Please wait a minute...
Acta Phys. Chim. Sin.  2012, Vol. 28 Issue (07): 1726-1732    DOI: 10.3866/PKU.WHXB201204261
Nitric Acid Modification of Graphene Nanosheets Prepared by Arc- Discharge Method and Their Enhanced Electrochemical Properties
SHEN Bao-Shou1,2, FENG Wang-Jun1, LANG Jun-Wei2, WANG Ru-Tao2, TAI Zhi-Xin2, YAN Xing-Bin2
1School of Science, Lanzhou University of Technology, Lanzhou 730050, P. R. China; 2State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Download:   PDF(2483KB) Export: BibTeX | EndNote (RIS)      


Large-scale synthesis of few-layer graphene nanosheets (GNSs) with high crystallinity and electrical conductivity (1680 S·m-1) is achieved by an arc-discharge method. The GNSs exhibited good morphologies as observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). However, electrochemical testing showed that the performance of the graphene (GNS) electrodes in supercapacitors was poor. To increase the surface active sites for electrochemical reactions and promote the wettability by aqueous electrolyte of the GNSs, a nitric acid treatment was used to chemically modify their surface. The acid treatment introduced more oxygen/nitrogen-containing functional groups onto the GNS surface, and clearly enhanced the hydrophilicity. The nitric-acid-modified GNSs (H-GNSs) showed vastly better electrode performance, with a maximum specific capacitance of 65.5 F·g-1 (about 30 times that of original GNSs) at a current density of 0.5 A·g-1 in 2 mol·L-1 KOH electrolyte. In addition, the H-GNS electrode showed good cycling stability and lifetime after running 2000 cycles. Therefore, H-GNSs may be an attractive candidate as electrode materials for supercapacitors.

Key wordsGraphene      Arc-discharge      Chemical modification      Specific capacitance      Supercapacitor     
Received: 23 February 2012      Published: 26 April 2012
MSC2000:  O646  

The project was supported by the Top Hundred Talents Program of the Chinese Academy of Sciences, Postdoctoral Science Foundation of China (20100480728), and Youth Science Foundations of Gansu Province, China (1107RJYA274).

Corresponding Authors: FENG Wang-Jun, YAN Xing-Bin     E-mail:;
Cite this article:

SHEN Bao-Shou, FENG Wang-Jun, LANG Jun-Wei, WANG Ru-Tao, TAI Zhi-Xin, YAN Xing-Bin. Nitric Acid Modification of Graphene Nanosheets Prepared by Arc- Discharge Method and Their Enhanced Electrochemical Properties. Acta Phys. Chim. Sin., 2012, 28(07): 1726-1732.

