珊瑚状氮掺杂多孔碳的制备及其超电容性能

doi:10.11949/0438-1157.20191428

摘要/Abstract

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

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

中图分类号:

O 646

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.

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.

图/表 11

图1 CNPCs的合成过程示意图

Fig.1 Schematic illustration for synthesis process of CNPCs

图2 菜籽饼(a), CNPC1(b), CNPC2(c)和CNPC3(d)的FESEM图

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

图3 CNPC2的TEM图(a)及 CNPC2的高分辨率TEM图(b)

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

图4 CNPCs的氮吸附-脱附等温线(a)和孔径分布曲线(b)

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

表1 CNPCs样品的孔结构参数

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

图5 CNPCs的XRD谱图(a)和拉曼光谱图(b)

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

图6 CNPCs的XPS谱图

Fig.6 XPS spectra of CNPCs

表2 碳、氧、氮元素和表面含氮官能团的含量

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

图7 CNPCs电极在扫描速率为10 mV·s-1下的循环伏安曲线(a)和CNPC2电极在不同扫描速率下的循环伏安曲线(b)

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)

图8 CNPCs电极在0.05 A·g-1电流密度下的GCD曲线(a); CNPCs电极在不同电流密度时的比容(b); CNPCs电容器的Ragone图(c); CNPC2电极在5 A·g-1电流密度下10000次循环后的比容保持率(d)

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)

图9 CNPCs电极的Nyquist图(a)和Bode图(b)

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

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