聚3，4-乙撑二氧噻吩（PEDOT）的制备及电化学性能的研究
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摘要
超级电容器由于其巨大的市场潜力而成为国家中长期发展的能源领域中重要的前沿技术之一。电极材料是决定超级电容器性能的关键部分。导电聚合物价格相对低廉、比容量高的特点使其成为高性能超级电容器研究中的一个热点。本论文以导电聚合物PEDOT为研究对象,利用化学氧化法合成不同P型掺杂PEDOT材料,研究PEDOT材料电导率和电化学性能,为进一步制备高性能PEDOT材料及后续器件研究提供有力的依据。
首先,本论文选择聚苯乙烯磺酸钠(PSSNa)、对氨基苯磺酸钠、对甲基苯磺酸、氨基磺酸、樟脑磺酸五种物质作为掺杂剂,以FeCl3·6H2O为氧化剂,制备了五个系列PEDOT材料。掺杂剂种类对PEDOT电导率有较大的影响。相同制备条件下制备的PEDOT材料电导率由高至低对应的掺杂剂依次为:樟脑磺酸、氨基磺酸、对甲基苯磺酸、对氨基苯磺酸钠、聚苯乙烯磺酸钠。EDOT单体与掺杂剂及氧化剂的摩尔比、反应时间、氧化剂的添加方式均能影响PEDOT的导电性能。实验结果表明,当EDOT单体:掺杂剂:氧化剂2:1:40、反应时间为41h、氧化剂采用一次性添加方式时,所制备的PEDOT电导率最高,可达10.4S/cm。
然后,本论文研究了所制备的PEDOT的电化学性能。结果表明这些PEDOT材料都具有较高的比容量和较好的充放电性能及循环稳定性。掺杂剂种类对PEDOT电化学性能有较大的影响,其中以樟脑磺酸为掺杂剂时PEDOT电化学性能最好,而以PSSNa为掺杂剂时PEDOT电化学性能最差。实验结果表明,当以樟脑磺酸为掺杂剂,EDOT:C_(10)H_(16)O_4S:FeCl_3·6H_2O摩尔比为2:1:40、反应时间为41h时所制备的PEDOT电极材料经过充放电老化后比容量可保持在150F/g左右。
Supercapacitors are one of the most important advanced technologies in the long-term development of national energy industry because of its huge market potentiality. Electrode materials are critical for the performance of supercapacitors. Conductive polymers have become a hot spot in the researches of the high performance supercapacitors for the lower cost and high specific capacitance. In this thesis, the study was focused on the synthesis and properties of poly (3,4-ethylenedioxythiophene) (PEDOT), a kind of conductive polymers, to evaluate its potentials and process as an electrode materials of supercapacitors.
Firstly, polystyrene sulfonic acid sodium(PSSNa), sodium sulfanilate, p-toluenesulfoni, sulfamic acid and camphorsulfonicacid were selected as the doping agent. Five series of PEDOT materials were prepared with FeCl_3·6H_2O as the oxidant. The doping agents seriously affect the conductivity of PEDOT materials. The conductivity of PEDOT materials prepared with the same conditions decreases with the doping agent in the following order: camphorsulfonicacid, sulfamic acid, p-toluenesulfoni, sodium sulfanilate, PSSNa. The molar ratio of the EDOT monomer to the doping agent and the oxidant, the reaction time and the oxidant feeding way all can affect the conductive properties of PEDOT materials. The highest conductivity was found as 10.4S/cm with the PEDOT/camphorsulfonicacid material prepared with the molar ratio of monomer: doping agent: oxidant ass 2:1:40, the reaction time of 40h, and the oxidant one-time feeding way.
Then, the electrochemical performance of PEDOT materials were investigated in detail. Results show that these PEDOT materials have high specific capacitance, good charge-discharge performance and stability and good cycle stability. The doping agents influence the electrochemical properties significantly. The highest electrochemical performance was observed with the PEDOT/camphorsulfonicacid material, while the lowest electrochemical performance was found with the PEDOT/PSSNa materials. The specific capacitance of PEDOT/camphorsulfonicacid electrode materials is determined as 150 F/g after charge-discharge when the molar ratio of monomer: doping agent: oxidant is set as 2:1:40 abd the reaction time is controlled as 41h during the synthesis procedure.