URL:     OR

(1) Winter, M.; Brodd, R. J. Chem. Rev. 2004, 104, 4245. doi: 10.1021/cr020730k
(2) Conway, B. E. J. Electrochem. Soc. 1991, 138, 1539. doi: 10.1149/1.2085829
(3) Xiong, S. L.; Yuan, C. Z.; Zhang, X. G.; Xi, B. J.; Qian, Y. T.Chem. Eur. J. 2009, 15, 5320. doi: 10.1002/chem.200802671
(4) Wu, Z. S.;Wang, D.W.; Ren,W. C.; Zhao, J. P.; Zhou, G. M.;Li, F.; Cheng, H. M. Adv. Funct. Mater. 2010, 20, 3595. doi: 10.1002/adfm.201001054
(5) Lang, J.W.; Kong, L. B.;Wu,W. J.; Luo, Y. C.; Kang, L. Chem. Commun. 2008, 4213.
(6) Li, Y. M.; Van Zijll, M.; Chiang, S.; Pan, N. J. Power Sources2011, 196, 6003. doi: 10.1016/j.jpowsour.2011.02.092
(7) Chang, J. K.; Tsai,W. T. J. Electrochem. Soc. 2005, 152, A2063.
(8) Zhang, H.; Cao, G. P.;Wang, Z. Y.; Yang, Y. S.; Shi, Z. J.; Gu,Z. N. Electrochem. Commun. 2008, 10, 1056. doi: 10.1016/j.elecom.2008.05.007
(9) Nam, K.W.; Kim, K. B. J. Electrochem. Soc. 2002, 149, A346.
(10) Lei, Z. B.; Christov, N.; Zhao, X. S. Energy Environ. Sci. 2011,4, 1866. doi: 10.1039/c1ee01094h
(11) Allen, M. J.; Tung, V. C.; Kaner, R. B. Chem. Rev. 2010, 110,132. doi: 10.1021/cr900070d
(12) Zhang, H. X.; Lv, J.; Li, Y. M.;Wang, Y.; Li, J. H. ACS Nano2010, 4, 380. doi: 10.1021/nn901221k
(13) Yoo, J. J.; Balakrishnan, K.; Huang, J.; Meunier, V.; Sumpter, B.G.; Srivastava, A.; Conway, M.; Reddy, A. L. M.; Yu, J.; Vajtai,R.; Ajayan, P. M. Nano Lett. 2011, 11, 1423. doi: 10.1021/nl200225j
(14) Wang, Y.; Shi, Z. Q.; Huang, Y.; Ma, Y. F.;Wang, C. Y.; Chen,M. M.; Chen, Y. S. J. Phys. Chem. C 2009, 113, 13103. doi: 10.1021/jp902214f
(15) Li, Z. J.; Yang, B. C.; Zhang, S. R.; Zhao, M. X. Appl. Surf. Sci.2011, 258, 3726.
(16) Wang, D.W.; Li, F. Z.;Wu, S.; Ren,W.; Cheng, H. M.Electrochem. Commun. 2009, 11, 1729. doi: 10.1016/j.elecom.2009.06.034
(17) Liu, C. G.; Yu, Z. N.; Neff, D.; Zhamu, A.; Jang, B. Z. Nano Lett. 2010, 10, 4863. doi: 10.1021/nl102661q
(18) Stoller, M. D.; Park, S.; Zhu, Y.W.; An, J. H.; Ruoff, R. S. Nano Lett. 2008, 8, 3498. doi: 10.1021/nl802558y
(19) Liu,W.W.; Yan, X. B.; Lang, J.W.; Xue, Q. J. J. Mater. Chem.2011, 21, 13205. doi: 10.1039/c1jm11930c
(20) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.;Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A.Science 2004, 306, 666. doi: 10.1126/science.1102896
(21) Tung, V. C.; Allen, M. J.; Yang, Y.; Kaner, R. B. Nat. Nanotechnol. 2009, 4, 25. doi: 10.1038/nnano.2008.329
(22) Emtsev, K. V.; Bostwick, A.; Horn, K.; Jobst, J.; Kellogg, G. L.;Ley, L.; McChesney, J. L.; Ohta, T.; Reshanov, S. A.; Rohrl, J.;Rotenberg, E.; Schmid, A. K.;Waldmann, D.;Weber, H. B.;Seyller, T. Nat. Mater. 2009, 8, 203. doi: 10.1038/nmat2382
