氮硫双掺杂活性炭材料的制备和电容性能

doi:10.3866/PKU.WHXB201501281

摘要/Abstract

摘要：

以头发和蔗糖为原料, 通过水热碳化和KOH活化两步法制备了氮硫双掺杂微孔炭材料. 利用扫描电子显微镜, 透射电子显微镜, 氮气吸脱附, X射线光电子能谱, 电子能谱和傅里叶交换红外光谱等手段系统表征了所制备活性炭材料的微观形貌, 孔隙结构和表面化学性质. 并在6 mol·L^-1 KOH溶液中研究了所制备活性炭材料的电容性能. 氮气吸脱附测试表明, 所制备活性炭材料的比表面积最高可达1849.4 m²·g^-1, 孔道以微孔为主. 所制备活性炭材料氮元素含量为1.6%-2.5% (原子分数(x))), 硫元素含量为0.2%-0.5% (x). 由于N、O、S官能团的协同作用, 所制备碳材料表现出明显的赝电容. 活性炭材料的比电容值最高可达200 F·g^-1, 对应的能量密度为6.9 Wh·kg^-1. 功率密度达到10000 W·kg^-1时, 能量密度仍达到4.1 Wh·kg^-1. 本文的工作表明以生物质为原料可以方便制备氮硫双掺杂活性炭电极材料.

关键词: 碳材料, 超级电容器, 人的头发, 电化学性质, 水热处理

Abstract:

In this work, N, S co-doped microporous carbon materials were successfully prepared using human hair and sucrose as carbon precursors via a two-step method that combined hydrothermal treatment and post-KOH activation. The morphology, pore texture, and surface chemical properties of the activated carbon materials were investigated by scanning electron microscopy, transmission electron microscopy, N₂ adsorption/desorption, X-ray photoelectron spectroscopy, energy dispersive spectroscopy, and Fourier transform infrared spectroscopy. The electrochemical capacitive behavior of the prepared carbons was systematically studied in 6 mol·L^-1 KOH electrolyte. The maximum specific surface area of the prepared carbons was found to be 1849.4 m²·g^-1 with a porosity that mainly consisted of micropores. Nitrogen and sulfur contents varied from 1.6% to 2.5% and from 0.2% to 0.5% (atomic fraction (x)), respectively. The synergistic-positive effect of N, O, and S-containing groups caused the prepared carbons to exhibit a large pseudo-capacitance. High specific capacitances of up to 200 F·g^-1 at 0.2 A·g^-1 were observed, response to an energy density of 6.9 Wh·kg^-1. At a power density of 10000 W·kg^-1, the energy density was found to be 4.1 Wh·kg^-1. The present work highlights the significance of this new strategy to prepare N, S co-doped carbon materials from renewable biomass.

Key words: Carbon materials, Supercapacitor, Human hair, Electrochemical property, Hydrothermal treatment

MSC2000:

O646

点击下载补充材料PDF格式文件

李朝辉, 李仕蛟, 周晋, 朱婷婷, 沈红龙, 禚淑萍. 氮硫双掺杂活性炭材料的制备和电容性能[J]. 物理化学学报, 2015, 31(4): 676-684.

LI Zhao-Hui, LI Shi-Jiao, ZHOU Jin, ZHU Ting-Ting, SHEN Hong-Long, ZHUO Shu-Ping. Preparation and Supercapacitive Performance of N, S Co-Doped Activated Carbon Materials[J]. Acta Phys. -Chim. Sin., 2015, 31(4): 676-684.

