電場誘導聚碸摻雜複合薄膜之研究

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姓名

林彥興(Yen-Hsing Lin) 查詢紙本館藏

畢業系所

化學學系

論文名稱

電場誘導聚碸摻雜複合薄膜之研究
(Electric field induced polysulfone doped in hybrid membrane for vanadium redox flow battery)

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摘要(中)

離子交換薄膜一直都是燃料電池、釩液流電池或是各種能量儲存裝置最核心的部分。至今，釩液流電池的質子交換膜仍有幾個缺點有待改善，如(1)提高質子導電度、(2)降低釩離子滲透、(3)良好的耐久穩定性。
本研究利用具有高化學穩定度和機械強度的高分子材料PSU添加至SPEEK高分子中，並在外加電場下鑄造成質子交換膜。結果顯示，添加PSU確實改善複合薄膜的物理性質(降低膨潤率、釩離子滲透等)，且經由電場誘導後，SPEEK和PSU高分子受到電場極化，使薄膜中的親水孔道在垂直於薄膜表面的方向形成具有方向性且連續的緻密結構，因為此緻密結構，使大顆粒釩離子更不容易傳遞，更進一步降低釩離子的滲透，提升薄膜的質子選擇率。添加PSU高分子至SPEEK中所製備的有機複合薄膜，在經電場誘導後，S57/PSU-20+E薄膜的釩離子滲透率下降0.195×10−7 cm2/min，質子選擇率達到16.53×104 S min/cm3。在單電池的測試中，S57/PSU-20+E薄膜比起其他薄膜擁有較好的庫倫效率、能量效率，且在經過10圈充放電次數後，電容量保持率也明顯的優於市售的N117。
此一新穎至被薄膜的方法同時改進了多項物性，解決膜材開發面臨的兩難情況，該方法也能廣泛地應用於各種不同再生能源裝置的零件開發。

摘要(英)

The ion exchange membrane is the most important component in fuel cell or vanadium redox flow battery. There are few drawbacks on vanadium redox flow battery membrane. These disadvantages include: (1) Low proton conductivity, (2) High vanadium ion permeability, and (3) Insufficient chemical stability and mechanical strength for prolonged operation.
Present research examined the property of SPEEK and PSU blend and verify its applicability in Redox vanadium flow battery. The use of external electric field poling in the composite polymer system created preferentially ordered channel morphology with high structural integral hydrophobic region in the membrane, which has shown to effectively improved the ion conductivity, reduced the vanadium ion permeation, and raised the mechanical and chemical strength. The study has demonstrated that electric poling treatment created membrane bearing preferentially ordered hydrophilic channel morphology and densely packed hydrophobic region. Due to more densely packed amorphous hydrophobic domain, the membrane showed lower degree of vanadium ion permeability and higher degree of ion selectivity. The composite membrane of S57/PSU-20+E shows the vanadium ion permeability only 0.195×10−7 cm2 min−1, the ion selectivity up to 16.53×104 S min/cm3. In the VRB performance, S57/PSU-20+E membrane shows the better performance in Coulombic Efficiency and Energy Efficiency. After 10 cycles, the discharge capacity retention of S57/PSU-20+E is still superior to N117.
This approach resolved the long standing dilemma of high performance membrane developments encounter in many renewable energy technologies.

關鍵字(中)

★ 質子交換膜
★ 釩逆流電池
★ 磺酸化聚二醚酮
★ 聚碸

關鍵字(英)

★ blend membrane
★ vanadium redox ﬂow battery
★ sulfonated poly(ether ether ketone)
★ polysulfone

論文目次

中文摘要 I
Abstract II
謝誌 IV
目錄 V
圖目錄 IX
表目錄 XIII
第一章緒論 1
1-1 前言 1
1-2 全釩氧化還原液流電池簡介和組成 2
1-3 全釩氧化還原液流電池原理 3
1-4 研究動機 5
第二章基本原理與文獻回顧 8
2-1 全釩氧化還原液流電池背景介紹 8
2-1-1 釩電池的優點 8
2-1-2 釩電池的應用 10
2-2 釩電池質子交換膜介紹 12
2-3 質子交換膜的傳遞機制 13
2-4 PFSA系列 15
2-4-1 Nafion/無機複合薄膜 19
2-4-2 Nafion/有機複合薄膜 23
2-5 非PFSA系列 25
2-5-1 碳氫高分子薄膜 26
2-5-2 有機/無機複合高分子薄膜 29
2-5-3 酸鹼複合高分子薄膜 32
2-5-4 團聯共聚高分子 33
2-6 電場誘導性質探討 35
2-6-1 裝置設計及原理 35
2-6-2 外加電場於質子交換膜的應用 36
第三章實驗方法與原理 40
3-1 實驗儀器及技術原理 40
3-1-1 場發射掃描式電子顯微鏡 (FE-SEM) 40
3-1-2 熱重分析儀 (Thermal Gravimetric Analysis, TGA) 40
3-1-3 薄膜吸水量(Water Uptake)與膨潤率(Swelling) 41
3-1-4 離子交換容量 (Ion Exchange Capacity, IEC) 42
3-1-5 釩離子滲透率 (Vanadium permeability) 42
3-1-6 質子導電度測量 (Proton Conductivity) 44
3-1-7 複合薄膜機械強度測試 44
3-1-8 化學穩定性測試 46
3-2 物質合成及薄膜製備 47
3-2-1 磺酸化聚醚醚酮高分子 47
3-2-2 有機複合薄膜之製備 47
3-2-3 外加電場裝置設計 48
3-2-4 Nafion 117前處理 48
3-3 釩電池組裝 49
3-3-1 電解液製備 49
3-3-2 電池組裝及操數設定 50
3-3-3 常用的性能指標 52
3-4 實驗藥品 53
3-5 樣品命名規則 54
第四章結果與討論 55
4-1 複合薄膜材料性質與效能分析 56
4-1-1 磺酸化程度的鑑定 56
4-1-2 熱穩定性分析 57
4-1-3 複合薄膜機械效能測試 59
4-1-4 吸水性、膨潤率與離子交換容量(IEC)的比較 60
4-1-5質子導電度與離子交換容量(IEC)的比較 62
4-1-6 釩離子滲透率探討 63
4-1-7 Selectivity薄膜質子選擇率 64
4-1-8 單電池測試 65
4-2 外加電場誘導高分子複合薄膜探討及性質分析 67
4-2-1 SEM薄膜微結構影像 67
4-2-2 熱穩定性分析 69
4-2-3 複合薄膜機械效能測試 70
4-2-4 吸水性及膨潤率與質子導電度比較 71
4-2-5 離子交換容量(IEC) 73
4-2-6 釩離子滲透率 74
4-2-7 Selectivity薄膜質子選擇率 75
4-2-8 化學穩定度測試 76
4-2-9 單電池測試 78
4-2-10 充放電循環測試 80
4-2-11 自放電的測試 83
第五章結論與未來展望 84
5-1 結論 84
5-2 未來展望與研究建議 86
第六章參考文獻 88

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指導教授

諸柏仁(Po-jen Chu)

審核日期

2017-8-9

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