臺灣博碩士論文加值系統

質子交換膜是質子交換膜燃料電池中一個關鍵材料，而在過去數十年已被廣泛的研究。作為質子交換膜必須具備幾樣要素，如良好的機械特性、高化學穩定性以及高質子導電度。已有許多研究指出，部分氟化的高分子電解質相對於非氟化高分子電解質的傳統烴擁有許多先天優勢，優異的熱穩定性、良好的機械性能和相對經濟的價格，以及高疏水特性能提供更好的相分離形態和質子導電度。
本論文欲合成一系列部分含氟磺酸化碳氫高分子電解質。高分子主要由高立體障礙性多苯環結構組成的聚芳香醚，而高分子的主鏈與側鏈上將會引入三氟甲基取代基，並探討三氟甲基以及不同取代基數量對於質子交換膜之特性的影響。這些性質包括熱穩定性、吸水率、機械強度、尺寸穩定性、質子導電性和微相分離型態。最終將評估其作為質子交換膜應用於質子交換膜燃料電池可能性。

Proton exchange membranes as a key component in fuel cells have been widely studying over the past few decades. As proton exchange membranes should have some main characteristics, such as good mechanical properties, low oxidative stability and high proton conductivity. Many researchers have reported that partially fluorinated　polymer electrolytes own natural advantage over traditional non-fluorinated hydrocarbon polymer electrolytes in　terms of excellent thermal stabilities, good mechanical properties, relative economic cost and high hydrophobic ability can provide better phase separated morphology and proton conductivity.
Herein, a series of novel partially fluorinated sulfonated poly(arylene ether)s were synthesized. The sterically hindered multi-phenylated structure and the trifluoromethyl group were introduced on polymer backbone and phenyl side chain. The effect of trifluoromethyl group and number of trifluoromethyl substituent group on proton exchange membranes were investigated. The properties of these novel　sulfonated polymers such as thermal stability,　water uptake, mechanical strength, dimensional stability,　proton conductivity, and morphology are studied. Finally, the potential of these poly(arylene ether)s for proton exchange membrane fuel cells application are evaluated.