参考文献

(1) Horst, J. R.; Karl, F. K. Am. Chem. Soc. 1983, 7, 71.
(2) Ishida, M.; Jin, H. Ind. Eng. Chem. Res. 1996, 35, 2469. doi: 10.1021/ie950680s
(3) Fan, L. S.; Zeng, L.; Wang, W.; Luo, S.W. Energy Environ. Sci. 2012, 5, 7254. doi: 10.1039/c2ee03198a
(4) Adanez, J.; Abad, A.; Garcia-Labiano, F.; Gayan, P.; de Diego, L. F. Prog. Energy Combust. Sci. 2012, 38, 215. doi: 10.1016/j.pecs.2011.09.001
(5) Zhang, Y.; Doroodchi, E.; Moghtaderi, B. Energy Fuels 2012, 26, 287.
(6) Fang, H.; Haibin, L.; Zengli, Z. Int. J. Chem. Eng. 2009, 710515
(7) Lyngfelt, A.; Leckner, B.; Mattisson, T. Chem. Eng. Sci. 2001, 56, 3101. doi: 10.1016/S0009-2509(01)00007-0
(8) Johansson, M.; Mattisson, T.; Lyngfelt, A. J. Therm. Sci. 2006, 10, 93. doi: 10.2298/TSCI0603093J
(9) Saha, C.; Bhattacharya, S. Int. J. Chem. Eng. 2011, 36, 12048.
(10) Cho, P.; Mattisson, T.; Lyngfelt, A. Fuels 2004, 83, 1215. doi: 10.1016/j.fuel.2003.11.013
(11) Zhao, H. B.; Liu, L. M.; Wang, B.W.; Xu, D.; Jiang, L. L.; Zheng, C. G. Energy Fuels 2008, 22, 898. doi: 10.1021/ef7003859
(12) Dennis, J. S.; Scott, S. A. Fuels 2010, 89, 1623. doi: 10.1016/j.fuel.2009.08.019
(13) Lee, J. B.; Park, C. S.; Choi, S. I.; Song, Y.W.; Kim, Y. H.; Yang, H. S. J. Ind. Engin. Chem. 2005, 11, 96.
(14) Yang, J. B.; Cai, N. S.; Li, Z. S. Energy Fuels 2007, 21, 360.
(15) Guo, L.; Zhao, H. B.; Ma, J. C.; Mei, D. F.; Zheng, C. G. Chem. Eng. Technol. 2014, 37, 1211. doi: 10.1002/ceat.v37.7
(16) Zhu, X.; Li, K. Z.; Wei, Y. G.; Wang, H.; Sun, L. Y. Fuels 2014, 28, 754. doi: 10.1021/ef402203a
(17) Wang, C. P.; Cui, H. R.; Di, H. S.; Guo, Q. J.; Huang, F. Fuels 2014, 28, 4162. doi: 10.1021/ef500354w
(18) Azimi, G.; Leion, H.; Mattisson, T.; Rydén, M.; Snijkers, F.; Lyngfelt, A. Ind. Eng. Chem. Res. 2014, 53, 10358. doi: 10.1021/ie500994m
(19) Qin, W.; Wang, Y.; Dong, C.; Zhang, J.; Chen, Q.; Yang, Y. Energ. Appl. Surf. Sci. 2013, 282, 718. doi: 10.1016/j.apsusc.2013.06.041
(20) Wang, B.W.; Yan, R.; Zhao, H. B.; Zheng, Y.; Liu, Z. H.; Zheng, C. G. Energy Fuels 2011, 25, 3344. doi: 10.1021/ef2004078
(21) Qin, W.; Chen, Q.; Wang, Y.; Dong, C.; Zhang, J.; Li, W.; Yang, Y. Energ. Appl. Surf. Sci. 2013, 266, 350. doi: 10.1016/j.apsusc.2012.12.023
(22) Wang, S. Z.; Wang, G. X.; Jiang, F.; Luo, M.; Li, H. Y. Energy Environ. Sci. 2010, 3, 1353. doi: 10.1039/b926193a
(23) Liu, L.; Zachariah, M. R. Energy Fuels 2013, 27, 4977. doi: 10.1021/ef400748x
(24) Bao, J.; Li, Z.; Cai, N. Ind. Eng. Chem. Res. 2013, 52, 6119. doi: 10.1021/ie400237p
(25) Ksepko, E.; Siriwardane, R. V.; Tian, H. J.; Simonyi, T.; Sciazko, M. Energy Fuels 2012, 26, 2461. doi: 10.1021/ef201441k
(26) Moghtaderi, B.; Song, H. Energy Fuels 2010, 24, 5359.
(27) Yang, H. G.; Sun, C. H.; Qiao, S. Z.; Zou, J.; Liu, G.; Smith, S. C.; Cheng, H. M.; Lu, G. Q. Nature 2008, 453, 638. doi: 10.1038/nature06964
