聚（3，4-乙撑二氧噻吩）复合材料的制备及其电化学性质的研究
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摘要
超级电容器因具有比功率高、比电容高、循环性能好、成本低、“绿色”环保等众多优点而广泛应用于航空航天、交通运输、电子计算机等领域。目前,导电聚合物以其快速高效充放电、温度宽、环境友好、成本低的特性,成为一种很有前途的超级电容器电极材料。其中聚3, 4-乙撑二氧噻吩(简称为PEDOT)尤其备受关注,但是PEDOT因其理论比容量低等缺点而被限制发展。因此本文主要研究PEDOT的复合材料来克服其不足,具体内容如下:
(1)以碳纳米管(CNTs)为基体,制备不同CNTs质量百分比的PEDOT/CNTs纳米复合物,并探讨其电化学性能。考虑到CNTs分散性和相容性不良,因此对CNTs进行聚苯乙烯磺酸盐(PSS)的修饰,并水热法成功制备出核-壳型PEDOT/PSS-CNTs复合材料,其比电容达198.2 F·g-1,循环2000圈以后比电容衰减26.9%。同时,研究以该复合材料为电极组装成对称电容器来研究其电化学电容行为。
(2)由于金属氧化物的能量密度一般都比较高,因此本文采用微波法和界面聚合法分别制备PEDOT/RuO2·xH2O和PEDOT/MnO2纳米复合物。并证明PEDOT/RuO2·xH2O复合物在150 oC热处理后有良好的电化学可逆性和电容特性,而且在0.15 A g-1电流密度下比电容达到153.3 F g-1,当升高到0.8 A g-1时,比容量衰减量大约为17%。另外,制备的PEDOT/MnO2的纳米复合物证明是一种具有多孔孔道结构的无定型材料,当在-0.2~0.8 V (vs. SCE)范围内,电流密度为0.5 A·g-1时,单电极比容量达到196.3 F·g-1,500次循环后仍保持有90%的比容量。
(3)本文制备了PEDOT/PANI纳米复合物,并和活性碳组成混合电容器。该混合电容器在1.0 V的电位窗口下,以0.5 M H2SO4为电解质,当电流密度为1/2 A g-1时,比容量达30.7 F g-1,功率密度达到324.9 W kg-1。为了进一步提高该混合电容器的性能,我们考虑将含有+1价态的无机金属盐与H2SO4溶液组成混合电解液体系,电化学测试表明在0.5 M H2SO4 + 0.2 M K2SO4混合体系下,混合电容器的比电容,能量密度和功率密度具有明显的提高。
Supercapacitors has attracted wide attention and applied in many fields including aviation and aerospace, transportation, communication and computer because of high energy density, high specific capacitance, long cycle life, low cost and green environmental conservation. At present, conducting polymers (COPs) can be considered as a kind of promising materials owning to quick and efficient charge-discharge, temperature relief, environmental amicability and low cost. Among the COPs, poly (3, 4-ethylenedioxythiophene) (PEDOT) has drawn a wide interest. However, PEDOT also has some inevitable shortcomings such as the relatively small‘‘theoretic SC’’. Therefore, we focus on the PEDOT-based composite with good electrochemical capacitance behavior. The details are as follows:
(1) PEDOT/CNTs nanocomposite was synthesized by using the CNTs as the template, and the effect of various mass ratios of CNTs on the electrochemical capacitance of the composite was investigated. Moreover, due to the poor solubility and compatibility of CNTs, a non-covalent method was used to functionalize CNTs with poly (sodium 4-styrene sulfonate) (PSS), then the core-shell PEDOT/PSS-CNTs nanocomposite was successfully realized via hydrothermal polymerization. The nanocomposite had a specific capacitance of 198.2 F g-1 and a capacitance degradation of 26.9% after 2000 cycles. And the electrochemical measurements of the symmetric supercapacitor based on the PEDOT/PSS-CNTs nanocomposite were further studied.
(2) Due to the high energy density of the metal oxide, PEDOT/RuO2·xH2O and PEDOT/MnO2 nanocomposite could be synthesized by microwave-assisted and interfacial polymerization, respectively. As for the PEDOT/RuO2·xH2O nanocomposite, the composite system annealing at 150 oC might possess the most favorable electrochenmical properties with the specific capacitance of 153.3 F g-1 at the current density of 0.15 A g-1. While the current density was increased to 0.8 A g-1, the loss was up to about 17%. In other hand, the as-prepared PEDOT/MnO2 nanocomposite was proved to be amorphous and porous. The specific capacitance of nanocomposite was 196.3 F g-1 at the current density of 0.5 A g-1 with the potential range of -0.2~0.8 V (vs. SCE), and the capacity retention of the nanocomposite was about 90% after 500 cycles.
(3) Asymmetric supercapaciotors based on as-prepared PEDOT/PANI nanocomposite as a positive electrodes and activated carbon as a negative electrode were successfully fabricated. The results showed that the asymmetric supercapacitor could deliver the specific capacitance of 30.7 F g-1 and a power density of 324.9 W kg-1 in a potential window range between 0 and 1 V in 0.5 M H2SO4 aqueous electrolyte. In addition, the hybrid electrolyte including the inorganic compound including +1 metal ions and H2SO4 solution was investigated to further improve the electrochemical performance of the asymmetric supercapacitor. The electrochemical tests indicated that the specific capacitance, energy density and power density of the asymmetric supercapacitor had the most enhancements in the 0.5 M H2SO4 + 0.2 M K2SO4 hybrid electrolyte.
