Co3O4纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用

doi:10.15541/jim20180343

无机材料学报 ›› 2019, Vol. 34 ›› Issue (5): 487-492.DOI: 10.15541/jim20180343

Co₃O₄纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用

刘伟^1,^2,³,郑凯²,王东红^1,²,雷忆三^1,²(),范怀林³

^1. 电磁防护材料及技术山西省重点实验室, 太原 030032
^2. 中国电子科技集团公司第 33 研究所, 太原 030032
^3. 中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原 030001

收稿日期:2018-07-26 修回日期:2018-10-30 出版日期:2019-05-20 网络出版日期:2019-05-14
作者简介:刘伟(1990-), 男, 工程师. E-mail: lwucas2014@126.com
基金资助:
国家自然科学基金(U1710115);山西省自然科学基金(201701D121050);中国电科联合基金(6401B08110304)

Co₃O₄ Nanowire Arrays@Activated Carbon Fiber Composite Materials: Facile Hydrothermal Synthesis and Its Electrochemical Application

Wei LIU^1,^2,³,Kai ZHENG²,Dong-Hong WANG^1,²,Yi-San LEI^1,²(),Huai-Lin FAN³

^1. Shanxi Key Laboratory of Electromagnetic Protection Material and Technology, Taiyuan 030032, China
^2. The 33rd Institute of China Electronics Technology Group Corporation, Taiyuan 030032, China
^3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Received:2018-07-26 Revised:2018-10-30 Published:2019-05-20 Online:2019-05-14
Supported by:
National Natural Science Foundation of China U1710115(U1710115);Natural Science Foundation of Shanxi Province(201701D121050);Joint Foundation of China Electronic Technology Group Corporation(6401B08110304)

摘要/Abstract

摘要：

以Co(NO₃)₂·6H₂O为钴源, NH₄F和尿素作为添加剂, 通过水热法在粘胶基活性炭纤维(ACF)的表面生长了Co₃O₄纳米线, 制备了Co₃O₄@ACF复合材料并进行了结构形貌表征及电化学性能测试。结果表明: 针状的Co₃O₄纳米线阵列均匀地垂直生长在活性炭纤维表面, 形成了丰富的介孔结构。通过改变Co(NO₃)₂·6H₂O的用量, 可以获得不同负载量的Co₃O₄@ACF复合材料。当Co₃O₄负载量为47wt%时, Co₃O₄@ACF复合材料在1 A/g电流密度下的比电容高达566.9 F/g, 几乎是纯Co₃O₄的2倍; 在15 A/g的电流密度下, 其比电容仍可达到393.3 F/g, 表现了较好的倍率特性; 经过5000次循环充放电后, 其比电容仍可保持84.2%, 展现了优良的循环稳定性。

关键词: 活性炭纤维, 水热法, 四氧化三钴, 超级电容器

Abstract:

Co₃O₄@activated carbon fibers (ACF) composites were prepared through a facile hydrothermal method followed by calcination process, involving the growth of Co₃O₄ nanowires on ACF surface. Co(NO₃)₂·6H₂O was used as Co source, urea and NH₄F as additives. The structures and morphologies of Co₃O₄@ACF composites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), N₂adsorption/desorption measures, and thermogravimetric analysis (TGA). The electrochemical properties of Co₃O₄@ACF composites were investigated by cyclic voltammetry (CV), galvanostatic charge discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that Co₃O₄ nanowire arrays uniformly grew on the surface of ACF along the vertical direction, forming abundant mesoporous structures. Co₃O₄@ACF composites with various Co₃O₄fractions could be obtained by adding different amount of Co(NO₃)₂·6H₂O. Furthermore, Co₃O₄@ACF composite with 47wt% Co₃O₄fraction exhibited a high specific capacitance of 566.9 F/g at a current density of 1 A/g, which was almost twice as high as that of pure Co₃O₄. Even at 15 A/g, the composite still delivered a specific capacitance of 393.3 F/g, showing good rate capability. The specific capacitance of the composite could retain 84.2% of initial value after 5000 charging/discharging cycles, which indicates its superior cycling stability.

