石墨烯基超级电容器研究进展

doi:10.3969/j.issn.2095-4239.2014.01.001

摘要/Abstract

摘要： 超级电容器是最具应用前景的电化学储能技术之一.目前,超级电容器的研究重点是提高能量密度和功率密度,发展具有高比表面积,电导率和结构稳定性的电极材料是关键.石墨烯因具有比表面积大,电子导电性高,力学性能好的特点而成为理想的电容材料,但石墨烯的理论容量不高,在石墨烯基电极制备过程中容易发生堆叠现象,导致材料比表面积和离子电导率下降.因此,发展合适的制备方法,对石墨烯进行修饰或与其他材料形成复合电极材料是一种有效解决途径.本文对石墨烯基电极及其在双电层电容器,法拉第准电容器和混合型超级电容器中的应用的研究进展进行归纳,重点介绍了石墨烯凝胶薄膜电极的制备过程,以促进石墨烯基电极在超级电容器构筑中应用.

关键词: 石墨烯, 超级电容器, 导电聚合物, 金属氧化物, 能量密度, 功率密度

Abstract: As one of the most promising type of energy storage devices, supercapacitors have attracted a great attention in recent years. Current focuses of research lie in the development of approaches to increase energy density and power density through increasing specific surface area, electrical conductivity and structural stability of capacitor materials. Graphene provides an ideal candidate capacitor material due toits large surface area, outstanding electrical conductivity and mechanical properties.However, restacking of graphene particles often occurs during fabrication processes, which reduces the actual specific surface area and ion conductivity. Keys to resolve this issue include the development of an appropriate fabrication method of graphene, modification of graphene surface with functional groups and formulation of graphene-based composite materials. This paper reports our recent work on graphene-based electrodes and their applications in electric double layer capacitors, pseudo- capacitors and asymmetric supercapacitors. Specific attention is paid to the fabrication of graphene gel film electrodes.

Key words: graphene, supercapacitor, conducting polymer, metallic oxide, energy density, power density

中图分类号:

TM53

杨德志, 沈佳妮, 杨晓伟, 马紫峰. 石墨烯基超级电容器研究进展[J]. 储能科学与技术, 2014, 3(1): 1-8.

YANG Dezhi, SHEN Jiani, YANG Xiaowei, MA Zifeng. Progress in graphene based supercapacitors[J]. Energy Storage Science and Technology, 2014, 3(1): 1-8.

