原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究

doi:10.15541/jim20160333

无机材料学报 ›› 2017, Vol. 32 ›› Issue (4): 372-378.DOI: 10.15541/jim20160333

原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究

祁星耀, 周清锋, 崔芒伟, 杨永珍, 蒋海伟, 梁伟, 康利涛

(太原理工大学材料科学与工程学院, 太原 030024)

收稿日期:2016-05-24 修回日期:2016-07-10 出版日期:2017-04-20 网络出版日期:2017-03-24
作者简介:祁星耀(1979–), 男, 硕士研究生. E-mail: kangltxy@163.com
基金资助:
国家自然科学基金(51502194);山西省科学技术基金(2014021019-4);山西省科技关键创新研究团队(2012041011);高性能陶瓷和超微观结构的国家重点实验室开放项目(SKL201511SIC)

Capacitive Performance of Zn-Ni Hydroxide Nano-sheet Arrays on Nickel Foams via a Mild Chemical-bath Deposition Process

QI Xing-Yao, ZHOU Qing-Feng, CUI Mang-Wei, YANG Yong-Zhen, JIANG Hai-Wei, LIANG Wei, KANG Li-Tao

(College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China)

Received:2016-05-24 Revised:2016-07-10 Published:2017-04-20 Online:2017-03-24
About author:QI Xing-Yao. E-mail: kangltxy@163.com
Supported by:
National Natural Science Foundation of China (51502194);Science and Technology Foundation of Shangxi Province (2014021019-4);Science and Technology Innovation Team of Shanxi Province (2012041011);Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure (SKL201511SIC)

摘要/Abstract

摘要：

通过简单、低成本的化学浴沉积法在泡沫镍上原位生成了Zn-Ni 氢氧化物(Zn-Ni double hydroxides)纳米片。SEM观察结果表明, Zn-Ni 氢氧化物纳米片均匀附着在泡沫镍表面, 形成均一的多孔纳米片阵列层。此外, 还有大量的Zn-Ni 氢氧化物纳米片聚集成多孔团聚体, 分布于泡沫镍骨架的空隙处, 从而获得较高的活性物质负载量(4.27 mg/cm²)。CV、CP和电化学阻抗测试表明, Zn-Ni 氢氧化物纳米片在2 mol/L KOH电解液中充放电电流密度1 A/g时, 比电容为746.2 F/g(面积电容为3.18 F/cm²); 3000次充放电循环后, 仍保持70.9%的初始比电容。

关键词: 氢氧化锌, 氢氧化镍, 复合氢氧化物, 泡沫镍, 超级电容器

Abstract:

Zn-Ni hydroxide nano-sheets were successfully deposited on nickel foams through a mild, cost-effective chemical bath method. SEM observation shows that these interconnected nano-sheets form a uniform marray layer and completely cover the surface of nickel foam. At the same time, additional homogeneously-precipitated hydroxide nano-sheets locate in the skeleton voids of nickel foams as aggregated porous clumps, resulting in a relatively high mass-loading of 4.27 mg/cm². Afterwards, the electrochemical capacitive behaviors of this binder-free electrode were investigated by cyclic voltammetry, galvanostatic charge/discharge tests and electrochemical impedance spectroscopy. It is found that the Zn-Ni hydroxide electrode exhibits a specific capacitance of 746.2 F/g (areal capacitance of 3.18 F/cm²) at a current density of 1 A/g in 2 mol/L KOH electrolyte. Meanwhile, the Zn-Ni hydroxide electrode also shows a decent long-life cycling stability, retaining 70.9% of the initial capacitance after 3000 charge-discharge cycles.

Key words: znic hydroxide, nickel hydroxide, double hydroxides, Ni foam, supercapacitor

中图分类号:

TQ174

祁星耀, 周清锋, 崔芒伟, 杨永珍, 蒋海伟, 梁伟, 康利涛. 原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究[J]. 无机材料学报, 2017, 32(4): 372-378.

QI Xing-Yao, ZHOU Qing-Feng, CUI Mang-Wei, YANG Yong-Zhen, JIANG Hai-Wei, LIANG Wei, KANG Li-Tao. Capacitive Performance of Zn-Ni Hydroxide Nano-sheet Arrays on Nickel Foams via a Mild Chemical-bath Deposition Process[J]. Journal of Inorganic Materials, 2017, 32(4): 372-378.

图/表 10

图1 酸化泡沫镍和Ni@Zn-Ni氢氧化物的XRD图谱

Fig. 1 XRD patterns of acidified Ni foams and Ni@Zn-Ni DHs

图2 泡沫镍的不同放大倍率SEM照片

Fig. 2 Different magnificent SEM images of the Ni foam substrate

图3 Ni@Zn-Ni氢氧化物(a), 在泡沫镍骨架表面的Zn-Ni 氢氧化物纳米片(b~d)和在泡沫镍中空位置的Zn-Ni 氢氧化物纳米片(e~f)的SEM照片

Fig. 3 SEM images of the Ni@Zn-Ni electrode (a), Zn-Ni on the surface of the nickel foam skeletons(b-d), Zn-Ni in the void space of the nickel (foam e-f)

图4 Ni@Zn-Ni DHs样品的氮吸附-脱附等温曲线和孔径分布曲线(插图)

Fig. 4 Nitrogen adsorption/desorption isotherms and pore size distribution (inset) of Ni@Zn-Ni DHs

图5 Ni@Zn-Ni DHs电极在不同扫描速率下的CV曲线(a)和在不同电流密度下的恒电流充放电曲线(b), 酸化泡沫镍在1 A/g下的恒电流充放电曲线(c)

Fig. 5 (a) Cyclic voltammetric and (b) galvanostatic charge-discharge curves of Ni@Zn-Ni DHs at various scan rates and current densities, (c) GCD curve of acidified Ni foam at current density of 1 A/g

图6 Ni@Zn-Ni DHs电极在不同放电电流密度下的面积电容(a)和比电容(b)

Fig. 6 (a) Areal capacitance and (b) specific capacitance of Ni@Zn-Ni DHs electrodes at different discharge current densities

图7 Zn-Ni 氢氧化物样品在5 A/g下3000次循环测试中比电容变化和每1000次循环过程中的充放电曲线

Fig. 7 Stability test in terms of specific capacitance and galvanostatic charge-discharge curves after every 1000 cycle at a current density of 5 A/g (insert) for Ni@Zn-Ni DHs

图8 3000次充放电循环前后的Ni@Zn-Ni DHs样品在2 mol/L KOH电解液中的阻抗谱图

Fig. 8 Nyquist plots of Ni@Zn-Ni DHs before and after 3000 charge-discharge cycles in 2 mol/L KOH aqueous electrolyte.

图9 3000次充放电循环后Ni@Zn-Ni氢氧化物样品的XRD图谱

Fig. 9 XRD patterns of Ni@Zn-Ni sample after 3000 charge- discharge cycles

图10 Ni@Zn-Ni DHs电极在3000次充放电循环后的SEM照片

Fig. 10 SEM images of the Ni@Zn-Ni DHs electrode after 3000 charge-discharge cyclesSEM images of Zn-Ni nano-sheets grown on the surface of the Ni foam skeletons (a, b); Zn-Ni nano-sheets accommodated in the voids between skeletons of the Ni foam (c, d)

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原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究

Capacitive Performance of Zn-Ni Hydroxide Nano-sheet Arrays on Nickel Foams via a Mild Chemical-bath Deposition Process

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