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研究生： 王澤瑋
Wang, Tse-Wei
論文名稱： 高溫質子交換膜燃料電池用之含氟聚苯咪唑/離子液體複合材料合成與性質之研究
Synthesis and properties of fluorine-containing polybenzimidazole/ionic liquids composites for high-temperature proton exchange membrane fuel cells
指導教授： 許聯崇
Hsu, Lien-Chung
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 115
中文關鍵詞： 燃料電池 、聚苯咪唑 、質子交換膜 、離子液體
外文關鍵詞： polybenzimidazole, fuel cell, ionic liquids, PEM
相關次數： 點閱：74  下載：3 
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    • 本論文研究利用 3,3’-diaminobenzidine 和 2,2-bis(4-carboxyphenyl)-hexafluoropropane 兩種單體合成出有機溶劑可溶之含氟聚苯咪唑高分子 (fluorine-containing Polybenzimidazole, HFPBI)。並藉由此含氟之聚苯咪唑高分子與離子液體 1-hexyl-3-methylimidazolium trifluoromethanesulfonate (HMI-Tf) 製備出質子交換膜燃料電池 (PEMFC) 用 HFPBI/HMI-Tf 複材薄膜。並以 1H-NMR、FTIR 分析鑑定此複材薄膜之組成與結構。
    由熱重損失分析 (TGA) 鑑定 HFPBI/HMI-Tf 複材薄膜之熱氧化穩定性，可發現此複材薄膜能保持熱穩定性直到 300 ℃，可以忍受較高的工作溫度，顯示出此複合膜材，可以符合新一代高溫 PEMFC 的高操作溫度需求。以交流阻抗分析方法，針對在無水狀況下，探討溫度與不同成分比例的 HMI-Tf 與 HFPBI 組成之複合膜材對於離子導電率的影響，可發現 HFPBI/HMI-Tf 複材薄膜之離子導電度可以被大幅提昇。
    然而添加 HMI-Tf 會降低 HFPBI 的機械性質和提昇其甲醇滲透率，但 HFPBI/HMI-Tf 複材薄膜仍然擁有一定的穩定性，因此 HFPBI/HMI-Tf 複材薄膜可有助於在高溫 PEMFC 上的應用。

    In this study, we report the preparation and characterization of composite membranes based on a fluorine-containing polybenzimidazole (HFPBI) with an ionic liquid, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate (HMI-Tf). An organosoluble HFPBI was synthesized from 3,3’-diaminobenzidine and 2,2-bis(4-carboxyphenyl)-hexafluoropropane. The structures of the HFPBI/HMI-Tf composite membranes was characterized by 1H-NMR and FTIR, and different HMI-Tf concentrations have been prepared to investigate. The thermooxidative stability was studied with TGA, all of the membranes demonstrated terrific thermal properties, and indicated that the HFPBI/HMI-Tf composite membranes could fit the requirement for PEMFC work at higher temperatures up to 300 °C. The ionic conductivity of the HFPBI/HMI-Tf composite membranes increased with both the temperature and the HMI-Tf content. The composite membranes achieve high ionic conductivity (1.6x10-2 S/cm) at 250 ℃ under anhydrous conditions. Although the addition of HMI-Tf resulted in a slight decrease in the methanol barrier ability and mechanical properties of the HFPBI membranes, the HFPBI/HMI-Tf composite membranes have demonstrated high thermal stability up to 300 ℃, and have become attractive candidates for high-temperature (>200 ℃) polymer electrolyte membrane fuel cells.

    摘要 I Abstract II 總目錄 III 圖目錄 VII 表目錄 X Scheme 目錄 XI 第一章 緒論 1 1-1 前言 1 1-2 研究動機及目的 4 第二章 文獻回顧與原理 7 2-1 燃料電池簡介 7 2-1-1 燃料電池的由來 7 2-1-2 燃料電池的種類與其發展 9 2-2 PEMFC 與 DMFC 簡介 16 2-2-1 PEMFC 操作原理 16 2-2-2 DMFC 操作原理 17 2-2-3 PEMFC 電極觸媒之作用 19 2-3 質子交換膜簡介 21 2-4 Polybenzimidazole (PBI) 之介紹 24 2-4-1 Polybenzazoles 簡介 24 2-5 質子傳導機制 28 2-5-1 Vehicle mechanism 30 2-5-2 Grotthuss mechanism 32 2-6 離子液體簡介及其應用 35 2-6-1 離子液體簡介 35 2-6-2 離子液體之發展 36 2-7 高溫質子交換膜燃料電池的特色 38 第三章 實驗方法與步驟 43 3-1實驗材料 43 3-2實驗儀器 45 3-3實驗步驟 46 3-3-1 含氟 HFPBI 之合成 46 3-3-2 含氟 HFPBI 之薄膜製備 47 3-3-3 HFPBI 薄膜酸質子化之製備 49 3-3-4 離子液體之選擇 50 3-3-5 HFPBI/Ionic Liquids 複合薄膜製備 51 3-4 儀器分析原理與方法 54 3-4-1 固有黏度 (Inherent viscosity) 測定 54 3-4-2 傅利葉轉換紅外線光譜分析 (FTIR) 54 3-4-3 核磁共振光譜分析 (NMR) 55 3-4-4 熱重損失分析 (TGA) 56 3-4-5 熱差掃瞄分析 (DSC) 56 3-4-6 熱機械分析 (TMA) 57 3-4-7 機械性質分析 58 3-4-8 甲醇滲透分析 59 3-4-9 交流阻抗分析 (AC impedance) 60 3-4-10 質子導電率分析 64 第四章 結果與討論 65 4-1 HFPBI/Ionic Liquids 複合膜材製備及性質之探討 65 4-1-1 與 HFPBI 相容的離子液體之選擇 65 4-2 HFPBI 合成結構之鑑定 68 4-2-1 HFPBI 固有黏度測定 69 4-2-2 HFPBI 核磁共振光譜分析 (NMR) 69 4-3 HFPBI/HMI-Tf 複合膜材之結構鑑定分析 70 4-3-1 核磁共振光譜分析 (NMR) 70 4-3-2 傅利葉轉換紅外線光譜分析 (FTIR) 71 4-4 HFPBI/HMI-Tf 複合膜材之熱性質分析 72 4-4-1 熱重損失分析 (TGA) 72 4-4-2 熱差掃瞄分析 (DSC) 75 4-4-3 熱機械分析 (TMA) 75 4-5 HFPBI/HMI-Tf 複合膜材之機械性質分析 78 4-6 HFPBI/HMI-Tf 複合膜材之甲醇滲透分析 80 4-7 HFPBI/HMI-Tf 複合膜材之離子導電率分析 82 第五章 結論 102 參考文獻 104

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