NiCo2S4@ACF异质电极材料的绿色制备及其超级电容性能研究

doi:10.15541/jim20180158

摘要/Abstract

摘要：

传统的NiCo₂S₄硫化过程需要高温加热, 耗能较大, 并且单纯的硫化物导电性差。本工作通过绿色环保的室温硫化法成功制备出以活性炭纤维(ACF)为核, NiCo₂S₄为壳的复合异质结电极材料(NiCo₂S₄@ACF)。NiCo₂S₄@ACF复合电极材料的层状结构, 有效增大了与电解液的接触面积, 改善了电子的传输路径, 使其具有更优良的电化学性能。当电流密度为1 A/g时, 其比电容值高达1541.6 F/g (678 μF/cm²)。另外, NiCo₂S₄@ACF和ACF分别作正负极组装成的非对称超级电容器(Asymmetric Supercapacitors, ASC)展现了良好的电化学性能: 能量密度高, 当功率密度为800 W/kg时, 能量密度高达49.38 Wh/kg; 循环性能稳定, 循环充放电2000圈后比电容仍能保持90.27%。研究表明, NiCo₂S₄@ACF复合电极材料是一种应用前景广阔的超级电容器电极材料。

关键词: NiCo₂S₄@ACF, 异质结, 绿色制备, 非对称超级电容器

Abstract:

Traditional NiCo₂S₄vulcanization process requires high-temperature and high energy supply, and has disadvantage of low conductivity. In this study, an environmental friendly vulanization method was utilized to prepare unique NiCo₂S₄@ACF core-shell heterstructure materials with activated carbon fiber (ACF) as skeleton at room temperature. NiCo₂S₄@ACF composite electrode material owns layered structures, which can effectively expand contact area with electrolyte, improve electron transmission path, and better create electrochemical performance. Specific capacitance of NiCo₂S₄@ACF composite electrode materials reached 1541.6 F/g (678 μF/cm²) at the current density of 1 A/g. In addition, the asymmetric supercapacitors (ASC) device fabricated with NiCo₂S₄@ACF as positive electrode and ACF as negative electrode exhibited energy density as high as 49.38 Wh/kg at the power density of 800 W/kg, and preeminent cycle stability up to 90.28% after 2000 cycles. All these data demonstrated that NiCo₂S₄@ACF is a promising potential application in the field of high-performance supercapacitors in the future.

Key words: NiCo₂S₄@ACF, heterostructure, green preparation, asymmetric supercapacitors

中图分类号:

TQ069

赵世怀,杨紫博,赵晓明,徐文文,温昕,张庆印. NiCo₂S₄@ACF异质电极材料的绿色制备及其超级电容性能研究[J]. 无机材料学报, 2019, 34(2): 130-136.

ZHAO Shi-Huai, YANG Zi-Bo, ZHAO Xiao-Ming, XU Wen-Wen, WEN Xin, ZHANG Qing-Yin. Green Preparation and Supercapacitive Performance of NiCo₂S₄@ACF Heterogeneous Electrode Materials[J]. Journal of Inorganic Materials, 2019, 34(2): 130-136.

图/表 7

图1 NiCo2S4@ACF复合电极材料的制备流程图

Fig. 1 Preparation process of NiCo2S4@ACF composite electrode material

图2 制备原料及复合电极材料的SEM照片

Fig. 2 SEM images of raw materials and composite electrode material(a-b) Pretreatment ACF; (c) NiCo2S4 microspheres; (d) NiCo2S4@ACF precursor; (e-f) NiCo2S4@ACF

图3 NiCo2S4@ACF复合材料的XRD图谱

Fig. 3 XRD pattern of NiCo2S4@ACF composites

图4 NiCo2S4@ACF复合电极材料(a)不同扫描速率下的CV曲线和(b)不同电流密度下恒流充放电曲线; NiCo2S4@ACF、NiS@ACF和CoS@ACF复合电极材料的(c)倍率曲线和(d)能斯特阻抗曲线, (d)中插图为放大图和等效电路图

Fig. 4 (a) CV characteristics of NiCo2S4@ACF composite electrode materials at different scan rates, (b) GCD curves of NiCo2S4@ACF composite electrodes at various current densities, (c) specific capacitance and (d) Nyquist plots of NiCo2S4@ACF, NiCo2S4@ACF, NiS@ACF and CoS@ACF composite electrodes with inset in (d) showing magnified curves and equivalent circuit

图5 (a) NiCo2S4@ACF和ACF电极在扫描速率为20 mV/s时的CV曲线; 非对称电容器(b)在不同电压窗口、扫描速率为20 mV/s时和(c)在电压窗口为0~1.6 V、不同扫速下的CV曲线, (d)在不同电流密度下的GCD曲线, (e)在不同电流密度时的容量值以及(f)在电流密度为7 A/g下的循环曲线

Fig. 5 CV curves (a) of NiCo2S4@ACF electrode and ACF electrode at scan rate of 20 mV/s; and (b) ASC device in different voltage window at 20 mV/s and (c) ASC device in a voltage window of 0-1.6 V at different scan rates, (d) GCD curves and (e) specific capacitance of ASC device at various current densities, and (f) cycling performance of ASC device at current density of 7 A/g

图6 非对称电容器的拉贡图

Fig. 6 Ragon plots of the ASC device

表1 水系下不同非对称电容器的能量密度和功率密度

Table 1 Energy densities and powder densities of different ASC in an aqueous system

Sample	Energy density/ (Wh∙kg^-1)	Power density/ (W∙kg^-1)	Ref.
NiCo₂S₄@ACF	49.38	800.00	This work
NiCo₂S₄nanoboxes	17.10	2250.00	[26]
NiCo₂S₄ nanosheets	45.50	512.00	[17]
NiCo₂S₄@graphene	43.40	254.30	[27]
NiCo₂S₄/Ppy	34.62	120.19	[15]
NiCo₂S₄ hollow microsphere	24.70	428.00	[16]
NiCo₂S₄@ NiMoO₄/NF	21.40	58.00	[14]
NiCo₂S₄@RGO	21.90	417.10	[28]

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NiCo₂S₄@ACF异质电极材料的绿色制备及其超级电容性能研究

Green Preparation and Supercapacitive Performance of NiCo₂S₄@ACF Heterogeneous Electrode Materials

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