本論文主要合成一系列含氟磺酸化聚芳香醚高分子應用於質子交換膜與燃料電池元件探討，主要改良龐俊傑學長之結構，將含氟之二氟單體分別與七苯環、八苯環和九苯環二醇單體進行親核性聚縮合反應得到三種含氟聚芳香醚高分子(HFA series)。以三種不同濃度(2.5、3與3.5 c.c.)的磺酸化試劑進行磺酸化後，得到九種不同磺酸化程度與微相分離型態之含氟聚芳香醚高分子(SHFA series)，藉由控制二氟單體上三氟甲基基團的數目進而控制磺酸根基團接枝的數目，使質子交換膜能同時保有高導電度與良好尺寸安定性。
所有單體、高分子與磺酸化高分子皆透過FT-IR及1H -NMR鑑定結構無誤，GPC量測三種高分子之分子量結果介於75,000~117,000 g/mol，且皆具有良好成膜性，其熱裂解溫度(Td5%)皆高於588oC。九種磺酸化高分子之(Td5%)皆高於227oC，展現良好熱穩定性。離子交換能力(Ion exchange capacity, IEC)介於2.61~3.32 mmol/g。在80oC下，薄膜仍保有完整形貌，其吸水率為74.55%~200%，且具有良好尺寸安定性(15.21%~37.5%)與機械性質(0.46~1.115 GPa)。質子導電度方面皆高於173.9 mS/cm且遠勝於Nafion 211(123 mS/cm)。透過TEM與SAXS可知此系列磺酸化高分子擁有良好微相分離型態。最後元件效率部分，其中SHFA7-2.92效率高達1.318 W/cm2，高於Nafion 211之1.248 W/cm2。綜合上述，此系列材料(SHFA series)具有作為質子交換膜燃料電池極大的潛力。

This thesis is the study on fluorine-containing poly(arylene ether)s as proton exchange membrane and high-efficiency fuel cell device. Three fluorine-containing poly(arylene ether)s (HFA series) were synthesized by nucleophilic polycondensation reaction of the fluorine-containing bisfluoro monomer and three bisphenol monomers(9-phenyls, 8-phenyls and 7-phenyls). Nine fluorine-containing sulfonated poly(arylene ether)s (SHFA series) with different sulfonation levels and microphase separation patterns were obtained by three sulfonation reagents at different concentrations (2.5, 3, and 3.5 c.c.). The proton exchange membrane can maintain high conductivity and good dimensional stability by controlling the number of trifluoromethyl groups which controls the number of sulfonate groups grafted.
The structures of materials were confirmd by FT-IR and 1H -NMR. The weight-average molecular weight of three polymers ranging from 75,000 to 117,000 g/mol. The polymers show thermal degradation temperatures up to 588oC. Nine sulfonated polymers show thermal degradation temperatures up to 227oC and IEC values between 2.61 and 3.32 mmol/g. The films maintain the complete morphology as its water uptake ranging from 74.55% to 200% at 80oC, also have good dimensional stability (15.21%~37.5%) and mechanical properties (0.46 ~ 1.115GPa). The proton conductivity is up to 173.9 mS/cm and better than Nafion 211(123 mS/cm). Sulfonated polymers show good microphase separation by TEM and SAXS. In fuel cell performance, the power density of SHFA7-2.92 is 1.318 W/cm2 which is better than Nafion 211(1.248 W/cm2). In summary, these materials (SHFA series) have the greatest potential as a proton exchange membrane fuel cell.