目錄
中文審定書 i
英文審定書 ii
致謝 iii
摘要 iv
Abstract v
目錄 vi
圖目錄 xi
表目錄 xvi
第一章 緒論 1
1-1 前言 1
1-2 燃料電池種類 2
1-3 質子交換膜燃料電池 3
1-4 質子交換膜 5
1-4-1 全氟磺酸離子薄膜 (Perfluorosulfonic Acid Ionomer Membranes) 6
1-4-2 部分氟化高分子(Partially Perfluorinated Acid Ionomer Membranes) 7
1-4-3 非氟磺酸離子薄膜(Nonfluorinated Acid Ionomer Membranes) 7
1-4-4 鹼性離子薄膜(Alkaline Ionomer Membranes) 8
1-4-5 酸-鹼錯合物(Acid-base complexes) 9
1-5 高分子結構設計(Polymer Architectures for PEMs) 10
1-5-1 磺酸化交替型高分子(Sulfonated alternating polymer) 11
1-5-2 磺酸化無規共聚高分子(Sulfonated random copolymer) 12
1-5-3 磺酸化多嵌段共聚高分子(Sulfonated multiblock copolymers) 13
1-5-4 磺酸化分枝型高分子(Sulfonated branched polymers) 14
1-6 文獻回顧 16
1-6-1 磺酸化交替型與共聚型高分子 16
1-6-2 磺酸化多嵌段共聚高分子與局部密集磺酸化高分子 21
1-7 燃料電池市場 26
1-8 研究目的 29
第二章 實驗藥品、儀器與量測 30
2-1 實驗藥品 30
2-2 實驗儀器 32
2-2-1 高磁場液態磁核共振儀器 (Nuclear Magnetic Resonance，NMR) 32
2-2-2 基質輔助雷射脫附游離飛行質譜儀 (MALDI TOF/TOF) 32
2-2-3 凝膠滲透層析儀 (Gel Permeation Chromatography，GPC) 32
2-2-4 傅立葉紅外線光譜儀 (Fourier Transform infrared spectro scopy，FT-IR) 33
2-2-5 熱重量分析儀 (Thermogravimetric Analyzer，TGA) 33
2-2-6 熱示差掃描卡量計 (Differential Scanning Calorimetr，DSC) 33
2-2-7 熱機械分析儀 (Thermal Mechanical Analyzer，TMA) 34
2-2-8 穿透式電子顯微鏡 (Transmission Electron Microscope，TEM) 34
2-2-9 小角度(低掠角/穿透式)X光散射儀 (Grazing Incidence/ Transmission Small-angel X-ray Scattering，SAXS) 34
2-3 量測方式 35
2-3-1 磺酸化後處理 35
2-3-2 離子交換能力測定 (Ion exchange capacity, IEC) 35
2-3-3 吸水率、尺寸安定性測試 (Water uptake, Dimensional stability) 36
2-3-4 Hydration number (λ) 36
2-3-5 氧化、水解穩定性 (Oxidative and hydrolytic stability) 36
2-3-6 質子導電度 (Proton conductivity) 37
2-4 氫氧燃料電池元件 (Fuel Cell) 37
第三章 磺酸化多苯環聚芳香醚薄膜導入三氟甲基取代基之影響 39
3-1 目的 39
3-2 實驗 41
3-2-1 反應流程圖 41
3-2-2 二醇單體合成步驟 44
3-2-3 二氟單體合成步驟 49
3-2-4 高分子聚合步驟 51
3-2-5 高分子薄膜製備 54
3-2-6 高分子磺酸化 54
3-3 結果與討論 56
3-3-1 分子量 56
3-3-2 核磁共振光譜分析(NMR) 56
3-3-3 傅立葉紅外線光譜(FT-IR)分析 59
3-3-4 TGA熱穩定性分析 60
3-3-5 機械強度特性分析 62
3-3-6 吸水率、尺寸安定性以及λ值 65
3-3-7 氧化及水解穩定性 68
3-3-8 質子導電度 69
3-3-9 微相分離型態 70
3-3-10 燃料電池元件 71
3-4 結論 73
第四章 探討三氟甲基取代基數目對於磺酸化聚芳香 醚薄膜特性之影響 74
4-1 目的 74
4-2 實驗 75
4-2-1 反應流程圖 75
4-2-2 多氟單體製備 77
4-2-3 高分子聚合 80
4-2-4 高分子磺酸化 81
4-3 結果與討論 83
4-3-1 分子量、單體與高分子結構鑑定 83
4-3-2 傅立葉紅外線光譜(FT-IR)分析 87
4-3-3 TGA熱穩定性分析 89
4-3-4 機械強度特性分析 93
4-3-5 吸水率、尺寸安定性以及λ值 97
4-3-6 質子導電度 100
4-3-7 微相分離型態 102
4-3-8 小角度X光散射儀 104
4-3-9 燃料電池元件測試 105
4-4 結論 107
第五章　含氟磺酸化多苯環聚芳香醚應用於質子交換膜燃料電池之研究 108
5-1 目的 108
5-2 實驗 109
5-2-1 反應流程圖 109
5-2-2 單體製備 111
5-2-3 高分子聚合 113
5-2-4 磺酸化反應 115
5-3 結果與討論 116
5-3-1 分子量 116
5-3-2 單體與高分子結構鑑定 117
5-3-3 FT-IR分析 119
5-3-4 熱穩定性分析 121
5-3-5 機械強度分析 123
5-3-6 吸水率與穩定性量測 124
5-3-7 氧化與水解穩定性 126
5-3-8 質子導電度 127
5-3-9 微相分離型態 129
5-3-10 燃料電池元件效率 130
5-4 結論 131
第六章 部分含氟之無規共聚磺酸化聚芳香醚薄膜之合成與特性研究 132
6-1 目的 132
6-2 實驗 133
6-2-1 反應流程 133
6-2-2 多氟單體製備 135
6-2-3 高分子聚合 137
6-2-4 高分子磺酸化 139
6-3 結果與討論 141
6-3-1 分子量與結構鑑定 141
6-3-2 熱穩定性分析 146
6-3-3 機械強度分析 146
6-3-4 吸水率與穩定性量測 148
6-3-5 氧化與水解穩定性 150
6-3-6 質子導電度 151
6-3-7 微結構分析 153
6-3-8 燃料電池元件 154
6-4 結論 155
第七章 總結 156
第八章 參考文獻 158
附錄(依章節排序) 163
A-1 MALDI-TOF MASS 163
A-2 核磁共振光譜 169
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