Effects of palladium/nickel doping on the electrochemical properties of carbon nanotubes electrode materials for supercapacitors
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摘要: 面向将具有高长径比、高比表面积和高电导率的碳纳米管用于超级电容器领域,并改善其与金属电极之间存在的接触电阻。应用无电沉积法对碳纳米管进行过渡金属钯的掺杂,以金属有机骨架为媒介对碳纳米管进行过渡金属镍的掺杂。分别将掺杂钯、掺杂镍的碳纳米管与聚乙烯醇复合,修饰玻碳电极和碳布,并将修饰的碳布作为电极材料组装成超级电容器。分别对所修饰玻碳电极与超级电容器进行循环伏安和交流阻抗测试。掺钯与掺镍碳纳米管修饰玻碳电极的比电容分别为9.89 F/g和5.99 F/g,掺钯与掺镍碳纳米管修饰碳布组装超级电容器的比电容分别为175.77 mF/g和61.92 mF/g。可见掺钯降低碳纳米管修饰玻碳电极和超级电容器内阻、提高电化学性能的效果优于掺镍,这为掺杂碳纳米管在超级电容器等储能领域的应用起到借鉴作用。Abstract: This work aims to use carbon nanotubes with high aspect ratio, high specific surface area and high conductivity in the field of supercapacitors and improve the contact resistance between them and metal electrodes. Carbon nanotubes were doped with transition metal palladium by electroless deposition method and transition metal nickel by metal organic frameworks. Palladium and nickel doped carbon nanotubes/polyvinyl alcohol composites were used to modify glassy carbon electrodes and carbon cloth, respectively, and the modified carbon cloth was used as electrode material to assemble supercapacitors. Then the modified glassy carbon electrodes and supercapacitors were tested by cyclic voltammetry and alternating-current impedance. The results show that the values of specific capacitance of Pd-doped and Ni-doped carbon nanotubes modified glassy carbon electrodes are 9.89 F/g and 5.99 F/g, respectively. And the values of specific capacitance of supercapacitors assembled using carbon cloth modified with Pd-doped and Ni-doped carbon nanotubes are 175.77 mF/g and 61.92 mF/g, respectively. It can be seen that the effect of Pd doping on reducing the internal resistance and improving the electrochemical perfor-mance of carbon nanotubes modified glassy carbon electrode and supercapacitor is better than that of Ni doping, which serves as a reference for the application of doped carbon nanotubes in supercapacitors and other energy storage devices.
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Key words:
- doping /
- carbon nanotubes /
- transition metal /
- glassy carbon electrodes /
- supercapacitors /
- electrochemical test /
- palladium /
- nickel
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图 6 循环伏安(CV)对比图:(a) 不同扫描速率下酸处理的CNTs-PVA/GCE;(b) 不同含量酸处理的CNTs-PVA/GCE;(c) 不同处理阶段的CNTs-PVA/GCE
Figure 6. Comparison of cyclic voltammetry (CV): (a) Acid-treated CNTs-PVA/GCE under different scanning rates; (b) CNTs-PVA/GCE with different content of acid-treated; (c) CNTs-PVA/GCE at different treatment stages
表 1 不同处理阶段CNTs-PVA/GCE超级电容器的比电容
Table 1. Specific capacitance of CNTs-PVA/GCE supercapacitors at different treatment stages
Working electrode Area of CV curve/(A·V−1) Specific capacitance/(F·g−1) PVA/GCE 2.0×10−5 0.56 GCE 2.4×10−5 0.67 CNTs-PVA/GCE 1.5×10−4 4.26 Ni-CNTs-PVA/GCE 2.1×10−4 5.99 Pd-CNTs-PVA/GCE 3.2×10−4 9.89 表 2 组装CNTs-PVA/CC超级电容器的比电容
Table 2. Specific capacitance of assembled CNTs-PVA/CC supercapacitors
Electrodes for assembling supercapacitors Area of CV curve/(A·V−1) Specific capacitance/(mF·g−1) CC 3.51×10−5 13.50 CNTs-PVA/CC 2.55×10−4 98.08 Ni-CNTs-PVA/CC 1.61×10−4 61.92 Pd-CNTs-PVA/CC 4.57×10−4 175.77 -
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