电弧放电法制备石墨烯的硝酸改性及其电化学性能增强

doi:10.3866/PKU.WHXB201204261

物理化学学报 >> 2012, Vol. 28 >> Issue (07): 1726-1732.doi: 10.3866/PKU.WHXB201204261

电弧放电法制备石墨烯的硝酸改性及其电化学性能增强

申保收^1,2, 冯旺军¹, 郎俊伟², 王儒涛², 邰志新², 阎兴斌²

1. 兰州理工大学理学院, 兰州 730050;
2. 中国科学院兰州化学物理研究所, 固体润滑国家重点实验室, 兰州 730000

收稿日期:2012-02-23 修回日期:2012-04-26 发布日期:2012-06-07
通讯作者: 冯旺军, 阎兴斌 E-mail:wjfeng@lut.cn; xbyan@licp.cas.cn
基金资助:
中国科学院“百人计划”项目, 中国博士后科学基金(20100480728)及甘肃省青年科技基金计划项目(1107RJYA274)资助

Nitric Acid Modification of Graphene Nanosheets Prepared by Arc- Discharge Method and Their Enhanced Electrochemical Properties

SHEN Bao-Shou^1,2, 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

Received:2012-02-23 Revised:2012-04-26 Published:2012-06-07
Contact: FENG Wang-Jun, YAN Xing-Bin E-mail:wjfeng@lut.cn; xbyan@licp.cas.cn
Supported by:
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).

摘要/Abstract

摘要：

采用电弧放电法大规模制备了层数少, 导电率高, 结晶性好的石墨烯纳米片(GNSs). 通过扫描电镜(SEM)和透射电镜(TEM)表征发现制得的石墨烯形貌良好. 然而电化学测试表明GNSs作为电极材料的电容性能不好. 为了增加材料表面电化学反应活性点, 促进GNSs在水系电解液中的润湿性, 我们对所制备的GNSs表面进行了硝酸改性处理. 结果显示硝酸处理后的石墨烯纳米片(H-GNSs)表面新增了较多的含氧氮官能团,其亲水性得到了显著提高. 对H-GNSs的电化学研究表明: 硝酸改性处理后的GNSs在2 mol·L^-1 KOH溶液中电流密度为0.5 A·g^-1时, 比电容可达65.5 F·g^-1, 约为改性前的30 倍; 此外, H-GNSs作为电极材料连续进行2000次充放电测试后还展示出了良好的循环稳定性, 是一种潜在的超级电容器电极材料.

关键词: 石墨烯, 电弧放电, 化学改性, 比电容, 超级电容器

Abstract:

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 words: Graphene, Arc-discharge, Chemical modification, Specific capacitance, Supercapacitor

MSC2000:

O646

申保收, 冯旺军, 郎俊伟, 王儒涛, 邰志新, 阎兴斌. 电弧放电法制备石墨烯的硝酸改性及其电化学性能增强[J]. 物理化学学报, 2012, 28(07): 1726-1732.

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[J]. Acta Phys. -Chim. Sin., 2012, 28(07): 1726-1732.

参考文献

(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]	方佳丽,陈新,李唱,吴玉莲. 原位液体室透射电镜观察金纳米棒/石墨烯复合物的形成和运动过程[J]. 物理化学学报, 2019, 35(8): 808-815.
[2]	姜哲,于飞,马杰. 石墨烯基吸附剂的设计及其对水中抗生素的去除[J]. 物理化学学报, 2019, 35(7): 709-724.
[3]	杨康,帅骁睿,杨化超,严建华,岑可法. 基于室温离子液体的活化石墨烯粉末超级电容储能性能[J]. 物理化学学报, 2019, 35(7): 755-765.
[4]	杨化超,薄拯,帅骁睿,严建华,岑可法. 润湿特性对超级电容器储能动力学的影响机理[J]. 物理化学学报, 2019, 35(2): 200-207.
[5]	胡奇,金传洪. 透射电子显微镜下原位观察石墨烯液体池中水的辐解和凝结[J]. 物理化学学报, 2019, 35(1): 101-107.
[6]	神祥艳,何建江,王宁,黄长水. 石墨炔在电化学储能器件中的应用[J]. 物理化学学报, 2018, 34(9): 1029-1047.
[7]	陈克,孙振华,方若翩,李峰,成会明. 锂硫电池用石墨烯基材料的研究进展[J]. 物理化学学报, 2018, 34(4): 377-390.
[8]	孙成珍,白博峰. 气体分子在二维石墨烯纳米孔中的选择性渗透特性[J]. 物理化学学报, 2018, 34(10): 1136-1143.
[9]	王海燕,石高全. 层状双金属氢氧化物/石墨烯复合材料及其在电化学能量存储与转换中的应用[J]. 物理化学学报, 2018, 34(1): 22-35.
[10]	钱慧慧,韩潇,肇研,苏玉芹. 柔性Pd@PANI/rGO纸阳极在甲醇燃料电池中的应用[J]. 物理化学学报, 2017, 33(9): 1822-1827.
[11]	杜惟实,吕耀康,蔡志威,张诚. 基于三维多孔石墨烯/含钛共轭聚合物复合多孔薄膜的柔性全固态超级电容器[J]. 物理化学学报, 2017, 33(9): 1828-1837.
[12]	田爱华,魏伟,瞿鹏,夏修萍,申琦. SnS₂纳米花/石墨烯纳米复合物的一步法合成及其增强的锂离子存储性能[J]. 物理化学学报, 2017, 33(8): 1621-1627.
[13]	杨翼,罗来明,陈迪,刘洪鸣,张荣华,代忠旭,周新文. 石墨烯负载PtPd纳米催化剂的合成及其电催化氧化甲醇性能[J]. 物理化学学报, 2017, 33(8): 1628-1634.
[14]	王雷,于飞,马杰. 石墨烯基电极材料的设计和构建及其在电容去离子中的应用[J]. 物理化学学报, 2017, 33(7): 1338-1353.
[15]	王美淞,邹培培,黄艳丽,王媛媛,戴立益. 高活性、可循环的Pt-Cu@3D石墨烯复合催化剂的制备和催化性能[J]. 物理化学学报, 2017, 33(6): 1230-1235.

电弧放电法制备石墨烯的硝酸改性及其电化学性能增强

Nitric Acid Modification of Graphene Nanosheets Prepared by Arc- Discharge Method and Their Enhanced Electrochemical Properties

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 10