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研究生： 涂嘉惠
Tu, Chia-Hui
論文名稱： 高溫型質子交換膜燃料電池用之新交聯型聚苯基喹喔啉薄膜合成與性能研究
Synthesis and Properties of Novel Cross-linked Polyphenylquinoxalines Membranes for High Temperature Proton Exchange Membrane Fuel Cells
指導教授： 許聯崇
Hsu, Lien-Chung
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 79
中文關鍵詞： 交聯型聚苯基喹喔啉 、高溫型質子交換膜燃料電池 、長時間測試
外文關鍵詞： cross-linked polyphenylquinoxaline, high-temperature proton exchange membrane fuel cell (PEMFC), long-term durability test
相關次數： 點閱：68  下載：3 
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    • 本論文利用benzyl 4-hydroxyphenyl ketone和1,2-diamino-4-fluorobenzene以1,4-diazabicyclo[2.2.2]octane 作為催化劑，一步驟合成出自聚合聚苯基喹喔啉之單體3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline 和2-(4-hydroxyphenyl)- 3-phenyl-6-fluoroquinoxaline，並利用此單體合成出含醚基的聚苯基喹喔啉(Polyphenylquinoxaline，PPQ)，而此含有醚基團的PPQ 可溶於一般有機溶劑中方便加工，然而 PPQ 在摻雜過程中會發生溶解的情形，造成機械性質大幅下降，無法進行後續單電池元件製作與測試，因此本研究利用硫酸作為交聯劑，進行熱交聯反應，製備出不同交聯程度的共價鍵交聯聚苯基喹喔啉，並進行機械性質、抗氧化性質、熱性質等測試。研究顯示，交聯薄膜具有穩定的熱性質、機械性質與抗氧化，且交聯後能提升PPQ於磷酸中的溶解阻抗。
    薄膜進行磷酸摻雜後，始具備質子傳導的能力，而磷酸摻雜量隨交聯度的增加略有下降，在160 ℃下，交聯後薄膜均有0.009S/cm以上的質子導電度。單電池測試方面，分為十四天開關測試(150 ℃下負載電流0.2A/cm2操作12小時而後關閉燃料降回室溫 )與三十天穩定測試(150 ℃下負載電流0.2A/cm2操作720小時)。結果顯示交聯薄膜在14天開關測試開路電壓衰退速率為0.15 mV/h，操作電壓表現穩定，30天穩定測試中的電壓率退速率為0.039 mV/h，證實交聯後的PPQ薄膜可視為一種新穎式的高溫型質子交換膜燃料電池之材料。

    In this work, a self-polymerizable quinoxaline monomer was synthesized via one-pot synthesis. A 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline and 2-(4-hydrox-yphenyl) -3-phenyl-6-fluoroquinoxaline mixture was synthesized from benzyl 4-hydroxyphenyl ketone and 1,2-diamino-4-fluorobenzene, and catalyzed by 1,4-diazabicyclo[2.2.2]octane. Then, an AB-type polyphenylquinoxaline (PPQ) was synthesized from the monomer.
    The polyphenylquinoxaline was used for cross-linking. Cross-linked PPQ membranes were prepared using sulfuric acid. The membranes exhibited great mechanical properties, oxidative stability, and thermal properties. However, they dissolve in high-concentration phosphoric acid. The acid content of phosphoric-acid-doped membranes decreased slightly with cross-linking, but all membranes could reach 0.009 S/cm proton conductivity at 160 °C. Membrane electrode assemblies were fabricated with an active area of 4 cm2 and Pt loading of 1 mg/cm2. A startup and shutdown test (operated at 150 °C with 0.2 A/cm2 for 12 h and then 12 h off at room temperature) and a 30-day long-term durability test (150 °C with 0.2 A/cm2) were conducted. In the startup and shutdown test, the cross-linked membrane showed a low open-circuit voltage decay rate of 0.15 mV/h. In the 30-day long-term durability test, the voltage decay rate was 0.039 mV/h. In both tests, the cross-linked membrane showed stable performance. Therefore, the cross-linked PPQ membrane can be regarded as a novel material for high-temperature proton exchange membrane fuel cells.

    摘要 I Extended Abstract II 誌謝 IX 總目錄 X 表目錄 XIV 圖目錄 XV 第一章 緒論 1 1.1 前言 1 1.2 研究背景 4 1.3 研究動機與目的 5 第二章 文獻回顧與原理 6 2.1 質子交換膜燃料電池簡介 6 2.2 質子交換膜燃料電池原理 8 2.3 Polyphenylquinoxaline (PPQ)之簡介 11 2.4 PPQ 合成 13 2.5 質子傳導原理 17 2.6 質子交換膜性質提升 19 2.7 單電池測試與衰退機制 22 2.7.1 單電池衰退機制 22 2.7.2 電池長時間穩定性測試 23 第三章 實驗方法及步驟 26 3.1 實驗材料 26 3.2 實驗儀器 26 3.3 實驗步驟 28 3.3.1 PPQ之單體3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxalie和2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline合成 28 3.3.2 PPQ高分子合成與薄膜製備 29 3.3.3 PPQ 之薄膜製備 30 3.3.4 CPPQ高分子交聯薄膜製備 30 3.4 結構鑑定 31 3.4.1 傅利葉轉換紅外線光譜分析 (FT-IR) 31 3.4.2 核磁共振光譜分析 (1H-NMR) 32 3.4.3 元素分析(EA) 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 熱機械分析儀 (TMA) 35 3.5.5 抗氧化分析 (Oxidative stability tests) 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 自聚合PPQ單體與高分子合成 42 4.1.2 CPPQ交聯薄膜製備 43 4.1.3 固有黏度 (Inherent viscosity) 46 4.1.4 傅利葉轉換紅外線光譜分析 (FT-IR) 46 4.1.5 核磁共振光譜分析 (1H-NMR) 49 4.1.6 元素分析(EA) 50 4.2 交聯薄膜性質分析 51 4.2.1 熱性質分析（TGA） 51 4.2.2 熱機械分析 (TMA) 53 4.2.3 抗氧化分析 (Oxidative stability tests) 54 4.2.4 薄膜摻雜磷酸之分析 (Acid content analysis) 56 4.2.5 質子導電度分析 (Proton conductivity) 58 4.2.6 機械性質分析 (Mechanical properties) 60 4.3 PPQ-20薄膜單電池元件測試分析 62 4.3.1 單電池元件效能分析 62 4.3.2 單電池十四天開關測試 (Startup and shutdown tests) 64 4.3.3 單電池三十天穩定測試 (Long-term durability tests) 66 第五章 結論與未來展望 69 第六章 參考文獻 71

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