本篇論文氯氧化鋯摻合Nafion溶液性質及聚四氟碳化物/Nafion/磷酸鋯製作複合膜。主要分為三部分，第一部份是將 ZrOCl2•8H2O加入DuPont 5 wt% Nafion溶液中，利用黏彈儀探討其溶液性質；第二部份，是將ZrOCl2•8H2O加入以甲醇/水(4/1 weight ratio)稀釋成0.91 wt％之 DuPont Nafion 溶液，利用黏彈儀(viscoelasticity analyzer)、Zeta potential，探討ZrOCl2在Nafion溶液中，粒徑大小、溶液聚集型態、黏彈性質及物理性質等。第三部份是從第一部份中取出五種不同之ZrOCl2/Nafion重量比溶液，利用方法-2製備PTFE/Nafion-Zr(HPO4)2複合膜，再製作MEA進行單電池測試，以探討溶液之物理性質對製備複合膜之影響。
第一部份，由黏彈儀數據發現ZrOCl2/Nafion=0.0781~0.1172 g/g也就是ZrOCl2濃度為0.02 M~0.03 M (編號為Zr-N-48 ~ Zr-N-72)，隨頻率的增加，有些微的shear thickening現象；第二部份，由黏彈儀數據發現ZrOCl2/Nafion=0~0.0391 g/g也就是ZrOCl2濃度為0 M~0.1 M皆有聚電解質的現象;由zeta potential 數據發現，在未加入ZrOCl2時，0.91 wt％ Nafion/甲醇/水溶液之zeta potential 値較小；由particle size 數據發現，未加入ZrOCl2時， particle size 較大。第三部份PTFE-Nafion-Zr(HPO4)2複合膜，由ZrOCl2/Nafion g/g=0.0391也就是ZrOCl2濃度為0.01 M 之ZrOCl2-Nafion溶液所製成的複合膜之SEM圖，發現其纖維具明顯孔洞，我們認為此濃度之溶液比較容易進入PTFE填補內層孔洞所致。而其PEMFC燃料電池效能在溫度為110 ℃(RH=51.7％)電壓＝0.4 V時，電流＝1045 mA/cm2;120 ℃(RH=38.2％) 電壓＝0.4 V時，電流＝790 mA/cm2及130 ℃(RH=28.8％) 電壓＝0.4 V時，電流＝525 mA/cm2，其效能皆高於PTFE-Nafion複合膜。因此，我們認為ZrOCl2濃度為0.01 M 之ZrOCl2-Nafion溶液(ZrOCl2/Nafion重量比=0.0391)最適合製作應用於PEMFC複合膜。

In this study, there are three system. First, we chose the addition of ZrOCl2•8H2O (Aldrich) to DuPont 5 wt% Nafion solution. Then we used dynamic viscoelasticity analyzer to study physical properties. Second, we added ZrOCl2•8H2O to 1 wt％ DuPont Nafion solution that was diluted with MeOH/H2O (weight ratio 4 / 1) before. And we used dynamic viscoelasticity analyzer, Zeta potential and dynamic light scattering to study physical properties, particle size and flocculation properties. Third, we selected five ZrOCl2/Nafion wt ratio to prepare of PTFE-Nafion-Zr(HPO4)2 composite membranes.
First system, the viscoelasticity data reveal polyelectrolyte behavior of Zr-N-48、Zr-N-72 solution. Second system, the viscoelasticity data reveal polyelectrolyte behavior of all these solution. The Zeta potential data of the 1 wt％ Nafion/MeOH/H2O solution without ZrOCl2 is smaller and Particle size is larger than others. Third, the performance of single cell was the best when the ZrOCl2/Nafion wt ratio was 0.0391,and achieved 1045 mA/cm2 at 0.4 V, 110 ℃(RH=51.7 %); 790 mA/cm2 at 0.4 V, 120 ℃(RH=38.2 %) and 525 mA/cm2 at 0.4 V, 130 ℃(RH=28.8 %) base on H2/O2 and at a pressure of 1 atm.

目 錄
目錄……………………………………………………………………….I

一、 前言……………………………….....…………………………….1
1.1 簡介………………………………………………………………….1
1.1-1 Nafion(全氟磺酸樹酯) 薄膜及其溶液性質簡介……..…..…….2
1.1-2聚四氟乙烯(PTFE)簡介……………….…..………….………….5
1.1-3 高分子溶液之物裡性質...…………………….…………………6
1.1-4氫氧質子交換膜燃料電池(PEMFC)……...……………..……….7
1.1-5 Nafion薄膜摻合Zr(HPO4)2製作燃料電池….…………………..8
1.2 研究目的…………………………………………………….……12

二、 實驗方法與步驟……………………….…...……………………14
2.1 實驗試藥…………………………...……………………………..14
2.2 儀器設備及原理…………………...….………………………….15
2.2-1動態黏彈儀…………………...….………………..…………….15
2.2-2 Zeta potential analyzer………………...….…………..……...….19
2.2-3掃描式電子顯微鏡……………...….……………..……........….24
2.2-4質子交換膜燃料電池(PEMFC)高溫性能測試……………..….24
2.3 實驗方法…………………………...…………….……………….27

三、 結果與討論…………………………...………………………….35
3.1 ZrOCl2/Nafion溶液溶解性…………………………….....………35
3.2 ZrOCl2/Nafion之動態黏彈性……………………………….……36
3.2-1動態剪切黏度………….……………….………….……………36
3.2-2動態剪切模數………………………...….…….…..……………44
3.3 ZrOCl2/Nafion/MeOH/water之動態黏彈儀研究…….………….50
3.3-1動態剪切黏度……….……………….....………….……………50
3.3-2動態剪切模數…………………………..………….……………52
3.3-3 ZrOCl2/Nafion/MeOH/H2O之Zeta電位…………..….…..……55
3.4 PTFE-Nafion-Zr(HPO4)2複合膜………….………………………64
3.4-1 PTFE-Nafion-Zr(HPO4)2複合膜製備方法比較...…………...…64
3.4-2 PTFE-Nafion-Zr(HPO4)2複合膜製備(方法-2) ……………...…69
3.4-2-1 SEM電子顯微鏡觀察…….……………...……….…...…….69
3.4-2-2能量分散性X射線顯微(EDX)元素分析……….……..……77
3.4-3 PTFE-Nafion-Zr(HPO4)2複合膜製作MEA單電池測試………79

四、 結論……….…………………………………………..…………...86

五、 參考文獻………………..……………………….………………...88

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