镍掺杂四氧化三钴纳米线阵列的制备及其超级电容特性

doi:10.15541/jim20170287

摘要/Abstract

摘要：

采用直流电化学沉积与高温氧化相结合的合成方法, 在氧化铝模板的辅助下, 成功制备了一种新颖的Ni掺杂的Co₃O₄纳米线阵列, 利用X射线衍射仪、扫描电镜和高分辨透射电镜等对所制备的纳米线阵列的物相和形貌进行了表征, 结果表明：所制备的Ni掺杂Co₃O₄纳米线形貌和尺寸均匀、垂直于基底排列, 纳米线的平均直径约为80 nm, 长度约为1.4 μm, 整个纳米线由纳米颗粒堆积而成, 其中Co : Ni的比例约为20 : 1。利用循环伏安和恒流充放电技术在2 mol/L的KOH电解液中对材料的电化学性能进行了测试, 结果显示所制备的纳米线阵列具有优异的电化学电容特性, 当电流密度为10 mA/cm²时, 纳米线阵列的面积比电容为173 mF/cm², 经过1000次充放电后, 比电容值仍能保持最初值的98%, 表现出良好的循环稳定性。优异的性能可归因于材料的比表面积较大以及镍掺杂后材料导电特性的提高。

关键词: 纳米线, 四氧化三钴, 掺杂, 模板法, 超级电容

Abstract:

The novel Ni-doped Co₃O₄ nanowire array was synthesized successfully by electrochemical deposition with the aid of anodic aluminum oxide (AAO) template, followed by oxidation at high temperature. The phase composition and morphology were characterized by X-ray diffraction, scanning electron microscope and high resolution transmission electron microscope. The results show that as-prepared Ni-doped Co₃O₄ nanowire array perpendicular to the substrate displays highly uniform shape and size, with an average diameter of 80 nm and length of 1.4 μm. The nanowire with coarse surface is composed of small crystalline nanoparticles. Average atom ratio of Co to Ni in the nanowire is 20 : 1. Electrochemical characterization was performed using cyclic voltammetry and galvanostatic charge-discharge in a 2 mol/L KOH aqueous solution electrolyte. The test results indicate that the Ni-doped Co₃O₄ nanowire array exhibits a specific capacitance of 173 mF/cm² at current density of 10 mA/cm², and a good cycling stability with 98% capacity retention over 1000 cycles. Excellent electrochemical performance can be attributed to the large specific surface area and the enhanced conductivity achieved by incorporating of Ni.

Key words: nanowires, Co₃O₄, doping, template method, supercapacitor

中图分类号:

O646

王军霞, 赵建伟, 秦丽溶, 赵秉林, 蒋正艳. 镍掺杂四氧化三钴纳米线阵列的制备及其超级电容特性[J]. 无机材料学报, 2018, 33(5): 501-506.

WANG Jun-Xia, ZHAO Jian-Wei, QIN Li-Rong, ZHAO Bing-Ling, JIANG Zheng-Yan. Synthesis and Supercapacitor Property of Ni-doped Co₃O₄ Nanowire Array[J]. Journal of Inorganic Materials, 2018, 33(5): 501-506.

图/表 8

图1 纳米线阵列电极的制备流程图

Fig. 1 Fabrication process of the electrode based on nanowire array

图2 不同倍数下未氧化的纳米线阵列的SEM照片

Fig. 2 SEM images of the nanowire array before oxidation with different magnification

图3 不同倍数下氧化后的纳米线阵列的SEM照片

Fig. 3 SEM images of the nanowire array after oxidation with different magnifications

图4 Ni掺杂Co3O4纳米线的HRTEM照片和电子衍射图片(插图)

Fig. 4 HRTEM image of the Ni-doped Co3O4 nanowire array and corresponding SAED pattern (inset)

图5 Ni掺杂的Co3O4纳米线阵列的XRD图谱(a)和EDS图谱(b)

Fig. 5 XRD pattern (a) and EDS pattern (b) of the Ni-doped Co3O4 nanowire array

图6 不同扫描速率下电极的CV曲线(a)和不同电流密度下的恒流充放电曲线(b)

Fig. 6 (a) CV curves at different scan rate and (b) Galvanostatic charge-discharge curves at different current densities for the electrode

表1 实验制备的材料与文献中类似材料的电容值对比

Table 1 Comparison of the capacitances between product in this study and other similar materials in literature

Electrode materials	Current density	Specific capacitance	Ref.
Ni-doped Co₃O₄ nanowire array	10.0 mA·cm^-2	173.00 mF·cm^-2	This work
ZrO₂-WO₃ nanotubular arrays	10.0 mV·s^-1	40.03 mF·cm^-2	[20]
NiO nanoflake/glass electrodes	10.0 mV·s^-1	74.80 mF·cm^-2	[21]
MnO₂-TiO₂/C nano arrays	0.1 mA·cm^-2	26.10 mF·cm^-2	[22]
MnO₂/TiO₂ nanotube arrays	64.0 mA·cm^-2	40.40 mF·cm^-2	[23]
Aligned carbon nanotubes	800.0 mV·s^-1	2.61 mF·cm^-2	[24]

图7 电极的比电容和充放电效率随循环次数的变化关系

Fig. 7 Change of specific capacitance and columbic efficiency of the electrode with cycle number

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