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研究生： 傅瑋誠
Fu, Wei-cheng
論文名稱： 在離子液體中電化學製備多孔性聚(3,4-二氧乙基噻吩)電極應用於超級電容器
Electrochemical preparation of porous poly (3,4-ethylenedioxythiophene) electrodes from room temperature ionic liquids for supercapacitors
指導教授： 孫亦文
Sun, I-Wen
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2015
畢業學年度： 103
語文別： 中文
論文頁數： 120
中文關鍵詞： 超級電容器 、離子液體 、導電高分子 、聚(3,4-二氧乙基噻吩)
外文關鍵詞： Supercapacitor, ionic liquid, conducting polymer, PEDOT
相關次數： 點閱：100  下載：1 
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    • 本論文主要研究探討在不同離子液體和有機溶液中電聚合導電高分子poly(3,4-ethylenedioxthioiphene)(PEDOT)製備成超級電容器的電極，並使用離子液體1-ethyl-3-methylimidazolium tetrafluoroborate ([EMI][BF4])和0.1M KClO4水溶液作為兩種不同電容電解液，對PEDOT電極進行電容的效能檢測，此外也會對不同電解液中製備的PEDOT電極進行性質的分析，由上述檢測和分析來探討電解液對PEDOT電極在超級電容應用上的影響。
    論文中使用四種不同電解液來製備PEDOT電極分別為三種不同陰陽離子搭配的離子液體1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMI][TFSI])、1-butyl-3-methylimidazolium tetrafluoroborate ([BMI][BF4])、1-allyl-3-(2-methoxyethyl)-imidazolium bis(trifluoromethylsulfonyl)imide ([AMO][TFSI])以及有機溶液acetonitrile加上0.1M LiClO4輔助電解質，製備後的PEDOT電極以掃瞄式電子顯微鏡和X射線光電子能譜進行電極的表面結構分析和組成分析，分析結果發現在[BMI][BF4]離子液體中製備的PEDOT電極表面會有網狀多孔的形貌且具有較高的陰離子摻雜程度，相較於其他電解液中製備的PEDOT電極會有較高的電化學活性和良好的電容效果。
    電容效能的測試上，以對稱型二極式的電容器裝置在水溶液和離子液體兩種電容電解液中進行。由測試結果發現以[BMI][BF4]離子液體製備的PEDOT電極組成的電容器會有最好的電容效果，在水溶液系統下，會有較高的比電容191 F/g，最大能量密度可達5.4 Wh/Kg，在離子液體系統下，最高比電容為183 F/g，由於離子液體會有較大的電位窗，使得最大能量密度可達12.5 Wh/Kg。從電容比較結果發現，使用離子液體作為製備電解液，能夠大幅提昇PEDOT電極的電容效果。

    Poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes for supercapacitor applications were prepared by current pulse method from different electrolytes including room temperature ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMI][TFSI]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMI][BF4]), 1-allyl-3-(2-methoxyethyl)-imidazolium bis(trifluoromethylsulfonyl)imide ([AMO][TFSI]) and organic solution of 0.1M LiClO4 in acetonitrile (ACN).The SEM and XPS studies show that the PEDOT films electropolymerized in [BMI][BF4] are highly porous and have a higher degree of anion doping than the PEDOT films polymerized in other ionic liquds and LiClO4/ACN electrolytes.
    The electrochemical performance of the symmetrical supercapacitor based on PEDOT electrodes were investigated in [EMI][BF4] ionic liquid, and 0.1M KClO4 aqueous electrolytes by cyclic voltammetry and galvanostatic charge-discharge test. The PEDOT electrodes were prepared from [BMI][BF4] ionic liquid exhibit higher capacitative performance than the other PEDOT electrodes. The PEDOT electrodes were prepared from [BMI][BF4] ionic liquid show high specific capacitance values of 191 F/g (in 0.1M KClO4 aqueous electrolyte) and 183 F/g (in [EMI][BF4] ionic liquid). The symmetrical supercapacitor based on PEDOT electrodes and [EMI][BF4] ionic liquid electrolyte shows maximum specific energy of 12.5 Wh/Kg and good cycle durability.
    This study shows using ionic liquids as electrolytes for preparing PEDOT electrodes is an efficient way to improve performance of supercapacitors.

