N-doped ordered mesoporous carbon spheres derived by confined pyrolysis for high supercapacitor performance

doi:10.1016/j.jmst.2019.05.029

Abstract

Abstract:

Herein, we report a confined pyrolysis strategy to prepare mesoporous carbon nanospheres by which surface area of carbon spheres is increased, pore size is enlarged and effective N-doping is achieved. In this method, the mesoporous polymer sphere as carbon precursor and 2-methylimidazole as nitrogen precursor are encapsulated in a compact silica shell which provides a confined nano-space for the pyrolysis treatment. The in situ generated gases from mesoporous polymer sphere and 2-methylimidazole under pyrolysis diffuse into the pores of mesoporous polymer sphere in the confined compact silica shell, resulting in increased surface area, larger pore size and N-doping due to self-activation effect. As electrodes in supercapacitor, the N-doped mesoporous carbon nanospheres exhibit a signiﬁcantly enhanced speciﬁc capacitance of 326 F g^-1 at 0.5 A g^-1, which is 2 times higher than that of mesoporous carbon spheres under unconfined pyrolysis condition, exhibiting its potential for electrode materials with high performance.

Key words: Confined pyrolysis, N-doping, Ordered large mesoporous spheres, Supercapacitor

Juan Du, Lei Liu, Yifeng Yu, Yue Zhang, Haijun Lv, Aibing Chen. N-doped ordered mesoporous carbon spheres derived by confined pyrolysis for high supercapacitor performance[J]. J. Mater. Sci. Technol., 2019, 35(10): 2178-2186.

Figures/Tables 10

Fig. 1. Schematic preparation of N-MCS, MCS and TGA analysis of MPS, MPS/Hmin and Hmim (blue frame) (a), TEM images of MPS@SiO2 core-shell spheres (b, c), SEM images with inset showing EDS analysis (d) and TEM images (e) of N-MCS, TEM images of MCS (f), nitrogen adsorption-desorption isotherms (g) and pore size distribution curves (h) of N-MCS and MCS.

Table 1 Textural properties of MCS and N-MCS samples (SBET: BET surface area; Smicro: micropore surface area determined by thet-plot; Vt: total pore volume at P/P0$\widetilde{0}$.99; Vmicro: micropore volume; Vn = Vmicro/Vt; BJH method was applied to analyze the pore size distribution using the desorption branch of isotherm).

Sample	S_BET (m² g^-1)	S_micro (m² g^-1)	V_t (cm³ g^-1)	V_micro (cm³ g^-1)	V_n (%)	Pore size (nm)
MCS	696	493	0.60	0.23	38.3	3.0
N-MCS	1602	781	2.09	0.31	14.8	8.0

Fig. 2. Small angle XRD patterns of MCS and N-MCS (a), XPS patterns (b), C1s (c), O1s (d) and N1s (e) spectrum of MCS and N-MCS, schematic of nitrogen species incorporated into carbon framework (f).

Fig. 3. Schematic illustration for activation and N-doping of N-MCS inside compact silica shell.

Fig. 4. TGA analysis of composite of MPS with EDA, Thiourea and Pyridine (a), TEM images (b), nitrogen adsorption-desorption isotherms (c), pore size distribution curves (d), XPS patterns (e), C1s (f), O1s (g) and N1s (h) spectrum and C, N and O contents (i) of N-MCS-EDA, N-MCS-Thiourea and N-MCS-Pyridine.

Table 2 Textural properties of N-MCS samples with other nitrogen precursors.

Sample	S_BET (m² g^-1)	S_micro (m² g^-1)	V_t (cm³ g^-1)	V_micro (cm³ g^-1)	V_n (%)	Pore size (nm)
N-MCS-EDA	1208	388	4.57	0.07	1.53	9.4
N-MCS-Thiourea	1288	627	1.31	0.22	16.8	9.4
N-MCS-Pyridine	892	496	1.26	0.19	15.1	6.7

Fig. 5. CV (a) and GCD (b) curves at the scan rates of 5 mV s-1 and current density of 0.5 A g-1 respectively; specific capacitances obtained by different GCD (c), CV (d) and GCD (e) curves at different scan rates and current densities of N-MCS, Nyquist plots (f) of N-MCS (Z’ : real part of impedance; Z’’: imaginary part of impedance).

Table 3 Parameters of equivalent circuit for N-MCS (CPE: capacitor layer that formed during the charge-discharge process).

R_s (Ω)	R_ct (Ω)	Z_W (Ω)	C_dl (F)	CPE (F)
0.3415	0.0014	1.807	0.0060	0.7264

Fig. 6. CV curves at 50 mV s-1 (a) and GCD curves at 1 A g-1 (b) in different voltage windows for N-MCS, CV curves at different scan rates (c), GCD curves at different current densities (d) of N-MCS, specific capacitance of N-MCS at different current density (e) in two-electrode system and Ragone plots comparison with the reported carbon spheres with different structure of N-MCS (f).