(28) Xie, X.W.; Li, Y.; Liu, Z. Q.; Haruta, M.; Shen, W. J. Nature 2009, 458, 746. doi: 10.1038/nature07877
(29) Zhou, X.; Xu, Q.; Lei, W.; Zhang, T.; Qi, X.; Liu, G.; Deng, K.; Yu, J. Small 2014, 10, 674. doi: 10.1002/smll.201301870
(30) Zhu, J.; Ng, K. Y. S.; Deng, D. Cryst. Growth Des. 2014, 14, 2811. doi: 10.1021/cg5000777
(31) Liu, X. H.; Zhang, J.; Wu, S. H.; Yang, D. J.; Liu, P.; Zhang, H. M.; Wang, S. R.; Yao, X. D.; Zhu, G. S.; Zhao, H. J. RSC Adv. 2012, 2, 6178. doi: 10.1039/c2ra20797d
(32) Guo, H.; Barnard, A. S. J. Colloid Interface Sci. 2012, 386, 315. doi: 10.1016/j.jcis.2012.07.011
(33) Cornell, R. M.; Schwertmann, U. The Iron Oxides: Structure, Properties, Reactions, Occurrence and Uses;Wiley-VCH: New York, USA, 2003.
(34) Dong, C. Q.; Liu, X. L.; Qin, W.; Lu, Q.; Wang, X. Q.; Shi, S. M.; Yang, Y. P. Appl. Surf. Sci. 2012, 258, 2562. doi: 10.1016/j.apsusc.2011.10.092
(35) Payne, M. C.; Teter, M. P.; Allan, D. C.; Arias, T. A.; Joannopoulos, J. D. Rev. Mod. Phys. 1992, 64, 1045. doi: 10.1103/RevModPhys.64.1045
(36) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B: Condens. Matter Mater. Phys. 1992, 46, 6671. doi: 10.1103/PhysRevB.46.6671
(37) Leung, T. C.; Chan, C. T.; Harmon, B. N. Phys. Rev. B 1991, 44, 2923. doi: 10.1103/PhysRevB.44.2923
(38) Guo, H. B.; Barnard, A. S. Phys. Rev. B 2011, 83, 094112. doi: 10.1103/PhysRevB.83.094112
(39) Song, J. J.; Niu, X. Q.; Ling, L. X.; Wang, B. J. Fuel Process. Technol. 2013, 115, 26. doi: 10.1016/j.fuproc.2013.04.003
(40) Wong, K.; Zeng, Q. H.; Yu, A. B. J. Phys. Chem. C 2011, 115, 4656. doi: 10.1021/jp1108043
(41) Martin, G. J.; Cutting, R. S.; VauGhan, D. J.; Warren, M. C. Am. Mineral. 2009, 94, 1341. doi: 10.2138/am.2009.3029
(42) Sandratskii, L. M.; Uhl, M.; Kübler, J. J. Phys.: Condes. Matter 1996, 8, 983. doi: 10.1088/0953-8984/8/8/009
(43) White, J. A.; Bird, D. M. Phys. Rev. B: Condes. Matter Mater. Phys. 1994, 50, 4954. doi: 10.1103/PhysRevB.50.4954
(44) Govind, N.; Petersen, M.; Fitzgerald, G.; King-Smith, D.; Andzelm, J. Comput. Mater. Sci. 2003, 28, 250. doi: 10.1016/S0927-0256(03)00111-3
(45) Rohmann, C.; Metson, J. B.; Idriss, H. Phys. Chem. Chem. Phys. 2014, 16, 14287. doi: 10.1039/c4cp01373e
(46) Gilbert, B.; Frandsen, C.; Maxey, E. R.; Sherman, D. M. Phys. Rev. B 2009, 79, 035108. doi: 10.1103/PhysRevB.79.035108
(47) Al-Kuhaili, M. F.; Saleem, M.; Durrani, S. M. A. J. Alloy. Compd. 2012, 521, 178. doi: 10.1016/j.jallcom.2012.01.115
(48) Turkdogan, E. T.; Vinters, J. V. Metall. Trans. 1974, 5, 11.
(49) Dong, C. Q.; Sheng, S. H.; Qin, W.; Lu, Q.; Zhao, Y.; Wang, X. Q.; Zhang, J. J. Appl. Surf. Sci. 2011, 257, 8647. doi: 10.1016/j.apsusc.2011.05.042
(50) Wang, B.W.; Yan, R.; Lee, D. H.; Liang, D. T.; Zheng, Y.; Zhao, H. B.; Zheng, C. G. Energy Fuels 2008, 22, 1012. doi: 10.1021/ef7005673

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