Preparation and electrochemistry properties of NiCo2O4 nanowire/SiC composite fiber
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摘要: 以正硅酸乙酯(TEOS)为硅源，聚乙烯吡咯烷酮(PVP)为助纺剂，采用静电纺丝结合碳热还原制备出结晶度较高的β-SiC纤维，其比表面积为92.6 m2/g，表现出双电层电容储能特征，比电容为155.7 F/g。然后，利用水热法在SiC纤维表面生长出大量直径约为15 nm的NiCo2O4纳米线，得到NiCo2O4纳米线/SiC复合纤维。测试表明，NiCo2O4纳米线/SiC复合纤维中镍和钴元素分别以Ni2+/Ni3+和Co2+/Co3+价态形式存在，由于NiCo2O4纳米线与SiC纤维的协同作用，NiCo2O4纳米线/SiC复合纤维比电容显著提高，并表现出双电层和赝电容并存的特征，比电容可达300.3 F/g，当功率密度为58.1 W/kg时，NiCo2O4纳米线/SiC复合纤维能量密度为60.1 W·h/kg。Abstract: The β-SiC fibers with high degree of crystallinity were obtained by electrospinning combined with carbothermal reduction method using tetraethyl orthosilicate (TEOS) as silicon source and polyvinylpyrrolidone (PVP) as spinning agent. The specific surface area of β-SiC fibers is 92.6 m2/g, which show the electric double layer capacitance. The specific capacitance of β-SiC fibers is up to 155.7 F/g. A large number of NiCo2O4 nanowires with a diameter of about 15 nm were grown on the surface of SiC fibers via hydrothermal method in order to obtain NiCo2O4 nanowires/SiC composite fibers. The results show that nickel and cobalt elements are present in the form of Ni2+/Ni3+ and Co2+/Co3+, respectively. The specific capacitance is significantly improved by the synergistic effect of NiCo2O4 nanowires and SiC fiber, and the NiCo2O4 nanowires/SiC composite fibers show both electric double layer and pseudo capacitance. The specific capacitance of NiCo2O4 nanowires/SiC composite fibers is up to 300.3 F/g. When the power density is 58.1 W/kg, the energy density of NiCo2O4 nanowires/SiC composite fibers is 60.1 W·h/kg.
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Key words:
- NiCo2O4 nanowire /
- SiC /
- composite fibers /
- carbothermal reduction /
- hydrothermal method /
- electrochemistry
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图 1 SiC纤维及NiCo2O4纳米线/SiC复合纤维XRD图谱(a)及NiCo2O4纳米线/SiC复合纤维的多峰高斯拟合图谱(b)
Figure 1. XRD patterns of SiC fiber and NiCo2O4 nanowire/SiC composite fiber(a) and muti-peak Guassian fitting spectrum of NiCo2O4 nanowire/SiC composite fiber(b)
图 2 NiCo2O4纳米线/SiC复合纤维的XPS图谱
Figure 2. XPS spectra of NiCo2O4 nanowire/SiC composite fiber
图 3 SiC纤维(a)及NiCo2O4纳米线/SiC复合纤维(b) 的SEM图像和EDS图谱
Figure 3. SEM images and EDS spectra of SiC fiber(a) and NiCo2O4 nanowire/SiC composite fiber(b)
图 4 SiC纤维及NiCo2O4纳米线/SiC复合纤维的N2吸附-脱附曲线(a)及孔径分布曲线(b)
Figure 4. N2 adsorption-desorption curves(a) and pore size distribution curves of SiC fiber and NiCo2O4 nanowire/SiC composite fibers(b)
图 5 SiC纤维(a)和NiCo2O4纳米线/SiC(b)复合纤维电极的循环伏安(CV)曲线
Figure 5. Cyclic voltammetry(CV) curves of SiC fiber(a) and NiCo2O4 nanowire/SiC composite fiber(b) electrode
图 6 SiC纤维(a)和NiCo2O4纳米线/SiC复合纤维(b)电极1.2 V窗口电压在2 mV/s扫描速率下电容电荷存储贡献及NiCo2O4/SiC复合纤维电极0.6 V窗口电压在2 mV/s扫描速率下电容电荷存储贡献(c)
Figure 6. Capacitance charge storage contributions of SiC fiber (a) and NiCo2O4 nanowire/SiC composite fiber (b) electrodes at 1.2 V window voltage and 2 mV/s scan rate and capacitance charge storage contribution of NiCo2O4 nanowire/SiC composite fiber electrodes at 0.6 V window voltage and 2 mV/s scan rate (c)
图 7 SiC电极(a)和NiCo2O4/SiC电极(b)充放电曲线、SiC和NiCo2O4/SiC电极在50 mA/g电流密度下充放电曲线(c)和充放电与电流密度关系曲线(d)
Figure 7. Charge-discharge curves of SiC electrode (a) and NiCo2O4/SiC electrode (b), charge-discharge curves at current density of 50 mA/g (c) and current density dependence of specific capacitance (d) of SiC and NiCo2O4/SiC electrodes
图 8 SiC和NiCo2O4/SiC电极的阻抗图谱
Figure 8. Electrochemical impedance spectroscopy of SiC and NiCo2O4/SiC electrodes
图 9 SiC(a)及NiCo2O4/SiC(b)电极的能量密度曲线
Figure 9. Energy density curves of SiC(a) and NiCo2O4/SiC(b) electrodes
图 10 SiC及NiCo2O4/SiC电极的循环寿命曲线(a)、SiC(b)和NiCo2O4/SiC(c)电极在100 mA/g电流密度下循环前后充放电曲线、SiC和NiCo2O4/SiC电极循环后阻抗图谱(d)
Figure 10. Cycling performance of SiC and NiCo2O4/SiC electrodes (a), Charge-discharge curves of SiC (b) and NiCo2O4/SiC (c) electrodes before and after cycling at 100 mA/g current density, electrochemical impedance spectroscopy of SiC and NiCo2O4/SiC electrodes after cycling (d)
表 1 SiC纤维及NiCo2O4纳米线/SiC复合纤维的孔结构特征参数
Table 1. Pore structure characteristic parameters of SiC fiber and NiCo2O4 nanowire/SiC composite fibers
Fiber Specific surface area/(m2·g–1) Average pore diameter/nm Pore volume/(cm3·g–1) SiC 92.6 4.6 0.1 NiCo2O4/SiC 233.2 7.0 0.4 
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