(23) Sutter, P.W.; Flege, J. I.; Sutter, E. A. Nat. Mater. 2008, 7, 406.doi: 10.1038/nmat2166
(24) Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Ahn, J.H.; Kim, P.; Choi, J. Y.; Hong, B. H. Nature 2009, 457, 706.doi: 10.1038/nature07719
(25) Yang, X.; Dou, X.; Rouhanipour, A.; Zhi, L.; Rader, H. J.;Mullen, K. J. Am. Chem. Soc. 2008, 130, 4216. doi: 10.1021/ja710234t
(26) Subrahmanyam, K. S.; Panchakarla, L. S.; Govindaraj, A.; Rao,C. N. R. J. Phys. Chem. C 2009, 113, 4257.
(27) Wu, Z.; Ren,W.; Gao, L.; Zhao, J.; Chen, Z.; Liu, B.; Tang, D.;Yu, B.; Jiang, C.; Cheng, H. ACS Nano 2009, 3, 411. doi: 10.1021/nn900020u
(28) Yan, L.;Wang, Z. Y.; Zhang, H.; Fang, J.; Cao, G. P.; Shi, Z. J.;Wang, B. Y. Journal of Inorganic Materials 2010, 25, 725. doi: 10.3724/SP.J.1077.2010.00725
(29) Yu, D. S.; Dai, L. M. J. Phys. Chem. Lett. 2009, 1, 467.
(30) Du, Q. L.; Zheng, M. B.; Zhang, L. F.;Wang, Y.W.; Chen, J. H.;Xue, L. P.; Dai,W. J.; Ji, G. B.; Cao, J. M. Electrochim. Acta2010, 55, 3897. doi: 10.1016/j.electacta.2010.01.089
(31) Qian, Y.; Lu, S. B.; Gao, F. L. J. Mater. Sci. 2011, 46, 3517. doi: 10.1007/s10853-011-5260-y
(32) Lu, X.J.; Dou, H.; Yang, S. D.; Hao, L.; Zhang, F.; Zhang, X. G.Acta Phys. -Chim. Sin. 2011, 27, 2333. [卢向军, 窦辉, 杨苏东, 郝亮, 张方, 张校刚. 物理化学学报, 2011, 27, 2333.]doi: 10.3866/PKU.WHXB20111022
(33) Wang, H. L.; Casalongue, H. S.; Liang, Y. Y.; Dai, H. J. J. Am. Chem. Soc. 2010, 132, 7472. doi: 10.1021/ja102267j
(34) Liang, M. H.; Zhi, L. J. J. Mater. Chem. 2009, 19, 5871. doi: 10.1039/b901551e
(35) Lang, J.W.; Yan, X. B.; Yuan, X. Y.; Yang, J.; Xue, Q. J.J. Power Sources 2011, 196, 10472. doi: 10.1016/j.jpowsour.2011.08.017
(36) Shen, B. S.; Ding, J. J.; Yan, X. B.; Feng,W. J.; Li, J.; Xue, Q. J.Appl. Surf. Sci. 2012, 258, 4523. doi: 10.1016/j.apsusc.2012.01.019
(37) Kong, L. B.; Lang, J.W.; Liu, M.; Luo, Y. C.; Kang, L. J. Power Sources 2009, 194, 1194. doi: 10.1016/j.jpowsour.2009.06.016
(38) Wu, Y. P.;Wang, B.; Ma, Y. F.; Huang, Y.; Li, N.; Zhang, F.;Chen, Y. S. Nano Res. 2010, 3, 661. doi: 10.1007/s12274-010-0027-3
(39) Chen, C. M.; Huang, J. Q.; Zhang, Q.; Gong,W. Z.; Yang, Q.H.;Wang, M. Z.; Yang, Y. G. Carbon 2012, 50, 659. doi: 10.1016/j.carbon.2011.09.022
(40) Bichat, M. P.; Raymundo-Piñero, E.; Béguin, F. Carbon 2010,48, 4351. doi: 10.1016/j.carbon.2010.07.049
(41) Lufrano, F.; Staiti, P. Energy Fuels 2010, 24, 3313. doi: 10.1021/ef901447y
(42) Wang, J.; Chen, M. M.;Wang, C. Y.;Wang, J. Z.; Zheng, J. M.J. Power Sources 2011, 196, 550. doi: 10.1016/j.jpowsour.2010.07.030

