蒽醌掺杂聚吡咯在电极材料中的应用
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摘要
导电聚合物作为电容器电极材料使用时,经常由于工作电压范围不够宽,电容量不够大,导致其在应用上受到限制。本文把在较负电位处具有良好赝电容行为的蒽醌掺杂进聚吡咯中,扩大了聚吡咯电极的工作电压范围,提高了复合电极的电容量。另外由于蒽醌对氧具有良好的电催化还原活性,将蒽醌掺杂的聚吡咯应用到微生物燃料电池阴极中,该阴极兼有防水和催化的双重效果,其良好的导电子和质子能力减少了阴极反应阻力,减少了阴极制备过程的复杂程序。
首先在金电极上通过电化学方法制备蒽醌及其衍生物掺杂的聚吡咯电极。与高氯酸根离子掺杂的聚吡咯相比,检测发现蒽醌及其衍生物磺酸盐掺杂的聚吡咯电极有更宽的工作电压范围和更高的单位质量电容量。其中蒽醌单磺酸盐(9, 10-蒽醌-2-磺酸钠盐)掺杂的聚吡咯(PPy/AQS)电极的电容性能最好,工作电压范围为-0.9至0.5 V,扫描速度为5 mV/s时其单位质量电容量高达608 F/g。这主要是由于:1.蒽醌磺酸盐的掺杂能明显改变聚吡咯电极表面的形貌,其电极表面主要由纳米至亚微米级的颗粒组成,因此增大了电极的比表面积。2.蒽醌在较负电位处良好的氧化还原特性提高了总体电极的单位质量电容量并扩大了电极的工作电压范围。
通过电化学测试,证明了PPy/AQS在Au电极和不锈钢网上的PPy/AQS均具有良好的电催化氧还原性能,且明确了其中对氧还原起催化作用的关键成分是蒽醌/氢蒽醌氧化还原电对。
通过恒电流法,蒽醌掺杂的聚吡咯(PPy/AQS)均匀地电沉积在不锈钢网上,将其作为阴极组装进微生物燃料电池后进行测试,电池平稳运行,防水效果良好,沉积电量为100 C/cm2的PPy/AQS阴极无膜微生物燃料电池,其最高功率密度能达到575 mW/m2。随着阴极厚度增加,电极的内阻增大,氧气透过阴极的难度加大,微生物燃料电池的性能下降。通过在PPy/AQS阴极上涂覆一层石墨黑催化剂,这种改进后的微生物燃料电池功率密度能达到1857 mW/m~2,与同样使用石墨黑作为催化剂,PDMS作为防水层,不锈钢网作为支撑体的阴极微生物燃料电池相比,PPy/AQS上涂覆石墨黑的阴极MFC电池性能更好,这主要归功于PPy/AQS阴极良好的导电子和质子能力。此种合成微生物燃料电池阴极的方法为构建大容量的微生物燃料电池体系提供了一种新的思路。
The application of conductive polymer is often limited by short working voltage range and small electric capacity as a kind of supercapacitor electrode material. Situated in a relative negative potential, anthraquinone with a good pseudo-capacitive behavior is doped into PPy to enlarge the working voltage range and enhance the electric capacity of the composite electrode. Besides, a coating of anthraquinone doped polyprrole is applied to construct the cathodes of microbial fuel cells (MFCs), because of its good electrical catalytic reduction activities of the oxygen. The PPy/AQS is hydrophobic and oxygen electric catalytic, which is suitable for MFC cathode. In the same time, the ability of good conducting electrons and protons reduces the reaction resistance in MFC cathodes, finally the preparation method is also convenient and simple.
A layer of PPy doped with anthraquinone and its derivatives was prepared on gold electrode by electrochemical methods. Results show that these PPy electrodes doped with anthraquinone result in a wider working potential range and a higher specific capacitance compared to the PPy electrodes doped with ClO4-. Among the samples investigated, the resulting PPy/AQS (9, 10-anthraquinone-2-sulfonic acid sodium salt) composite exhibits the highest specific capacitance of 608 F/g at a scan rate of 5 mV/s within a potential range between ?0.9 and 0.5 V. The major reasons are: (1)The incorporation of anthraquinone sulfonate species into the polymer matrix can significantly improve the surface area of PPy composites that are composed of submicron-/nano-sized particles, which enlarge the specific surface area of the electrodes. (2)Electrodes achieve a higher specific capacitance and a wider working potential range due to the good redox characteristics of anthraquinone in a relative negative potential.
The oxygern reduction behavior of PPy/AQS is detected, it proves that PPy/AQS on Au and stainless steel electrode show good oxygen reduction reaction activity, the experiment validate that anthraquinone/anthrahydroquinone redox center is the key issue to the oxygen reduction.
AQS doped polypyrrole conductive polymer is electrodeposited onto stainless steel mesh by constant current method. The PPy/AQS film is uniformly formed on the metal mesh electrode. The MFC with PPy/AQS cathode can run steady and show good waterproof features, the 100 C/cm2 PPy/AQS cathode MFC exhibit a maximum power density of 575 mW/m2. Increasing film thickness seems to result in a reduction in power performance due to the increased ohmic resistance of the cathode material and the enhanced difficulty for oxygen diffusion inside the cathode. The graphite coated on the PPy/AQS layer is used as the catalyst, the maximal power density of the modified MFC was 1857 mW/m2, which is much higher than MFC whose cathode is fabricated by PDMS and graphite on stainless steel, this is owed to the good electron and proton conductivity of PPy/AQS. These results indicate that the one-step fabrication method holds potential in the implementation of this for air-breathing MFC applications on a large scale.
