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論文名稱 Title |
分子量對磺酸化聚芳香醚高分子應用於質子交換膜燃料電池的影響 Effect of Molecular Weight on the Application of Sulfonated Poly(arylene ether) Polymers for Proton Exchange Membrane Fuel Cells |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
101 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2018-07-19 |
繳交日期 Date of Submission |
2018-07-20 |
關鍵字 Keywords |
燃料電池、質子導電度、分子量、微相分離型態、質子交換膜 proton conductivity, fuel cell, proton exchange membrane, molecular weight, micro-phase separation pattern |
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統計 Statistics |
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中文摘要 |
本論文主要是延續之前實驗室的研究,將SA7、SA8、SA9系列中選擇SA8做為這一次研究的材料,藉由控制反應的時間與溶劑量來聚合成適當的分子量,並進一步的研究分子量的差異對於薄膜特性的影響,探討在不同分子量情況下的微相分離型態,及組裝成燃料電池元件之後的元件效率影響。 所有單體、高分子與磺酸化高分子皆透過FT-IR、1H -NMR及mass鑑定結構無誤,GPC量測不同高分子之分子量,使其介於65,000~180,000 g/mol,且皆具有良好成膜性,其熱裂解溫度(Td5%)皆高於510oC。九種磺酸化高分子之(Td5%)皆高於252oC,展現良好熱穩定性。離子交換能力(Ion exchange capacity, IEC)介於2.4~3.2 mmol/g。在80oC下,除了SA8-3.2之外,薄膜皆仍保有完整形貌,其吸水率為86%~157%,且具有良好尺寸安定性(17%~44%)與機械性質(0.29~0.46GPa)。質子導電度方面皆高於225 mS/cm且遠勝於Nafion 211(151mS/cm)。透過黏度、TEM與DLS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SA8-3.2的元件效率高達1.3 W/cm2,與Nafion 211之效率機幾乎相同。綜合上述,改變SA8材料之分子量會對薄膜的微相分離型態產生影響,進而導致高分子量之元件效率會較低分子量來的高。 |
Abstract |
This thesis is mainly a continuation of the previous laboratory research( SA7 series, SA8 series, SA9 series), selected SA8 as the material for this study, by controlling the reaction time and the amount of solvent to polymerize into the appropriate molecular weight, and study the influence of the difference in molecular weight on the characteristics of the film. Discussed the microphase separation pattern under different molecular weight conditions and the effect of efficiency after assembly into fuel cell components. The structures of materials were confirmd by FT-IR, 1H -NMR, and mass.The molecular weights of different polymers were measured by GPC, ranging from 65,000 to 180,000 g/mol.The polymers show thermal degradation temperatures are higher than 510oC. Three sulfonated polymers show thermal degradation temperatures are higher than 252oC. The IEC values between 2.4 to 3.2 mmol/g. At 80oC, except SA8-3.2, the film still retains its full morphology, its water uptake is