参考文献

[1] Winter M,Brodd R J. What are batteries,fuel cells and superca- pacitors?[J]. Chem. Rev. ,2004,104(10):4245-4270.
[2] Miller J R,Simon P. Electrochemical capacitors for energy management[J]. Science ,2008,321(5889):651-652.
[3] Conway B E. Electrochemical Supercapacitors:Scientific Fundamentals and Technological Applications[M]. New York:Plenum Press,1999.
[4] Service R F. New supercapacitor promises to pack more electrical punch[J]. Science ,2006,313(5789):902.
[5] Simon P,Gogotsi Y. Materials for electrochemical capacitors[J]. Nat. Mater. ,2008,7:845-854.
[6] Largeot C,Portet C,Chmiola J, et al . Relation between the ion size and pore size for an electric double-layer capacitor[J]. J. Am. Chem. Soc. ,2008,130(9):2730-2731.
[7] Vivekchand S R C,Rout C S,Subrahmanyam K S, et al. Graphene-based electrochemical supercapacitors[J]. J. Chem. Sci. ,2008,120(1):9-13.
[8] Stoller M D,Park S J,Zhu Y W, et al. Graphene-based ultracapacitors[J]. Nano Lett. ,2008,8(10):3498-3502.
[9] Zhang L L,Zhao X S. Carbon-based materials as supercapacitor electrodes[J]. Chem. Soc. Rev. ,2009,38:2520-2531.
[10] Wei W,Cui X,Chen W, et al. Manganese oxide-based materials as electrochemical supercapacitor electrodes[J]. Chem. Soc. Rev. ,2011,40:1697-1721.
[11] Wang Y,Xia Y. Recent progress in supercapacitors:From materials design to system construction[J]. Adv. Mater. ,2013,25(37):5336-5342.
[12] Lee C,Wei X D,Kysar J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene[J]. Science ,2008,321(5887):385-388.
[13] Novoselov K S,Geim A K,Morozov S V, et al. Electric field effect in atomically thin carbon films[J]. Science ,2004,306(5696):666-669.
[14] Balandin A A,Ghosh S,Bao W Z, et al. Superior thermal conductivity of single-layer graphene[J]. Nano Lett. ,2008,8(3):902-907.
[15] Zhang K,Mao L,Zhang L L, et al. Surfactant-intercalated,chemically reduced graphene oxide for high performance supercapacitor electrodes[J]. J. Mater. Chem. ,2011,21(20):7302-7307.
[16] Yoon Y,Lee K,Baik C, et al. Anti-solvent derived non-stacked reduced graphene oxide for high performance supercapacitors[J]. Adv. Mater. ,2013,25(32):4437-4444.
[17] Wang G,Sun X,Lu F, et al. Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors[J]. Small ,2012,8(3):452-459.
[18] Hantel M M,Kaspar T,Nesper R, et al . Partially reduced graphite oxide as an electrode material for electrochemical double-layer capacitors[J]. Chem. Eur. J. ,2012,18(29):9125-9136.
[19] Yang X,Qiu L,Cheng C, et al . Ordered gelation of chemically converted graphene for next-generation electroconductive hydrogel films[J]. Angew. Chem. Int. Ed. ,2011,50(32):7325-7328.
[20] Yang X,Cheng C,Wang Y, et al . Liquid-mediated dense integration of graphene materials for compact capacitive energy storage[J]. Science ,2013,341(6145):534-537.
[21] Wang Z L,Xu D,Wang H G, et al . In situ fabrication of porous graphene electrodes for high-performance energy storage[J]. ACS Nano ,2013,7(3):2422-2430.
[22] Luan V H,Tien H N,Hoa L T, et al . Synthesis of a highly conductive and large surface area graphene oxide hydrogel and its use in a supercapacitor[J]. J. Mater. Chem. A ,2013,1(2):208-211.
[23] Cranford S,Buehler M. Packing efficiency and accessible surface area of crumpled graphene[J]. Phys. Rev. B ,2011,84(20):205451.
[24] Khanra P,Kuila T,Bae S H, et al . Electrochemically exfoliated graphene using 9-anthracene carboxylic acid for supercapacitor application[J]. J. Mater. Chem. ,2012,22(46):24403-24410.
[25] Ghosh S,An X,Shah R, et al . Effect of 1-pyrene carboxylic-acid functionalization of graphene on its capacitive energy storage[J]. J. Phys. Chem. C ,2012,116(39):20688-20693.
[26] Ai W,Zhou W,Du Z, et al . Benzoxazole and benzimidazole heterocycle-grafted graphene for high-performance supercapacitor electrodes[J]. J. Mater. Chem. ,2012,22(44):23439-23446.
[27] Gopalakrishnan K,Govindaraj A,Rao C N R. Extraordinary supercapacitor performance of heavily nitrogenated graphene oxide obtained by microwave synthesis[J]. J. Mater. Chem. A ,2013,1(26):7563-7565.
[28] Qian T,Yu C,Wu S, et al . A facilely prepared polypyrrole-reduced graphene oxide composite with a crumpled surface for high performance supercapacitor electrodes[J]. J. Mater. Chem. A ,2013,1(22):6539-6542
[29] Liu J,An J,Ma Y, et al . Synthesis of a graphene-polypyrrole nanotube composite and its application in supercapacitor electrode[J]. J. Electrochem. Soc. ,2012,159(6):828-833.
[30] Mao L,Zhang K,Chan H S O, et al . Surfactant-stabilized graphene/polyaniline nanofiber composites for high performance supercapacitor electrode[J]. J. Mater. Chem. ,2012,22(1):80-85.
[31] Mao L,Chan H S O,Wu J. Cetyltrimethylammonium bromide intercalated graphene/polypyrrole nanowire composites for high performance supercapacitor electrode[J]. RSC Advances ,2012,2(28):10610-10617.
[32] Cong H P,Ren X C,Wang P, et al . Flexible graphene-polyaniline composite paper for high-performance supercapacitor[J]. Energy & Environmental Science ,2013,6(4):1185-1191.
[33] Lai L,Yang H,Wang L, et al . Preparation of supercapacitor electrodes through selection of graphene surface functionalities[J]. ACS Nano ,2012,6(7):5941-5951.
[34] Jaide V,Ramaprabhu S. Poly( p -phenylenediamine)/graphene nanocomposites for supercapacitor applications[J]. J. Mater. Chem. ,2012,22(36):18775-18783.
[35] Liu Y,Deng R,Wang Z, et al . Carboxyl-functionalized graphene oxide-polyaniline composite as a promising supercapacitor material[J]. J. Mater. Chem. ,2012,22(27):13619-13624.
[36] Xiang C,Li M,Zhi M, et al . Reduced graphene oxide/titanium dioxide composites for supercapacitor electrodes:Shape and coupling effects[J]. J. Mater. Chem. ,2012,22(36):19161-19167.
[37] Lee M T,Fan C Y,Wang Y C, et al . Improved supercapacitor performance of MnO 2 -graphene composites constructed using a supercritical fluid and wrapped with an ionic liquid[J]. J. Mater. Chem. A ,2013,1(10):3395-3405.
[38] Li Y,Zhao N,Shi C, et al . Improve the supercapacity performance of MnO 2 -decorated graphene by controlling the oxidization extent of graphene[J]. J. Phys. Chem. C ,2012,116(48):25226-25232.
[39] Li Z,Mi Y,Liu X, et al . Flexible graphene/MnO 2 composite papers for supercapacitor electrodes[J]. J. Mater. Chem. ,2011,21(38):14706-14711.
[40] Liu W W,Feng Y Q,Yan X B, et al . Superior micro-supercapacitors based on graphene quantum dots[J]. Adv. Funct. Mater. ,2013,23(33):4111-4122.
[41] Yan J,Fan Z,Sun W, et al . Advanced asymmetric supercapacitors based on Ni(OH) 2 /graphene and porous graphene electrodes with high energy density[J]. Adv. Funct. Mater. ,2012,22(12): 2632-2641.
[42] Zhang J,Jiang J,Li H, et al . A high-performance asymmetric supercapacitor fabricated with graphene-based electrodes[J]. Energy & Environmental Science ,2011,4(10):4009-4015.
[43] Fan Z,Yan J,Wei T, et al . Asymmetric supercapacitors based on graphene/MnO 2 and activated carbon nanofiber electrodes with high power and energy density[J]. Adv. Funct. Mater. ,2011,21(12):2366-2375.
[44] Wang W,Hao Q,Lei W, et al . Graphene/SnO 2 /polypyrrole ternary nanocomposites as supercapacitor electrode materials[J]. RSC Advances ,2012,2(27):10268-10274.
[45] Andrew B. R&D considerations for the performance and application of electrochemical capacitors[J]. Electrochim. Acta ,2007,53:1083-1091.