糖蜜基多孔碳球电极材料的制备及应用

doi:10.7503/cjcu20150874

摘要/Abstract

摘要：

以工业制糖的副产物糖蜜为新型碳源, 替代传统多孔碳生产原料, 制备出性能优异的多孔碳球超级电容器电极材料; 探索了制备方法, 优化了反应条件. 利用全功能表面吸附仪、扫描电子显微镜及电化学方法对材料的结构、形貌和电化学性能进行了表征. 结果表明, 制得的多孔碳球比表面积高达2547 m²/g, 且展现出优异的双电层电容性(170.5 F/g). 本研究可解决制糖企业对糖蜜无法大规模利用的问题, 并为多孔碳的制备寻求新方法.

关键词: 糖蜜, 多孔碳, 比电容

Abstract:

Porous carbon spheres for supercapacitor electrodes employing beet molasses which was a new raw material instead of conventional carbonaceous materials as precursor were produced in different ways. Porous carbons were prepared at various condition variables. The morphology, physical structure and electrochemical properties of the materials were characterized by scanning electron microscopy(SEM), nitrogen physisorption and electrochemical method. The materials had surface area of 2547 m²/g and specific capacitance of 170.5 F/g, which showed large surface area and well electrical double-layer capacitor. In a word, the problem of the use of molasses on a large scale in sugar industry may be solved. Moreover, a new way of producing porous carbons will be provided.

Key words: Molasse, Porous carbon, Specific capacitance

中图分类号:

O646
O613.71

TrendMD:

韩雪, 邹博, 顾小雪, 庞丽云, 曹礼媛, 刘琦, 郭玉鹏. 糖蜜基多孔碳球电极材料的制备及应用. 高等学校化学学报, 2016, 37(6): 1135.

HAN Xue, ZOU Bo, GU Xiaoxue, PANG Liyun, CAO Liyuan, LIU Qi, GUO Yupeng. Preparation and Application of Molasses-based Porous Carbon Spheres for Supercapacitor Electrodes^†. Chem. J. Chinese Universities, 2016, 37(6): 1135.

图/表 7

Fig.1 Preparation illustration of several porous carbonsa. Hydrothermal carbonization at 180 ℃ for 6 h in high-pressure autoclave; b. beet molasses dried in an oven; c. and g. heat treatment at 500 and 800 ℃ in a tube furnace in N2 atmosphere, respectively; d. hydrochar activated by KOH; e. and f. hydrochar and dried beet molasses were activated by 85% H3PO4 in a muffle furnace, respectively.

Table 1 Reaction conditions of different porous carbons

Sample	Reaction temperature/℃	m(Activator)/ m(carbon)	Time/h	Sample	Reaction temperature/℃	m(Activator)/ m(carbon)	Time/h
KC-1	800	3	1	PC-2	550	4	1
KC-2	800	5	1	PC'-1	600	4	0.5
PC-1	500	3	1	PC'-2	600	2	1

Fig.2 SEM images of molasses(A), hydrochar(B) and different porous carbons(C—H)(C) KC-1; (D) KC-2; (E) PC'-1; (F) PC'-2; (G) PC-1; (H) PC-2.

Fig.3 N2 adsorption-desorption isotherms(A) and pore size distributions (B) of several porous carbons■ KC-1; ● KC-2; ▲ PC-1; ▼ PC-2; ◆ PC'-1; ? PC'-2.

Table 2 Textural property of commercial AC and different porous carbons prepared by several processes

Sample	BET surface area/(m²·g^-1)	Total pore volume/(cm³·g^-1)	Micropore volume/ (cm³·g^-1)	Micropore area/(m²·g^-1)	External surface area/(m²·g^-1)	Average pore diameter/nm
KC-1	2547	1.32	0.49	883	1664	2.07
KC-2	2478	1.80		715	3193	2.91
PC-1	340	0.14	0.08	166	173
PC-2	326	0.18	0.05	99	226	2.29
PC'-1	970	0.86	0.04	98	872	3.53
PC'-2	831	0.62	0.01	44	787	2.96
Commercial AC-1	1100	0.90	0.50

Fig.4 Cyclic voltammetry curves(A) and galvanostatic charging/discharging curves of KC-2(B)(A) a—e, ν/(mV·s-1): 10, 20, 30, 40, 50; (B) a—e, j/(mA·cm-2): 10, 20, 30, 40, 50.