    摘要 I 致謝 VIII 本文目錄 IX 表目錄 XII 圖目錄 XIII 第一章 緒論 1 1-1 超級電容器應用與發展 1 1-2 電容器種類與簡介 3 1-2-1 傳統電容器 3 1-2-2 超級電容器 4 1-3 離子液體 8 第二章 基礎理論與文獻回顧 10 2-1 導電高分子 10 2-1-1 導電機制 12 2-1-2常見應用於超級電容器之導電高分子介紹 16 2-1-3導電高分子PEDOT介紹 21 2-2 文獻回顧 25 2-3 研究動機 31 第三章 實驗部分 33 3-1 藥品、材料與儀器設備 33 3-1-1 藥品與材料 33 3-1-2 儀器設備 34 3-2 實驗方法 35 3-2-1 離子液體合成 35 3-2-2 銀/氯化銀 (Ag/AgCl,sat’KCl)參考電極的製作 42 3-2-3 導電高分子PEDOT電極之製作 43 3-2-3-1 在有機溶液中電聚合PEDOT 43 3-2-3-2 在離子液體中電聚合PEDOT 44 3-3 實驗儀器原理介紹 46 3-3-1 掃瞄式電子顯微鏡(Scanning Electron Microscopy, SEM) 46 3-3-2 X射線光電子能譜(X-ray photoelectron spectroscopy, XPS) 47 3-4 電容測試實驗方法和原理 48 3-4-1 三極式循環伏安法測試(Cyclic Voltammetry, CV) 48 3-4-2 二極式循環伏安法測試 52 3-4-3 定電流充放電測試(Galvanostatic charge and discharge) 53 3-4-4 電化學阻抗圖譜分析(Electrochemical Impedance Spectroscopy, EIS) 56 第四章 實驗結果與討論 58 4-1 定電流脈衝法製備PEDOT電極之最佳條件 58 4-1-1 以不同電流值製備PEDOT電極 58 4-1-2 以不同電流值製備PEDOT電極之電容行為檢測 61 4-2 在不同電解液中製備PEDOT電極之比較 66 4-2-1 在不同電解液中製備PEDOT電極 66 4-2-2 不同電解液中製備PEDOT電極之三極式循環伏安法測試 68 4-2-3 在不同電解液中製備PEDOT電極之SEM分析 72 4-2-4 在不同電解液中製備PEDOT電極之XPS分析 74 4-3 PEDOT電極之電容效能測試 82 4-3-1 水溶液系統電容效能測試 82 4-3-1-1 水溶液系統之二極式循環伏安法測試 82 4-3-1-2 水溶液系統之定電流充放電測試 84 4-3-1-3 水溶液系統之能量密度及功率密度討論 87 4-3-1-4 水溶液系統之電化學阻抗分析討論 88 4-3-1-5 水溶液系統之電容循環壽命穩定性討論 91 4-3-2 離子液體系統電容效能測試 93 4-3-2-1 離子液體系統之二極式循環伏安法測試 93 4-3-2-2 離子液體系統之定電流充放電測試 95 4-3-2-3 離子液體系統之能量密度及功率密度討論 98 4-3-2-4 離子液體系統之電化學阻抗分析討論 100 4-3-2-5 離子液體系統之電容循環壽命穩定性討論 102 4-4不同輔助電解質對製備PEDOT電極之影響 104 4-4-1 含不同輔助電解質之電解液中製備PEDOT電極 104 4-4-2 以不同輔助電解質製備PEDOT電極之SEM分析 106 4-4-3 離子液體系統中電容效能測試 108 4-4-3-1 離子液體系統之二極式循環伏安法測試 108 4-4-3-2 離子液體系統之定電流充放電測試 109 結論 113 參考文獻 116

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