Preparation of coral-like nitrogen-doped porous carbons and its supercapacitive properties

doi:10.11949/0438-1157.20191428

Abstract

Abstract:

Under the condition of melamine as the nitrogen source and potassium carbonate as the activator, coral-like nitrogen-doped graded porous carbons (CNPCs) were prepared from rapeseed cake. Field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption and desorption techniques were used to study the effects of melamine dosage on the morphology, composition and pore structure of CNPCs. The results show that the as-prepared CNPC₂ has a high surface area up to 2050 m²·g^-1 when the dosage of melamine is 2 g. The specific capacitance of CNPCs is up to 274 F·g^-1 at a current density of 0.05 A·g^-1 in 6 mol·L^-1 KOH electrolyte. As the current density increases to 50 A·g^-1, the specific capacitance of CNPCs retains 169 F·g^-1, showing excellent rate performance. After 10000 charge and discharge cycles, the capacitance retention is 96%, demonstrating good cycle stability. This work provides a simple, green method for the mass production of high-performance porous carbon materials for energy storage from biomass.

Key words: biomass, coral-like, nitrogen-doped, activated carbon, electrochemistry

摘要：

在三聚氰胺为氮源、碳酸钾为活化剂的条件下，由菜籽饼制得了珊瑚状氮掺杂分级多孔碳(CNPCs)。采用场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、氮吸脱附等表征手段，研究了三聚氰胺的用量对CNPCs微观形貌、组成及孔隙结构的影响。结果表明，当三聚氰胺的用量为2 g时，所得CNPC₂的比表面积达2050 m²·g^-1。以6 mol·L^-1 KOH为电解液，在0.05 A·g^-1的电流密度下，CNPCs的比容可达274 F·g^-1；当电流密度为50 A·g^-1时，CNPCs的比容为169 F·g^-1，显示了优异的倍率性能。经过10000次充放电测试后，比容保持率达96%，展现了良好的循环稳定性。此工作为从生物质大规模生产高性能储能用多孔碳材料提供了一种简单、绿色的方法。

关键词: 生物质, 珊瑚状, 氮掺杂, 活性炭, 电化学

CLC Number:

O 646

Honghui BI, Shuai JIAO, Feng WEI, Xiaojun HE. Preparation of coral-like nitrogen-doped porous carbons and its supercapacitive properties[J]. CIESC Journal, 2020, 71(6): 2880-2888.

毕宏晖, 焦帅, 魏风, 何孝军. 珊瑚状氮掺杂多孔碳的制备及其超电容性能[J]. 化工学报, 2020, 71(6): 2880-2888.

Figures/Tables 11

Fig.1 Schematic illustration for synthesis process of CNPCs

Fig.2 FESEM images of rapeseed cake(a), CNPC1 (b), CNPC2 (c) and CNPC3 (d)

Fig.3 TEM image of CNPC2(a) and HRTEM image of CNPC2(b)

Fig.4 Nitrogen adsorption-desorption isotherms(a) and pore size distribution curves(b) of CNPCs

Table 1 Pore structure parameters of CNPCs

Samples

D_ap/

S_BET/

(m²·g^-1)

S_mic/

(m²·g^-1)

V_t/

(cm³·g^-1)

V_mic/

(cm³·g^-1)

CNPC₁

CNPC₂

CNPC₃

Fig.5 XRD patterns (a) and Raman spectra (b) of CNPCs

Fig.6 XPS spectra of CNPCs

Table 2 Contents of carbon, oxygen and nitrogen elements and surface nitrogen-containing functional groups

Samples	C 1s/ %	O 1s/ %	N 1s/ %	N functional group ratios/%(area)
Samples	C 1s/ %	O 1s/ %	N 1s/ %	N-6	N-5	N-Q	N-O
CNPC₁	72.65	24.92	2.42	11.57	52.89	28.51	7.03
CNPC₂	67.94	28.58	3.48	36.49	42.82	14.37	6.32
CNPC₃	66.03	30.55	3.42	21.64	29.53	33.03	15.80

Fig.7 CV curves of CNPCs electrodes at a scanning rate of 10 mV·s-1(a) and CV curves of CNPC2 electrode at different scanning rates (b)

Fig.8 GCD curves of CNPCs electrodes at 0.05 A·g-1 (a); specific capacitances of CNPCs electrodes at different current densities(b); Ragone plots of CNPCs supercapacitors(c); capacitance retention of CNPC2 electrode at 5 A·g-1 after 10000 cycles(d)

