双金属氧化物和复合材料的合成及其在超级电容器中的应用进展

doi:10.15541/jim20160452

无机材料学报 ›› 2017, Vol. 32 ›› Issue (5): 459-468.DOI: 10.15541/jim20160452

双金属氧化物和复合材料的合成及其在超级电容器中的应用进展

田晓冬^{1, 2}, 李肖^{1, 2}, 杨桃^{1, 2}, 宋燕¹, 刘占军¹, 郭全贵¹

(1. 中国科学院山西煤炭化学研究所, 中国科学院炭材料重点实验室, 太原 030001; 2. 中国科学院大学, 北京 100049)

收稿日期:2016-08-08 修回日期:2016-09-19 出版日期:2017-05-20 网络出版日期:2017-05-02
作者简介:田晓冬(1988–), 男, 博士研究生. E-mail: tianxiaodong0124@163.com
基金资助:
国家自然科学基金 (50602046, U1610119, U1610252);山西省自然科学基金 (2012011219-3);山西省重点研发计划 (201603D112007);中国科学院山西煤炭化学研究所杰出青年人才项目 (Y2SC921751);中国科学院青年创新促进会资助 (118800QCH1);National Natural Science Foundation of China (50602046, U1610119, U1610252);Natural Science Foundation of Shanxi Province (2012011219-3);Key Research and Development Program of Shanxi Province (201603D112007);Outstanding Young Scientist Fund of Institute of Coal Chemistry (Y2SC921751);Youth Innovation Promotion Association of the Chinese Academy of Sciences (118800QCH1)

Recent Advances on Synthesis and Supercapacitor Application of Binary Metal Oxide

TIAN Xiao-Dong^{1, 2}, LI Xiao^{1, 2}, YANG Tao^{1, 2}, SONG Yan¹, LIU Zhan-Jun¹, GUO Quan-Gui¹

(1. Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China)

Received:2016-08-08 Revised:2016-09-19 Published:2017-05-20 Online:2017-05-02
About author:TIAN Xiao-Dong. E-mail: tianxiaodong0124@163.com

摘要/Abstract

摘要：

作为一种介于传统静电电容器和电池之间的新型储能器件, 超级电容器的整体性能受限于电极材料。研究发现, 赝电容材料拥有数十倍于碳基材料的比容量。而双金属氧化物作为一种新型赝电容材料, 因其多重氧化态、多金属离子特性和高理论容量, 在电化学储能领域备受关注。本工作系统介绍了双金属氧化物及其复合材料的合成及性质, 对双金属氧化物及其复合材料在超级电容器电极材料方面的应用进行了简要概述, 并展望了其发展前景和重点发展方向, 以及需要解决的科学问题。

关键词: 双金属氧化物, 复合材料, 超级电容器, 合成方法, 应用, 综述

Abstract:

Supercapacitors (SCs) have been regarded as ‘bridges’ between traditional capacitors and batteries, and the integrated performance of SC is essentially determined by its electrode materials. It is found that the capacitance of pseudocapacitive electrode materials can be ten times higher than that of carbon-based electrode materials. As one of the most promising electroactive materials, binary transition metal oxides (BTMOs) and their corresponding composites have been widely studied for energy storage due to their rich redox properties involving multiple oxidation states and different ions. This review presents an extensive description of BTMO materials and the most commonly used synthetic methods. Furthermore, several notable BTMOs and their composites in the application of SCs are reviewed and their prospect and direction of development as well as the scientific problems remaining to be solved are pointed out.

Key words: binary transition metal oxides, composite, supercapacitor, synthetic method, application, review

中图分类号:

TQ174

田晓冬, 李肖, 杨桃, 宋燕, 刘占军, 郭全贵. 双金属氧化物和复合材料的合成及其在超级电容器中的应用进展[J]. 无机材料学报, 2017, 32(5): 459-468.

TIAN Xiao-Dong, LI Xiao, YANG Tao, SONG Yan, LIU Zhan-Jun, GUO Quan-Gui. Recent Advances on Synthesis and Supercapacitor Application of Binary Metal Oxide[J]. Journal of Inorganic Materials, 2017, 32(5): 459-468.

图/表 10

表1 使用溶剂热/水热方法制备BTMOs的参数及其相关性能

Table 1 Parameters and performance of BTMOs synthesized by solvothermal method

Materials	Parameters	Specific capacitance	Ref.
NiMoO₄nanospheres	H₂O, 140℃, 12 h	974.4 F/g (1 A/g)	[27]
NiMoO₄ nanorods	Ethanol-H₂O, 140℃, 12 h	944.8 F/g (1 A/g)	[27]
MnMoO₄ nanosheets on Ni foam	H₂O, 150℃, 8 h	1271 F/g (5 mV/s)	[28]
CoMoO₄ nanoplate arrays on Ni foam	H₂O, 180℃, 12 h	1.26 F/cm² (4 mA/cm²)	[29]
NiMoO₄ nanowire arrays on carbon cloth	H₂O, 140℃, 8 h	414.7 F/g (0.25 A/g)	[30]

图1 (a)在碳布上水热沉积NiMoO4纳米线阵列示意图, 140℃水热不同时间SEM照片(b~d)和180℃水热沉积SEM照片(e)[30]