Fig. 7. Cycle stability of the electrode at 2.0 A g-1 at two-electrode system of N-MCS (a), CV (b) and GCD (c) curves of MCS, N-MCS-EDA, N-MCS-Thiourea and N-MCS-Pyridine at scan rate of 5 mV s-1 and current density of 1 A g-1 and capacitance of different samples with different nitrogen precursors (d).

References

[1]	H. Sun, Y. Zhu, B. Yang, Y. Wang, Y. Wu, J. Du, J. Mater. Chem. A 4 (2016)12088-12097.
[2]	Y. Liu, Z. Wang, W. Teng, H. Zhu, J. Wang, A.A. Elzatahry, D. Al-Dahyan, W. Li,Y. Deng, D. Zhao, J. Mater. Chem. A 6 (2018) 3162-3170.
[3]	Q. Yue, M. Wang, J. Wei, Y. Deng, T. Liu, R. Che, B. Tu, D. Zhao, Angew. Chem. Int. Ed. 51(2012) 10368-10372.
[4]	J. Zhang, J. Wang, Z. Shi, Z. Xu, Chin. Chem. Lett. 29(2018) 620-623.
[5]	J. Han, G. Xu, B. Ding, J. Pan, H. Dou, D.R. MacFarlane, J. Mater. Chem. A 2(2014) 5352-5357.
[6]	J. Wei, D. Zhou, Z. Sun, Y. Deng, Y. Xia, D. Zhao, Adv. Funct. Mater. 23(2013)2322-2328.
[7]	J. Wei, Z. Sun, W. Luo, Y. Li, A.A. Elzatahry, A.M. Al-Enizi, Y.Deng, D. Zhao, J. Am. Chem. Soc. 139(2017) 1706-1713.
[8]	Y. Wang, B. Chang, D. Guan, X. Dong, J. Solid State Electrochem. 16(2015)1783-1791.
[9]	Z. Sun, Y. Liu, B. Li, J. Wei, M. Wang, Q. Yue, Y. Deng, S. Kaliaguine, D. Zhao, ACSNano 7 (2013) 8706-8714.
[10]	Z. Wang, Y. Zhu, W. Luo, Y. Ren, X. Cheng, P. Xu, X. Li, Y. Deng, D. Zhao, Chem. Mater. 28(2016) 7773-7780.
[11]	G. Wang, J. Zhang, S. Kuang, J. Zhou, W. Xing, S. Zhuo, Electrochim. Acta 153(2015) 273-279.
[12]	L. Yao, Q. Wu, P. Zhang, J. Zhang, D. Wang, Y. Li, X. Ren, H. Mi, L. Deng, Z. Zheng, Adv. Mater. 30(2018) 1706054.
[13]	S. Zhu, L. Li, J. Liu, H. Wang, T. Wang, Y. Zhang, L. Zhang, R.S. Ruoff, F. Dong,ACS Nano 12 (2018) 1033-1042.
[14]	H. Zhang, O. Noonan, X. Huang, Y. Yang, C. Xu, L. Zhou, C. Yu, ACS Nano 10(2016) 4579-4586.
[15]	W. Yang, W. Yang, L. Kong, A. Song, X. Qin, G. Shao, Carbon 127 (2018)557-567.
[16]	N. Parveen, A.I. Al-Jaafari, J.I. Han, Electrochim. Acta 293 (2019) 84-96.
[17]	N.P. Wickramaratne, J. Xu, M. Wang, L. Zhu, L. Dai, M. Jaroniec, Chem. Mater. 26(2014) 2820-2828.
[18]	D. Gu, H. Bongard, Y. Meng, K. Miyasaka, O. Terasaki, F. Zhang, Y. Deng, Z. Wu,D. Feng, Y. Fang, B. Tu, F. Sch¨uth, D. Zhao, Chem. Mater. 22(2010) 4828-4833.
[19]	L. Kong, C. Wang, X. Yin, X. Fan, W. Wang, J. Huang, ACS Appl. Mater. Interface7(2015) 5312-5319.
[20]	W. Luo, T. Zhao, Y. Li, J. Wei, P. Xu, X. Li, Y. Wang, W. Zhang, A.A. Elzatahry, A. Alghamdi, Y. Deng, L. Wang, W. Jiang, Y. Liu, B. Kong, D. Zhao, J. Am. Chem. Soc. 138(2016) 12586-12595.
[21]	Y. Ding, L.E. Mo, C. Gao, X. Liu, T. Yu, W. Chen, S. Chen, Z.-Q. Li, L. Hu, ACS Sustain. Chem. Eng. 6(2018) 9822-9830.
[22]	J. Fan, X. Ran, Y. Ren, C. Wang, J. Yang, W. Teng, L. Zou, Y. Sun, B. Lu, Y. Deng, D. Zhao, Langmuir 32 (2016) 9922-9929.
