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 CSTR: 32189.14.10.15541/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)

参考文献 40

[1]	SIMON P, GOGOTSI Y.Materials for electrochemical capacitors. Nature Materials, 2008, 7(11): 845-854.
[2]	WANG G, ZHANG L, ZHANG J.A review of electrode materials for electrochemical supercapacitors. Chemical Society Reviews, 2012, 41(2): 797-828.
[3]	CHEN X, CHEN C, ZHANG Z, et al.Nitrogen-doped porous carbon for supercapacitor with long-term electrochemical stability. Journal of Power Sources, 2013, 230: 50-58.
[4]	KANG J, HIRATA A, KANG L, et al.Enhanced supercapacitor performance of MnO2 by atomic doping. AngewandteChemie, 2013, 125(6): 1708-1711.
[5]	SU Z, YANG C, XU C, et al.Co-electro-deposition of the MnO2- PEDOT: PSS nanostructured composite for high areal mass, flexible asymmetric supercapacitor devices. Journal of MaterialsChemistry A, 2013, 1(40): 12432-12440.
[6]	HUANG L, CHEN D, DING Y, et al.Nickel-cobalt hydroxide nanosheets coated on NiCo2O4 nanowires grown on carbon fiber paper for high-performance pseudocapacitors. Nano Letters, 2013, 13(7): 3135-3139.
[7]	GAMBY J, TABERNA P L, SIMON P, et al.Studies and characterisations of various activated carbons used for carbon/carbon supercapacitors. Journal of Power Sources, 2001, 101(1): 109-116.
[8]	FUERTES A B, LOTA G, CENTENO T A, et al.Templated mesoporous carbons for supercapacitor application. ElectrochimicaActa, 2005, 50(14): 2799-2805.
[9]	CHMIOLA J, YUSHIN G, DASH R, et al.Effect of pore size and surface area of carbide derived carbons on specific capacitance. Journal of Power Sources, 2006, 158(1): 765-772.
[10]	FUTABA D, HATA K, YAMADA T, et al.Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nature Materials, 2006, 5(12): 987-994.
[11]	TAO K, LI P, KANG L, et al.Facile and low-cost combustion-synthesized amorphous mesoporous NiO/carbon as high mass-loading pseudocapacitor materials. Journal of Power Sources, 2015, 293: 23-32.
[12]	LI W, CHEN J, ZHAO J, et al.Application of ultrasonic irradiation in preparing conducting polymer as active materials for supercapacitor. Materials Letters, 2005, 59(7): 800-803.
[13]	HU C, CHANG K, LIN M, et al.Design and tailoring of the nanotubular arrayed architecture of hydrous RuO2 for next generation supercapacitors. Nano Letters, 2006, 6(12): 2690-2695.
[14]	WANG G, HUANG J, CHEN S, et al.Preparation and supercapacitance of CuO nanosheet arrays grown on nickel foam. Journal of Power Sources, 2011, 196(13): 5756-5760.
[15]	LI Y, CHANG S, LIU X, et al.Nanostructured CuO directly grown on copper foam and their supercapacitance performance. ElectrochimicaActa, 2012, 85: 393-398.
[16]	HUANG J, WU H, CAO D, et al.Influence of Ag doped CuOnanosheet arrays on electrochemical behaviors for supercapacitors. Electrochimica Acta, 2012, 75: 208-212.
[17]	XIE K, LI J, LAI Y, et al.Polyaniline nanowire array encapsulated in titania nanotubes as a superior electrode for supercapacitors. Nanoscale, 2011, 3(5): 2202-2207.
[18]	KULAL P, DUBAL D, LOKHANDE C, et al.Chemical synthesis of Fe2O3 thin films for supercapacitor application. Journal of Alloys and Compounds, 2011, 509(5): 2567-2571.
[19]	WU M, LEE R, JOW J, et al.Nanostructured iron oxide films prepared by electrochemical method for electrochemical capacitors. Electrochemical and Solid-State Letters, 2009, 12(1): A1-A4.
[20]	DUBAL D, FULARI V, LOKHANDE C.Effect of morphology on supercapacitive properties of chemically grown β-Ni(OH)2 thin films. Microporous and Mesoporous Materials, 2012, 151: 511-516.
[21]	HSU H, CHANG K, SALUNKHE R, et al.Synthesis and characterization of mesoporous Ni-Co oxy-hydroxides for pseudocapacitor application. Electrochimica Acta, 2013, 94: 104-112.
