一步法制备三维还原氧化石墨烯/NiO超级电容器电极材料及其性能研究

doi:10.15541/jim20180032

摘要/Abstract

摘要：

本研究以氧化石墨烯分散液(GO)和硝酸镍(Ni(NO₃)₂·6H₂O)为前驱体, 通过一步水热法制备自支撑三维还原氧化石墨烯/NiO复合电极材料(3D rGO/NiO)。用XRD和SEM等分析结果表明, 纳米NiO颗粒均匀分散在三维多孔石墨烯表面。当GO与Ni(NO₃)₂·6H₂O质量比为1 : 4时, 3D rGO/NiO在电流密度为1 A·g^-1 下比电容可达1208.8 F·g^-1; 当电流密度从0.2 A·g^-1增加到10 A·g^-1时, 复合电极材料电容保持率高于72.6%; 在电流密度为10 A·g^-1下进行恒流充放电循环测试10000次后, 其比电容仍然保持为初始比电容的93%, 表明该复合电极材料具有良好的倍率性能和循环稳定性能。3D rGO/NiO复合电极材料具有比纯NiO或rGO更优异的电化学性能。

关键词: 三维石墨烯, 氧化镍, 超级电容器, 水热法, 电化学性能

Abstract:

In this study, by using dispersions of graphene oxide (GO) and nickel nitrate (Ni(NO₃)₂·6H₂O) with different ratios as precursors, three-dimensional self-supported reduced graphene oxide/NiO composites (3D rGO/NiO) were prepared via a one-step hydrothermal method. The analysis results (XRD, SEM, etc) indicate that NiO nanoparticles are homogeneously dispersed on the surface of graphene layers. The specific capacitance of 3D rGO/NiO composite reaches 1208.8 F·g^-1 at a current density of 1 A·g^-1when the mass ratio of GO and Ni(NO₃)₂·6H₂O is 1 : 4. With the current density increasing from 0.2 to 10 A·g^-1, the specific capacitance retention of this composite is higher than 72.6%. After 10000 cycles, the specific capacitance of 3D rGO/NiO at a current density of 10 A·g^-1 remained at 93% of the initial specific capacitance. All of these demonstrated that the composite possesses good rate capability and cycle stability. The 3D rGO/NiO composite has excellent electrochemical performances when compared with pure NiO or rGO, which is attributed to the synergistic effect between NiO and rGO.

Key words: three-dimensional graphene, nickel oxide, supercapacitor, hydrothermal method, electrochemical properties

中图分类号:

O646

曾燕飞, 辛国祥, 布林朝克, 张邦文. 一步法制备三维还原氧化石墨烯/NiO超级电容器电极材料及其性能研究[J]. 无机材料学报, 2018, 33(10): 1070-1076.

ZENG Yan-Fei, XIN Guo-Xiang, BULIN Chao-Ke, ZHANG Bang-Wen. One-step Preparation and Electrochemical Performance of 3D Reduced Graphene Oxide/NiO as Supercapacitor Electrodes Materials[J]. Journal of Inorganic Materials, 2018, 33(10): 1070-1076.

图/表 7

图1 3D rGO/NiO复合电极材料的制备示意图

Fig. 1 Schematic illustration of the preparation of 3D rGO/NiO composite

图2 样品的XRD图谱(a)和TGA曲线(b)

Fig. 2 XRD patterns (a) and TGA curves (b) of samples

图3 3D rGO、3D rGO/NiO-1、3D rGO/NiO-2和3D rGO/ NiO-3的氮气吸附/脱附等温线(a); 3D rGO、3D rGO/NiO-1、3D rGO/NiO-2和3D rGO/NiO-3的孔径分布曲线(b)

Fig. 3 N2 absorption-desorption isotherm (a) and pore size distribution (b) of 3D rGO, 3D rGO/NiO-1, 3D rGO/NiO-2 and 3D rGO/NiO-3 samples

表1 3D rGO、3D rGO/NiO-1、3D rGO/NiO-2和3D rGO/NiO-3的表面性能

Table 1 Surface properties of 3D rGO, 3D rGO/NiO-1, 3D rGO/NiO-2 and 3D rGO/NiO-3

Sample	BET surface area/(m²∙g^-1)	Total pore volume/ (cm³∙g^-1)
3D rGO	239.0	0.383
3D rGO/NiO-1	227.8	0.351
3D rGO/NiO-2	222.0	0.306
3D rGO/NiO-3	190.7	0.293

图4 样品3D rGO/NiO-2的XPS图谱

Fig. 4 XPS spectra of sample 3D rGO/NiO-2

图5 3D rGO(a)、3D rGO/NiO-1(b)、3D rGO/NiO-2(c)及3D rGO/NiO-3(d)的SEM照片(左下为样品照片, (c)中右上插图为红框中的放大照片); 3D rGO/NiO-2的TEM(e)、HRTEM(f)和SAED ((e)中插图)照片

Fig. 5 SEM images of 3D rGO (a), 3D rGO/NiO-1(b), 3D rGO/NiO-2(c), 3D rGO/NiO-3(d) with the inserts (left bottom) showing the samples photographs and the right top one in (c) showing the magnified image in red square, and TEM (e) and HRTEM (f) images of 3D rGO/NiO-2 with the insert in (e) showing SAED image

图6 3D rGO、3D rGO/NiO-1、3D rGO/NiO-2、3D rGO/NiO-3和NiO在扫描速率为10 mV·s-1下的循环伏安曲线(a), 3D rGO/NiO-2在不同扫描速率下的循环伏安曲线(b), 3D rGO/NiO在电流密度为1 A·g-1下的恒流放电曲线(c), 3D rGO/NiO-2 在不同电流密度下的恒流放电曲线(d), 3D rGO、3D rGO/NiO和NiO的倍率性能图(e)以及3D rGO/NiO-2 在电流密度为10 A·g-1下循环寿命曲线(f)

Fig. 6 CV curves of 3D rGO, 3D rGO/NiO and NiO at a scan rate of 10 mV·s-1 (a), 3D rGO/NiO-2 at different scan rates (b), GCD curves of 3D rGO/NiO-1, 3D rGO/NiO-2 and 3D rGO/NiO-3 at a current density of 1 A·g-1 (c), GCD curves of 3D rGO/NiO-2 at different current density (d), specific capacitance of 3D rGO, 3D rGO/NiO-1, 3D rGO/NiO-2, 3D rGO/NiO-3 and NiO at different current densities (e), and cycling performance of 3D rGO/NiO-2 at a current density of 10 A·g-1 after 10000 cycles (f)

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