Fig. 1 (a) Schematic illustration of the formation processes of the NiMoO4 NW arrays on carbon cloth via hydrothermal; SEM images of the prepared NiMoO4 NW arrays on carbon cloth at 140℃ for different hours (b-d) and SEM inage of NiMoO4 NW arrays at 180℃(e) [30]

图2 NiCo2O4多孔微米球的扫描电镜(a)和透射电镜(b)照片[32]

Fig. 2 FE-SEM and TEM images of porous NiCo2O4 microsphere[32]

图3 NiCo2O4中空亚微米球的TEM (a~c)和HRTEM(d)以及相应的SAED照片(d插图)[40]

Fig. 3 TEM images (a-c), HRTEM image (d) and corresponding SAED pattern (inset in (d)) of the mesoporous NiCo2O4 hollow submicrospheres[40]

图4 NiMoO4·xH2O、CoMoO4和 CoMoO4-NiMoO4·xH2O在20 mV/s扫描速度下的CV曲线(a)以及比容量随电流密度的变化曲线(b)[42]

Fig. 4 (a) CV curves of NiMoO4·xH2O, CoMoO4, and CoMoO4-NiMoO4·xH2O bundles at a scan rate of 20 mV/s; (b) Specific capacitances of NiMoO4·xH2O, CoMoO4, and CoMoO4-NiMoO4·xH2O bundles at controlled current densities[42]

图5 (a)不同结构双金属过渡金属氧化物形成示意图, (b)tube-in-tube 结构NiCo2O4不同扫速下CV曲线图, (c)不同结构样品比容量随电流密度的变化曲线[47]

Fig. 5 (a) Schematic illustration for the formation process of the ternary TMOs with complex 1D nanostructures including tube-in-tube, nanotube, and solid 1D nanostructures; (b) CV curves of NiCo2O4 tube-in-tube nanostructures at various scan rates ranging from 1-20 mV•s-1; (c) the specific capacitance at various current density of NiCo2O4 tube-in-tube, nanotube, and 1D solid nanostructures[47]

图6 NGF7.5循环5000次之后不同放大倍数的FESEM照片[48]

Fig. 6 FESEM images of NGF7.5 after 5000 charge-discharge cycles at (a) low and (b) high magnification[48]

图7 (a)卷绕电极和(b)纤维状全固态超级电容器制备示意图; 不同弯曲状态纤维状电容器的(c)光学照片、(d) CV曲线以及(e, f) 500次循环的容量保持率曲线[48]

Fig. 7 Schematic diagram showing (a) the fabrication of the winding electrode and (b) the fabrication process of the fiber solid-state NCO SCs; (c) Photos of fiber SCs in straight and bending states; (d) CV curves at 80 mV/s in straight and bending states, respectively. (e, f) The capacitance stability of fiber SCs in straight and bending states for 500 cycles, respectively[48]

图8 不同样品循环稳定性比较[51]

Fig. 8 Comparison of cycle stability of different samples[51]

表2 不同制备方法得到的NiCo2O4电化学性能的比较

Table 2 Comparison of the electrochemical performance of NiCo2O4 obtained by different methods

Materials	Method	C/(F•g^-1)	Rate capability	Cycle performance	Ref.
NiCo₂O₄ nanorobs on carbon nanofibers	Coprecipitation	1026 (1 A/g)	48.7% (20/1)	91.5% (2 A/g, 2000)	[26]
NiCo₂O₄ nanosheets on carbon nanofibers	Coprecipitation	1002 (1 A/g)	51.9% (20/1)	96.4% (2 A/g, 2400)	[26]
NiCo₂O₄microspheres	Microwave assisted synthesis	774 (2 mV/s)	52.3% (100/2)	-	[32]
Ordered mesoporous NiCo₂O₄	Hard template	739 (2.86 A/g)	55.2% (28.6/2.86)	95%(28.6 A/g, 2500)	[38]
NiCo₂O₄hollow submicropheres	Soft template	987 (1 A/g)	62.8% (50/1)	No capacity loss (5 A/g, 5000)	[40]
NiCo₂O₄ nanowires	Microemulsion	1481 (0.5 A/g)	42.2% (8/0.5)	91.4% (2 A/g, 2000)	[44]
NiCo₂O₄tube-in-tube structure	Electrospinning	1756 (1 A/g)	83.0% (20/1)	92.4% (5 A/g, 5000)	[47]
Flower like NiCo₂O₄/3D graphene foam	Electrodeposition	1402 (1 A/g)	77.0% (20/1)	76.6% (5 A/g, 5000)	[48]
NiCo₂O₄@Ppy nanowire arrays on carbon textiles	Hydrothermal	2244 (1 A/g)	60.5% (30/1)	82.9% (3 A/g, 10000)	[54]
Si/NiCo₂O₄ heterostructure	Hydrothermal	1972 (2 A/g)	54.4% (10/2)	78% (10 A/g, 2000)	[55]

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双金属氧化物和复合材料的合成及其在超级电容器中的应用进展

Recent Advances on Synthesis and Supercapacitor Application of Binary Metal Oxide

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