化学学报 ›› 2014, Vol. 72 ›› Issue (11): 1175-1181.DOI: 10.6023/A14060430 上一篇    下一篇

研究论文

聚苯胺共价接枝碳纳米管复合材料的制备及其超电容性能的研究

高珍珍a, 佟浩a, 陈建慧a, 岳世鸿a, 白文龙a, 张校刚a, 潘燕飞b, 石明a, 宋玉翔a   

  1. a 南京航空航天大学 材料科学与技术学院 江苏省能量转换材料与技术重点实验室 南京 210016;
    b 南京航空航天大学 理学院 南京 210016
  • 投稿日期:2014-06-03 发布日期:2014-11-06
  • 通讯作者: 佟浩, 张校刚 E-mail:tongh@nuaa.edu.cn;azhangxg@163.com
  • 基金资助:

    项目受南京航空航天大学基本科研业务费理工融合专项基金(No. 3082014NZ2014102)、中国博士后基金(No. 2011M500910)、江苏省博士后基金(No. 1201014B)、国家自然科学基金(Nos. 51372116, 21173120)和中央高校基本科研业务费专项创新工程自由探索计划(Nos. ZT2013073, ZT2013086)资助.

Preparation and Supercapacitive Performance of Polyaniline Covalently Grafted Carbon Nanotubes Composite Material

Gao Zhenzhena, Tong Haoa, Chen Jianhuia, Yue Shihonga, Bai Wenlonga, Zhang Xiaoganga, Pan Yanfeib, Shi Minga, Song Yuxianga   

  1. a Nanjing University of Aeronautics and Astronautics, College of Material Science and Engineering, Jiangsu Key Laboratory of Material and Technology for Energy Conversion, Nanjing 210016, China;
    b College of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 210016
  • Received:2014-06-03 Published:2014-11-06
  • Supported by:

    Project supported by the Fundamental Research Technological Convergence Special Fund of Nanjing University of Aeronautics and Astronautics (No. 3082014NZ2014102), Chinese Postdoctoral Foundation (No. 2011M500910), Postdoctoral Foundation of Jiangsu Province (No. 1201014B), Natural Science Foundation of China (Nos. 51372116, 21173120) and Undergraduate Innovative Project Foundation of NUAA (Nos. ZT2013073, ZT2013086).

以氨基化的碳纳米管为基体, 通过低温原位聚合的方法将聚苯胺共价接枝于碳纳米管表面, 通过透射电镜(TEM)、X射线衍射(XRD)、紫外可见光(UV-vis)、傅里叶红外(FT-IR)、拉曼(Raman)及电化学方法对复合材料进行了表征. 结果表明通过低温原位聚合的方法可以使聚苯胺均匀接枝于碳纳米管表面. 电化学测试结果表明, 碳纳米管共价接枝聚苯胺作为超级电容器材料在0.5 A/g条件下聚苯胺的电容贡献值为754.8 F/g, 同时其倍率性能以及循环稳定性方面都明显优于聚苯胺非共价修饰的碳纳米管复合材料.

关键词: 碳纳米管, 聚苯胺, 共价, 超电容

Recently, covalent functionalization carbon nanotubes have been received special attention because of the expansive application prospect in the areas of nanoscience and nanotechnology. Moreover, covalent functionalization of carbon nanotubes can improve the solubilization of carbon nanotubes. In particular, polyaniline, due to its high electronic conductivity, good environmental stability, easy preparation and reversible acid-base doping-dedoping chemistry, has been one of the most studied conducting polymers. Recently, CNTs-PANI composites were investigated widely, such as supercapacitor, optoelectronic devices, sensing and catalysis as well. In this work, we perform in situ polymerization method at low temperatures obtaining uniform structures PANI grafted on CNTs (which has been covalently functionalized with NH2 groups on its surface) composites. Concerning CNTs-NH-PANI composites, PANI could be covalently grafted onto CNTs through NH2 groups. Due to the fact that CNTs-NH-PANI composites have abundant -NH2 groups on their surface, serving as anchor centers for polymerization of aniline monomer. Introduction of NH2 groups can not only increase the dispersion of carbon nanotubes itself, but also can be as growth sites to form PANI uniform grafted to the "core-shell" structure of carbon nanotubes in the growth process of PANI. More importantly, PANI uniformly grafted on CNTs is prone to disperse the bundle of CNTs into separated lines and improve water dispersibility of obtained CNTs-NH-PANI composites. Potential application of the composite material as high performance supercapacitor has been explored. Composite material samples were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical methods and so on. TEM results showed that the hierarchical CNTs-PANI composites with uniform morphology have been successfully prepared due to hydrophilic groups OH and NH2 are successfully covalently functionalized on the surface of CNTs. Moreover, the electrochemical measurement show that CNTs-NH-PANI composites have high specific capacitance as supercapacitor material. At the current density of 0.1 A/g, the specific capacity can reach 251.2 F/g. For PANI, the capacitance contribution is higher in covalently grafted CNTs-g-PANI composites than PANI-c-CNTs. At the charge-discharge test, the composite material capacity retention stability rate at 64% after 5000 charge discharge test, higher than that of PANI-c-CNTs 48% significantly at the current density of 1 A/g.

Key words: carbon nanotube, polyaniline, covalently, supercapacitor