含氮碳微米管电极材料的制备及在电容器中的应用

doi:10.7503/cjcu20170474

摘要/Abstract

摘要：

以天然生物质芦花为原料, 采用直接碳化和化学活化碳化2种方法在不同碳化温度下制备了一系列含氮碳微米管材料. 对优选的化学活化的 JJCZH-750(即碳化温度750 ℃并经HCl除杂的样品)含氮碳微米管进行了X射线衍射、红外光谱、拉曼光谱、扫描电子显微镜、透射电子显微镜、热重分析、 X射线光电子能谱、 N₂吸附-脱附及电化学性能表征. 测试结果显示, 样品的碳含量为94.36%(质量分数), 氮含量为1.24%(质量分数), 并且显示出部分石墨化的趋势; 样品具有很高的热稳定性(400 ℃前失重5 %); 样品的管壁具有以微孔为主(峰值在1.2 nm)并伴有介孔的特征; JJCZH-750的比电容值达170 F/g, 经过5000周循环伏安法测试后, 比电容值仍保持在153 F/g.

关键词: 生物质碳化, 含氮碳微米管, 芦花, 电容器

Abstract:

A series of N-doped carbon microtubes was prepared by using Reed catkins as the precursor and with both direct carbonization and chemical activation methods at different temperatures. The chemical activation method is more efficient, simpler and cost less compared to the traditional preparation method of N-doped carbon microtubes. The chemical activation material JJCZH-750(JJ stands for Reed catkins, Z stands for Zinc chloride, C stands for carbonization and 750 the optimized temperature) was optimized. The carbon microtubes were characterized by X-ray diffraction, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis(TGA), X-ray photoelectron spectroscopy, N₂ adsorption-desorption analysis, and electrochemical measurements. The results show that carbon accounts for 94.36%(mass fraction) and nitrogen accounts for 1.24%(mass fraction) of the sample, which shows a tendency to exist as graphite. TGA analysis of the samples indicates a high thermal stability with a mass loss lower than 5% below 400 ℃. N₂ sorption isotherms show that the samples is predominantly microporous(peak 1.2 nm) and occasionally mesoporous. Electrochemical measurements suggest that Reed catkins-based JJCZH-750 carbon microtubes have a specific capacitance up to 170 F/g, which remains at 153 F/g after 5000 cycles in a voltammetry test, showing a potential as electrode material in electrochemical capacitors.

Key words: Carbonized biomass, N-Doped carbon microtube, Reed catkin, Electrochemical capacitor

中图分类号:

O646
O613.71

TrendMD:

杨东生, 王磊, 陈玲, 周晋雅, 冯炜, 张建会. 含氮碳微米管电极材料的制备及在电容器中的应用. 高等学校化学学报, 2018, 39(5): 1055.

YANG Dongsheng,WANG Lei,CHEN Ling,ZHOU Jinya,FENG Wei,ZHANG Jianhui. Preparation and Properties of N-Doped Carbon Microtubes as the Electrode Material in Electrochemical Capacitor. Chem. J. Chinese Universities, 2018, 39(5): 1055.

图/表 9

Fig.1 Preparation of Reed catkins-based carbon materials

Fig.2 N2 adsorption-desorption isotherms of different carbonized samples Note:a. JJCZH-550; b. JJCH-750; c. JJCZH-750; d. JJCH-950; e. JJCZH-950.

Fig.3 SEM images of JJ(A—C) and JJCZH-750(D—F) with different magnifications

Fig.4 XPS of JJCZH-750

Fig.5 TEM images of JJCZH-750

Fig.6 XRD pattern(A), IR spectrum(B), Raman spectrum(C) and TGA(D) curve of JJCZH-750

Fig.7 N2 adsorption-desorption isotherm(A) and pore size distribution curve(B) of JJCZH-750

Fig.8 Electrochemical measurement of JJCZH-750(A, B) and JJCH-750(C, D) Note:(A), (C) Cyclic voltammetry curves; (B), (D) galvanostatic charge-discharge curves.

