多氟磺酸離子性高分子(PFSA)為一種已知且曾經被大量研究之高分子，除
了被過度延伸的成就之外，它也遭遇：(1)價格昂貴；(2)低濕或高溫條件操作下喪
失質子導電度，兩大無法解決之困難。由於多氟磺酸離子性高分子滲透膜之氣體
滲透率過大，因此經常加速觸媒層中奈米組成物的裂解以及導致在相對應電極之
氣體純度下降而影響效率；更嚴重的情況是，因為多氟磺酸離子性高分子提供極
高度酸性之環境，因此加速白金觸媒之老化及造成各組成物的裂解。從科技角度
的觀點，上述的許多缺點已經引領大量的研究團隊投入到尋找替代固態高分子電
解質的研究領域。
本論文將著眼於設計供質子交換膜燃料電池觸媒層使用的非多氟磺酸
(non-PFSA)固態高分子電解質。在此之非多氟磺酸高分子主要以發展具有高立體阻
礙之聚芳香醚高分子為主。

The current material of choice for the proton exchange membrane (PEM) and for the solid electrolyte in the catalyst layer currently comes from a class of materials known as PerFluoroSulfonic Acid ionomer (PFSA). Despite its ubiquitous and it is costly, suffers from a loss of conductivity at low relative humidity and/or elevated temperatures, and despite it’s relative chemical stability it may exacerbate Pt catalyst dissolution and contribute to the rate of component degradation. Alternating ionomers are sought.
This proposal addresses the challenge of developing non-PFSA ionomers for use as proton conducting media in catalysts layer. It does this by focusing on the development of a class of materials classified as sterically-encumbered poly(arylene ether)s.

