石墨烯/钴镍双氢氧化物复合材料的制备及其超电容特性

doi:10.11944/j.issn.1000-0518.2015.05.140321

摘要/Abstract

摘要：

采用氧化石墨(GO)还原法制备石墨烯(GNS),以氨水为沉淀剂,在石墨烯存在的情况下,通过Co²⁺和Ni²⁺化学共沉积的方法合成了石墨烯/钴镍双氢氧化物复合电极材料,采用红外光谱(FT-IR)、X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、比表面积测试(BET)等技术手段表征了产物的组成、结构和形貌,用循环伏安、恒电流充放电等测试方法对复合材料的电化学性能进行了研究。研究发现,石墨烯纳米片均匀分散在钴镍双氢氧化物中,改善了钴镍双氢氧化物的传导性和结构稳定性。电化学测试表明,在1 A/g的电流密度下,复合材料比电容高达2770 F/g,且循环500次后,比电容仍能保持93.4%,呈示该复合材料具有优异的电化学性能。

关键词: 石墨烯, 钴镍双氢氧化物, 超级电容器, 电化学性能

Abstract:

The graphene(GNS)/Co-Ni layered double hydroxides(LDH) composites were synthesized through a chemical co-precipitation process of Co²⁺ and Ni²⁺ using NH₃·H₂O as a precipitator in the presence of graphene. The compositions, microstructures and morphologies of these samples were systematically characterized by Fourier transform infrared(FT-IR) spectroscopy, X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM) and nitrogen adsorption(BET). The electrochemical performance of these composites was investigated by cyclic voltammetry and constant current charge/discharge techniques. It is found that Co-Ni LDH nanoparticles are well dispersed on the surface of GNS as the spacer to prevent the GNS from aggregation and improve the conductivity and structure stability of the Co-Ni LDH. The results show that the GNS/Co-Ni LDH electrode exhibits excellent electrochemical performance. Its specific capacitance as a single electrode is up to 2770 F/g and remains about 93.4% of the initial value after 500 potential cycles at the current density of 1 A/g.

Key words: graphene, Co-Ni layered double hydroxides, supercapacitor, electrochemical performances

中图分类号:

金小青, 曹杰, 胡忠山, 冯晓娟, 韩玉琦. 石墨烯/钴镍双氢氧化物复合材料的制备及其超电容特性[J]. 应用化学, 2015, 32(5): 583-590.

JIN Xiaoqing, CAO Jie, HU Zhongshan, FENG Xiaojuan, HAN Yuqi. Synthesis and Supercapacitor Properties of Graphene/Co-Ni Layered Double Hydroxides Composites[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 583-590.