ranging from 86% to 157%, and it has good dimensional stability (17%~44%) and mechanical properties (0.29~0.46GPa). The proton conductivity is up to 225 mS/cm and much more better than Nafion 211 (151 mS/cm). Through the viscosity, TEM and DLS, this series of sulfonated polymers has a good micro-phase separation pattern. The final component efficiency section, in which SA8-3.2's element efficiency is as high as 1.3 W/cm2, is almost the same as that of the Nafion 211. In summary, changing the molecular weight of the SA8 material will affect the micro-phase separation pattern of the film, which will result in a higher molecular weight of material has higher element efficiency. |
目次 Table of Contents |
目錄 論文中文審定書 ⅰ 論文英文審定書 ⅱ 誌謝 ⅲ 摘要 ⅴ Abstract ⅵ 目錄 ⅶ 圖目錄 ⅺ 表目錄 ⅹⅳ 第一章 序論 1 1-1 前言 1 1-2 燃料電池種類區分 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 1-3-2 質子傳導機制 6 1-4 質子交換膜種類 8 1-4-1 全氟離子性高分子薄膜(Perfluorinated polymer membrane) 8 1-4-2 部分氟化高分子薄膜(Partially fluorinated polymer membrane) 9 1-4-3 非氟化高分子薄膜(Non-Perfluorinated polymer membrane 10 1-4-4 酸鹼高分子薄膜(Acid-base blends polymer membrane) 10 1-4-5 有機/無機混成薄膜(Organic/Inorganic blend membrane) 10 1-5 質子交換膜結構設計 11 1-5-1 交替型共聚高分子 12 1-5-2 無規型共聚高分子 12 1-5-3 接枝型共聚高分子 12 1-5-4 嵌段型共聚高分子 12 1-6 文獻回顧 13 1-6-1 交替型共聚高分子文獻回顧 13 1-6-2 無規型共聚高分子文獻回顧 15 1-6-3 接枝型共聚高分子文獻回顧 17 1-6-4 嵌段型共聚高分子文獻回顧 19 1-6-5 磺酸化高分子薄膜分子量文獻回顧 21 1-7 研究動機 22 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 黏度計(Viscometer) 31 2-3-3 動態光散射儀(Dynamic light scattering, DLS) 32 2-4 磺酸化薄膜特性量測 33 2-4-1 交流阻抗分析儀(AC Impedance) 33 2-5 元件效率量測分析與MEA製備 34 2-5-1 自動薄膜塗佈機(Automatic Film Applicator) 34 2-5-2 超音波霧化噴塗機(Ultrasonic Spraying System) 35 2-5-2-1觸媒製備(Catalyst Preparation) 35 2-5-2-2燃料電池元件條件(MEA Conditioning) 35 2-5-2-3燃料電池測試(Fuel Cell Testing) 36 第三章 實驗步驟 37 3-1 實驗藥品總表 37 3-2 實驗流程 39 3-2-1 二氟單體流程 39 3-2-2 二醇單體流程 39 3-2-3 高分子聚合與磺酸化高分子流程 40 3-3 二氟單體合成 41 3-4 二醇單體合成 46 3-5 高分子聚合 49 3-6 高分子薄膜製備 51 3-7 高分子磺酸化 51 3-8 磺酸化高分子之薄膜製備與特性量測 52 3-8-1 薄膜製備與酸的置換 52 3-8-2 離子交換能力(Ion exchange capacity, IEC)測定 53 3-8-3 吸水率及尺寸安定性測試 54 3-8-4 Hydration number(λ) 55 3-8-5 氧化、水解穩定性(Oxidative、Hydrolytic stability)量測 55 第四章 結果與討論 56 4-1 材料結構鑑定 56 4-1-1 1H NMR圖譜、mass圖譜分析 56 4-1-2 GPC分析 57 4-1-3 IEC數值量測 58 4-1-4 FT-IR傅立葉紅外線光譜分析 58 4-2 熱穩定與機械性質分析 60 4-2-1 TGA熱穩定性分析 60 4-2-2 TMA機械性質分析 62 4-3 