Fig.9 Nyquist plots(a) and Bode plots (b) of CNPCs electrodes

References 39

1	Quiroz-Cardoso O, Oros-Ruiz S, Solis-Gomez A, et al. Enhanced photocatalytic hydrogen production by CdS nanofibers modified with graphene oxide and nickel nanoparticles under visible light[J]. Fuel, 2019, 237: 227-235.
2	Dou Q Y, Lu Y N, Su L J, et al. A sodium perchlorate-based hybrid electrolyte with high salt-to-water molar ratio for safe 2.5 V carbon-based supercapacitor[J]. Energy Storage Mater., 2019, 23: 603-609.
3	Xia J S, Zhang N, Chong S K, et al. Three-dimensional porous graphene-like sheets synthesized from biocarbon via low-temperature graphitization for a supercapacitor[J]. Green Chem., 2018, 20: 694-700.
4	He X J, Xie X Y, Wang J X, et al. From fluorene molecules to ultrathin carbon nanonets with an enhanced charge transfer capability for supercapacitors[J]. Nanoscale, 2019, 11(14): 6610-6619.
5	禹兴海, 罗齐良, 潘剑, 等. 一种生物炭基柔性固态超级电容器的制备及性能研究[J]. 化工学报, 2019, 70(9): 3590-3600.
	Yu X H, Luo Q L, Pan J, et al. Preparation and properties of flexible supercapacitor based on biochar and solid gel-electrolyte[J]. CIESC Journal, 2019, 70(9): 3590-3600.
6	Liu X G, Ma C D, Li J X, et al. Biomass-derived robust three-dimensional porous carbon for high volumetric performance supercapacitors[J]. J. Power Sources, 2019, 412: 1-9.
7	Liu Y, Shi Z J, Gao Y F, et al. Biomass-swelling assisted synthesis of hierarchical porous carbon fibers for supercapacitor electrodes[J]. ACS Appl. Mater. Interfaces, 2016, 8(42): 28283-28290.
8	Yu P F, Liang Y R, Dong H W, et al. Rational synthesis of highly porous carbon from waste bagasse for advanced supercapacitor application[J]. ACS Sustainable Chem. Eng., 2018, 6(11): 15325-15332.
9	Zhang Y, Liu S S, Zheng X Y, et al. Biomass organs control the porosity of their pyrolyzed carbon[J]. Adv. Funct. Mater., 2017, 27(3): 1604687.
10	后振中, 彭龙贵, 李颖, 等. 分级多孔聚吡咯膜的界面自组装合成与电化学电容性[J]. 化工学报, 2018, 69 (9): 4121-4128.
	Hou Z Z, Peng L G, Li Y, et al. Interfacial self-assembly synthesis and electrochemical capacitance of hierarchical porous polypyrrole films[J]. CIESC J., 2018, 69 (9): 4121-4128.
11	Zhao G Y, Chen C, Yu D F, et al. One-step production of O-N-S co-doped three-dimensional hierarchical porous carbons for high-performance supercapacitors[J]. Nano Energy, 2018, 47: 547-555.
12	Zhang Q, Han K H, Li S J, et al. Synthesis of garlic skin-derived 3D hierarchical porous carbon for high-performance supercapacitors[J]. Nanoscale, 2018, 10(5): 2427-2437.
13	Dai S G, Liu Z, Zhao B, et al. A high-performance supercapacitor electrode based on N-doped porous graphene[J]. J. Power Sources, 2018, 387: 43-48.
14	Lv B J, Li P P, Liu Y, et al. Nitrogen and phosphorus co-doped carbon hollow spheres derived from polypyrrole for high-performance supercapacitor electrodes[J]. Appl. Surf. Sci., 2018, 437: 169-175.
15	Wang B, Wang Y H, Peng Y Y, et al. Nitrogen-doped biomass-based hierarchical porous carbon with large mesoporous volume for application in energy storage[J]. Chem. Eng. J., 2018, 348: 850-859.
16	Dong S A, He X J, Zhang H F, et al. Surface modification of biomass-derived hard carbon by grafting porous carbon nanosheets for high-performance supercapacitors[J]. J. Mater. Chem. A, 2018, 6(33): 15954-15960.
17	Li X G, Guan B Y, Gao S Y, et al. A general dual-templating approach to biomass-derived hierarchically porous heteroatom-doped carbon materials for enhanced electrocatalytic oxygen reduction[J]. Energy Environ. Sci., 2019, 12(2): 648-655.
18	Shao J Q, Song M Y, Wu G, et al. 3D carbon nanocage networks with multiscale pores for high-rate supercapacitors by flower-like template and in-situ coating[J]. Energy Storage Mater., 2018, 13: 57-65.
19	Yu S K, Sun N, Hu L F, et al. Self-template and self-activation synthesis of nitrogen-doped hierarchical porous carbon for supercapacitors[J]. J. Power Sources, 2018, 405: 132-141.
