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研究生： 黃靖穎
Huang, Ching-Ying
論文名稱： 高溫質子交換膜燃料電池用之含氟聚苯咪唑/多壁奈米碳管奈米複合材料合成與性質之研究
Synthesis and Properties of Fluorine-containing Polybenzimidazole/MWNTs Nanocomposites for High-Temperature PEMFC
指導教授： 許聯崇
Hsu, Lien-Chung Steve
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： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 124
中文關鍵詞： 質子交換膜燃料電池 、聚苯咪唑 、奈米複合材料
外文關鍵詞： PEMFC, PBI, nanocomposite
相關次數： 點閱：66  下載：0 
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    • 本論文研究利用3,3’-diaminobenzidine、2, 2-bis(4-carboxyphenyl) hexafluoropropane兩種單體合成分子結構中帶有含氟基團之聚苯咪唑(Polybenzimidazole，PBI)高分子，並以FTIR、1H-NMR分析鑑定此含氟PBI (HFPBI)之組成與結構。將市售之MWNTs-COOH改質為MWNTs-imi，並以FTIR、XPS、拉曼光譜分析鑑定其結構。將MWNTs-imi以不同比例混摻入HFPBI中，製備為PBI/MWNTs-imi奈米複合材薄膜由於改質後之奈米碳管表面具有imidazole官能基，可強化有機高分子與無機填充材之間的交互作用力。由場發射掃描式電子顯微鏡分析可看出MWNTs-imi在PBI中具有良好的相容性與分散性。PBI本身具有堅硬的結構，因此擁有良好的熱穩定性，經由TGA分析添加MWNTs-imi之PBI複合膜材，發現加入碳管並不會影響PBI之熱穩定性。此PBI複合膜材的機械性質與摻雜磷酸後之機械性質皆能藉由奈米碳管的添加而有大幅的改善。在質子導電率方面，導電度隨著溫度和摻雜磷酸之含量增加而提升，在PBI中添加無機物通常會造成質子導電率下降，但本研究在添加MWNTs-imi後，含浸磷酸之PBI奈米複合材薄膜的導電度並不會降低。

    First, an organosoluble fluorine-containing polybenzimidazole (HFPBI) was synthesized, using 3, 3’ -diaminobenzidine and 2,2-bis(4-carboxyphenyl)-hexafluoropropane as monomers. The structure of HFPBI was characterized by FT-IR, 1H-NMR. The 5 % weight loss temperature(T5d) of the polymer was at 518 °C.
    Second, MWNTs-imi were prepared from commercially available MWNTs-COOH and 1-(3-Aminopropyl)imidazole. The functionalized MWNTs were then characterized by FT-IR, XPS analysis, Raman spectroscopy and TGA.
    PBI/MWNTs-imi nanocomposite membranes were then prepared by solution-casting. SEM, TGA, tensile tests and AC impedance were used to characterize the properties of the nanocomposites. SEM analysis indicated that MWNTs-imi were well-dispersed and showed good compatibility with PBI matrix. The thermal stability of PBI/MWNTs-imi was great, T5d was at about 527 °C. In comparison with pure PBI, both the elastic modulus and tensile strength were enhanced after adding MWNTs-imi. From the results of four-point probe detector analysis, the electrical conductivity of the nanocomposite membrane was low, so there was thus no risk of short-circuit during the fuel cell operation when the MWNTs-imi content was lower than 1.0 wt%. Finally, the proton conductivity of the acid-doped nanocomposite membrane was almost the same as the pure acid-doped PBI membrane.

    摘要 I Abstract II 誌謝 III 總目錄 IV 圖目錄 VIII 表目錄 XII Scheme 目錄 XIII 第一章 緒論 1 1-1 前言 1 1-2 研究動機及目的 5 第二章 文獻回顧與原理 8 2-1 燃料電池簡介與發展 8 2-1-1 質子交換膜燃料電池 11 2-1-2直接甲醇燃料電池 14 2-2 高分子質子交換膜簡介 16 2-3 Polybenzimidazole(PBI)之介紹 22 2-3-1 PBI之特性 22 2-3-2 PBI之合成與種類 23 2-4 PBI薄膜之改質方式 27 2-5 PBI薄膜摻雜磷酸之質子傳導機制 30 2-6 有機/無機奈米複合材料 37 2-6-1 有機/無機奈米複合材之簡介 37 2-6-2 有機/無機奈米複合材之特性 38 2-7 奈米碳管(Carbon nanotubes)之簡介 39 第三章 實驗方法與步驟 45 3-1 實驗材料 45 3-2 實驗儀器 46 3-3 實驗步驟 48 3-3-1 含氟PBI (HFPBI)之合成 48 3-3-2 含氟HFPBI之薄膜製備 49 3-3-3 多壁奈米碳管的改質 50 3-3-4 HFPBI/modified-MWNTs 複合薄膜之製備 51 3-3-5 PBI薄膜摻雜磷酸之方法 52 3-4 結構鑑定 54 3-4-1 傅立葉轉換紅外線光譜儀(FTIR)分析 54 3-4-2 核磁共振光譜(1H-NMR)分析 54 3-4-3 X射線光電子能譜儀(X-ray photoelectron spectroscopy) 55 3-5 性質分析 57 3-5-1 固有黏度(Inherent viscosity)測定 57 3-5-2 奈米碳管分散穩定度(Dispersion stability)測試 57 3-5-3 熱重損失分析(TGA) 58 3-5-4 動態熱機械分析(DTMA) 58 3-5-5 交流阻抗分析(AC impedance) 59 3-5-6 薄膜拉伸機械性質分析 66 3-5-7 拉曼光譜分析 67 3-5-8 場發射掃描式電子顯微鏡(FE-SEM) 67 第四章 結果與討論 69 4-1 含氟PBI結構鑑定及性質分析 69 4-1-1 PBI之結構鑑定 70 (1)傅立葉轉換紅外線光譜(FTIR)分析 70 (2)核磁共振光譜分析(NMR) 71 4-1-2 PBI之固有黏度測定 71 4-1-3 熱重損失分析(TGA) 72 4-2 改質多壁奈米碳管之結構鑑定及性質分析 73 4-2-1傅立葉轉換紅外線光譜(FTIR)分析 73 4-2-2熱重損失分析(TGA) 73 4-2-3 X射線光電子能譜(X-ray photoelectron spectrum) 74 4-2-4 拉曼光譜分析(Raman spectrum) 76 4-2-5奈米碳管之分散穩定性(Dispersion stability) 77 4-3 PBI/MWNTs奈米複合材薄膜之性質分析 79 4-3-1場發射掃描式電子顯微鏡分析(FE-SEM) 79 4-3-2熱重損失分析(TGA) 80 4-3-3 機械性質分析 81 4-3-4 動態熱機械分析(DTMA) 85 4-3-5 電子導電率分析 86 4-3-6 質子導電率分析 87 第五章 結論 113 參考文獻 115

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