首先在金电极上通过电化学方法制备蒽醌及其衍生物掺杂的聚吡咯电极。与高氯酸根离子掺杂的聚吡咯相比,检测发现蒽醌及其衍生物磺酸盐掺杂的聚吡咯电极有更宽的工作电压范围和更高的单位质量电容量。其中蒽醌单磺酸盐(9, 10-蒽醌-2-磺酸钠盐)掺杂的聚吡咯(PPy/AQS)电极的电容性能最好,工作电压范围为-0.9至0.5 V,扫描速度为5 mV/s时其单位质量电容量高达608 F/g。这主要是由于:1.蒽醌磺酸盐的掺杂能明显改变聚吡咯电极表面的形貌,其电极表面主要由纳米至亚微米级的颗粒组成,因此增大了电极的比表面积。2.蒽醌在较负电位处良好的氧化还原特性提高了总体电极的单位质量电容量并扩大了电极的工作电压范围。
通过电化学测试,证明了PPy/AQS在Au电极和不锈钢网上的PPy/AQS均具有良好的电催化氧还原性能,且明确了其中对氧还原起催化作用的关键成分是蒽醌/氢蒽醌氧化还原电对。
通过恒电流法,蒽醌掺杂的聚吡咯(PPy/AQS)均匀地电沉积在不锈钢网上,将其作为阴极组装进微生物燃料电池后进行测试,电池平稳运行,防水效果良好,沉积电量为100 C/cm2的PPy/AQS阴极无膜微生物燃料电池,其最高功率密度能达到575 mW/m2。随着阴极厚度增加,电极的内阻增大,氧气透过阴极的难度加大,微生物燃料电池的性能下降。通过在PPy/AQS阴极上涂覆一层石墨黑催化剂,这种改进后的微生物燃料电池功率密度能达到1857 mW/m~2,与同样使用石墨黑作为催化剂,PDMS作为防水层,不锈钢网作为支撑体的阴极微生物燃料电池相比,PPy/AQS上涂覆石墨黑的阴极MFC电池性能更好,这主要归功于PPy/AQS阴极良好的导电子和质子能力。此种合成微生物燃料电池阴极的方法为构建大容量的微生物燃料电池体系提供了一种新的思路。
The application of conductive polymer is often limited by short working voltage range and small electric capacity as a kind of supercapacitor electrode material. Situated in a relative negative potential, anthraquinone with a good pseudo-capacitive behavior is doped into PPy to enlarge the working voltage range and enhance the electric capacity of the composite electrode. Besides, a coating of anthraquinone doped polyprrole is applied to construct the cathodes of microbial fuel cells (MFCs), because of its good electrical catalytic reduction activities of the oxygen. The PPy/AQS is hydrophobic and oxygen electric catalytic, which is suitable for MFC cathode. In the same time, the ability of good conducting electrons and protons reduces the reaction resistance in MFC cathodes, finally the preparation method is also convenient and simple.
A layer of PPy doped with anthraquinone and its derivatives was prepared on gold electrode by electrochemical methods. Results show that these PPy electrodes doped with anthraquinone result in a wider working potential range and a higher specific capacitance compared to the PPy electrodes doped with ClO4-. Among the samples investigated, the resulting PPy/AQS (9, 10-anthraquinone-2-sulfonic acid sodium salt) composite exhibits the highest specific capacitance of 608 F/g at a scan rate of 5 mV/s within a potential range between ?0.9 and 0.5 V. The major reasons are: (1)The incorporation of anthraquinone sulfonate species into the polymer matrix can significantly improve the surface area of PPy composites that are composed of submicron-/nano-sized particles, which enlarge the specific surface area of the electrodes. (2)Electrodes achieve a higher specific capacitance and a wider working potential range due to the good redox characteristics of anthraquinone in a relative negative potential.
The oxygern reduction behavior of PPy/AQS is detected, it proves that PPy/AQS on Au and stainless steel electrode show good oxygen reduction reaction activity, the experiment validate that anthraquinone/anthrahydroquinone redox center is the key issue to the oxygen reduction.
AQS doped polypyrrole conductive polymer is electrodeposited onto stainless steel mesh by constant current method. The PPy/AQS film is uniformly formed on the metal mesh electrode. The MFC with PPy/AQS cathode can run steady and show good waterproof features, the 100 C/cm2 PPy/AQS cathode MFC exhibit a maximum power density of 575 mW/m2. Increasing film thickness seems to result in a reduction in power performance due to the increased ohmic resistance of the cathode material and the enhanced difficulty for oxygen diffusion inside the cathode. The graphite coated on the PPy/AQS layer is used as the catalyst, the maximal power density of the modified MFC was 1857 mW/m2, which is much higher than MFC whose cathode is fabricated by PDMS and graphite on stainless steel, this is owed to the good electron and proton conductivity of PPy/AQS. These results indicate that the one-step fabrication method holds potential in the implementation of this for air-breathing MFC applications on a large scale.
引文
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