磷酸燃料電池 (Phosphoric acid fuel cell, PAFC) 為高溫型之燃料電池，其操作溫度為100-250oC，和質子交換膜燃料電池(Proton exchange membrane fuel cell, PEMFC) 比起來具備較高的一氧化碳毒化 (CO poisoning) 容忍度、可簡化水熱管理等好處。然而磷酸燃料電池卻有電解質隨著時間而洩漏的問題，影響到電池之長效穩定性，使其發展受到限制。
本研究以鹼性雙氧水改質之二氧化鈦 (Alkaline hydrogen peroxide modified TiO2, AHP-TiO2) 顆粒改質聚苯並咪唑薄膜 (Polybenzimidazole, PBI)，旨在提高薄膜留存水及磷酸之能力，以維持電池之長效穩定性。
為了觀察二氧化鈦改質前後的變化，本研究以FTIR確認鹼性雙氧水是否能提高二氧化鈦表面的OH官能基；由BET分析二氧化鈦之比表面積及孔徑分布，並搭配TGA之數據精確計算出表面氫氧官能基的密度。於PBI膜材方面，藉由SEM觀察膜材之表面形貌與厚度，並且以拉伸機測試其機械強度變化。
在電性表現方面，本實驗以交流阻抗法 (AC impedance analysis) 得知PBI膜之質子傳導度 (Proton conductivity)；並以燃料電池測試機台 (Mini 150) 測試本研究製備的質子交換膜應用於磷酸燃料電池之效能。經過眾多分析及測試後發現，添加2% AHP-TiO2的PBI膜可以提高約2倍的質子傳導度；電池測試方面，其最大功率密度在170oC時可達961mW/cm2；在長效測試方面，經過92 h的長效測試 (0.2A/cm2, 170oC) 後電池電壓僅下降3%。

Recently, high temperature fuel cells, such as phosphoric acid fuel (PAFC), have been studied. It has been previously reported that increasing the operation temperature of fuel cells can be advantageous to not only increase its electrocatalytic activities and tolerance to impurities (such as carbon monoxide), but also simplify the hydrothermal management system and increase overall energy conversion efficiency. However, the electrolyte in the membrane will leach out during operation, and this problem limits the development of phosphoric acid fuel cell.
In this thesis, in order to overcome the electrolyte leaching issue, we used polybenzimidazole (PBI) membrane as the substrate and developed the composite proton exchange membrane which was composed of the filler “titanium dioxide (TiO2)”. And then, we used alkaline hydrogen peroxide (AHP) to increase the hydroxyl group on the TiO2 surface to further enhance the durability of fuel cell.
About the characterization analysis, we used Fourier transform infrared spectroscopy (FTIR), BET and thermogravimetric analysis (TGA) to determine the enhancement of hydroxyl group on the TiO2 surface after AHP modification. Then we used scanning electron microscope (SEM) to observe the surface morphology and thickness of the PBI membrane. Tensile test was used to understand the effect of the addition of TiO2 on mechanical properties. Finally, we conducted AC impedance analysis to measure the proton conductivity and single cell test/life time test to know the performance of fuel cell.
The results show that the proton conductivity of 2% AHP-TiO2/RPBI was twice pristine PBI. In single cell test, the best performance of 2% AHP-TiO2/RPBI can reach 961 mW/cm2. In life time test, 2% AHP-TiO2/RPBI just decayed 3% of its voltage after 92 h of operation under 170oC and 0.2 A/cm2.

摘要 i
Abstract ii
誌謝 iv
總目錄 v
表目錄 viii
圖目錄 ix
第一章 緒論 1
1-1 前言 1
1-2 燃料電池簡介 1
1-3 燃料電池之種類及其原理 2
1-3-1 磷酸燃料電池 (Phosphoric acid fuel cell, PAFC) 3
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) 5
1-3-4 熔融碳酸鹽燃料電池 (Molten carbonate fuel cell, MCFC) 6
1-3-5 固體氧化物燃料電池 (Solid oxide fuel cell, SOFC) 7
1-4 研究目的 10
第二章 文獻回顧與儀器基本原理 11
2-1 燃料電池之電化學理論 11
2-1-1 電極熱力學 11
2-1-2 電極反應動力學 12
2-2 質子交換膜簡介 14
2-3 應用於磷酸燃料電池之質子交換膜 15
2-4 摻雜填充物之質子交換膜 16
2-4-1 摻雜二氧化鈦之質子交換膜 16
2-4-2 摻雜氧化石墨烯之質子交換膜 18
2-5 質子交換膜之親水化處理 19
2-6 儀器分析原理及操作 20
2-6-1 氮氣吸脫附儀 (BET) 20
2-6-2 熱重分析儀 (TGA) 21
2-6-3 傅立葉轉換紅外線光譜儀 (FTIR) 22
2-6-4 掃描式電子顯微鏡(SEM) 23
2-6-5 拉伸測試 (Tensile test) 23
2-6-6 交流阻抗分析-質子傳導度測試 (AC impedance analysis) 24
第三章 實驗方法 27
3-1 實驗藥品與材料 27
3-2 實驗設備 27
3-3 分析儀器 28
3-4 使用基材之介紹 28
3-5 實驗流程圖 29
3-6 電極之製備 31
3-7 鹼性雙氧水改質二氧化鈦 32
3-8 質子交換膜之製備 33
3-9 酸摻雜 (Acid doping) 與膜電極組 (MEA) 之製備 34
3-10 質子傳導度測試 34
3-11 單電池測試 (Single cell test) 35
3-12 電池長效性測試 (Life time test) 36
第四章 結果與討論 37
4-1 TiO2與AHP-TiO2性質分析 37
4-1-1 表面官能基分析 (FTIR) 37
4-1-2 比表面積 (BET) 與熱穩定性分析 (TGA) 37
4-2 PBI膜與TiO2/PBI複合膜之性質分析 39
4-2-1 表面形貌分析 (SEM) 39
4-2-2 磷酸摻雜 (Acid doping) 測試 42
4-2-3 拉伸測試(Tensile test) 43
4-2-4 質子傳導度測試(EIS) 45
4-3 電池測試 46
4-3-1 短效測試 46
4-3-2 長效測試 49
第五章 結論 51
第六章 未來展望 52
參考文獻 53

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