联二噻吩-EDOT类新型齐聚物的合成与电聚合及聚合物性能

发布时间：2018-01-06 03:34

本文关键词：联二噻吩-EDOT类新型齐聚物的合成与电聚合及聚合物性能　出处：《江西科技师范大学》2015年硕士论文　论文类型：学位论文

【摘要】：自导电高分子于1977年被Shirakawa, MacDiarmid和Heeger三位科学家发现以来,导电高分子的研究开发就一直受到全世界科学家们的广泛关注。PEDOT因其高的电导率(ca.500 S/cm)、高的电化学及其热稳定性、低带隙和低氧化电位等突出的优点而被广泛应用于电致变色、超级电容器等领域。将3,4-二氧乙撑噻吩(EDOT)单元和其他单元结合起来可使合成的共轭单体/聚合物具备一些优异的性质,而基于联二噻吩单元(构建联二噻吩单元也很方便)所合成的共聚物具有优异的光电性能。鉴于此,本论文将联二噻吩单元和EDOT单元结合起来,设计合成了一系列以联二噻吩单元为核、端基以EDOT单元封端的新型低聚物。采用紫外、荧光、理论计算和双光子荧光等技术手段研究了低聚物的结构、电子性能和光学性能。同时,电化学低聚物获得了相应的其聚合物,探讨了聚合物在电致变色和超级电容器领域的应用。最后用电化学层层自组装技术构建了PEDOT膜和PBEDOT-BT膜交替的三层结构电极。研究表明所制备的联二噻吩-EDOT类新型共聚物为性能优异的电致变色材料和超级电容器电极材料。1采用Stille偶联反应,设计合成了五种烷基链修饰联二噻吩单元核和以EDOT单元封端的联二噻吩-EDOT聚物,通过核磁共振谱等手段对其进行了结构表征和纯度鉴定,用紫外、荧光、理论计算、双光子荧光技术等技术手段研究了其结构与性能的关系。单体合成路线简单且产率高(60%左右)。合成的单体为中等荧光强度(荧光量子产率在0.10-0.18之间)的蓝色发光材料,而其双光子荧光性能较弱(双光子吸收截面在0.8 GM-7.76 GM之间)且有明显的溶剂化效应。烷基链长度对单体在溶液中的光物理性质影响较大,主要是由于烷基链的空间位阻效应可使联二噻吩单元核和相邻EDOT环之间的扭转角发生较大的扭转。合成的单体可在微型有机激光器、光电发射装置等光学器件中得到广泛应用。2在CH2Cl2-Bu4NPF6(0.10 mol L-1)电解液中将5种低聚物作为单体采用阳极氧化法聚合获得了相应的共聚合物,在CH3CN-Bu4NPF6体系中系统研究了五种聚合物的电化学性能及电致变色性能。对聚合物的化学结构、电化学性质及表面形貌等性质用CV、FT-IR、SEM、热重、紫外和荧光等手段进行了表征和研究。研究结果表明所得聚合物具有良好的氧化还原活性、优异的电化学稳定性和热稳定性,其微观形貌为光滑、平整的形貌。所得聚合物具有良好的电致变色性能：光学对比度最高可达41.4%,着色效率在96.8-293.2 cm2C-1之间,响应时间最快为0.2 s。表明联二噻吩-EDOT共聚物是潜在的电致变色器件材料。3采用恒电压(0.7 V vs.Ag/AgCl)法成功制备了联二噻吩-EDOT的共聚物,采用循环伏安法、恒流充放电法以及交流阻抗法等手段考察了共聚物的电容性能。研究结果表明,所合成共聚物具有良好的电容性能(5 mV s-1下(138.2 F g-1-203.4 F g-1之间))和倍率性能(78.8%-91.0%)、优异的循环稳定性(循环1000圈初始电容保持率最高可达84.6%)。所构建的对称电容器器件具有较高的能量密度(最高可达11.6 Wh/kg)和功率密度(最高可达13.9Wh/kg),均高于商业电容器的能量密度(通常5-10Wh/kg)。结果表明,这几个导电聚合物可作超级电容器潜在的电极材料。4.基于PBEDOT-BT共聚物有着良好的电容性能,以BEDOT-BT和EDOT为前驱体,通过简单的层层电化学沉积法成功制备了PEDOT/PBEDOT-BT/PEDOT三层结构。在CH3CN-Bu4NPF6(0.1 mol L-1)溶液中采用循环伏安法、恒流充放电法、交流阻抗技术等手段研究了PEDOT/PBEDOT-BT/PEDOT三层结构的电容性能,采用AFM、SEM、截面SEM等手段研究了其微观结构。研究结果表明PEDOT/PBEDOT-BT/PEDOT三层结构为多孔纳米结构且具有较高的比电容和良好的电化学稳定性。所构建的对称电容器具有相对较高的比电容(96.8 Fg-1)和相当高的能量密度(260.1 Wh kg-1)。
[Abstract]:The conductive polymer by the Shirakawa in 1977, since the MacDiarmid and Heeger of three scientists found that the research and development of conductive polymers have attracted extensive attention of.PEDOT scientists around the world because of its high conductivity (ca.500 S/cm), high electrochemical and thermal stability, low band gap and low oxidation potential advantages and widely the application in electrochromic, field of super capacitor. 3,4- two oxygen ethylene thiophene (EDOT) unit and other units together can make the synthesis of conjugated monomer / polymer have some excellent properties, and based on two (two thiophene thiophene unit construction unit is also very convenient) copolymers synthesized with excellent optical properties. In view of this, this paper will combined two thiophene unit and EDOT unit combined, designed and synthesized a series of the two thiophene unit as the core, to end the new low EDOT unit terminated Polymer. By UV, fluorescence, theoretical calculation and two-photon fluorescence techniques on the oligomer structure, electronic properties and optical properties. At the same time, the corresponding electrochemical oligomers of the polymer, discusses the application of polymer electrochromic and super capacitor in the field of electricity. The electrochemical self-assembly technique construction the three layer structure of PEDOT membrane and PBEDOT-BT membrane electrode alternately. The results indicate that the prepared two novel -EDOT thiophene copolymer as excellent electrochromic materials and electrode materials for super capacitor.1 through Stille coupling reaction, five kinds of alkyl chain modified two thiophene unit and EDOT unit nuclear terminated two -EDOT