Fig.9 Long term cycle stability of the JJCZH-750 at a scan rate of 0.1 V/s

参考文献 25

[1]	Reich S., Thomsen C., Maultzsch J., Carbon Nanotubes Basic Concepts and Physical Properties, WILEY-VCH Verlag GmbH & Co. KGaA., Weinheim, 2004, 3
[2]	Saito R., Dresselhaus G., Dresselhaus M.S., Physical Properties of Carbon Nanotubes, Imperial College Press, London, 1998, 35
[3]	Iijima S., Tanaka K., Carbon Nanotubes and Graphene, Elsevier Ltd., Amsterdam, 2014, 10
[4]	Hu J.Q., Bando Y., Xu F. F., Adv. Mater., 2004, 16(2), 153—156
[5]	Xu L.Q., Zhang W. Q., Ding Y. W., Phys. Chem. B, 2004, 108(30), 10859—10862
[6]	Wang X.F., Liu X. Q., Lai L. F., Adv. Funct. Mater., 2008, 18(12), 1809—1823
[7]	Shen G.Z., Bando Y., Zhi C. Y., J. Phys. Chem. B, 2006, 110(22), 10714—10719
[8]	Wang X.R., Zhao X., Yang J., Lu C. H., Du. X. W., Carbon, 2009, 47(7), 1877—1880
[9]	Kiselev N.A., Hutchison J. L., Moravsky A. P., Rakova E. V., Dreval E. V., Hetherington C. J. D., Zakharov D. N., Sloan J., Loutfy R. O., Carbon, 2004, 42, 149—161
[10]	Zhang J.P., Lu H. Y., Sun G. P., Flad R., Wu N. Q., Huan X. J., He K. Y., Wang Y. L., Sci. Rep-UK, 2016, 6, 18664
[11]	Ci W.S., Science and Technology of Tianjin Agriculture and Forestry, 2011, 2, 35—37
	(慈维顺. 天津农林科技, 2011, 2, 35—37)
[12]	Qasem S.M., Haimour N. M., Sayed S. A., Akash B. A., Energ. Source, 2004, 26, 751—760
[13]	Ding J., Wang H.L., Li Z., Kohandehghan A., Cui K., Xu Z. W., Zahiri B., Tan X. H., Lotfabad E. M., Olsen B. C., Mitlin D., ACS Nano, 2013, 12, 11004—11015
[14]	Sevilla M., Fuertes A.B., Chem. Phys. Lett., 2010, 490, 63—68
[15]	Barin G.B., Gimenez I. F., Costa L. P., Filho A. G. S., Barreto L. S., [J]. Mater. Sci., 2014, 49(2), 665—672
[16]	Pei J.C., Lignocellulosic Chemistry, the Fourth Edition, China Light Industry Press, Beijing, 2012, 91
	(裴继诚. 植物纤维化学, 第4版, 北京: 中国轻工业出版社, 2012, 91)
[17]	Hu B., Wang K., Wu L.H., Yu S. H., Markus A., Titirici M. M., Adv. Mater., 2010, 22, 813—828
[18]	Mao J.Z., Zhang L. M., Xu F., Cellulose Chem. Technol., 2012, 46, 193—205
[19]	Arepalli S., Nikolaev P., Gorelik O., Hadjiev V.G., Holmes W., Files B., Yowell L., Carbon, 2004, 42(8/9), 1783—1791
[20]	Chmiola J., Yushin G., Portet C., Simon P., Taberna P.L., Science, 2006, 313(5794), 1760—1763
[21]	Liu M.X., Qian J. S., Zhao Y. H., Zhu D. Z., Gan L. H., Chen L. W., J. Mater. Chem. A, 2015, 3, 11517—11526
[22]	Zhao Y.H., Liu M. X., Gan L. H., Ma X. M., Zhu D. Z., Xu Z. J., Chen L. W., Energ. Fuel, 2014, 28(2), 1561—1568
[23]	Wang Y., Ben T., Qiu S.L., Chem. [J]. Chinese Universities, 2016, 37(6), 1042—1049)
	(王昀, 贲腾, 裘式纶. 高等学校化学学报, 2016, 37(6), 1042—1049)
[24]	Yan P.L., Li A. L., Zhang B. Q., Shi J. Y., Gan Y., Li C., Chem. [J]. Chinese Universities, 2015, 36(11), 2304—2310
	(严鹏丽, 李爱龙, 张丙青, 施晶莹, 甘阳, 李灿. 高等学校化学学报, 2015, 36(11), 2304—2310)
[25]	Conway B.E., Electrochemical Supercapacitors Scientific Fundamentals and Technological Applications, Kluwer Academic/Plenum Publishers, New York, 1999, 51