组氨酸功能化碳点/石墨烯气凝胶的制备及超级电容器性能

doi:10.15541/jim20190630

摘要/Abstract

摘要：

通过一步水热法制备组氨酸功能化碳点/石墨烯气凝胶(His-CDs/GA)。该材料具有独特的三维多孔结构、丰富的含氮和含氧官能团, 有利于电解液离子的快速扩散和提供更多的活性位点。当GO与His-CDs的质量比为2 : 1时, His-CDs/GA-2在1 A·g ^-1电流密度下比电容达到304 F·g ^- ¹, 比GA(172 F·g ^-1)提高了76.7%; 当电流密度从1 A·g ^-1增加到50 A·g ^-1, 其比电容保持率为71.4%; 在电流密度10 A·g ^-1下, 循环充放电30000次后, 比电容仍保留93.5%。由His-CDs/GA组装的对称超级电容器展现出高能量密度(在功率密度为250 W/kg时, 能量密度达到10.14 Wh/kg)和良好的循环性能(在5 A·g ^-1下循环充放电20000次后, 比电容保持率为88.4%)。结果表明, His-CDs/GA是一种应用前景广阔的超级电容器电极材料。

关键词: 石墨烯气凝胶, 组氨酸功能化碳点, 电容性能, 超级电容器

Abstract:

Histidine-functionalized carbon dot/graphene aerogel (His-CDs/GA) were synthesized via the one-step hydrothermal method. The as-prepared His-CDs/GA exhibits unique three-dimensional porous structure, rich nitrogen and oxygen-containing functional groups, which facilitate the rapid diffusion of electrolyte ions and provide more active sites. When the mass ratio of GO and His-CDs is 2 : 1, the specific capacitance of His-CDs/GA-2 reaches 304 F·g ^-1 at a current density of 1 A·g ^-1, which increases 76.7% compared with that of GA (172 F·g ^- ¹). With the current density increasing from 1 A·g ^-1 to 50 A·g ^-1, the specific capacitance retention of His-CDs/GA-2 achieves 71.4%. The specific capacitance of His-CDs/GA-2 still remains 93.5% over 30000 cycles at 10 A·g ^-1. In addition, a symmetrical supercapacitor assembled by His-CDs/GA possesses a high energy density of 10.14 Wh/kg at a power density of 250 W/kg, and good cyclic performance with 88.4% capacitance retention at 5 A·g ^-1 over 20000 cycles. The results show that His-CDs/GA is a promising electrode material for supercapacitors.

Key words: graphene aerogel, histidine-functionalized carbon dot, capacitance performance, supercapacitor

中图分类号:

O646

丁卓峰, 杨永强, 李在均. 组氨酸功能化碳点/石墨烯气凝胶的制备及超级电容器性能[J]. 无机材料学报, 2020, 35(10): 1130-1136.

DING Zhuofeng, YANG Yongqiang, LI Zaijun. Synthesis and Supercapacitor Performance of Histidine-functionalized Carbon Dots/Graphene Aerogel[J]. Journal of Inorganic Materials, 2020, 35(10): 1130-1136.

图/表 17

图1 His-CDs/GA的制备示意图

Fig. 1 Schematic illustration of His-CDs/GA preparation

图2 His-CDs的TEM照片(插图: HRTEM照片)

Fig. 2 TEM image of His-CDs (Inset: HRTEM image)

图3 GA(a)、His-CDs/GA-1(b)、His-CDs/GA-2(c)和His-CDs/ GA-3(d)的SEM照片; GA(e)和His-CDs/GA-2(f)的TEM照片

Fig. 3 SEM images of GA(a), His-CDs/GA-1(b), His-CDs/ GA-2(c), and His-CDs/GA-3(d), and TEM images of GA(e) and His-CDs/GA-2(f)

图4 GA、His-CDs/GA-1、His-CDs/GA-2和His-CDs/GA-3的XRD图谱

Fig. 4 XRD patterns of GA, His-CDs/GA-1, His-CDs/GA-2 and His-CDs/GA-3

图5 GA和His-CDs/GA-2的XPS总谱(a)和His-CDs/GA-2的N 1s图谱(b)

