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博碩士論文 etd-0629115-114830 詳細資訊
Title page for etd-0629115-114830
論文名稱
Title
探討三氟甲基數目對於磺酸化聚芳香醚高分子薄膜特性之影響
Effect of number of trifluorinemethyl group on the properties of Sulfonated Poly(arylene ether)s membranes
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
124
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2015-07-13
繳交日期
Date of Submission
2015-07-30
關鍵字
Keywords
三氟甲基、聚芳香醚高分子、燃料電池、質子交換膜
poly(arylene ether)s, trifluoromethyl, fuel cells, proton exchange membrane
統計
Statistics
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中文摘要
本研究主要以含氟磺酸化聚芳香醚高分子作為燃料電池質子交換膜使用,利用自行製備之兩種不同含氟量的二氟單體,分別與兩種市售的單體4,4-dihydroxybiphenyl及4,4'-(9-Fluorenylidene)diphenol經親和性聚縮核反應得到四種高分子。經後磺酸化後,得到八種不同磺化程度的含氟磺酸化聚芳香醚高分子,並著重探討含有不同數量的三氟甲基官能基對於質子交換膜之影響。
由GPC量測其分子量結果顯示四種高分子的分子量介於2.17×10^5~3.27×10^5 g/mol,且所有高分子及磺酸化高分子皆具有良好的成膜特性,離子交換能力(Ion exchange capacity, IEC)介於0.2-2.69 mmol/g之間,所有高分子及磺酸化高分子結構皆透過FTIR及NMR鑑定結構無誤。本研究所合成的高分子由於主鏈為多苯環結構,使得四種高分子與八種磺酸化高分子的薄膜都展出良好的熱穩定性,其熱裂解溫度均分別高於510 oC及230 oC。S12FP1-S18FP4在80 oC的吸水率則介於0.9~149 %,厚度方向的尺寸安定性則介於0~33 %,同時具有良好的化學穩定性、機械性質及高水解穩定性。含氟磺酸化高分子的質子導電度亦會隨著IEC數值、溼度、溫度得增加而上升,特別是S12FP1-2.47在80oC、相對溼度95%的條件下,尺寸變化率僅有35%,質子導電度卻高達220 mS/cm。隨著三氟甲基官能基的數量增加使得磺酸化聚芳香醚高分子薄膜的疏水性增加,薄膜的吸水率便不易膨潤,但卻由於親疏水段鏈段的調控形成了良好的微相分離型態,大幅改善了過往碳氫離子性高分子材料在高溫、高濕情況下,因過大的吸水率,導致薄膜過度澎潤使得尺寸安定性變差的情況。綜合上述,本論文在碳氫離子高分子結構中導入適當的三氟甲基官能基不僅能讓質子交換膜擁有良好尺寸安定性,同時保有高質子導電度。
Abstract
A series of sterically-encumbered, sulfonated, fluorine-containing poly(arylene ether) copolymers were synthesized so as to compare the effects of incorporating trifluorinemethyl groups on the proton conductivity and performance of fuel cells of membranes prepared. The polymers were prepared by polymerization of 4,4-dihydroxybiphenyl or 4,4'-(9-Fluorenylidene) diphenol with two novel monomers. The weight-average molecular weight of polymers ranging from 2.17×10^5 g/mol to 3.27×10^5g/mol. Subsequent sulfonation and solution casting provided membranes possessing ion exchange capacities ranging from 0.2 to 2.69 mmol g-1. Good thermal properties of polymers were indicated by observing decomposition temperatures (Td5%) over oC in acid-form in nitrogen atmospheres. Water uptake ranged from 0.9 to 149 %, and dimensional stability (in-plane) ranged from 0 to 33% at 80 oC.
All the sulfonated polymers exhibited highly chemical stability, mechanical properties and high hydrolytic stability. Especially the S12FP1-2.47 membrane exhibited only 35% in-plane dimensional changing at 80 oC in the water and the proton conductivity up to 220 mS/cm at 80 oC/95%RH. We infer that introducing the trifluorinemethyl into the polymer by way of incorporating highly sulfonated, multi-phenylated moieties provides mechanically-robust and dimensionally-stable proton exchange membranes.
目次 Table of Contents
目錄
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原理…3
1-4質子交換膜傳導機制…5
1-5質子交換膜種類…7
1-5-1全氟離子性高分子薄膜(Perfluorinated polymer)…7
1-5-2部分氟化高分子薄膜(Partially perfluorinated polymer)…8
1-5-3非氟離子性高分子薄膜(Non-perfluorinated polymer)…9
1-5-4酸鹼高分子薄膜(Acid-base blends polymer)……9
1-5-5有機/無機混摻薄膜(Organic/Inorganic blend membrane)……9
1-6質子交換膜結構設計……10
1-7文獻回顧……12
1-8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高磁場液態磁核共振儀器(Nuclear Magnetic Resonance,NMR)……20
2-1-2基質輔助雷射脫附游離飛行質譜儀(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
2-3-2(低掠角/穿透式)小角度X光散射儀 (Grazing Incidence/Transmission Small-angel X-ray Scattering)……28
2-4電性分析……29
2-4-1交流阻抗分析儀(AC Impedance)……29
2-5 燃料電池元件(Membrane electrode assambly, MEA)……29
第三章 實驗31
3-1藥品總表……31
3-2實驗流程……33
3-3多氟單體製備……34
3-3-12F (1) ……34
3-3-12F (2) ……35
3-3-12F (3) ……36
3-3-12F (4) ……37
3-3-18F (3) ……39
3-3-18F (4) ……40
3-4高分子聚合……42
3-4-1 12FP1高分子聚合……42
3-4-2 12FP4高分子聚合……43
3-4-3 18FP1高分子聚合……44
3-4-4 18FP4高分子聚合……45
3-5高分子磺酸化……46
磺酸化試劑……46
3-6磺酸化後處理……47
3-6-1薄膜製備……47
3-6-2離子交換能力(Ion exchange capacity, IEC)測定……47
3-6-3尺寸安定性、吸水率量測(Dimensional stability、Water uptake)……48
3-6-4 Hydration number (λ)……49
3-6-5氧化、水解穩定性(Oxidative、Hydrolytic stability)……49
第四章 結果與討論……50
4-1材料結構鑑定……50
4-1-1單體鑑定以及GPC分析……50
4-1-2傅立葉紅外線光譜(FT-IR)分析……56
4-2熱分析及機械特性……61
4-2-1 TGA熱穩定性分析……61
4-2-2 機械強度特性分析……65
4-3薄膜之物理、化學性質分析……69
4-3-1 吸水率、尺寸安定性與λ值……69
4-3-2 氧化與水解穩定性測試……73
4-4電性及微相型態分析……74
4-4-1 質子導電度探討……74
4-4-2 TEM微相分離型態觀察……77
4-4-3 (低掠角/穿透式)小角度X光散射儀……80
4-4-4 燃料電池元件測試……82
第五章 結論……85
第六章 參考文獻……86
第七章 附錄……91
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