电化学聚合制备含富勒烯交联聚合物薄膜及超级电容器应用

Synthesis of Cross-linked Thin Films Containing Fullerene Units and Their Performance of Supercapacitor

通过N-烷基咔唑基团修饰富勒烯C_(60),获得了3种不同取代基数目的富勒烯衍生物2Cz-C_(60)、4Cz-C_(60)和6Cz-C_(60);3种单体具有高的电化学聚合活性,通过阳极电化学聚合得到了3种结构明确的聚合物(Poly[2Cz-C_(60)]、Poly[4Cz-C_(60)]和Poly[6Cz-C_(60)]),它们同时在工作电极上沉积得到了厚度精确可控的交联薄膜,其生长速度分别为1.88、1.70和2.61 nm/圈.电化学聚合过程中沉积薄膜快速而均匀的生长,为瞬间成核、岛状生长模式,并最终形成球状堆积的交联薄膜.经循环伏安法测试表明沉积薄膜有多对氧化还原峰,具有可逆的n-型与p-型双极性掺杂特性,并表现出可逆的和快速电荷传递的氧化还原反应特性.另外这种富勒烯交联薄膜作为超级电容电极材料也表现出了相当可观的电荷储存能力.

A series of C60 derivatives functionalized by carbazole group with great electrochemical activity were designed and synthesized via Bingel reaction.Three monomers（2Cz-C60,4Cz-C60,6 Cz-C60） were finally obtained with different molar ratios between C60 and malonate used in Bingel reaction.The molecular structure of these monomers were fully characterized by proton nuclear magnetic resonance spectra,Matrix assisted laser desorption ionization time-of-flight mass spectrometry（MALDI-TOF-MS）,Fourier transform infrared spectroscopy（FTIR）,and UV-Vis absorption.Electrochemical polymerization of these monomers were processed to form linear or cross-linked organic conducting polymer films,denoted as Poly[2Cz-C60],Poly[4Cz-C60] and Poly[6Cz-C60],which were attributed to the coupling of electrochemical activity group of N-alkyl carbazole.Their electrochemical polymerization was processed under three-electrode system of the electrochemical workstation（ITO or glassy carbon as working electrode,titanium plate or Pt wire as counter electrode and Ag/Ag＋ as reference electrode）.The chemical structures of the polymers obtained were clearly dependent on the definite electrochemical condition such as potential,electrolyte,concentration and scan rate during the polymerization.The thickness of the films obtained by the electrochemical polymerization could be controlled precisely by controlling the cycles of cyclic voltammetry（CV）.The electrochemical polymerization of the polymers had the same features of instantaneous nucleation and layered growth concluded by the atomic force microscope images of the films under different CV cycles.Finally,the films show globular stacking features.After CV test,the bipolar characters（N-alkyl carbazole group as the p-doping and C60 group as the n-doping）,fast and reversible redox properties of the organic conducting polymers films have been found.Then we explored the charge storage ability of the polymers as the electrode materials,which possessed considerable development potential to some extent.