本研究提出使用多孔性的玻璃纖維與聚四氟乙烯薄膜製成的複合膜，應用於磷酸燃料電池中做為質子傳導膜。此複合膜藉由玻璃纖維浸泡86%磷酸水溶液以具備質子傳導能力，並藉由聚四氟乙烯薄膜形成防止磷酸洩漏的保護層。
玻璃纖維與聚四氟乙烯薄膜兩者於磷酸燃料電池操作溫度150~220℃範圍皆具熱穩定性，並對磷酸具化學穩定性，成本亦相當便宜。由顯微結構分析與壓汞測孔儀可得知，玻璃纖維是具有微米等級孔洞分佈的基材，與昔日孰知應用於磷酸燃料電池之碳化矽多孔隔膜具有相似的結構，並擁有比碳化矽更高的孔隙率(93%)可含浸磷酸；聚四氟乙烯薄膜則為具奈米等級孔洞的基材，可藉親水處理讓磷酸溶液得以滲入其奈米孔洞，兩種薄膜結合可兼具富含磷酸電解質與防止磷酸洩漏之功能，其於150℃之質子傳導能力可達0.71 S/cm。
於磷酸燃料電池之單電池測試時，陰陽極使用碳布做為擴散層，觸媒層使用鉑顆粒承載於XC72碳黑上，使用噴塗法將觸媒漿料均勻塗佈於擴散層上以完成電極之製作。使用冷壓方式組成膜電極組(Membrane Electrode Assembly, MEA)後，組成一單電池進行性能的量測與探討。其最好的性能發生於使用聚四氟乙烯黏著劑比例35%，黏著鉑觸媒與碳顆粒的電極，於150℃操作溫度下，提供純氧與氫氣，其電流密度為900mA/cm2時有最高功率密度296 mW/cm2。

The research proposes a composite membrane using glass microfiber and polytetrafluoroethylene(PTFE) thin film applied in phosphoric acid fuel cell as proton exchange membrane. The glass microfiber is soaked in 86% phosphoric acid to possess proton conductivity, and the PTFE thin film outside the glass microfiber prevents the leakage of phosphoric acid.
The glass microfiber and PTFE thin film both have thermal and chemical stability at phosphoric acid fuel cell’s working temperature 150~220℃.Otherwise, the two membrane are also very cheap. From the analysis of micron structure and mercury porosimeter, glass microfiber membrane has many micron pores that is similar to previous phosphoric acid porous membrane SiC’s structure. However, our glass microfiber has higher porosity(93%) than SiC matrix that can let glass microfiber possess more phosphoric acid contents. PTFE thin film has many nano pores. We can let PTFE nano pores fulfilled with phosphoric acid by hydrophilic treatment. The combination of two membranes possesses rich phosphoric acid electrolyte content and prevents leakage of phosphoric acid, and the composite membrane’s proton conductivity achieve 0.71 S/cm at 150℃.
When phosphoric acid fuel cell tests, anode and cathode use carbon cloth as diffusion layer. The catalyst layer is Pt/C. After cold pressing, we measure the MEA’s effects and study the phenomenon. A best fuel cell performance using the composite membrane with Pt/C and 35%PTFE binder exhibits a peak power density of 296mW/cm2 at 150℃ with H2 and pure O2.

摘要 i
Abstract ii
致謝 iii
圖目錄 vii
表目錄 x
第一章 緒論 1
1-1 前言 1
1-2燃料電池簡介 1
1-3燃料電池基本原理與種類 2
1-3-1 磷酸燃料電池(Phosphoric Acid Fuel cell, PAFC) 2
1-3-2 質子交換膜燃料電池(Proton Exchange Membrane Fuel Cell, PEMFC) 3
1-3-3 鹼性燃料電池(Alkaline Fuel Cell, AFC) 4
1-3-4 熔融碳酸鹽燃料電池(Molten Carbonate Fuel Cell, MCFC) 5
1-3-5 固體氧化物燃料電池(Solid Oxide Fuel Cell, SOFC) 6
1-4研究動機 10
第二章 文獻回顧與探討 11
2-1燃料電池原理 11
2-1-1電化學熱力學 11
2-1-2電化學動力學 12
2-1-3磷酸燃料電池電化學理論分析 13
2-2質子交換膜簡介 13
2-2-1 碳氟系高分子質子交換膜 14
2-3 磷酸燃料電池系列質子交換膜 16
2-3-1 碳化矽(SiC)多孔載體質子交換膜 16
2-3-3 磷酸燃料電池高分子質子交換膜 18
2-4 具複合薄膜之燃料電池研究 21
2-5 氣體擴散層與催化層的研究 22
2-5 儀器分析原理 24
2-5-1 掃描式電子顯微鏡(SEM) 24
2-5-2 熱重分析儀(Thermal Gravimetric Analysis, TGA) 24
2-5-3 差示熱分析儀(Differential Thermal Analyzer, DTA) 25
2-5-4 孔隙率分析 25
2-5-5 交流阻抗(AC Impedance)分析 26
第三章 研究方法與實驗步驟 30
3-1 實驗藥品 30
3-2 實驗儀器 30
3-3 陰陽極極製備 31
3-4 磷酸多孔隔膜 32
3-4-1使用膜材介紹 32
3-4-2膜材前處理及組裝 34
3-4-3封裝環PDMS製作 36
3-5實驗流程圖 36
3-6儀器操作內容 37
3-6-1 SEM表面微結構分析 37
3-6-2熱重分析儀 38
3-6-3水銀測孔儀量測 38
3-6-4交流阻抗分析 38
3-6-5燃料電池單電池測試 39
第四章 結果與討論 42
4-1 PTFE膜之親水處理 42
4-2 場發電子顯微鏡分析 44
4-2-1表面微結構分析(SEM) 44
4-2-2單電池測試後表面微結構分析(SEM) 46
4-2-3元素成分分析(EDS) 48
4-3 水銀測孔儀分析 50
4-4 熱穩定性分析 51
4-6 交流阻抗分析 53
4-6-1 玻璃纖維含浸磷酸之交流阻抗分析 54
4-6-2 PTFE奈米膜含浸磷酸之交流阻抗分析 55
4-7 單電池測試 60
4-7-1 玻璃纖維厚度效應 60
4-7-2 溫度效應 62
4-7-2 玻璃纖維、玻璃纖維/聚四氟乙烯複合薄膜之單電池測試比較 65
4-7-3 膜電極組封裝冷壓參數效應 66
4-7-4 膜電極組使用PDMS邊框之影響 67
4-7-5 電極觸媒漿料添加不同PTFE含量對於單電池的影響 68
4-7-5 磷酸多孔隔膜水氣去除之單電池測試 69
4-7-6 電極觸媒漿料添加不同PTFE含量經燒結後對於單電池的影響 70
4-7-7 使用商用電極之單電池測試 73
4-7-8 不同氣體擴散層之單電池測試 75
4-7-9 0.4V定電位長效型測試 76
第五章 結論 78
第六章 未來展望 79
參考文獻 80

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