目錄
論文審定書 i
致 謝 ii
摘 要 iii
Abstract iv
第一章. 序論 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工作機制 5
1-4質子傳導機制 7
1-5燃料電池的過電壓(overpotential)介紹 10
1-6 質子交換膜燃料電池種類 12
1-6-1全氟離子性高分子薄膜(Perfluorinated polymer) 13
1-6-2非氟離子性高分子薄膜(Non-perfluorinated polymer) 15
1-6-3部分氟化高分子(Partially perfluorinated polymer) 16
1-6-4酸鹼高分子薄膜(Acid-base blends polymer) 17
1-6-5有機/無機混成薄膜(organic/inorganic blend membrane) 18
1-7 碳氫離子性質子交換膜的分子設計(Polymer Architectures for Proton Exchange Membrane) 20
1-7-1交替式共聚高分子(Alternating copolymer) 22
1-7-2團聯式共聚高分子(Random copolymer) 22
1-7-3嵌段式共聚高分子(Block copolymer) 23
1-7-4 接枝式共聚高分子(Graft copolymer) 25
1-8 文獻回顧 27
1-8-1交替式磺酸化聚芳香醚高分子文獻回顧 27
1-8-2團聯式磺酸化聚芳香醚高分子文獻回顧 32
1-8-3嵌段式磺酸化聚芳香醚高分子文獻回顧 43
1-8-4接枝式磺酸化聚芳香醚高分子文獻回顧 46
1-9全球燃料電池市場之脈動 51
1-10 研究動機 54
第二章. 實驗儀器介紹與原理 56
2-1鑑定分析儀器 56
2-1-1高磁場液態磁核共振儀器(Nuclear Magnetic Resonance，NMR) 56
2-1-2基質輔助雷射脫附游離飛行質譜儀(MALDI TOF/TOF) 56
2-1-3凝膠滲透層析儀(Gel Permeation Chromatography，GPC) 57
2-2熱分析儀器 57
2-2-1熱重量分析儀(Thermogravimetric Analyzer，TGA) 57
2-2-2熱示差掃描卡量計(Differential Scanning Calorimetr，DSC) 58
2-2-3熱機械分析儀(Thermal Mechanical Analyzer，TMA) 58
2-3 微觀結構分析 58
2-3-1穿透式電子顯微鏡(Transmission Electron Microscope，TEM) 58
2-3-2原子力顯微鏡(Atomic force microscope，AFM) 59
2-4磺酸化後處理 60
2-5 燃料電池元件(Membrane electrode assambly, MEA) 62
第三章. 交替式共聚高分子之合成及特性研究 65
3-1使用藥品總表 65
3-2實驗流程 67
3-3 雙氟單體合成 68
3-4 高分子聚合 74
3-4-1 P1高分子聚合 74
3-4-2 P2高分子聚合 75
3-4-3 P3高分子聚合 76
3-4-4 P4高分子聚合 77
3-5 高分子磺酸化 78
3-6結果與討論 79
3-6-1單體鑑定以及GPC分析 79
3-6-2 TGA熱穩定性分析 81
3-6-3 磺酸化高分子溶解度測試與IEC數值量測 82
3-6-4 TGA熱穩定性分析 84
3-6-5 吸水率與λ值量測 85
3-6-6 薄膜尺寸安定性 87
3-6-7 質子導電度 88
3-6-8 TEM、AFM微相分離型態觀察 91
3-7 結論 98
3-8 補充資料 99
第四章. 交替式共聚高分子苯環取代基數目對質子導電度的影響 100
4-1 研究動機 100
4-2實驗流程 101
4-3雙酚單體合成 105
4-4高分子聚合 116
4-4-1 A7高分子聚合 116
4-4-2 A8高分子聚合 118
4-4-3 A9高分子聚合 120
4-5高分子薄膜製備 122
4-6高分子磺酸化 122
4-7結果與討論 124
4-7-1高分子TGA熱穩定性分析 124
4-7-2高分子機械強度 125
4-7-3傅立葉紅外線光譜(FT-IR)分析 130
4-7-4磺酸化後的高分子TGA熱穩定性分析 134
4-7-5薄膜之物理、化學性質分析 137
4-7-6質子導電度量測 143
4-7-7氧化與水解穩定性測試 145
4-7-8 TEM微相分離型態觀察 146
4-7-9 燃料電池元件測試 149
第五章. 含有酮基與碸基磺酸化聚芳香醚高分子之合成及特性研究 154
5-1研究動機 154
5-2實驗流程 156
5-3 高分子聚合 157
5-3-1 KP1高分子聚合 157
5-3-2 SP1高分子聚合 158
5-4 高分子磺酸化 159
5-5結果與討論 161
5-5-1 KP1&SP1高分子特性分析 161
5-5-2 高分子及磺酸化高分子1H NMR分析 162
5-5-3 KP1與SP1高分子之熱穩定性分析 166
5-5-4 IEC數值、吸水率、尺寸安定性及密度量測 167
5-5-5 質子導電度 171
5-5-6 TMA分析 173
5-5-7氧化與水解穩定性量測 173
5-5-8 TEM微相分離型態觀察 175
5-5-9 燃料電池元件效率 177
5-6結論 179
第六章. 甲醇可溶性固態高分子電解質應用於燃料電池觸媒層 180
6-1研究動機 180
6-2實驗方法 181
6-2-1單體合成流程圖 181
6-2-2 高分子合成流程圖 182
6-2-3磺酸化高分子流程圖 182
6-3高分子聚合 187
6-3-1 P4b聚合 187
6-3-2 P4c聚合 188
6-3-3高分子磺酸化 189
6-4結果與討論 191
6-4-1 單體、高分子結構鑑定與GPC分析 191
6-4-2 熱穩定性分析 192
6-4-3 吸水率 195
6-4-4 質子導電度 199
6-4-5 TEM微相分離型態觀察 201
6-4-6 燃料電池元件製作 203
6-5結論 218
6-6補充資料 219
第七章. 總結論 223
第八章. 未來工作 224
第九章. 參考文獻 226

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