臺灣博碩士論文加值系統

本論文利用2,2-bis (4-carboxyphenyl)-hexaflouopropane 和3,3’-diaminobenzidine兩種單體成功地合成出六氟聚苯咪唑高分子(fluorine-containing polybenzimidazole, 6F-PBI)，在成膜過程中添加離子液體1-hexyl-3methylimidazolium trifluoromethanesulfonate (HMI-Tf)與6F-PBI混摻，製備出一系列的聚苯咪唑/離子液體複合薄膜，並進行機械性質和熱性質等測試。研究顯示，HMI-Tf的添加使複合薄膜的熱性質與機械性質下降，卻提升了質子導電度，在160 ℃下均達0.0021 S/cm。
　　薄膜進行磷酸摻雜後，在磷酸摻雜量僅有129 %的複合薄膜於160 ℃下均有0.015 S/cm以上的質子導電度。在單電池測試部分，分為十四天開關測試與三十天穩定測試。在開關測試 (160 ℃下負載電流200 mA/cm2操作12小時而後關閉燃料降回室溫)，複合薄膜維持穩定的開路電壓，顯示能防止燃料的穿越。而在三十天穩定測試 (160 ℃下負載電流200 mA/cm2操作720小時)，複合薄膜輸出電壓衰退速度為0.054 mV/h，顯示此複合薄膜能做為一種良好的高溫型質子交換膜。

In this work, fluorine-containing polybenzimidazole (6F-PBI) was synthesized successfully. We added 1-hexyl-3methylimidazolium trifluoromethanesulfonate (HMI-Tf) into PBI solution to prepare a series of PBI/ionic liquids composite membranes. All composite membranes showed lower mechanical properties than pristine PBI membranes, but reached 0.0021 S/cm proton conductivity at 160 ℃ before phosphoric acid doped. Furthermore, phosphoric acid doped composite membranes, prepared with acid content of only 129%, could reach 0.015 S/cm proton conductivity at 160 ℃. Membrane electrode assemblies were fabricated with a size of 4 cm2 and a Pt loading of 1 mg/cm2. The composite membrane showed a little open circuit voltage change rate and proved stable in startup and shutdown tests (operated at 160 ℃ with 200 mA/cm2 for 12 h and then kept off for 12 h at room temperature). In long-term durability tests (operated at 160 ℃ with 200 mA/cm2 for 720 h), the composite membrane showed the cell voltage decay rate of 0.054 mV/h, indicating high stability during operation.

摘要 I
Extended Abstract II
誌謝 X
總目錄 XI
表目錄 XV
圖目錄 XVI
第一章 緒論 1
1.1 前言 1
1.2 研究背景 5
1.3 研究動機與目的 7
第二章 文獻回顧與原理 9
2.1 質子交換膜燃料電池簡介 9
2.2 質子交換膜燃料電池原理 13
2.3 Polybenzimidazole (PBI)之簡介 17
2.4 離子液體之簡介及應用 19
2.4.1 離子液體簡介 19
2.4.2 離子液體之發展 20
2.5 質子傳導原理 22
2.6 單電池測試與衰退機制 24
2.6.1 單電池衰退機制 24
2.6.2 電池長時間穩定性測試 25
第三章 實驗方法及步驟 28
3.1 實驗材料 28
3.2 實驗儀器 28
3.3 實驗步驟 30
3.3.1 Polybenzimidazole (6F-PBI) 合成 30
3.3.2 Pristine PBI薄膜製備 31
3.3.3 PBI/HMI-Tf複合薄膜製備 31
3.4 結構鑑定 32
3.4.1 傅利葉轉換紅外線光譜分析 (FT-IR) 32
3.4.2 核磁共振光譜分析 (1H-NMR) 33
3.5 薄膜性質分析 34
3.5.1 固有黏度量測 (Inherent viscosity) 34
3.5.2 熱重損失分析儀 (TGA) 34
3.5.3 機械性質分析 (Mechanical properties) 35
3.5.4 熱機械分析 (TMA) 35
3.6 質子導電度量測 36
3.6.1 薄膜磷酸摻雜 36
3.6.2 質子導電度量測 (Proton conductivity) 36
3.7 膜電極製備 (Membrane electrode assemblies, MEAs) 39
3.7.1 觸媒漿料配製與塗佈 39
3.7.2 熱壓 39
3.8 單電池測試 40
3.8.1 單電池組裝 40
3.8.2 單電池效能測試 41
3.8.3 十四天開關測試 (Startup and shutdown tests) 41
3.8.4 三十天穩定測試 (Long-term durability tests) 41
第四章 結果與討論 42
4.1 合成結構鑑定與性質分析 42
4.1.1 6F-PBI之合成 42
4.1.2 6F-PBI固有黏度量測 42
4.1.3 傅利葉轉換紅外線光譜分析 (FT-IR) 43
4.1.4 核磁共振光譜分析 (1H-NMR) 45
4.2 PBI/HMI-Tf複合薄膜性質分析 46
4.2.1 熱重損失分析 (TGA) 46
4.2.2 熱機械分析 (TMA) 48
4.2.3 機械性質分析 (Mechanical properties) 51
4.2.4 薄膜摻雜磷酸之分析 (Acid content analysis) 52
4.2.5 質子導電度分析 (Proton conductivity) 54
4.3 PBI/HMI-Tf複合薄膜單電池元件測試分析 56
4.3.1 單電池元件效能分析 56
4.3.2 單電池十四天開關測試 (Startup and shutdown tests) 58
4.3.3 單電池三十天穩定測試 (Long-term durability tests) 60
第五章 結論與未來展望 64
第六章 參考文獻 66

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