Preparation and Electrochemical Properties of Hierarchically Porous Carbon Microspheres Derived from Metal Phenolic Precursor†

doi:10.7503/cjcu20170349

Abstract

Abstract:

A hierarchically porous carbonmircrosphere material was prepared by direct carbonization of metal biological macromolecular complex precursor, which was supramolecular self-assembledby zinc(Zn) ions coordinated to ellagic acid(EA). The microstructure and electrochemical properties of as-obtained carbon microspheres were studied by means of TG, FTIR, Raman, XRD, SEM, TEM and electrochemical test. The results show that carbonization temperature plays an important role in determining the structure, specific surface area and electrochemical performance of the carbon microsphere electrode materials. Carbonization at 1000 ℃ under nitrogen produced a micro-mesoporous carbonaceous microsphere material exhibiting lamellar graphene-like structure and high specific surface area of 1238 m²/g, and achieves a specific capacitance of 216 F/g at a scan rate of 5 mV/s in 6 mol/L KOH electrolyte. When the scan rate increased from 5 mV/s to 100 mV/s, the specific capacitor remained 84.67%. Moreover, the porous carbon shows less than 3% decay in specific capacitance values over 5000 cycles at a current density of 1 A/g. The porous carbon microsphere material has excellent electrochemical performance as an electrode material for supercapacitor.

Key words: Metal biological macromolecular complex, Supramolecular self-assembly, Ellagic acid, Hierarchically porous carbon, Supercapacitor

CLC Number:

O646

TrendMD:

ZHANG Baohai, LUO Min, YANG Shun, FU Rongrong, MA Jinfu. Preparation and Electrochemical Properties of Hierarchically Porous Carbon Microspheres Derived from Metal Phenolic Precursor^†[J]. Chem. J. Chinese Universities, 2018, 39(2): 310.

Figures/Tables 14

Fig.1 TG(a) and DSC(b) curves of the ZnEA sample

Fig.2 SEM images of the ZnEA sample (A) Low magnification; (B) high magnification.

Fig.3 SEM and TEM[inset of (D)] images of porous carbon microsphere samples (A) C-ZnEA-700; (B) C-ZnEA-800; (C) C-ZnEA-900; (D) C-ZnEA-1000.

Fig.4 FTTR spectra of the EA(a), ZnEA(b) and C-ZnEA-1000(c) samples(A) and XRD pattern of ZnEA(B) Inset of (B) shows the perspective view of the ZnEA molecular structure.

Fig.5 XRD patterns of as-ZnEA-700/800(A) and C-ZnEA-700/800/900/1000 samples(B) at different carbonization temperature and acid treatment

Fig.6 XPS spectra of the C-ZnEA-1000 sample(A) Survey; (B) O1s; (C) C1s.

Fig.7 Raman spectra of the samples C-ZnEA-700/800/900/1000

Fig.8 N2 adsorption-desorption isotherms(A) and the pore size distribution curves(B) of the C-ZnEA-700/800/900/1000 hierarchically porous carbon microsphere samples

Table 1 Porosity and properties of C-ZnEA-700/800/900/1000 porous carbon microsphere samples

Sample	BET surface area/(m²·g^-1)	Porevolum/(m³·g^-1)	Average pore width/nm
ZnEA	5.32	0.02	14.04
C-ZnEA-700	20.25	0.05	9.69
C-ZnEA-800	95.40	0.12	5.11
C-ZnEA-900	887.29	0.56	2.55
C-ZnEA-1000	1238.13	0.78	2.52

Fig.9 Electrochemical performance of C-ZnEA-700/800/900/1000 samples(A) Cyclic voltammograms curves at a scan rate of 5 mV/s; (B) the specific capacitance variations at different scan rates.

Fig.10 Glavanostatic charge-discharge curves of C-ZnEA-1000 at different current density and specific capacitance variation and IR drop of C-ZnEA-1000 with discharge current density(B)

Fig.11 Nyquist plots of C-ZnEA-700/1000 porous carbon microsphere electrode materialsInset: magnified portion at high frequency.

Fig.12 Cycle performance and Coulombic efficiency of C-ZnEA-1000(A) at 1 A/g and constant current charge-discharge curve of the Its cycle and 5000th cycle(B) The inset is the constant current charge-discharge diagram for the last 20 cycles of the cycle.