(1)以碳纳米管(CNTs)为基体,制备不同CNTs质量百分比的PEDOT/CNTs纳米复合物,并探讨其电化学性能。考虑到CNTs分散性和相容性不良,因此对CNTs进行聚苯乙烯磺酸盐(PSS)的修饰,并水热法成功制备出核-壳型PEDOT/PSS-CNTs复合材料,其比电容达198.2 F·g-1,循环2000圈以后比电容衰减26.9%。同时,研究以该复合材料为电极组装成对称电容器来研究其电化学电容行为。
(2)由于金属氧化物的能量密度一般都比较高,因此本文采用微波法和界面聚合法分别制备PEDOT/RuO2·xH2O和PEDOT/MnO2纳米复合物。并证明PEDOT/RuO2·xH2O复合物在150 oC热处理后有良好的电化学可逆性和电容特性,而且在0.15 A g-1电流密度下比电容达到153.3 F g-1,当升高到0.8 A g-1时,比容量衰减量大约为17%。另外,制备的PEDOT/MnO2的纳米复合物证明是一种具有多孔孔道结构的无定型材料,当在-0.2~0.8 V (vs. SCE)范围内,电流密度为0.5 A·g-1时,单电极比容量达到196.3 F·g-1,500次循环后仍保持有90%的比容量。
(3)本文制备了PEDOT/PANI纳米复合物,并和活性碳组成混合电容器。该混合电容器在1.0 V的电位窗口下,以0.5 M H2SO4为电解质,当电流密度为1/2 A g-1时,比容量达30.7 F g-1,功率密度达到324.9 W kg-1。为了进一步提高该混合电容器的性能,我们考虑将含有+1价态的无机金属盐与H2SO4溶液组成混合电解液体系,电化学测试表明在0.5 M H2SO4 + 0.2 M K2SO4混合体系下,混合电容器的比电容,能量密度和功率密度具有明显的提高。
Supercapacitors has attracted wide attention and applied in many fields including aviation and aerospace, transportation, communication and computer because of high energy density, high specific capacitance, long cycle life, low cost and green environmental conservation. At present, conducting polymers (COPs) can be considered as a kind of promising materials owning to quick and efficient charge-discharge, temperature relief, environmental amicability and low cost. Among the COPs, poly (3, 4-ethylenedioxythiophene) (PEDOT) has drawn a wide interest. However, PEDOT also has some inevitable shortcomings such as the relatively small‘‘theoretic SC’’. Therefore, we focus on the PEDOT-based composite with good electrochemical capacitance behavior. The details are as follows:
(1) PEDOT/CNTs nanocomposite was synthesized by using the CNTs as the template, and the effect of various mass ratios of CNTs on the electrochemical capacitance of the composite was investigated. Moreover, due to the poor solubility and compatibility of CNTs, a non-covalent method was used to functionalize CNTs with poly (sodium 4-styrene sulfonate) (PSS), then the core-shell PEDOT/PSS-CNTs nanocomposite was successfully realized via hydrothermal polymerization. The nanocomposite had a specific capacitance of 198.2 F g-1 and a capacitance degradation of 26.9% after 2000 cycles. And the electrochemical measurements of the symmetric supercapacitor based on the PEDOT/PSS-CNTs nanocomposite were further studied.
(2) Due to the high energy density of the metal oxide, PEDOT/RuO2·xH2O and PEDOT/MnO2 nanocomposite could be synthesized by microwave-assisted and interfacial polymerization, respectively. As for the PEDOT/RuO2·xH2O nanocomposite, the composite system annealing at 150 oC might possess the most favorable electrochenmical properties with the specific capacitance of 153.3 F g-1 at the current density of 0.15 A g-1. While the current density was increased to 0.8 A g-1, the loss was up to about 17%. In other hand, the as-prepared PEDOT/MnO2 nanocomposite was proved to be amorphous and porous. The specific capacitance of nanocomposite was 196.3 F g-1 at the current density of 0.5 A g-1 with the potential range of -0.2~0.8 V (vs. SCE), and the capacity retention of the nanocomposite was about 90% after 500 cycles.
(3) Asymmetric supercapaciotors based on as-prepared PEDOT/PANI nanocomposite as a positive electrodes and activated carbon as a negative electrode were successfully fabricated. The results showed that the asymmetric supercapacitor could deliver the specific capacitance of 30.7 F g-1 and a power density of 324.9 W kg-1 in a potential window range between 0 and 1 V in 0.5 M H2SO4 aqueous electrolyte. In addition, the hybrid electrolyte including the inorganic compound including +1 metal ions and H2SO4 solution was investigated to further improve the electrochemical performance of the asymmetric supercapacitor. The electrochemical tests indicated that the specific capacitance, energy density and power density of the asymmetric supercapacitor had the most enhancements in the 0.5 M H2SO4 + 0.2 M K2SO4 hybrid electrolyte.
引文
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