Casado Nerea, Hernández Guiomar, Veloso Antonio, Devaraj Shanmukaraj, Mecerreyes David, Armand Michel
POLYMAT, University of the Basque Country UPV/EHU , Joxe Mari Korta Centre, Avda. Tolosa 72, 20018 Donostia-San Sebastián, Spain.
CIC EnergiGUNE, Alava Technology Park , C/Albert Einste in 48, 01510 Miñano, Alava, Spain.
ACS Macro Lett. 2016 Jan 19;5(1):59-64. doi: 10.1021/acsmacrolett.5b00811. Epub 2015 Dec 27.
The development of new redox polymers is being boosted by the increasing interest in the area of energy and health. The development of new polymers is needed to further advance new applications or improve the performance of actual devices such as batteries, supercapacitors, or drug delivery systems. Here we show the synthesis and characterization of a new polymer which combines the present most successful conjugated polymer backbone and the most successful redox active side group, i.e., poly(3,4-ethylenedioxythiophene) (PEDOT), and a nitroxide stable radical. First, a derivative of the 3,4-ethylenedioxythiophene (EDOT) molecule with side nitroxide stable radical group (TEMPO) was synthesized. The electrochemical polymerization of the PEDOT-TEMPO monomer was investigated in detail using cyclic voltammetry, potential step, and constant current methods. Monomer and polymer were characterized by NMR, FTIR, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS), electron spin resonance (ESR) spectroscopy, elemental analysis, cyclic voltammetry, and four-point probe conductivity. The new PEDOT-TEMPO radical polymer combines the electronic conductivity of the conjugated polythiophene backbone and redox properties of the nitroxide group. As an example of application, this redox active polymer was used as a conductive binder in lithium ion batteries. Good cycling stability with high Coulombic efficiency and increased cyclability at different rates were obtained using this polymer as a replacement of two ingredients: conductive carbon additive and polymeric binders.
能源和健康领域日益增长的兴趣推动了新型氧化还原聚合物的发展。需要开发新型聚合物以进一步推进新应用或改善实际器件（如电池、超级电容器或药物递送系统）的性能。在此，我们展示了一种新型聚合物的合成与表征，该聚合物结合了目前最成功的共轭聚合物主链和最成功的氧化还原活性侧基，即聚（3,4 - 亚乙二氧基噻吩）（PEDOT）和一种氮氧化物稳定自由基。首先，合成了带有侧基氮氧化物稳定自由基基团（TEMPO）的3,4 - 亚乙二氧基噻吩（EDOT）分子的衍生物。使用循环伏安法、电位阶跃法和恒流法详细研究了PEDOT - TEMPO单体的电化学聚合。通过核磁共振（NMR）、傅里叶变换红外光谱（FTIR）、基质辅助激光解吸电离飞行时间质谱（MALDI - TOF MS）、电子自旋共振（ESR）光谱、元素分析、循环伏安法和四点探针电导率对单体和聚合物进行了表征。新型PEDOT - TEMPO自由基聚合物结合了共轭聚噻吩主链的电子导电性和氮氧化物基团的氧化还原特性。作为应用实例，这种氧化还原活性聚合物被用作锂离子电池中的导电粘合剂。使用该聚合物替代两种成分：导电碳添加剂和聚合物粘合剂，获得了具有高库仑效率的良好循环稳定性以及在不同速率下提高的循环性能。