首先,本论文选择聚苯乙烯磺酸钠(PSSNa)、对氨基苯磺酸钠、对甲基苯磺酸、氨基磺酸、樟脑磺酸五种物质作为掺杂剂,以FeCl3·6H2O为氧化剂,制备了五个系列PEDOT材料。掺杂剂种类对PEDOT电导率有较大的影响。相同制备条件下制备的PEDOT材料电导率由高至低对应的掺杂剂依次为:樟脑磺酸、氨基磺酸、对甲基苯磺酸、对氨基苯磺酸钠、聚苯乙烯磺酸钠。EDOT单体与掺杂剂及氧化剂的摩尔比、反应时间、氧化剂的添加方式均能影响PEDOT的导电性能。实验结果表明,当EDOT单体:掺杂剂:氧化剂2:1:40、反应时间为41h、氧化剂采用一次性添加方式时,所制备的PEDOT电导率最高,可达10.4S/cm。
然后,本论文研究了所制备的PEDOT的电化学性能。结果表明这些PEDOT材料都具有较高的比容量和较好的充放电性能及循环稳定性。掺杂剂种类对PEDOT电化学性能有较大的影响,其中以樟脑磺酸为掺杂剂时PEDOT电化学性能最好,而以PSSNa为掺杂剂时PEDOT电化学性能最差。实验结果表明,当以樟脑磺酸为掺杂剂,EDOT:C_(10)H_(16)O_4S:FeCl_3·6H_2O摩尔比为2:1:40、反应时间为41h时所制备的PEDOT电极材料经过充放电老化后比容量可保持在150F/g左右。
Supercapacitors are one of the most important advanced technologies in the long-term development of national energy industry because of its huge market potentiality. Electrode materials are critical for the performance of supercapacitors. Conductive polymers have become a hot spot in the researches of the high performance supercapacitors for the lower cost and high specific capacitance. In this thesis, the study was focused on the synthesis and properties of poly (3,4-ethylenedioxythiophene) (PEDOT), a kind of conductive polymers, to evaluate its potentials and process as an electrode materials of supercapacitors.
Firstly, polystyrene sulfonic acid sodium(PSSNa), sodium sulfanilate, p-toluenesulfoni, sulfamic acid and camphorsulfonicacid were selected as the doping agent. Five series of PEDOT materials were prepared with FeCl_3·6H_2O as the oxidant. The doping agents seriously affect the conductivity of PEDOT materials. The conductivity of PEDOT materials prepared with the same conditions decreases with the doping agent in the following order: camphorsulfonicacid, sulfamic acid, p-toluenesulfoni, sodium sulfanilate, PSSNa. The molar ratio of the EDOT monomer to the doping agent and the oxidant, the reaction time and the oxidant feeding way all can affect the conductive properties of PEDOT materials. The highest conductivity was found as 10.4S/cm with the PEDOT/camphorsulfonicacid material prepared with the molar ratio of monomer: doping agent: oxidant ass 2:1:40, the reaction time of 40h, and the oxidant one-time feeding way.
Then, the electrochemical performance of PEDOT materials were investigated in detail. Results show that these PEDOT materials have high specific capacitance, good charge-discharge performance and stability and good cycle stability. The doping agents influence the electrochemical properties significantly. The highest electrochemical performance was observed with the PEDOT/camphorsulfonicacid material, while the lowest electrochemical performance was found with the PEDOT/PSSNa materials. The specific capacitance of PEDOT/camphorsulfonicacid electrode materials is determined as 150 F/g after charge-discharge when the molar ratio of monomer: doping agent: oxidant is set as 2:1:40 abd the reaction time is controlled as 41h during the synthesis procedure.
引文
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