論文中文審定書 i
論文英文審定書 ii
致謝 iii
摘要 iv
Abstract v
目錄 vii
圖目錄 xii
表目錄 xvi
第一章 序論 1
1-1 前言 1
1-2 燃料電池簡介 2
1-3 質子交換膜燃料電池 4
1-3-1 元件構造 4
1-3-2 工作原理 5
1-4 質子傳導機制 6
1-4-1 Grotthus Mechanism 6
1-4-2 Vehicular Mechanism 7
1-4-3 Surface Mechanism 7
1-5 質子交換膜 8
1-5-1 質子交換膜性質 8
1-5-2 質子交換膜種類 8
1-6 碳氫離子性高分子結構設計 11
1-6-1 交替型共聚高分子(Alternating copolymer) 12
1-6-2 無規型共聚型高分子(Random copolymer) 12
1-6-3 嵌段型共聚高分子(Block copolymer) 12
1-6-4 接枝型共聚高分子(Graft copolymer) 12
1-7 文獻回顧 13
1-7-1 交替型共聚高分子文獻回顧 13
1-7-2 無規型共聚高分子文獻回顧 16
1-7-3 接枝式共聚高分子文獻回顧 19
1-7-4 嵌段式共聚高分子文獻回顧 20
1-8 研究動機 23
第二章 儀器介紹與原理 24
2-1 鑑定分析儀器 24
2-1-1 高磁場液態核磁共振儀(Nuclear Magnetic Resonance, NMR) 24
2-1-2 基質輔助雷射脫附游離飛行時間質譜儀(MALDI TOF/TOF) 25
2-1-3 凝膠滲透層析儀(Gel Permeation Chromatography, GPC) 26
2-1-4 傅立葉紅外線光譜儀(Fourier Transform infrared spectro scopy, FT-IR) 27
2-2 熱分析儀器 28
2-2-1 熱重量分析儀(Thermogravimetric Analyzer, TGA) 28
2-2-2 熱機械分析儀(Thermal Mechanical Analyzer, TMA) 29
2-3 微觀分析儀器 30
2-3-1 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 30
2-3-2 小角度X光散射儀(Small-angel X-ray Scattering) 31
2-4 磺酸化薄膜特性量測 32
2-4-1 交流阻抗分析儀(AC Impedance) 32
2-5 元件效率量測分析與MEA製備 33
2-5-1 自動薄膜塗佈機(Automatic Film Applicator) 33
2-5-2 超音波霧化噴塗機(Ultrasonic Spraying System) 34
2-5-3 燃料電池元件(Membrane electrode assembly, MEA) 35
第三章 實驗步驟 36
3-1 實驗藥品總表 36
3-2 實驗流程 38
3-2-1 二氟單體流程 38
3-2-2 二醇單體流程 38
3-2-3 高分子聚合流程 40
3-2-4 高分子磺酸化流程 41
3-3 二氟單體合成 42
3-4 二醇單體合成 47
3-5 高分子聚合 61
3-5-1 HFA7 61
3-5-2 HFA8 63
3-5-3 HFA9 65
3-5-4 高分子薄膜製備 67
3-6 高分子磺酸化 68
3-7 磺酸化高分子之薄膜製備與特性量測 70
3-7-1 薄膜製備與酸的置換 70
3-7-2 IEC 測定 71
3-7-3 吸水率及尺寸安定性測試 73
3-7-4 Hydration number(λ) 73
3-7-5 氧化、水解穩定性 74
第四章 結果與討論 75
4-1 材料結構鑑定 75
4-1-1 GPC分析 75
4-1-2 1H NMR圖譜分析 76
4-1-3 FT-IR傅立葉紅外線光譜分析 78
4-2 熱穩定與機械性質分析 82
4-2-1 TGA熱穩定性分析 82
4-2-2 TMA機械性質分析 85
4-3 磺酸化薄膜之物理、化學性質分析 88
4-3-1 薄膜吸水率、尺寸安定性及λ值 88
4-3-2 薄膜氧化及水解穩定性 91
4-4 磺酸化薄膜之電性及微相分離型態分析 93
4-4-1 質子導電度數據分析 93
4-4-2 TEM微相分離型態分析 96
4-4-3 小角X-RAY分析 97
4-5 燃料電池元件效率分析 99
第五章 結論 101
第六章 參考文獻 102
第七章 附錄 109
附錄7-1 MALDI-TOF 109
附錄7-2 NMR 113

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