS hierarchical hollow cubes (a); TEM image of the NiS hierarchical hollow cubes (b); electrochemical performance of the NiS hierarchical hollow cubes[(c)—(e)] [64]

图10 合成核壳多孔碳-PANI复合物的流程图(a);核壳多孔碳-PANI复合物的结构表征(b) [66];核壳多孔碳-PANI复合物的电化学性能[(c)、(d)]

Fig.10 Schematic illustration of synthetic process for the attainment of nanoporous carbon-PANI core-shell nanocomposite materials(a); structural characterization of the nanoporous carbon-PANI core-shell nanocomposite materials (b)[66]; electrochemical performance of the carbon-PANI (CP-CP) nanocomposite[(c), (d)]

图11 合成Co3O4/NiCo2O4双壳结构的纳米笼制备的示意图(a); Co3O4/NiCo2O4双壳结构的纳米笼的结构表征(b); Co3O4/NiCo2O4双壳结构的纳米笼和氧化钴纳米粒子的电化学性能[(c)、(d)] [67]

Fig.11 Schematic illustration of the formation process of Co3O4/NiCo2O4 DSNCs (a); structural characterization of the Co3O4/NiCo2O4 DSNCs and Co3O4 NCs (b); electrochemical performance of Co3O4/NiCo2O4 DSNCs and Co3O4 NCs [(c), (d)] [67]

图12 四壳中空CoS2十二面体合成流程图(a); 四壳中空CoS2十二面体的电化学性能(b); 四壳中空CoS2十二面体的扫描电镜、透射电镜以及高分辨透射电镜图[(c)、(d)] [68]

Fig.12 Schematic illustration for the fabrication of quadruple-shelled CoS2 hollow dodecahedrons electrodes by stepwise synthesis approach (a); electrochemical performance of the quadruple-shelled CoS2 hollow dodecahedrons (b); SEM, TEM and HRTEM images of quadruple-shelled CoS2 hollow dodecahedrons [(c),(d)][68]

表1 MOFs和MOFs衍生的0维材料的电化学性能

Table 1 Electrochemical performance of MOFs and MOFs-derived zero-dimensional materials

类别	MOF前体	电解质	电流密度/(A·g^-1)	电化学性能/(F·g^-1)	参考文献
双金属MOF	Ni/Co-MOF	3 mol·L^-1 KOH	1	1067	[31]
	Co/Fe-MOF	1 mol·L^-1 LiOH	1	319.5	[32]
	ZIF-CoZn	3 mol·L^-1 KCl	1	340.7	[35]
多面体	ZIF-8	2 mol·L^-1 KOH	0.5	187	[46]
	Zn/Co-ZIF	6 mol·L^-1 KOH	1	1266	[47]
	ZIF-67	6 mol·L^-1 KOH	1	2291.4	[48]
	Fe-Co-ZIF	1 mol·L^-1 KOH	1	510	[49]
	ZIF-67	3 mol·L^-1 KOH	2.5	1288.3	[50]
中空结构	MIL-101-NH₂	1 mol·L^-1 H₂SO₄	0.1	261	[55]
	ZIF-67	3 mol·L^-1 KOH	5.55 F·cm^-2	1110	[56]
	Co₃O₄/FeIII-MOF-5	6 mol·L^-1 KOH	1	326.7	[57]
	[CH₃NH₃][Ni(HCOO)₃]	2 mol·L^-1 KOH	1	874.5	[64]
核壳结构	ZIF-8	1 mol·L^-1 H₂SO₄	5 mV·s^-1	1100	[66]
	ZIF-67	1 mol·L^-1 KOH	5	972	[67]
	ZIF-67	2 mol·L^-1 KOH	1	375.2	[68]

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