Table 2 Comparison of capacitance of MOFs derived porous carbon supercapacitor*

Material	Electrolyte(potential window/V)	Rate capability(%) (scan rate or current density)	Capacitance/(F·g^-1)(scan rate or current density)	Cycle life(%) (Cycling No.)	Ref.
Zn-bdc derived porous carbon	6 mol/L KOH (-1—0)	65(1—100 mV/s)	170 (1 mV/s)	98(5000)	[22]
MOF-5 derived 3D porous carbon	6 mol/L KOH (-0.9—0.1)	82.9(0.05—20 A/g)	212(0.05 A/g)	95.9(1000)	[23]
Al-PCP derived carbons	30% KOH (-1—0)	75(0.1—1 A/g)	232.8(0.1 A/g)		[24]
ZIF-8 derived porous carbon	1 mol/L H₂SO₄ (0—0.6)	60(5—200 mV/s)	251(15 mV/s)	92(2000)	[25]
HPC microsphere derived from ZnEA	6 mol/L KOH (-1.1—-0.1)	84.67(5—100 mV/s)	216(5 mV/s)	97(5000)	This work

References 25

[1]	Conway B.E., Electrochemical Supercapacitors. Scientific Fundamentals and Technological Applications, Plenum Press, New York, 1999
[2]	Wang G., Zhang L., Zhang J., Chem. Soc. Rev., 2012, 41(2), 797—828
[3]	Fu R. R., Luo M., Ma Y. H., Yang S., Chem. J. Chinese Universities, 2016, 37(8), 1485—1490)
	(付蓉蓉,罗民,马永华,杨顺. 高等学校化学学报, 2016,37(8), 1485—1490)
[4]	Sarangapani S., Tilak B. V., Chen C. P., J. Electrochem. Soc., 1996, 143(11), 3791—3799
[5]	Luo M., Ding X. Y., Dou Y. Y., Zhao L., Inorg. Chem., 2015, 31(1), 54—60
	(罗民, 丁肖怡, 窦元运, 赵亮. 无机化学学报, 2015,31(1), 54—60)
[6]	Zhu Y., Murali S., Stoller M. D., Ganesh K. J., Cai W., Ferreira P. J., Pirkle A., Wallace R. M., Cychosz K. A., Thommes M., Su D., Stach E. A., Ruoff R. S., Science,2011, 332(6037), 1537—1541
[7]	Li W., Zhang F., Dou Y., Wu Z., Liu H., Qian X., Gu D., Xia Y., Tu B., Zhao D., Advanced Energy Materials, 2011, 1(3), 382—386
[8]	Li Z., Xu Z., Tan X., Wang H., Holt C. M. B., Stephenson T., Olsen B. C., Mitlin D., Energy & Environmental Science, 2013, 6(3), 871—878
[9]	Tamai H., Kunihiro M., Morita M., Yasuda H., J. Mater. Sci., 2005, 40(14), 3703—3707
[10]	Vivekchand S. R. C., Rout C. S., Subrahmanyam K. S., Govindaraj A., Rao C. N. R., J. Chem. Sci., 2008, 120(1), 9—13
[11]	Zhang L. L., Gu Y., Zhao X. S., J. Mater. Chem. A, 2013, 1(33), 9395—9408
[12]	Frackowiak E., Beguin F., Carbon,2001, 39(6), 937—950
[13]	Jiang H. L., Liu B., Lan Y. Q., Kuratani K., Akita T., Shioyama H., Zong F., Xu Q., J. Am. Chem. Soc., 2011, 133(31), 11854—11857
[14]	Liu B., Shioyama H., Akita T., Xu Q., J. Am. Chem. Soc., 2008, 130(16), 5390
[15]	Przewloka S. R., Shearer B. J., Holzforschung,2002, 56(1), 13—19
[16]	Yang S. J., Antonietti M., Fechler N., J. Am. Chem. Soc., 2015, 137(25), 8269
[17]	Nelson K. M., Mahurin S. M., Mayes R. T., Williamson B., Teague C. M., Binder A. J., Baggetto L., Veith G. M., Dai S., Microporous and Mesoporous Materials, 2016, 222, 94—103
[18]	Liu H.Y., HU X., Ming Y. X., Liu Y., Huang J. W., Ji L. N.,Inorg. Chem., 1998, (4), 5—21
	(刘海洋, 胡希, 明应晓, 刘义, 黄锦汪, 计亮年. 无机化学学报, 1998, (4), 5—21)
[19]	Zhang L., Hu Y. H., J. Phys. Chem. C, 2010, 114(6), 2566—2572
[20]	Kimitsuka Y., Hosono E., Ueno S., Zhou H., Fujihara S., Inorg. Chem., 2013, 52(24), 14028—14033
[21]	Zhang S.L.,Raman Spectroscopy and Low Dimensional Nanometer Semiconductor, Science Press, Beijing, 2008, 98
	(张树霖.拉曼光谱学与低维纳米半导体 , 北京: 科学出版社 2008, 98)
[22]	Yang Y., Hao S., Zhao H., Wang Y., Zhang X., Electrochim. Acta, 2015, 180, 651—657
[23]	Yu M., Zhang L., He X., Yu H., Han J., Wu M., Materials Letters, 2016, 172, 81—84
[24]	Yan X., Li X., Yan Z., Komarneni S., Applied Surface Science, 2014, 308, 306—310
[25]	Salunkhe R. R., Kamachi Y., Torad N. L., Hwang S. M., Sun Z., Dou S. X., Kim J. H., Yamauchi Y., J. Mater. Chem. A, 2014, 2(46), 19848—19854