[23]	J. Du, L. Liu, Z. Hu, Y. Yu, Y. Qin, A. Chen, Adv. Funct. Mater. 28(2018) 1802332.
[24]	J. Choma, D. Jamio?a, K. Augustynek, M. Marszewski, M. Gao, M. Jaroniec, J. Mater. Chem. 22(2012) 12636.
[25]	J. Tang, J. Liu, C. Li, Y. Li, M.O. Tade, S. Dai, Y. Yamauchi, Angew. Chem. Int. Ed. 54(2015) 588-593.
[26]	D. Zhu, Y. Wang, L. Gan, M. Liu, K. Cheng, Y. Zhao, X. Deng, D. Sun, Electrochim. Acta 158 (2015) 166-174.
[27]	X. Han, X. Wu, C. Zhong, Y. Deng, N. Zhao, W. Hu, Nano Energy 31 (2017)541-550.
[28]	V. Selvamani, R. Ravikumar, V. Suryanarayanan, D. Velayutham, S. Gopukumar, Electrochim. Acta 190 (2016) 337-345.
[29]	Y. Deng, Y. Xie, K. Zou, X. Ji, J. Mater. Chem. A 4 (2016) 1144-1173.
[30]	K. Guo, X. Wang, L. Hu, T. Zhai, H. Li, N. Yu, ACS Appl. Mater. Interface 10(2018) 19820-19827.
[31]	Y. Fang, G. Zheng, J. Yang, H. Tang, Y. Zhang, B. Kong, Y. Lv, C. Xu, A.M. Asiri, J. Zi, F. Zhang, D. Zhao, Angew. Chem. Int. Ed. 53(2014) 5366-5370.
[32]	G. Moussa, S. Hajjar-Garreau, P.L. Taberna, P. Simon, C. Matei Ghimbeu, J. Carbon Res. 4(2018) 20.
[33]	C. Zhu, M. Takata, Y. Aoki, H. Habazaki, Chem. Eng. J. 350(2018) 278-289.
[34]	Q. Sun, W.C. Li, A.H. Lu, Small 9 (2013) 2086-2090.
[35]	Y. Fan, X. Yang, B. Zhu, P.F. Liu, H.T. Lu, J. Power Sources 268 (2014) 584-590.
[36]	X. Fang, J. Zang, X. Wang, M.S. Zheng, N. Zheng, J. Mater. Chem. A 2 (2014)6191-6197.
[37]	C. Zhang, K.B. Hatzell, M. Boota, B. Dyatkin, M. Beidaghi, D. Long, W. Qiao, E. C.Kumbur, Y. Gogotsi, Carbon 77 (2014) 155-164.
[38]	W. Yang, Y. Feng, D. Xiao, H. Yuan, Int. J. Energy Res. 39(2015) 805-811.
[39]	X. Zhang, J. Ma, W. Yang, Z. Gao, J. Wang, Q. Liu, J. Liu, X. Jing, CrystEngComm16(2014) 4016-4022.
[40]	Y. Fan, P.F. Liu, Z.J. Yang, T.W. Jiang, K.L. Yao, R. Han, X.X. Huo, Y.Y. Xiong,Electrochim. Acta 163 (2015) 140-148.
[41]	X. Xu, Y. Liu, M. Wang, C. Zhu, T. Lu, R. Zhao, L. Pan, Electrochim. Acta 193(2016) 88-95.
[42]	S. Liu, Y. Cai, X. Zhao, Y. Liang, M. Zheng, H. Hu, H. Dong, S. Jiang, Y. Liu, Y. Xiao,J. Power Sources 360 (2017) 373-382.
[43]	Q. Zhang, L. Li, Y. Wang, Y. Chen, F. He, S. Gai, P. Yang, Electrochim. Acta 176(2015) 542-547.
[44]	X. Li, L. Zhang, G. He, Carbon 99 (2016) 514-522.
[45]	M. Liu, J. Qian, Y. Zhao, D. Zhu, L. Gan, L. Chen, J. Mater. Chem. A 3 (2015)11517-11526.
[46]	L. Mao, Y. Zhang, Y. Hu, K.H. Ho, Q. Ke, H. Liu, Z. Hu, D. Zhao, J. Wang, RSC Adv. 5(2015) 9307-9313.
[47]	Y.H. Dai, H. Jiang, Y.J. Hu, Y. Fu, C.Z. Li, Ind. Eng. Chem. Res. 53(2014)3125-3130.
[48]	B. Chang, S. Zhang, H. Yin, B. Yang, Appl. Surf. Sci. 412(2017) 606-615.
[49]	F. Sun, H. Wu, X. Liu, F. Liu, H. Zhou, J. Gao, Y. Lu, Nano Res. 9(2016)3209-3221.
[50]	M. Li, S. Xiang, X. Chang, C. Chang, J. Solid State Electrochem. 21(2016)485-494.
[51]	Z. Ye, F. Wang, C. Jia, K. Mu, M. Yu, Y. Lv, Z. Shao, Chem. Eng. J. 330(2017)1166-1173.