thiophene polymers synthesized by nuclear magnetic resonance spectroscopy characterized and the purity of their identification, UV, fluorescence, theoretical calculation, two-photon fluorescence technology Study on the relationship between the structure and properties of the monomer. The synthesis route is simple and high in yield (about 60%). The monomer synthesis is medium (fluorescence intensity of fluorescence quantum yield between 0.10-0.18) blue light emitting materials, and the two-photon fluorescence properties (weak two-photon absorption cross section at 0.8 GM-7.76 GM) and a solvent the effect is obvious. The alkyl chain length has great effect on the photophysical properties of the monomer in solution, mainly due to the steric effect of the alkyl chain can make the torsion angle between two adjacent EDOT and thiophene unit nuclear ring large torsion. Monomer synthesized in the micro organic laser has been widely used..2 in CH2Cl2-Bu4NPF6 optical devices such as photoelectric emission devices (0.10 mol L-1) in 5 kinds of electrolyte oligomers as monomers by anodic oxidation polymerization were obtained corresponding polymers, in the system of CH3CN-Bu4NPF6 system. The five kinds of polymer electrochemical properties and electrochromic properties. The chemical structure of the polymer, electrochemical properties and surface morphology properties by CV, FT-IR, SEM, TGA, UV and fluorescence were characterized and studied. The results show that the polymer has good redox activity, excellent electrochemical stability the thermal stability and its morphology was smooth and flat morphology. The resulting polymers have good electrochromic performances: the optical contrast of up to 41.4%, coloring efficiency in 96.8-293.2 cm2C-1, the fastest response time of 0.2 S. showed that two thiophene -EDOT copolymer is a potential electrochromic material electrochromic device with constant voltage.3 (0.7 V vs.Ag/AgCl) two -EDOT thiophene copolymers were successfully synthesized, using cyclic voltammetry, galvanostatic charge discharge and AC impedance method were used to study the influence of capacitor co polymer The performance. The results show that the synthesized copolymer has good capacitance performance (5 mV S-1 (F g-1-203.4 F 138.2 g-1)) and ratecapability (78.8%-91.0%), excellent cycle stability (1000 cycles in the initial capacitance retention rate of up to 84.6%). Symmetric capacitor devices constructed with high energy density (up to 11.6 Wh/kg) and power density (up to 13.9Wh/kg), were higher than that of commercial capacitors energy density (usually 5-10Wh/kg). The results show that these can be used as a conductive polymer supercapacitor electrode materials based on.4. potential of PBEDOT-BT copolymer has good capacitance performance, with BEDOT-BT and EDOT as precursor. PEDOT/PBEDOT-BT/PEDOT three layer structure were prepared by electrochemical deposition layers were successfully simple. In CH3CN-Bu4NPF6 (0.1 mol L-1) solution by cyclic voltammetry, constant current charge discharge and AC impedance. Capacitance performance, operation means of the three layer structure of PEDOT/PBEDOT-BT/PEDOT by AFM, SEM, SEM section studied its microstructure. The results show that the PEDOT/PBEDOT-BT/PEDOT three layer structure as the porous structure and high specific capacitance and good electrochemical stability. The asymmetric capacitor has relatively high specific capacitance (96.8 Fg-1) and high energy density (260.1 Wh kg-1).

【学位授予单位】：江西科技师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O631;TM53

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