[22]	ZHOU Q, CUI M, TAO K, et al.High areal capacitance three-dimensional Ni@Ni(OH)2 foams via in situ oxidizing Ni foams in mild aqueous solution. Applied Surface Science, 2016, 365: 125-130.
[23]	ZHOU C, ZHANG Y, LI Y, et al.Construction of high-capacitance 3D CoO@polypyrrole nanowire array electrode for aqueous asymmetric supercapacitor. Nano letters, 2013, 13(5): 2078-2085.
[24]	ZHANG G, WU H, HOSTER H, et al.Single-crystalline NiCo2O4nanoneedle arrays grown on conductive substrates as binder-free electrodes for high-performance supercapacitors. Energy & Environmental Science, 2012, 5(11): 9453-9456.
[25]	JIANG J, LI Y, LIU J, et al.Building one-dimensional oxide nanostructure arrays on conductive metal substrates for lithium-ion battery anodes. Nanoscale, 2011, 3(1): 45-58.
[26]	JIANG J, LI Y, LIU J, et al.Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage. Advanced Materials, 2012, 24(38): 5166-5180.
[27]	LIU Y, LIU Z, LU N, et al.Facile synthesis of polypyrrole coated copper nanowires: a new concept to engineered core-shell structures. Chemical Communications, 2012, 48(20): 2621-2623.
[28]	ZHONG J, WANG A, LI G, et al.Co3O4/Ni(OH)2 composite mesoporousnanosheet networks as a promising electrode for supercapacitor applications. Journal of Materials Chemistry, 2012, 22(12): 5656-5665.
[29]	MING B, LI J, KANG F, et al.Microwave-hydrothermal synthesis of birnessite-type MnO2nanospheres as supercapacitor electrode materials. Journal of Power Sources, 2012, 198: 428-431.
[30]	TOUPIN M, BROUSSE T, BÉLANGER D. Influence of microstucture on the charge storage properties of chemically synthesized manganese dioxide. Chemistry of Materials, 2002, 14(9): 3946-3952.
[31]	YU M, ZENG Y, ZHANG C, et al.Titanium dioxide@polypyrrole core-shell nanowires for all solid-state flexible supercapacitors. Nanoscale, 2013, 5(22): 10806-10810.
[32]	ZHENG H, ZHAI T, YU M, et al.TiO2@C core-shell nanowires for high-performance and flexible solid-state supercapacitors. Journal of Materials Chemistry C, 2013, 1(2): 225-229.
[33]	LI J, YANG M, WEI J, et al.Preparation and electrochemical performances of doughnut-like Ni(OH)2-Co(OH)2 composites as pseudocapacitor materials. Nanoscale, 2012, 4(15): 4498-4503.
[34]	LIU M, MIAO Y, ZHANG C, et al.Hierarchical composites of polyaniline-graphene nanoribbons-carbon nanotubes as electrode materials in all-solid-state supercapacitors. Nanoscale, 2013, 5(16): 7312-7320.
[35]	WU X, XING W, ZHANG L, et al.Nickel nanoparticles prepared by hydrazine hydrate reduction and their application in supercapacitor. Powder Technology, 2012, 224: 162-167.
[36]	FAN Z, YAN J, WEI T, et al.Asymmetric supercapacitors based on graphene/MnO2 and activated carbon nanofiber electrodes with high power and energy density. Advanced Functional Materials, 2011, 21(12): 2366-2375.
[37]	GUAN C, LIU J, CHENG C, et al.Hybrid structure of cobalt monoxide nanowire@nickelhydroxidenitratenanoflake aligned on nickel foam for high-rate supercapacitor. Energy & Environmental Science, 2011, 4(11): 4496-4499.
[38]	ZHU Y, JI X, PAN C, et al.A carbon quantum dot decorated RuO2 network: outstanding supercapacitances under ultrafast charge and discharge. Energy & Environmental Science, 2013, 6(12): 3665-3675.
[39]	KONG L, LANG J, LIU M, et al.Facile approach to prepare loose-packed cobalt hydroxide nano-flakes materials for electrochemical capacitors. Journal of Power Sources, 2009, 194(2): 1194-1201.
[40]	DENG J, KANG L, BAI G, et al.Solution combustion synthesis of cobalt oxides (Co3O4 and Co3O4/CoO) nanoparticles as supercapacitor electrode materials. ElectrochimicaActa, 2014, 132: 127-135.

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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