臺灣博碩士論文加值系統

燃料電池質子交換膜是許多學者極力研究的領域，本研究利用單體3,3’ diaminobenzidine(DAB)和2,2-Bis(4-carboxyphenyl)hexafluoropropane(2B-HFA)以溶液縮聚法合成含氟聚苯並咪唑(PBI)。PBI在浸泡於酸時其機械強度會大幅下降，為了修補其缺點故添加聚偏氟乙烯(PVDF)，從紅外線光譜儀分析可知成功合成含氟聚苯並咪唑，在一系列磺化含氟PBI/PVDF複合膜中可觀察到PVDF的特性吸收峰越來越明顯；從熱重損失分析可知此一系列薄膜的熱裂解溫度(Td)大約在540~565℃間，顯示了此複合膜具有耐高溫的特性；隨著磺化程度增加，吸水率有逐漸提升的趨勢，磺化40%含氟PBI吸水率可達17.31%；而質子傳導率則是隨著磺化程度增加，磺化30%含氟PBI薄膜呈現最高的導電度，可達7.61×10-4 S/cm。

Proton exchange membrane fuel cell is strongly field of study to many scholars, fluorine-containing polybenzimidazole (PBI) was synthesized from 3,3’-diaminobenzidin and 2,2-bis(4-carboxyphenyl)-hexafluoropropane by solution polycondensation. When PBI soaked in phosphoric acid, mechanical strength drops significantly, added polyvinylidene fluoride (PVDF) to fill the shortcoming. Further from Infrared spectroscopy analysis shows that a successful synthesis of fluorine-containing polybenzimidazole, Characteristics of PVDF can be observed more and more obvious peaks; Thermogravimetric analysis shows that this series of film, showing the composite film has high temperature properties; As the sulfonation degree increases, water absorption trend has gradually improved, 40% sulfonated PBI water absorption of up to 17.31%; proton conductivity is increased with the degree of sulfonation, sulfonated PBI film 30% of fluoride with the highest conductivity up to 7.61 × 10-4 S/cm.

摘 要 ii
ABSTRACT iii
目 錄 iv
表 目 錄 vii
圖 目 錄 viii
第一章 緒論 1
1-1 前言 1
1-2 質子交換膜介紹 3
1-2-1 離子聚合質子交換膜(Ionomer membrane)的種類 5
1-2-1-1 全氟化合物高分子(Perfluorinated Polymer) 6
1-2-1-2 薄型的 PFSA 強化膜(Thin,reinforced PFSA membrane) 7
1-2-1-3 高分子層導入交換膜 8
1-2-1-4 部分氟化高分子(Partially fluorinated Polymer) 9
1-2-1-5 碳氫化合物高分子(Hydrocarbon Polymer) 10
1-2-1-6 離子團簇 13
1-3 質子交換膜燃料電池內部之輸送現象 14
1-3-1 質子交換膜工作原理 15
1-4 燃料電池的介紹 17
1-4-1 燃料電池的發展與現況 18
1-4-2 燃料電池的種類 22
1-4-2-1 鹼性燃料電池 22
1-4-2-2 磷酸燃料電池 24
1-4-2-3 熔融碳酸鹽燃料電池 24
1-4-2-4 固態氧化物燃料電池 25
1-4-2-5 質子交換膜燃料電池 26
1-5 直接甲醇燃料電池 27
第二章 研究動機與文獻回顧 34
2-1 研究動機與目的 34
2-2 文獻回顧 37
2-2-1 聚苯並咪唑(PBI)的製備方法 37
2-2-1-1 熔融縮聚法 37
2-2-1-2 溶液聚合法 38
2-2-1-3 母體法 38
2-2-1-4 親核取代法 39
2-2-2 PBI的應用 39
2-2-3 介電原理 40
2-2-3-1 介電性質 40
2-2-3-2 極化 40
2-2-3-3 鐵電性質 41
2-2-3-4 介電常數 42
2-2-3-5 介電鬆弛理論 46
2-2-4 交流阻抗原理 48
2-2-4-1交流阻抗之應用 48
2-2-4-2交流阻抗之分析 50
2-2-5 磺酸化的原理 51
2-2-6 PBI相關改質 52
第三章 實驗儀器與實驗步驟 56
3-1 實驗藥品與材料 56
3-2 實驗器材 58
3-3 實驗步驟 62
3-3-1 純PBI合成(DAB + IPA)(200℃,24h) 62
3-3-2 含氟PBI之合成(200℃, 24h) 63
3-3-3 含氟PBI之合成(160℃,8h) 64
3-3-4 磺化含氟PBI之合成(160℃,8h) 65
3-3-5磺化含氟PBI接枝PVDF 66
3-3-6 薄膜製備 67
3-4 樣品分析測試 68
第四章 結果與討論 72
4-1 純PBI合成(DAB + IPA)(200℃, 24h) 72
4-1-1 傅立葉紅外線光譜儀之分析 72
4-1-2 熱重損失之分析(TGA) 73
4-2 含氟PBI之合成(200℃, 24h) 75
4-2-1 傅立葉紅外線光譜儀之分析 75
4-2-2 熱重損失之分析(TGA) 76
4-3 含氟PBI之合成(160℃, 8h) 78
4-3-1 傅立葉紅外線光譜儀之分析 78
4-3-2 熱重損失之分析(TGA) 79
4-3-3 薄膜的性質測試 80
4-3-4 傅立葉紅外線光譜儀之分析 81
4-3-5 熱重損失之分析(TGA) 82
4-3-6 掃描電子顯微鏡之分析(SEM) 83
4-3-7 掃描電子顯微鏡之元素分析(SEM-EDS) 85
4-4 磺化含氟PBI之合成(160℃,8h) 86
4-4-1 傅立葉紅外線光譜儀之分析 86
4-4-2 X光繞射分析(XRD) 88
4-4-2 熱重損失之分析(TGA) 89
4-4-3 含水率之檢測分析 90
4-4-4 離子交換容量之檢測分析 94
4-4-5 介電常數之檢測分析 97
4-4-6 AC交流阻抗之檢測分析 103
4-4-7 動態機械分析檢測(DMA) 106
4-4-8 熱示差卡掃描分析(DSC) 108
第五章 結論 109
第六章 致謝 111
參考文獻 112

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