参考文献

[1]	Sun G W,Long D H,Liu X J,et al.Asymmetric Capacitance Response from the Chemical Characteristics of Activated Carbons KOH Electrolyte[J]. J Electroanal Chem,2011,659(2):161-167.
[2]	Niu Z Q,Zhou W Y,Chen J. Compact-designed Supercapacitors Using Free-standing Single-walled Carbon Nanotube Films[J]. Energy Environ Sci,2011,4(4):1440-1446.
[3]	Milczarek G,Ciszewski A,Stepniak I. Oxygen-doped Activated Carbon Fiber Cloth as Electrode Material for Electr-chemical Capacitor[J]. J Power Sources,2011,196(18):7882-7885.
[4]	Zhu Y W,Murali S,Stoller M D,et al.Carbon-based Supercapacitors Produced by Activation of Graphene[J]. Science,2011,332(6037):1537-1541.
[5]	Susanti D,Tsai D S,Huang Y S. Structures and Electrochemical Capacitive Properties of RuO2 Vertical Nanorods Encased in Hydrous RuO2[J]. J Phys Chem C,2007,111(26):9530-9537.
[6]	Lin Y H,Wei T Y,Chen H C,et al.Manganese Oxide/Carbon Aerogel Composite:An out Standing Supercapacitor Electrode Material[J]. Adv Energy Mater,2011,1(5):901-907.
[7]	Gupta V,Gupta S,Miura N. Potentiostatically Deposited Nanostructured CoxNi1-x Layered Doublehydroxides as Electrode Materials for Redox-supercapacitors[J]. J Power Sources,2008,175(1):680-685.
[8]	XU Huan, HU Zhong'ai, HU Yingying, et al. Solvothermal Synthesis and Performances of NiO/Reduced Graphene Oxide for Supercapacitor Electrode Material with Long Cycle Stability[J]. Chinese J Appl Chem,2014,31(3):328-335(in Chinese). 徐欢,胡中爱,胡英瑛,等. NiO/rGo的溶剂热合成以及作为高循环稳定性超级电容器电极材料的性能表征[J]. 应用化学,2014,31(3):328-335.
[9]	Zhu T,Chen J S,Lou X W. Shape-controlled Synthesis of Porous Co3O4 Nanostructures for Application in Supercapacitors[J]. J Mater Chem,2010,20(33):7015-7020.
[10]	Wang K,Huang J,Wei Z. Conducting Polyaniline Nanowire Arrays for High Performance Supercapacitors[J]. J Phys Chem C,2010,114(17):8062-8067.
[11]	Guan H,Fan L Z,Zhang H. Polyaniline Nanofibers Obtained by Interfacial Polymerization for High-rate Supercapacitors[J]. Electrochim Acta,2010,56(2):964-968.
[12]	Biswas S,Drzal L T. Multilayered Nanoarchitecture of Graphene Nanosheets and Polypyrrole Nanowires for High Performance Supercapacitor Electrodes[J]. Chem Mater,2010,22(20):5667-5671.
[13]	Singh V,Joung D,Zhai L,et al.Graphene Based Materials:Past, Present and Future[J]. Prog Mater Sci,2011,56(8):1178-1271.
[14]	Wang L,Wang D,Dong X Y,et al.Layered Assembly of Graphene Oxide and Co-Al layered Double Hydroxide Nanosheets as Electrode Materials for Supercapacitors[J]. Chem Commum,2011,47(12):3556-3558.
[15]	NIU Yulian,JIN Xin,ZHENG Jia,et al.Synthesis and Electrochemical Property of Graphene/Co-Ni Double Hydroxides Composites[J]. Chinese J Inorg Chem,2012,28(9):1878-1884(in Chinese). 牛玉莲,金鑫,郑佳,等. 石墨烯/钴镍双金属氢氧化物复合材料的制备及电化学性能研究[J]. 无机化学学报,2012,28(9):1878-1884.
[16]	YAN Lin,KONG Hui,LI Zaijun. Synthesis and Supercapacitor Property of Three-dimensional Graphene/Ni-Al Layered Double Hydroxide Composite[J]. Acta Chim Sin,2013,71:822-828(in Chinese). 严琳,孔惠,李在均,等. 3D石墨烯/镍铝层状双金属氢氧化物的制备及超级电容性能[J]. 化学学报,2013,71:822-828.
[17]	Gupta V,Kawaguchi T,Miura N. Synthesis and Electrochemical Behavior of Nanotructured Cauliflower-shape Co-Ni/Co-Ni Oxides Composites[J]. Mater Res Bull,2009,44(1):202-206.
[18]	ZHOU Zhuojun,ZHU Yanjuan,ZHANG Zhongju,et al.Study on the Preparation of Y-doped Multiphase Nano-Ni(OH)2 by a Supersonic Precipitation Method and Its Electrochemical Performance[J]. Rare Met Mater Eng,2011,40(7):1287-1291(in Chinese). 周焯均,朱燕娟,张仲举,等. 超声波沉淀法制备Y掺杂纳米多相Ni(OH)2及其性能研究[J]. 稀有金属材料与工程,2011,40(7):1287-1291.
[19]	ZHANG Luojiang. Preparation and Supercapacitive Properties of Graphene/Layered Double Hydroxides Composites[D]. Nanjing:Nanjing University of Aeronautics and Astronautics,2012(in Chinese). 章罗江. 石墨烯/双氢氧化物复合材料的制备及其超电容特性[D]. 南京:南京航空航天大学,2012
[20]	Du Z F,Yin X M,Zhang M,et al.In Situ Synthesis of SnO2/Graphene Nanocom Posite and Their Application as Anode Material for Lithium Ion Battery[J]. Mater Lett,2010,64(19):2076-2079.
[21]	JIANG Jianwei,ZHANG Xiaogang,SU Linghao,et al.Preparation and Electrochemical Capacitance Performance of Co-Based Layered Double Hydroxides with Different Trivalent Metal Cations[J]. Chinese J Inorg Chem,2010,26(9):1623-1628(in Chinese). 蒋建伟,张校刚,苏凌浩,等. 层板金属离子不同的钴基双氢氧化物制备及其电化学性能[J]. 无机化学学报,2010,26(9):1623-1628.
[22]	LIU Maocheng. Study on Pseudo-Capacitive Properties of Binary Metal Oxides and Their Composite Materials[D]. Lanzhou:Lanzhou University of Technology,2013(in Chinese). 刘卯成. 双金属氧化物及其复合材料的赝电容行为研究[D]. 兰州:兰州理工大学,2013.
[23]	YU Liqiu,CHEN Shuli,CHANG Sha,et al.Supercapacitance of NiCo2O4 Nanowire Arrays Grown on Nickel Foam[J]. Acta Phys Chim Sin,2011,27(3):615-619(in Chinese). 于丽秋,陈书礼,常莎,等. 泡沫镍负载的NiCo2O4纳米线阵列电极的超级电容性能[J]. 物理化学学报,2011,27(3):615-619.