Fig. 5 Total survey XPS spectra (a) of GA and His-CDs/GA-2 and N 1s spectrum (b) of His-CDs/GA-2

图6 GA、His-CDs/GA-1、His-CDs/GA-2和His-CDs/GA-3在10 mV·s-1扫描速率下的循环伏安曲线(a)和1 A·g-1电流密度下的恒流充放电曲线(b)

Fig. 6 CV curves (a) at 10 mV·s-1 and GCD curves (b) at 1 A·g-1 of GA, His-CDs/GA-1, His-CDs/GA-2, and His-CDs/ GA-3

图7 His-CDs/GA-2在不同扫描速率下的循环伏安曲线(a)和在不同电流密度下的充放电曲线(b); GA、His-CDs/GA-1、His-CDs/GA-2和His-CDs/GA-3的倍率性能图(c); GA和His-CDs/GA-2在10 A·g-1下的循环性能图(d)

Fig. 7 CV curves at different scan rates (a) and GCD curves at different current densities (b) of His-CDs/GA-2; Rate capabilities of GA, His-CDs/GA-1, His-CDs/GA-2 and His-CDs/GA-3 (c); Cycling performances of GA and His-CDs/GA-2 at 10 A·g-1 (d)

图8 His-CDs/GA-2//His-CDs/GA-2的拉贡图

Fig. 8 Ragon plots of His-CDs/GA-2//His-CDs/GA-2

图S1 His-CDs的尺寸分布图

Fig. S1 Size distribution of His-CDs

图S2 His-CDs的XRD图谱(a)和红外光谱图(b)

Fig. S2 XRD pattern (a) and IR spectrum (b) of His-CDs

图S3 GA、His-CDs/GA-1、His-CDs/GA-2和His-CDs/GA-3的拉曼谱图

Fig. S3 Raman spectra of GA, His-CDs/GA-1, His-CDs/GA-2 and His-CDs/GA-3

图S4 GA、His-CDs/GA-1、His-CDs/GA-2和His-CDs/GA-3的氮气吸附/脱附等温线(a)和孔径分布曲线(b)

Fig. S4 N2 absorption-desorption isotherms (a) and pore size distributions (b) of GA, His-CDs/GA-1, His-CDs/GA-2 and His-CDs/GA-3

图S5 His-CDs/GA-2的C1s(a)和O1s(b) XPS图谱

Fig. S5 C1s (a) and O1s (b) XPS spectra of His-CDs/GA-2

表S1 His-CDs/GA-2与其它石墨烯基电极比电容的比较

Table S1 Comparison of the specific capacitance of His-CDs/GA-2 and other graphene-based electrodes

Electrode	Specific capacitance/ (F·g^-1)	Current density/ (A·g^-1)	Ref.
RGO/CD	278	0.2	[1]
N-OMCN@GN	242.3	1	[2]
N/S-rGAs	180.5	1	[3]
GQDs-3DG	268	1.25	[4]
GQD/3DG	242	1.17	[5]
3D graphene layers	231.2	1	[6]
3D bubble-like graphene frameworks	277	1	[7]
His-CDs/GA-2	304	1	This work

图S6 4种电极的的交流阻抗图谱, 插图为EIS测量的等效电路

Fig. S6 AC impedance plots of 4 electrodes with inset showing the equivalent ciruit from the EIS measurements

图S7 His-CDs/GA-2//His-CDs/GA-2对称电容器在不同扫描速率下的循环伏安曲线(a)和在不同电流密度下的充放电曲线(b)

Fig. S7 CV curves (a) at different scan rates and GCD curves (b) at different current densities of His-CDs/GA-2//His-CDs/ GA-2 symmetrical supercapacitor

图S8 His-CDs/GA-2//His-CDs/GA-2对称电容器在5 A·g-1下循环20000次的循环性能图

Fig. S8 Cycling performance at 5 A·g-1 over 20000 cycles of His-CDs/GA-2//His-CDs/GA-2 symmetrical supercapacitor

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