[1] WANG Hai-Yan, SHI Gao-Quan. Layered Double Hydroxide/Graphene Composites and Their Applications for Energy Storage and Conversion[J]. Acta Phys. Chim. Sin., 2018, 34(1): 22-35.
[2] QIAN Hui-Hui, HAN Xiao, ZHAO Yan, SU Yu-Qin. Flexible Pd@PANI/rGO Paper Anode for Methanol Fuel Cells[J]. Acta Phys. Chim. Sin., 2017, 33(9): 1822-1827.
[3] DU Wei-Shi, Lü Yao-Kang, CAI Zhi-Wei, ZHANG Cheng. Flexible All-Solid-State Supercapacitor Based on Three-Dimensional Porous Graphene/Titanium-Containing Copolymer Composite Film[J]. Acta Phys. Chim. Sin., 2017, 33(9): 1828-1837.
[4] TIAN Ai-Hua, WEI Wei, QU Peng, XIA Qiu-Ping, SHEN Qi. One-Step Synthesis of SnS2 Nanoflower/Graphene Nanocomposites with Enhanced Lithium Ion Storage Performance[J]. Acta Phys. Chim. Sin., 2017, 33(8): 1621-1627.
[5] YANG Yi, LUO Lai-Ming, CHEN Di, LIU Hong-Ming, ZHANG Rong-Hua, DAI Zhong-Xu, ZHOU Xin-Wen. Synthesis and Electrocatalytic Properties of PtPd Nanocatalysts Supported on Graphene for Methanol Oxidation[J]. Acta Phys. Chim. Sin., 2017, 33(8): 1628-1634.
[6] WANG Lei, YU Fei, MA Jie. Design and Construction of Graphene-Based Electrode Materials for Capacitive Deionization[J]. Acta Phys. Chim. Sin., 2017, 33(7): 1338-1353.
[7] WANG Mei-Song, ZOU Pei-Pei, HUANG Yan-Li, WANG Yuan-Yuan, DAI Li-Yi. Three-Dimensional Graphene-Based Pt-Cu Nanoparticles-Containing Composite as Highly Active and Recyclable Catalyst[J]. Acta Phys. Chim. Sin., 2017, 33(6): 1230-1235.
[8] YANG Shao-Bin, LI Si-Nan, SHEN Ding, TANG Shu-Wei, SUN Wen, CHEN Yue-Hui. First-Principles Study of Na Storage in Bilayer Graphene with Double Vacancy Defects[J]. Acta Phys. Chim. Sin., 2017, 33(3): 520-529.
[9] LI Yi-Ming, CHEN Xiao, LIU Xiao-Jun, LI Wen-You, HE Yun-Qiu. Electrochemical Reduction of Graphene Oxide on ZnO Substrate and Its Photoelectric Properties[J]. Acta Phys. Chim. Sin., 2017, 33(3): 554-562.
[10] BAI Xue-Jun, HOU Min, LIU Chan, WANG Biao, CAO Hui, WANG Dong. 3D SnO2/Graphene Hydrogel Anode Material for Lithium-Ion Battery[J]. Acta Phys. Chim. Sin., 2017, 33(2): 377-385.
[11] WU Zhong, ZHANG Xin-Bo. Design and Preparation of Electrode Materials for Supercapacitors with High Specific Capacitance[J]. Acta Phys. Chim. Sin., 2017, 33(2): 305-313.
[12] LIAO Chun-Rong, XIONG Feng, LI Xian-Jun, WU Yi-Qiang, LUO Yong-Feng. Progress in Conductive Polymers in Fibrous Energy Devices[J]. Acta Phys. Chim. Sin., 2017, 33(2): 329-343.
[13] CAO Pengfei, HU Yang, ZHANG Youwei, PENG Jing, ZHAI Maolin. Radiation Induced Synthesis of Amorphous Molybdenum Sulfide/Reduced Graphene Oxide Nanocomposites for Efficient Hydrogen Evolution Reaction[J]. Acta Phys. Chim. Sin., 2017, 33(12): 2542-2549.
[14] QUAN Quan, XIE Shun-Ji, WANG Ye, XU Yi-Jun. Photoelectrochemical Reduction of CO2 Over Graphene-Based Composites:Basic Principle,Recent Progress,and Future Perspective[J]. Acta Phys. Chim. Sin., 2017, 33(12): 2404-2423.
[15] JIA Zhao-Yang, LIU Mei-Nan, ZHAO Xin-Luo, WANG Xian-Shu, PAN Zheng-Hui, ZHANG Yue-Gang. Lithium Ion Hybrid Supercapacitor Based on Three-Dimensional Flower-Like Nb2O5 and Activated Carbon Electrode Materials[J]. Acta Phys. Chim. Sin., 2017, 33(12): 2510-2516.