氯氧化鋯摻合Nafion溶液性質及聚四氟碳化物/Nafion/磷酸鋯複合膜製作

Physical Properties of ZrOCl2 Blended Nafion Solutions and the Preparation of PTFE-Nafion-Zr(HPO4)2 Composite Membranes

張慈容(Tzu-Jung Chang)

指導教授 ： 余子隆

元智大學/工程學院/化學工程與材料科學學系/碩士(2007年)

摘要

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。

關鍵字

黏彈性質 ； 界達電位 ； 動態光散射 ； 磷酸鋯 ； 質子交換膜燃料電池

並列摘要

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.

並列關鍵字

viscoelasticity, Zeta potential, Dynamic light scattering, Zirconium phosphate, Proton exchange membrane fuel cell (PEMFC)

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