物理化学学报 >> 2016, Vol. 32 >> Issue (4): 975-982.doi: 10.3866/PKU.WHXB201601281

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石墨烯负载新型π-共轭聚合物纳米复合电极材料的合成及其超级电容特性

周晓1,孙敏强1,2,王庚超1,*()   

  1. 1 华东理工大学材料科学与工程学院, 超细材料制备与应用教育部重点实验室, 上海市先进聚合物材料重点实验室, 上海 200237
    2 建德市顺发化工助剂有限公司, 杭州 311600
  • 收稿日期:2015-12-02 发布日期:2016-04-07
  • 通讯作者: 王庚超 E-mail:gengchaow@ecust.edu.cn
  • 基金资助:
    国家自然科学基金项目(51173042);上海市科委国际合作项目(15520720500)

Synthesis and Supercapacitance Performance of Graphene-Supported π-Conjugated Polymer Nanocomposite Electrode Materials

Xiao ZHOU1,Min-Qiang SUN1,2,Geng-Chao WANG1,*()   

  1. 1 Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science & Engineering, East China University of Science & Technology, Shanghai 200237, P. R. China
    2 Jiande Shunfa Chemical Adjuvant Co. Ltd., Hangzhou 311600, P. R. China
  • Received:2015-12-02 Published:2016-04-07
  • Contact: Geng-Chao WANG E-mail:gengchaow@ecust.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(51173042);Shanghai Municipality Research Project, China(15520720500)

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摘要：

采用γ射线辐照还原技术获得易分散石墨烯(GNS),并以其为载体,以樟脑磺酸为掺杂剂和软模板,借助化学氧化聚合方法制备出分级孔结构的石墨烯负载聚(1, 5-二氨基蒽醌)(GNS@PDAA)纳米复合材料。运用傅里叶变换红外(FTIR)光谱、拉曼光谱(Raman)、原子力显微镜(AFM)、能谱仪(EDS)、场发射扫描电镜(FE-SEM)和电化学测试等手段研究了不同GNS/DAA质量比对GNS@PDAA复合材料的形貌、结构及超级电容特性的影响。研究表明,当DAA/GNS质量比为6/1时,借助π-π堆叠和网络限域作用, PDAA以20-40 nm纳米颗粒的形式牢固沉积于石墨烯表面,材料内部存在大量10-30 nm尺寸的介孔。该GNS@PDAA复合材料在0.5 A·g-1时呈现最高的比电容(398.7 F·g-1),优异的倍率特性(在50 A·g-1下比电容保持率为71%)和非常好的循环性能(20000次循环后比电容损失仅为8.3%)。进而证实了GNS@PDAA复合材料所组装的超级电容器具有优异的串并联特性。

关键词: 石墨烯, π-共轭聚合物, 聚(1, 5-二氨基蒽醌), 纳米复合材料, 电极材料, 超级电容器

Abstract:

Well-dispersed graphene nanosheets (GNS) were prepared by the 60Co γ-ray irradiation reduction technique. On this basis, the hierarchical graphene nanosheet-supported poly(1, 5-diaminoanthraquinone) (GNS@PDAA) nanocomposites were synthesized by the chemically oxidative polymerization method using camphor sulfonic acid as both the dopant and soft template. The influence of the DAA/GNS mass ratios on the morphology, chemical structure, and supercapacitance performance for GNS@PDAA nanocomposites was investigated. The structure, morphology, and electrochemical properties of the composites were characterized by Fourier infrared spectroscopy (FTIR), Raman spectroscopy (Raman), atomic force microscope (AFM), energy dispersive spectroscopy (EDS), field emission scanning electron microscopy (FE-SEM), and electrochemical measurements. The results show that for the GNS@PDAA nanocomposite with DAA/GNS mass ratio of 6/1, the PDAA nanoparticles (20-40 nm diameter) are evenly deposited on the surface of GNS, which intercalate a large number of mesopores with 10-30 nmthrough strong π-π stacking and network confinement. As a result, the GNS@PDAA exhibits the highest specific capacitance (398.7 F·g-1 at 0.5 A·g-1), excellent rate capability (71% capacitance retention at 50 A·g-1), and superior cycling stability (only 8.3% capacitance loss after 20000 cycles). Furthermore, based on the GNS@PDAA nanocomposites as both negative and positive electrodes, the as-assembled supercapacitors showed an excellent series/parallel connection effect in aqueous system.

Key words: Graphene, π-Conjugated polymer, Poly(1, 5-diaminoanthraquinone), Nanocomposite, Electrode materials, Supercapacitors