Key words: activated carbon fiber, hydrothermal method, cobaltosic oxide, supercapacitor

中图分类号:

TB34

刘伟, 郑凯, 王东红, 雷忆三, 范怀林. Co₃O₄纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用[J]. 无机材料学报, 2019, 34(5): 487-492.

Wei LIU, Kai ZHENG, Dong-Hong WANG, Yi-San LEI, Huai-Lin FAN. Co₃O₄ Nanowire Arrays@Activated Carbon Fiber Composite Materials: Facile Hydrothermal Synthesis and Its Electrochemical Application[J]. Journal of Inorganic Materials, 2019, 34(5): 487-492.

图/表 8

图1 v-ACF、p-Co3O4及Co3O4@ACF复合材料的XRD图谱

Fig. 1 XRD patterns of v-ACF, p-Co3O4 and Co3O4@ACF composites

图2 Co3O4@ACF复合材料在空气中的热重曲线

Fig. 2 TG curves of Co3O4@ACF composites in air

图3 Co3O4@ACF复合材料的扫描电镜照片: (a) Co3O4@ACF-2; (b) Co3O4@ACF-1; (c) Co3O4@ACF-2; (d) Co3O4@ACF-5

Fig. 3 SEM images of Co3O4@ACF composites: (a) Co3O4@ACF-2; (b) Co3O4@ACF-1; (c) Co3O4@ACF-2; (d) Co3O4@ACF-5

图4 v-ACF、p-Co3O4及Co3O4@ACF复合材料的(a) N2等温吸附曲线和(b) BJH孔径分布曲线

Fig. 4 (a) N2 adsorption-desorption isotherms and (b) BJH pore size distribution curves of v-ACF, p-Co3O4 and Co3O4@ACF composites

表1 v-ACF、p-Co3O4和Co3O4@ACF复合材料的比表面积及孔体积数据

Table 1 Specific surface areas and pore volumes of v-ACF, p-Co3O4 and the Co3O4@ACF composites

Samples	S_total /(m²·g^-1)	S_micropore /(m²·g^-1)	V_total /(m³·g^-1)	V_micropore/(m³·g^-1)
Co₃O₄@ACF-1	153	80	0.21	0.03
Co₃O₄@ACF-2	177	103	0.26	0.04
Co₃O₄@ACF-5	32	-	0.15	-
p-Co₃O₄	20	-	0.07	-
v-ACF	785	693	0.43	0.33

图5 (a) 扫描速率为20 mV/s下各样品的CV曲线; (b)电流密度为1A/g时各样品的GCD曲线; (c) Co3O4@ACF-2在不同扫描速率下的CV曲线; (d) Co3O4@ACF-2在不同电流密度下的GCD曲线

Fig. 5 (a) CV curves of different samples at a scan rate of 20 mV/s; (b) Galvanostatic charge/discharge curves of different samples at 1 A/g; (c) CV curves of Co3O4@ACF-2 at different scan rates; (d) GCD curves of Co3O4@ACF-2 at various current densities

图6 各样品在不同电流密度下的比电容

Fig. 6 Specific capacitances of samples at different current densities

图7 (a) Co3O4@ACF-2样品在1 A/g 电流密度下经5000次充放电循环后比电容的变化曲线; (b) Co3O4@ACF-2样品在5000次充放电循环前后的Nyquist曲线(插图为局部放大图和等效电路图)

Fig. 7 (a) Cycling stability of the Co3O4@ACF-2 at a density of 1 A/g for 5000 cycles; (b) Nyquist plots of the Co3O4@ACF-2 before and after 5000 cycles with inserts showing magnified plots and equivalent circuit

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Co₃O₄纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用

Co₃O₄ Nanowire Arrays@Activated Carbon Fiber Composite Materials: Facile Hydrothermal Synthesis and Its Electrochemical Application

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