新型联苯胺基窄带隙共轭聚合物的光学及电化学性能研究  

Synthesis and Properties of Novel Benzidine-Based Narrow Band Gap Conjugated Polymer From Simple Monomers

作　　者：斯丽姆罕·热合麦提 李佳佳[1] 阿孜古丽·木尔赛力木[1,2] 凯丽比努尔罕·麦提萨伍提 Salima Rahmat;LI Jia-jia;Arzugul Muslim;Kalbinur Matsawut(School of Chemistry and Chemical Engineering,Xinjiang Normal University,Urumqi 830054,China;Xinjiang Key Laboratory of Energy Storage and Photoelectrocatalytic Materials,Urumqi 830054,China)

机构地区：[1]新疆师范大学化学化工学院,新疆乌鲁木齐830054 [2]新疆储能与光电催化材料重点实验室,新疆乌鲁木齐830054

出　　处：《光谱学与光谱分析》2022年第12期3751-3756,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(51763023);新疆储能与光电催化材料重点实验室重点项目(XJDX-1709-2022-01)资助。

摘　　要：随着化石燃料的日益枯竭,人类社会对能源的需求在不断增长。为了平衡能量应用需求并提升能量使用效率,开发高效能量转换材料与电化学储能材料成为当前研究的重要课题。导电聚合物基电极材料面临着相应储能器件能量密度、功率密度、循环性能不高的挑战,需进行结构改性提高电导率、改善界面性质。鉴于共轭高分子的电子结构、光学及电化学性质由共轭链骨架结构决定,对导电共轭聚合物进行结构修饰以提升其电荷传输性能和载流子迁移率,进而设计合成新型高迁移率导电聚合物基共轭聚合物是提高相应器件特性的关键所在。已有研究大多借助复杂的结构设计来实现提升迁移率,设计合成了结构简单,有助提升电荷迁移的新型窄带隙聚联苯胺基共轭聚合物聚物。通过光谱学及电化学方法对材料结构与性能进行了表征分析。采用核磁共振氢谱、红外光谱,X射线粉末衍射对单体及聚合物进行了结构表征,通过紫外光谱、紫外可见漫反射、循环伏安、计时电位、交流阻抗对其进行了光学及电化学性能测试。结果表明,成功制得具有预期结构的共轭聚合物,所得聚合物结晶性较佳,光学带隙E^(opt)_(g)为1.85 eV,HOMO及LUMO能级分别为-5.44和-3.59 eV,前者高于,后者则低于大部分文献值,呈现可同时促进p-型和n-型掺杂的结构特性,具备增强材料容纳电荷能力的性能优势。聚合物储能特性受化学结构、晶体结构及微观形貌综合影响。改善材料微观结构特性有助于提升其电子电导率,但层状致密块体形貌特征又使其离子电导率受限。电化学性能测试结果显示,聚合物具有一定电化学活性,具有较小的电荷转移阻抗,具备基本满足使离子顺利扩散的条件,0.05 A·g^(-1)时的放电比电容达256.6 F·g^(-1)。研究结果表明,制得的联苯胺基窄带隙共轭聚合物在光电转换、储能及微�With the increasing depletion of fossil fuels,the demand for energy in human society is increasing.In order to balance the energy application demand and improve energy efficiency,developing high-efficiency energy conversion materials and electrochemical energy storage materials has become an important research topic.Conductive polymer-based electrode materials faces the challenges of low energy and power density and poor cycle performance in corresponding energy storage devices.Structural modification is needed to improve their conductivity and interface properties.Since the skeleton structure of conjugated chains determines the electronic structure,optical and electrochemical properties of conjugated polymers,the structural modification of conductive conjugated polymers to improve their charge transport properties and carrier mobility,and then the design and synthesis of new high mobility conductive polymer based conjugated polymers is the key to improve the characteristics of their corresponding devices.Most of the reported studies use complex structural designs to improve mobility.This paper designed and synthesised a new narrow-band gap polybenzidine based conjugated polymer with simple structure and helpful to improve charge transfer.Spectroscopic and electrochemical methods characterized the structure and properties of the materials.The structures of the monomers and polymers were characterized by^(1)H NMR,FTIR and X-ray powder diffraction.Their optical and electrochemical properties were tested by UV-Vis spectrum,UV-Vis diffuse reflection,cyclic voltammetry,chronopotentiometry and electrochemical impedance spectrum.The results show that the conjugated polymer with the expected structure is successfully prepared,and the obtained polymer has good crystallinity.The optical band gap E^(opt)_(g) is 1.85 eV,and the HOMO and LUMO energy levels are-5.44 and-3.59 eV,respectively.The former is higher than the values published in the literature,while the latter is lower than most literature values,indicating the poly

关 键 词：联苯胺基 共轭聚合物 窄带隙 电化学活性 

分 类 号：O631[理学—高分子化学]