Table 3 Specific capacitances of porous carbons in 6 mol/L KOH electrolyte at different current densities

Sample	Specific capacitance/(F·g^-1)
Sample	50 mA/cm²	40 mA/cm²	30 mA/cm²	20 mA/cm²	10 mA/cm²
KC-2	100.0	116.5	134.6	150.0	170.5
PC-1	54.7	60.9	68.2	80.6	137.0
PC'-2	91.7	101.2	108.9	121.6	142.2
Commercial AC-2	86.3	91.5	95.6	103.5	118.8

参考文献 27

[1]	Liu C., Li F., Ma L. P., Cheng H. M., Adv. Mater., 2010, 22, E28—E62
[2]	He Y. T., Wang L. X., Jia D. Z., Zhao H. Y., Chem. J. Chinese Universities, 2015, 36(1), 157—164
	(何一涛, 王鲁香, 贾殿赠, 赵洪洋. 高等学校化学学报, 2015, 36(1), 157—164)
[3]	Liu M. X., Qian J. S., Zhao Y. H., J. Mater. Chem. A, 2015, 3, 11517—11526
[4]	Zhu D. Z., Wang Y. W., Gan L. H., Electrochim.Acta, 2015, 158, 166—174
[5]	Kong L. B., Zhang J., Cai J. J., Yang Z. S., Luo Y. C., Kang L., Chem. Res. Chinese Universities, 2011, 27(2), 295—299
[6]	Ma X. M., Gan L. H., Liu M. X., J. Mater. Chem. A, 2014, 2(22), 8407—8415
[7]	Elzbieta F., Franç O. B., Carbon, 2001, 39(2001), 937—950
[8]	Zheng C., Zhou X., Cao H., Wang G., Liu Z., J. Power Sources, 2014, 258(2014), 290—296
[9]	Zhao Y. H., Liu M. X., Gan L. H., Energ. Fuel., 2014, 28, 1561—1568
[10]	Ma X. M., Liu M. X., Gan L. H., J. Solid State Electr., 2013, 17, 2293—2301
[11]	Zhao Q.L., Wang X.Y., Wu C., Liu J., Wang H., Gao J., Zhang Y. W., Shu H. B., J. Power Sources, 2014, 254(2014), 10—17
[12]	Guo Y. P., Yang S. F., Zhao J. Z., Wang Z. C., Zhao M. Y., Chem. J. Chinese Universities, 2000, 21(3), 335—338
	(郭玉鹏, 杨少凤, 赵敬哲, 王子忱, 赵慕愚. 高等学校化学学报, 2000, 21(3), 335—338)
[13]	Guo Y. P., Yu K. F., Wang Z. C., Xu H. D., Carbon, 2003, 41(8), 1645—1648
[14]	Guo Y. P., Yang S. F., Yu K. F., Zhao J. Z., Wang Z. C., Xu H. D., Mater. Chem. Phys., 2002, 74(3), 320—323
[15]	Li Y., Ding X. F., Guo Y. P., Wang L. L., Rong C. G., Qu Y. N., Ma X. Y., Wang Z. C., Mater. Chem. Phys., 2011, 127(3), 495—500
[16]	DingL. L., Zou B., Liu H. Q., Li Y. N., Wang Z. C., Su Y., Guo Y. P., Wang X. F., Chem. Eng. J., 2013, 225, 300—305
[17]	DingL. L., Zou B., Shen L., Zhao C., Wang Z. C., Guo Y. P., Wang X. F., Liu H. Q., Colloid Surface A, 2014, 446, 90—96
[18]	Zhang Y. M., Wang X. H., Yu H. Q., Meng P. R., J. Chem. Industry Eng., 2011, 32(6), 28—31
	(张艳梅, 王晓慧, 于浩强, 孟平蕊. 化学工业与工程技术, 2011, 32(6), 28—31)
[19]	Farshid G., Habibollah Y., Abbas E. S., Ghasem N., Renew. Energ., 2011, 36, 503—509
[20]	CazettaM. L., CelligoiM. A. P. C., BuzatoJ. B., Scrmino I. S., Bioresource Technol., 2007, 98, 2824—2828
[21]	Xu S., Hao N., Xu L., Liu Z. X., Yan M., Li Y., Ouyang P. K., Biochem. Eng. J., 2015, 99, 177—182
[22]	Aleksandra M. M., Magdalena R., Anna B., Waldemar R., Adam D., Bioresource Technol., 2015, 198, 445—455
[23]	Ding L. L., Wang Z. C., Li Y. N., Du Y. L., Liu H. Q., Guo Y. P., Mater. Lett., 2012, 74, 111—114
[24]	Zhang C. F., Kelsey B. H., Muhammad B., Boris D., Majid B., Long D. H., Qiao W. M., Emin C. K., Yury G., Carbon, 2014, 77, 155—164
[25]	Wu X. L., Jiang L. Y., Cao F. F., Guo Y. G., Wan L. J., Adv. Mater., 2009, 21, 2710—2714
[26]	Toshiyuki M., Liu X. J., Tetsuya L., Yousuke U., Yoshimitsu S., J. Power Sources, 1996, 60(2), 249—253
[27]	Chen X. Y., Chen C., Zhang Z. J., Xie D. H., Deng X., Liu J. W., J. Power Sources., 2013, 230, 50—58