20	Lin G X, Ma R G, Zhou Y, et al. KOH activation of biomass-derived nitrogen-doped carbons for supercapacitor and electrocatalytic oxygen reduction[J]. Electrochim. Acta, 2018, 261: 49-57.
21	Liang C, Liang S, Xia Y, et al. Synthesis of hierarchical porous carbon from metal carbonates towards high-performance lithium storage[J]. Green Chem., 2018, 20(7): 1484-1490.
22	Pan L, Wang Y X, Hu H, et al. 3D self-assembly synthesis of hierarchical porous carbon from petroleum asphalt for supercapacitors[J]. Carbon, 2018, 134: 345-353.
23	Zou K X, Deng Y F, Chen J P, et al. Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors[J]. J. Power Sources, 2018, 378: 579-588.
24	Zhang W, Yu C Y, Chang L B, et al. Three-dimensional nitrogen-doped hierarchical porous carbon derived from cross-linked lignin derivatives for high performance supercapacitors[J]. Electrochim. Acta, 2018, 282: 642-652.
25	Zuo S X, Chen J, Liu W J, et al. Preparation of 3D interconnected hierarchical porous N-doped carbon nanotubes[J]. Carbon, 2018, 129: 199-206.
26	Wei F, He X J, Zhang H F, et al. Crumpled carbon nanonets derived from anthracene oil for high energy density supercapacitor[J]. J. Power Sources, 2019, 428: 8-12.
27	Dong X M, Jin H L, Wang R Y, et al. High volumetric capacitance, ultralong life supercapacitors enabled by eaxberry-derived hierarchical porous carbon materials[J]. Adv. Energy Mater., 2018, 8(11): 1702695.
28	Zhao Y Q, Lu M, Tao P Y, et al. Hierarchically porous and heteroatom doped carbon derived from tobacco rods for supercapacitors[J]. J. Power Sources, 2016, 307: 391-400.
29	张璇, 杨佳兴, 金秋阳, 等. 超盐环境下含氮碳气凝胶的制备及其在超级电容器中的应用[J]. 化工学报, 2019, 70(7): 2748-2757.
	Zhang X, Yang J X, Jin Q Y, et al. Preparation of nitrogen-doped carbon aerogel under hypersaline condition and its application for supercapacitors[J]. CIESC Journal, 2019, 70(7): 2748-2757.
30	Wang Q, Qin B, Zhang X H, et al. Synthesis of N-doped carbon nanosheets with controllable porosity derived from bio-oil for high-performance supercapacitors[J]. J. Mater. Chem. A, 2018, 6(40): 19653-19663.
31	Wang T, Sun Y, Zhang L L, et al. Space-confined polymerization: controlled fabrication of nitrogen-doped polymer and carbon nicrospheres with refined hierarchical architectures[J]. Adv. Mater., 2019, 31(16): 1807876.
32	He H N, Huang D, Tang Y G, et al. Tuning nitrogen species in three-dimensional porous carbon via phosphorus doping for ultra-fast potassium storage[J]. Nano Energy, 2019, 57: 728-736.
33	贺新福, 龙雪颖, 吴红菊, 等. 氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能[J]. 化工学报, 2019, 70(6): 2308-2315.
	He X F, Long X Y, Wu H J, et al. Synthesis of N-doped graphene/porous carbon composite and its electrocatalytic performance on oxygen reduction reaction[J]. CIESC Journal, 2019, 70(6): 2308-2315.
34	Zhang Y T, Zhang K B, Ren S Z, et al. 3D nanoflower-like composite anode of α-Fe₂O₃/coal-based graphene for lithium-ion batteries[J]. J. Alloy. Compd., 2019, 792: 828-834.
35	Liu S M, Liang Y R, Zhou W, et al. Large-scale synthesis of porous carbon via one-step CuCl₂ activation of rape pollen for high-performance supercapacitors[J]. J. Mater. Chem. A, 2018, 6(25): 12046-12055.
36	Zhu Q L, Pachfule P, Strubel P, et al. Fabrication of nitrogen and sulfur co-doped hollow cellular carbon nanocapsules as efficient electrode materials for energy storage[J]. Energy Storage Mater., 2018, 13: 72-79.
37	Wan L, Song P, Liu J X, et al. Facile synthesis of nitrogen self-doped hierarchical porous carbon derived from pine pollen via MgCO₃ activation for high-performance supercapacitors[J]. J. Power Sources, 2019, 438: 227013.
38	Zhang Y T, Zhang K B, Jia K L, et al. Preparation of coal-based graphene quantum dots/α-Fe₂O₃ nanocomposites and their lithium-ion storage properties[J]. Fuel, 2019, 241: 646-652.
39	魏风, 毕宏晖, 焦帅, 等. 超级电容器用相互连接的类石墨烯纳米片[J]. 物理化学学报, 2020, 36(2): 1903043.
	Wei F, Bi H H, Jiao S, et al. Interconnected graphene-like nanosheets for supercapacitors[J]. Acta Phys.-Chim. Sin., 2020, 36(2): 1903043.

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