臺灣博碩士論文加值系統

本研究主要以磷鎢酸（phosphotungstic acid，PWA）摻雜聚乙烯醇（Polyvinyl alcohol，PVA）作為燃料電池用之質子交換膜，並探討不同的PWA摻雜比例質子交換複合膜之熱性質、離子導電度、離子交換容量、飽和含水率及甲醇滲透率等性質。由IR結果顯示PWA確實存在於PVA中，並藉由水合離子與PVA上的OH基產生作用力，形成一交聯性複合膜；由XRD及DSC結果發現複合膜之結晶性隨PWA的摻雜量增加而減少，並計算出PWA於複合膜中的晶粒大小約為15∼40nm。熱重分析結果得知，複合質子交換膜熱裂解溫度隨著PWA含量的增加而明顯上昇，表示藉由PWA的摻雜可提高其熱穩定性。複合膜之飽和含水率及甲醇滲透率皆隨PWA摻雜比例的增加而降低，下降趨勢在PWA40％以後趨於平緩。於離子交換容量（IEC）分析可知，當複合膜之PWA含量<40 %時，其離子交換點因為與PVA的OH基產生作用力而失去離子交換能力因此IEC隨之下降，當＞40 %時，複合膜的交聯程度達飽和，此後IEC隨PWA的摻雜量增加而上升，而反應在導電度實驗結果上，亦呈現相同趨勢。

The purpose of this study is using phosphotungstic acid (PWA) doped with Polyvinyl alcohol (PVA) to prepare a proton exchange membrane for the application of fuel cells. The thermal stability, ionic conductivity, ion exchange capacities and methanol permeability of the proton- exchange composite membranes with different phosph otungstic acid contents was investigated in this study. The success of doping the composite membrane was confirmed by the FT-IR spectra. According to results of the XRD and DSC, decrease of crystallinity for composite membrane with the increase of the PWA content. Up-take water and methanol permeability decreased with increased PWA content.

目 錄

中文摘要 -------------------------------------------------------------------------- i
英文摘要 -------------------------------------------------------------------------- ii
誌謝 -------------------------------------------------------------------------- iii
目錄 -------------------------------------------------------------------------- iv
表目錄 -------------------------------------------------------------------------- vi
圖目錄 -------------------------------------------------------------------------- vii
符號說明 -------------------------------------------------------------------------- ix
一、 緒論--------------------------------------------------------------------- 1
1.1 前言--------------------------------------------------------------------- 1
1.2 燃料電池的發展歷史------------------------------------------------ 4
1.3 燃料電池種類--------------------------------------------------------- 5
1.3.1 鹼性燃料電池--------------------------------------------------------- 5
1.3.2 質子交換膜燃料電池------------------------------------------------ 6
1.3.3 磷酸燃料電池--------------------------------------------------------- 6
1.3.4 熔融碳酸鹽燃料電池------------------------------------------------ 7
1.3.5 固態氧化物燃料電池------------------------------------------------ 7
二、 文獻回顧--------------------------------------------------------------- 7
2.1 質子交換膜的種類及特性比較------------------------------------ 10
2.2 直接甲醇型燃料電池之高分子電解質--------------------------- 16
2.3 影響直接甲醇燃料電池性能的因素------------------------------ 17
2.4 質子交換膜之甲醇滲透現象--------------------------------------- 18
2.4.1 Nafion®質子交換膜-------------------------------------------------- 18
2.4.2 非Nafion®之質子交換膜-------------------------------------------- 21
2.5 雜聚酸(Heteropoly acids)之質子交換複合膜-------------------- 26
2.6 電滲透牽曳係數（Electro-osmotic drag coefficient）---------- 28
2.7 研究目的與動機------------------------------------------------------ 31
三、 原理--------------------------------------------------------------------- 32
3.1 傅力葉紅外線吸收光譜儀------------------------------------------ 32
3.2 熱重量分析------------------------------------------------------------ 34
3.3 微差掃描熱卡計--------------------------------------------------------- 34
3.4 交流組抗分析------------------------------------------------------------- 35
3.5 X光繞射分析儀---------------------------------------------------------- 39
3.6 電滲透牽曳係數量測原理--------------------------------------------- 41
四、 實驗設備與步驟------------------------------------------------------ 47
4.1 實驗藥品--------------------------------------------------------------- 47
4.2 實驗儀器--------------------------------------------------------------- 48
4.3 薄膜製備------------------------------------------------------------------- 49
4.4 薄膜之分析與鑑定 50
4.4.1 傅立葉轉換紅外線分光分析 50
4.4.2 飽和含水率實驗------------------------------------------------------ 50
4.4.3 離子交換容量實驗--------------------------------------------------------------------------- 50
4.4.4 導電度實驗------------------------------------------------------------ 51
4.4.5 熱重分析實驗--------------------------------------------------------- 51
4.4.6 微差掃描熱卡計--------------------------------------------------------------------------- 52
4.4.7 甲醇滲透率實驗--------------------------------------------------------------------------- 52
4.4.8 X光繞射分析-------------------------------------------------------- 53
4.5 電滲透牽曳係數量測------------------------------------------------ 54
五、 結果與討論------------------------------------------------------------ 56
5.1 FTIR-ATR analysis--------------------------------------------------- 56
5.2 XRD分析-------------------------------------------------------------- 62
5.3 DSC分析--------------------------------------------------------------- 64
5.4 熱重分析--------------------------------------------------------------- 66
5.5 含水率分析------------------------------------------------------------ 70
5.6 離子交換容量分析--------------------------------------------------- 73
5.7 交流阻抗分析--------------------------------------------------------- 76
5.8 甲醇滲透率分析------------------------------------------------------ 79
5.9 有機/無機混成膜之電滲透牽曳係數分析----------------------- 82
六、 結論--------------------------------------------------------------------- 85
參考文獻 -------------------------------------------------------------------------- 87
作者簡介 -------------------------------------------------------------------------- 94

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