Preparation of poly 3,4-ethylenedioxythiophene/nanoporous gold composite electrode and its application in supercapacitors
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摘要: 通过一步法将单体3，4-乙烯二氧噻吩(EDOT)电化学聚合到具有高导电率和大比表面积的纳米多孔金(NPG)上，成功制备了具有完美核壳结构的聚3，4-乙烯二氧噻吩/纳米多孔金（PEDOT/NPG）复合电极材料。通过SEM、TEM、Raman和X射线能谱仪对复合电极材料的形貌、微观结构、振动特性和元素组成进行了分析和表征。使用电化学工作站对其电化学性能进行了系统的研究。在三电极体系中，PEDOT/NPG复合电极材料在3 A/g的低电流密度下，质量比电容可以达到555 F/g，其能量密度和功率密度分别为177.58 W·h/kg和1.73 kW/kg。同时该电极材料经过2 000次循环伏安测试后仍然可以保持最大电容的91.5%，电化学性能优异。
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关键词:
- 纳米多孔金 /
- 3，4-乙烯二氧噻吩 /
- 比电容 /
- 循环稳定性 /
- 电化学性能
Abstract: The poly 3,4-ethylenedioxythiophene/nanoporous gold (PEDOT/NPG) composite electrode materials were prepared by electrochemically polymerizing monomer 3,4-ethylenedioxythiophene (EDOT) onto NPG with high conductivity and large specific surface area by one-step method. The scanning electron microscope (SEM), transmission electron microscope (TEM), Raman spectroscopy (Raman) and X-ray energy spectrometer were used to analyze the morphological structure and elemental composition of the composite electrode material. The electrochemical performance of the electrochemical workstation was studied systematically. The PEDOT/NPG electrode material has a mass specific capacitance of 555 F/g at low current density of 3 A/g, and its energy density and power density are 177.58 W·h/kg and 1.73 kW/kg, respectively. The electrode material can still maintain 91.5% of the maximum capacitance after 2 000 cyclic voltammetry test and has excellent electrochemical performance. -
图 1 100 mV/s的扫描速率下PEDOT/NPG-1 (a)和PEDOT/NPG-20 (b)的电镀循环伏安曲线及PEDOT的沉积质量与电镀圈数的关系(c)
Figure 1. PEDOT/NPG-1 (a) and PEDOT/NPG-20 (b) plating cycle voltammetry curves and relationship between plating cycles and deposit quality of PEDOT (c) at a scanning rate of 100 mV/s
图 2 NPG的SEM图像((a)、(b))和不同电镀圈数的PEDOT/NPG复合电极材料的SEM图像：(c) PEDOT/NPG-1；(d) PEDOT/NPG-3；(e) PEDOT/NPG-5；(f) PEDOT/NPG-10；(g) PEDOT/NPG-15； (h) PEDOT/NPG-20
Figure 2. SEM images of the NPG morphology at different magnifications ((a), (b)) and SEM images of PEDOT/NPG composite electrode materials with different plating cycles: (c)PEDOT/NPG-1; (d) PEDOT/NPG-3; (e) PEDOT/NPG-5; (f) PEDOT/NPG-10; (g) PEDOT/NPG-15;(h) PEDOT/NPG-20
图 3 PEDOT/NPG-1复合电极材料的EDS能谱图
Figure 3. EDS maps of PEDOT/NPG-1 composite electrode material
图 4 PEDOT/NPG-1复合电极材料微观形貌的低倍 (a)和高倍(b) TEM图像
Figure 4. TEM images of PEDOT/NPG-1 composite electrode material morphology at low magnification (a) and high magnification (b)
图 5 不同电镀圈数的PEDOT/NPG复合电极材料在100 mV/s的扫描速率下的伏安曲线(a)和PEDOT/NPG-1在10 mV/s至100 mV/s的扫描速率下的伏安曲线(b)以及PEDOT/NPG-1复合电极材料的质量比电容与扫描速率的关系(c)
Figure 5. Voltammetry curves of PEDOT/NPG composite electrode materials with different plating cycles at a scanning rate of 100 mV/s (a) and PEDOT/NPG-1 at a scanning rate of 10 mV/s to 100 mV/s as well as relationship between mass specific capacitance and scanning rate of PEDO/NPG-1 (c)
图 6 PEDOT/NPG复合电极材料在1 mol/L HClO4电解质中的超电性能((a) PEDOT/NPG-1在不同电流密度下的恒电流充电/放电曲线；(b) PEDOT/NPG在不同电流密度下的比电容；(c) PEDOT/NPG-1在不同放电电流密度下的内阻；(d) PEDOT/NPG-1的Ragone图及其他文献[27-33])
Figure 6. Supercapacitance performance of PEDOT/NPG composite electrode material in 1 mol/L HClO4 electrolyte ((a) Galvanostatic charge/discharge curves of PEDOT/NPG-1 at different current densities; (b) Specific capacitance of PEDOT/NPG obtained at different current densities; (c) Internal resistance of PEDOT/NPG-1 at different discharge current densities; (d) Ragone plots of the PEDOT/NPG-l and others from the literatures[27-33])
图 7 扫描速率100 mV/s时PEDOT/NPG-1电极在1 mol/L HClO4溶液中经过2 000次循环后的电容保持率
Figure 7. Capacitance retention of the PEDOT/NPG-1 electrode after 2 000 cycles in 1 mol/L HClO4 solution at a scanning rate of 100 mV/s
图 8 PEDOT/NPG-1复合电极在电化学循环之前和2 000次循环之后的拉曼光谱
Figure 8. Raman spectra of PEDOT/NPG-1 composite electrode before electrochemical cycle and after 2 000 cycles
表 1 不同电镀圈数的聚3，4-乙烯二氧噻吩/纳米多孔金(PEDOT/NPG)复合电极对应的书写方式
Table 1. Corresponding writing methods for poly 3,4-ethylenedioxythiophene/nanoporous gold (PEDOT/NPG) composite electrodes with different plating cycles
Plating cycle Writing method 1 PEDOT/NPG-1 3 PEDOT/NPG-3 5 PEDOT/NPG-5 10 PEDOT/NPG-10 15 PEDOT/NPG-15 20 PEDOT/NPG-20 
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