磺酸化薄膜之物理、化學性質分析 64 4-3-1 薄膜吸水率、尺寸安定性及λ值 64 4-3-2 薄膜氧化及水解穩定性 69 4-4 磺酸化薄膜之電性及微相分離型態分析 70 4-4-1 質子導電度數據分析 70 4-4-2 黏度量測分析 71 4-4-3 TEM微相分離型態分析 72 4-4-4 動態光散射儀(DLS) 73 4-5 燃料電池元件效率分析 74 4-6 燃料電池元件壽命 75 第五章 結論 76 第六章 參考文獻 77 第七章 附錄 83 附錄7-1 MALDI-TOF 83 附錄7-2 NMR 85 圖目錄 圖 1-1台灣亞太燃料電池開發的氫燃料電池機車 1 圖 1-2質子交換膜燃料電池元件構造 4 圖 1-3質子交換膜燃料電池工作原理 5 圖 1-4質子傳遞機制:(1)Grotthus、(2)Vehicular、(3)Surface Mechanism 6 圖 1-5低濕環境及高濕環境下質子傳遞情況示意圖 7 圖 1-6全氟離子性高分子結構Nafion 8 圖 1-7 BAM之結構示意圖 9 圖 1-8 Nafion及sulfonated polyetherketone(PEEKK)的微觀型態示意圖 9 圖 1-9質子交換膜結構設計 11 圖 1-10 Ueda團隊所發表的高分子poly(1,10-dinaphthyl ether phenyl sulfone) 13 圖 1-11不同IEC值的poly(1,10-dinaphthyl ether phenyl sulfone)與Nafion在80 oC、95%RH環境下量測的質子導電度 13 圖 1-12 Steven Holdcroft研究團隊所發表的高分子sPPP、sPPB、sPPN, 與不同相對濕度下量測的質子導電度、OCV與元件效率圖 14 圖 1-13 Whangi Kim發表之團聯式磺酸化聚芳香醚高分子結構與元件效率 15 圖 1-14 Allan S. Hay團隊合成之高分子結構示意圖 16 圖 1-15 Guiver教授等人合成出含有靈活側鏈的接枝式共聚高分子 17 圖 1-16 Guiver教授等人合成高分子含有之剛硬苯環取代基側鏈 17 圖 1-17各種不同側鏈長度的磺酸化高分子 18 圖 1-18 各磺酸化高分子在不同相對濕度下的質子導電度 18 圖 1-19 Guiver教授及其研究團隊發表之triblock共聚高分子 19 圖 1-20三種高分子3(X50)、3(X70)與3(X100)的薄膜質子導電度 (a)於不同水溫下量測(b) 90oC不同濕度下量測 19 圖 1-21Ueda教授與他人共同發表之嵌段式磺酸化高分子 20 圖 1-22各嵌段式高分子薄膜TEM圖(a)RC (b)M10N5-SO3H (c)M20N10-SO3H 與(d)M20N15-SO3H,比例尺長度為100 nm 20 圖 1-23Masahiro Rikukawa團隊研究之不同分子量的高分子薄膜Hydration Number、質子導電度與元件效率極化曲線圖 21 圖 1-24SA8磺酸化高分子結構圖 22 圖 2-1高磁場液態核磁共振儀 24 圖 2-2基質輔助雷射脫附游離飛行時間質譜儀 25 圖 2-3凝膠滲透層析儀 26 圖 2-4傅立葉紅外線光譜儀 27 圖 2-5熱重量分析儀 28 圖 2-6熱機械分析儀 29 圖 2-7穿透式電子顯微鏡 30 圖 2-8黏度計 31 圖 2-9動態光散射儀 32 圖 2-10自動薄膜塗佈機 33 圖 3-1二氟單體流程圖 39 圖 3-2二醇單體流程圖 39 圖 3-3高分子聚合與磺酸化反應流程圖 40 圖 4-1 A8高分子之GPC圖 57 圖 4-2 A8分子量與聚合時間關係圖 57 圖 4-3 SA8之FTIR4000~500cm-1光譜圖 59 圖 4-4 SA8之FTIR2000~500cm-1光譜圖 59 圖 4-5 A8磺酸化前後TGA分析 61 圖 4-6 SA8薄膜的應力-應變圖 63 圖 4-7 SA8的薄膜吸水率 65 圖 4-8 SA8的Hydration Number 66 圖 4-9 SA8的尺寸安定性(L) 67 圖 4-10 SA8的尺寸安定性(W) 67 圖 4-11 SA8的尺寸安定性(T) 68 圖 4-12磺酸化高分子在80oC、不同相對濕度下的質子導電度 70 圖 4-13 SA8在不同轉速下的Viscosity 71 圖 4-14 SA8磺酸化高分子的TEM圖 72 圖 4-15 SA8磺酸化高分子薄膜之粒徑分析 73 圖 4-16磺酸化高分子在80oC、100%RH之氫氧燃料電池極化曲線 74 圖 4-17 SA8-2.7與Nfion211的加速老化測試 75 表目錄 表 1-1燃料電池種類 3 表 1-2 PEMFC與DMFC反應工作式 5 表 1-3各嵌段與高分子之分子量 20 表 1-4 SA7、SA8、SA9基本數據 22 表 3-1 磺酸化試劑調配比例 53 表 4-1 GPC數值表 56 表 4-2磺酸化試劑調配比例 58 表 4-3 A8高分子與磺酸化高分子之熱裂解溫度 61 表 4-4 A8高分子及磺酸化高分子之機械性質強度 62 表 4-5磺酸化薄膜吸水率與λ值 65 表 4-6磺酸化薄膜尺寸安定性 66 表 4-7氧化及水解穩定性 69 |
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