本文關(guān)鍵詞：聯(lián)二噻吩-EDOT類新型齊聚物的合成與電聚合及聚合物性能　出處：《江西科技師范大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 導(dǎo)電聚合物 超級電容器 電致變色 聯(lián)二噻吩 聚(3 4-二氧乙撐噻吩)

【摘要】：自導(dǎo)電高分子于1977年被Shirakawa, MacDiarmid和Heeger三位科學(xué)家發(fā)現(xiàn)以來,導(dǎo)電高分子的研究開發(fā)就一直受到全世界科學(xué)家們的廣泛關(guān)注。PEDOT因其高的電導(dǎo)率(ca.500 S/cm)、高的電化學(xué)及其熱穩(wěn)定性、低帶隙和低氧化電位等突出的優(yōu)點而被廣泛應(yīng)用于電致變色、超級電容器等領(lǐng)域。將3,4-二氧乙撐噻吩(EDOT)單元和其他單元結(jié)合起來可使合成的共軛單體/聚合物具備一些優(yōu)異的性質(zhì),而基于聯(lián)二噻吩單元(構(gòu)建聯(lián)二噻吩單元也很方便)所合成的共聚物具有優(yōu)異的光電性能。鑒于此,本論文將聯(lián)二噻吩單元和EDOT單元結(jié)合起來,設(shè)計合成了一系列以聯(lián)二噻吩單元為核、端基以EDOT單元封端的新型低聚物。采用紫外、熒光、理論計算和雙光子熒光等技術(shù)手段研究了低聚物的結(jié)構(gòu)、電子性能和光學(xué)性能。同時,電化學(xué)低聚物獲得了相應(yīng)的其聚合物,探討了聚合物在電致變色和超級電容器領(lǐng)域的應(yīng)用。最后用電化學(xué)層層自組裝技術(shù)構(gòu)建了PEDOT膜和PBEDOT-BT膜交替的三層結(jié)構(gòu)電極。研究表明所制備的聯(lián)二噻吩-EDOT類新型共聚物為性能優(yōu)異的電致變色材料和超級電容器電極材料。1采用Stille偶聯(lián)反應(yīng),設(shè)計合成了五種烷基鏈修飾聯(lián)二噻吩單元核和以EDOT單元封端的聯(lián)二噻吩-EDOT聚物,通過核磁共振譜等手段對其進行了結(jié)構(gòu)表征和純度鑒定,用紫外、熒光、理論計算、雙光子熒光技術(shù)等技術(shù)手段研究了其結(jié)構(gòu)與性能的關(guān)系。單體合成路線簡單且產(chǎn)率高(60%左右)。合成的單體為中等熒光強度(熒光量子產(chǎn)率在0.10-0.18之間)的藍色發(fā)光材料,而其雙光子熒光性能較弱(雙光子吸收截面在0.8 GM-7.76 GM之間)且有明顯的溶劑化效應(yīng)。烷基鏈長度對單體在溶液中的光物理性質(zhì)影響較大,主要是由于烷基鏈的空間位阻效應(yīng)可使聯(lián)二噻吩單元核和相鄰EDOT環(huán)之間的扭轉(zhuǎn)角發(fā)生較大的扭轉(zhuǎn)。合成的單體可在微型有機激光器、光電發(fā)射裝置等光學(xué)器件中得到廣泛應(yīng)用。2在CH2Cl2-Bu4NPF6(0.10 mol L-1)電解液中將5種低聚物作為單體采用陽極氧化法聚合獲得了相應(yīng)的共聚合物,在CH3CN-Bu4NPF6體系中系統(tǒng)研究了五種聚合物的電化學(xué)性能及電致變色性能。對聚合物的化學(xué)結(jié)構(gòu)、電化學(xué)性質(zhì)及表面形貌等性質(zhì)用CV、FT-IR、SEM、熱重、紫外和熒光等手段進行了表征和研究。研究結(jié)果表明所得聚合物具有良好的氧化還原活性、優(yōu)異的電化學(xué)穩(wěn)定性和熱穩(wěn)定性,其微觀形貌為光滑、平整的形貌。所得聚合物具有良好的電致變色性能：光學(xué)對比度最高可達41.4%,著色效率在96.8-293.2 cm2C-1之間,響應(yīng)時間最快為0.2 s。表明聯(lián)二噻吩-EDOT共聚物是潛在的電致變色器件材料。3采用恒電壓(0.7 V vs.Ag/AgCl)法成功制備了聯(lián)二噻吩-EDOT的共聚物,采用循環(huán)伏安法、恒流充放電法以及交流阻抗法等手段考察了共聚物的電容性能。研究結(jié)果表明,所合成共聚物具有良好的電容性能(5 mV s-1下(138.2 F g-1-203.4 F g-1之間))和倍率性能(78.8%-91.0%)、優(yōu)異的循環(huán)穩(wěn)定性(循環(huán)1000圈初始電容保持率最高可達84.6%)。所構(gòu)建的對稱電容器器件具有較高的能量密度(最高可達11.6 Wh/kg)和功率密度(最高可達13.9Wh/kg),均高于商業(yè)電容器的能量密度(通常5-10Wh/kg)。結(jié)果表明,這幾個導(dǎo)電聚合物可作超級電容器潛在的電極材料。4.基于PBEDOT-BT共聚物有著良好的電容性能,以BEDOT-BT和EDOT為前驅(qū)體,通過簡單的層層電化學(xué)沉積法成功制備了PEDOT/PBEDOT-BT/PEDOT三層結(jié)構(gòu)。在CH3CN-Bu4NPF6(0.1 mol L-1)溶液中采用循環(huán)伏安法、恒流充放電法、交流阻抗技術(shù)等手段研究了PEDOT/PBEDOT-BT/PEDOT三層結(jié)構(gòu)的電容性能,采用AFM、SEM、截面SEM等手段研究了其微觀結(jié)構(gòu)。研究結(jié)果表明PEDOT/PBEDOT-BT/PEDOT三層結(jié)構(gòu)為多孔納米結(jié)構(gòu)且具有較高的比電容和良好的電化學(xué)穩(wěn)定性。所構(gòu)建的對稱電容器具有相對較高的比電容(96.8 Fg-1)和相當(dāng)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).

【學(xué)位授予單位】：江西科技師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O631;TM53

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本文編號：1386129