本研究主要將不同含氟量多苯環單體與兩種市售單體4,4’-(9-Fluoreny-lidene)diphenol及4,4’-(Hexafluoroiso-propylidene)diphenol進行無規式共聚含氟聚芳香醚高分子並控制高分子的磺酸化程度，經磺酸化而得的各種不同的磺酸化高分子薄膜，其離子交換能力(Ion Exchange Capacity, IEC)介於1.32~2.69mmol/g之間，隨後著重探討三氟甲基官能基對於質子交換膜之影響並評估其作為固態電解質後應用於燃料電池之潛力。
材料分析方面，由凝膠滲透層析儀 (Gel Permeation Chromatography, GPC)量測各系列高分子的分子量介於9.2×104~1.1×105 g/mol，利用核磁共振光譜儀 (Nuclear Magnetic Resonance Spectroscopy, NMR)以及傅立葉紅外線光譜儀 (Fourier Transform infrared spectro scopy, FT-IR)鑑定結構正確無誤。而且所有高分子薄膜都表現出良好的熱穩定性及機械性質，其磺酸化高分子熱裂解溫度均高於210 oC。在室溫、環境濕度條件下，機械特性的抗拉強度最高達48MPa，楊氏系數介於0.41~0.57GPa。隨著含氟量的增加薄膜的尺寸安定性有明顯的提升，在高溫高濕環境下，薄膜能具備高於Nafion 211的質子導電度。透過穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM)觀察發現材料擁有明顯的微相分離型態，將sG2系列磺酸化高分子量測元件效率，最大功率密度可達269mW/cm2。

A series of sterically-encumbered, sulfonated, fluorine-containing poly(arylene ether) random copolymers were synthesized so as to compare the effects of incorporating trifluoromethyl groups on the proton conductivity and performance of fuel cells of membranes prepared. The polymers were prepared by polymerization of 4,4’-(9-Fluorenylidene)diphenol and 4,4’-(Hexafluoroiso-propylidene)diphenol with two novel monomers, 4,4’’’’-Difluoro-3,3’’’’-bistrifluoromethyl-2’’, 3’’, 5’’, 6’’-tetraphenyl-[1,1’; 4’,1’’;4’’,1’’’; 4’’’,1’’’’]-pentaphenyl and 4,4’’’’-difluoro-3,3’’’’-bis(trifluoromethyl)-2’’,3’’,5’’,6’’,4,4’’’’-difluoro-3,3’’’’-bis(trifluoromethyl)-2’’,3’’,5’’,6’’,-Tetra(trifluoromethyl)phenyl-[1,1’:4’,1’’:4’’,1’’’:4’’’,1’’’’-quinque phenyl]. The degree of sulfonation was controlled by different concentration of reagents so that the ion exchange capacity (IEC) value of sulfonated polymers were measured by titration method ranging from 1.32 to 2.69 mmol/g.
The weight-average molecular weight of polymers ranging from 9.2×104 to 1.1×105 g/mol. The designed chemical structures were confirmed by NMR and FTIR analysis. All polymer membranes exhibit good thermal stabilities and mechanical strength. The thermal decomposition temperature of polymers decreased with increasing IEC, ranging from 217oC to 267oC. Tensile strengths of sG1 and sG2 membranes ranged from 26~48MPa, with elongations at break ranging from 11~21% and Young’s moduli ranging from 0.44 to 0.57 GPa at room temperature, 60% relative humidity. The polymers incorporating trifluoromethyl groups not only enhanced dimensional stability but also increased proton conductivity with increasing IEC. TEM analysis of the polymers, in the dehydrated state, revealed isolated spherical aggregates of ions, which presumably coalesce when hydrated to provide highly conductive pathways. The maximum power density of sG2-2.00 at 80oC and 100 % RH is 260mW/cm2, respectively.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 v
圖次 ix
表次 xii
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和傳導機制 4
1-3-1工作機制 4
1-3-2傳導機制 5
1-4質子交換膜種類 7
1-4-1全氟離子性高分子薄膜 (Perfluorinated polymer) 7
1-4-2部分氟化高分子薄膜 (Partially perfluorinated polymer) 8
1-4-3非氟離子性高分子薄膜 (Non-perfluorinated polymer) 9
1-4-4酸鹼高分子薄膜 (Acid-base blends polymer) 9
1-4-5有機/無機混摻薄膜 (Organic/Inorganic blend membrane) 9
1-5質子交換膜的結構設計 10
1-6文獻回顧 12
1-7研究動機 19
第二章 實驗儀器介紹與原理 20
2-1鑑定分析儀器 20
2-1-1高磁場液態核磁共振儀 (Nuclear Magnetic Resonance, NMR) 20
2-1-2基質輔助雷射脫附游離飛行時間質譜儀 (MALDI TOF/TOF) 21
2-1-3 凝膠滲透層析儀 (Gel Permeation Chromatography, GPC) 22
2-1-4 傅立葉紅外線光譜儀 (Fourier Transform infrared spectro scopy, FT-IR) 23
2-2 熱分析儀器 24
2-2-1 熱重量分析儀 (Thermogravimetric Analyzer, TGA) 24
2-2-2熱示差掃描卡量計 (Differential Scanning Calorimetr, DSC) 25
2-2-3熱機械分析儀 (Thermal Mechanical Analyzer, TMA) 26
2-3 微觀結構分析 27
2-3-1穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 27
2-4電性分析 28
2-4-1交流阻抗分析儀 (AC Impedance) 28
2-5 元件效率分析 29
2-5-1熱壓裝置 (Hot pressing equipment) 29
2-5-2燃料電池元件 (Membrane electrode assembly, MEA) 30
第三章 實驗 32
3-1藥品總表 32
3-2實驗流程 34
3-3多氟單體製備 35
3-3-1 35
3-3-2 36
3-3-3 37
3-3-4 38
3-3-5 39
3-3-6 40
3-3-7 42
3-4高分子聚合 44
3-4-1 G1高分子聚合 44
3-4-2 G2高分子聚合 46
3-5高分子磺酸化 48
磺酸化試劑 48
3-6磺酸化後處理 50
3-6-1薄膜製備與酸的置換 50
3-6-2離子交換能力 (Ion exchange capacity, IEC)測定 50
3-6-3尺寸安定性、吸水率 (Dimensional stability、Water uptake)量測 51
3-6-4 Hydration number (λ) 52
3-6-5氧化、水解穩定性 (Oxidative、Hydrolytic stability)量測 52
第四章 結果與討論 53
4-1材料結構鑑定 53
4-1-1GPC分析和1H NMR單體鑑定 53
4-1-2傅立葉紅外線光譜 (FT-IR)分析 57
4-2熱分析及機械特性 60
4-2-1 TGA和DSC熱穩定性分析 60
4-2-2 TMA機械強度特性分析 64
4-3薄膜之物理、化學性質分析 67
4-3-1 吸水率、尺寸安定性與λ值 67
4-3-2 氧化與水解穩定性 71
4-4薄膜電性及微相型態分析 72
4-4-1 薄膜質子導電度分析 72
4-4-2 TEM微相分離型態分析 74
4-5元件分析 75
第五章 結論 77
參考文獻 78
附錄 82

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