新型光聚合燃料電池質子交換膜

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黃文翰(Wen-Han Huang) 查詢紙本館藏

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化學學系

論文名稱

新型光聚合燃料電池質子交換膜
(New photopolymerization-based proton exchange membranes for fuel cells)

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至系統瀏覽論文 (2028-7-1以後開放)

摘要(中)

中文摘要
目前，大部分燃料電池薄膜的製作方式都採用溶液澆鑄法（Solution Casting）。然而，這種方法在製作過程中常常使用對環境具有高度危害性的溶劑，例如NMP，這與綠色和永續發展的目標相違背。為了符合這些目標，需要開發新的製程，以減少製作時間並更換為無毒的溶劑，同時能夠生產符合燃料電池基本要求的材料。
本研究的主要目標是尋找同時具有光交聯和製膜性質的小分子材料。我們選擇了具有雙丙烯酸酯官能基的線性親水性小分子作為主要材料結構，並與具有路易士鹼特性的1-乙烯基咪唑作為氫離子傳導劑，以及帶有磷酸根的酸修飾甲基丙烯酸酯（EDM），作為構成整個薄膜的成分。在混合分散的過程中，我們僅使用乙醇。光固化過程中，我們使用單一365nm紫外光源並加入相應的光引發劑，以實現快速製膜，完整的薄膜製作僅需20秒。
在主結構材料的使用方面，包括Tetra(ethylene glycol)diacrylate（QEGDA）、Tetra(ethylene glycol)diacrylate（QEGDMA）和Tri(proplene glycol)diacrylate（TPGDA）。只要整體重量比不超過40wt％，就有足夠的咪唑分子和EDM來促進整體薄膜的傳導性。在主材料相對比例無法形成足夠網狀結構的情況下，可以通過調整照光時間和光引發劑的使用量，實現傳導性和薄膜強度之間的綜合平衡。使用QEGDA製作的薄膜表面非常均勻，當水吸收與咪唑的物質摩爾比為1:1時，在80℃時薄膜的導電率達到4.5×10¯²S/cm。其他薄膜在升溫過程中的導電率也都在1.0～3.5×10¯²S/cm之間。特別是通過光交聯製備的薄膜，在高吸水量條件下仍能保持低膨脹（體積比約為10～20%）的優勢，同時具有一定的化學穩定性。

摘要(英)

Abstract
Currently, the majority of fuel cell membrane production relies on the solution casting method, which often involves the use of environmentally harmful solvents such as NMP. In order to align with green and sustainable goals, it is necessary to develop new manufacturing processes that reduce production time and replace toxic solvents, while still producing materials that meet the basic requirements for fuel cell applications.
This study focuses on finding small molecule materials that possess both photo-crosslinking and film-forming properties. Linear hydrophilic small molecules with dual acrylate functional groups are chosen as the main material structure. These molecules are combined with 1-vinylimidazole, which acts as a proton conductor, and Acid Modify Methylacrylate (EDM) with phosphate groups, serving as the constituents of the entire film. The mixing dispersion is achieved using only ethanol. During the photo-curing process, a single UV light source with a wavelength of 365 nm is used, along with corresponding photo-initiators, enabling rapid film formation with a complete film being produced in just 20 seconds.
In the utilization of the main structural materials, namely Tetra(ethylene glycol)diacrylate (QEGDA), Tetra(ethylene glycol)diacrylate (QEGDMA), and Tri(proplene glycol)diacrylate (TPGDA), a sufficient amount of imidazole molecules and EDM is present to facilitate overall film conductivity, as long as the total weight ratio does not exceed 40wt%. In cases where the proportion of the main material forming a network structure is relatively low, a balance between conductivity and film strength is achieved by adjusting the light exposure time and the amount of photo-initiator used. Films produced using QEGDA exhibit a highly uniform surface. When the molar ratio of water uptake to imidazole is 1:1, the film demonstrates a conductivity of 4.51-2S/cm at 80℃. Other films also exhibit conductivity levels ranging from 1.0 to 3.51-2 S/cm during the temperature ramp-up process. Notably, films created through photo crosslinking display advantages such as maintaining low volume swelling (10-20%) under high water uptake conditions and possessing a certain degree of chemical stability.

關鍵字(中)

★ 燃料電池

關鍵字(英)

論文目次

目錄
中文摘要 i
Abstract ii
目錄 iv
圖目錄 viii
表目錄 xi
第一章緒論 1
1-1前言 1
1-2 實驗目標 4
第二章文獻回顧 5
2-1 燃料電池交換薄膜的種類及介紹 5
2-2 質子電池交換薄膜介紹 7
2-3 質子電池交換薄膜傳遞機制 9
2-4 光聚合製成質子交換膜的發展 11
2-4-1 光固化隔離膜材料與製作 12
2-4-1-a 光起始劑的選擇 13
2-4-1-b 光交聯聚合官能基-乙烯基 18
2-4-2 薄膜離子導電性材料 23
2-4-2-a 傳遞質子的鹼性分子-Imidazole 24
2-4-2-b 親水性的凝膠材料 30
2-5實驗動機 34
第三章實驗方法與原理 38
3-1 實驗藥品 38
3-2 薄膜的製備程序 39
3-2-1 小分子材料混合順序 39
3-2-2 光固化交聯薄膜製備 40
3-3 實驗儀器 41
3-4 實驗儀器與技術原理 42
3-4-1 差式掃描量熱分析(Differential scanning calorietry，DSC) 42
3-4-2 衰減全反射傅立葉紅外光譜儀(ATR-FTIR) 43
原理 43
3-4-3 熱重分析儀(TGA) 44
3-4-4 掃描電子顯微鏡(SEM) 45
3-4-5 薄膜吸水率(Water Uptake)及薄膜膨潤率(Swelling Ratio) 46
3-4-6 薄膜機械強度測試 47
3-4-7 化學穩定性測試 48
3-4-8 離子傳導度測試 49
3-5 樣品命名規則 50
第四章結果與討論 51
4-1 光聚合燃料電池薄膜結構的結構與狀況探討 55
4-1-1 衰減全反射傅立葉紅外光譜儀(ATR-FTIR) 56
4-1-2 不同Glycol Diacrylate及DSC測試含水量 61
4-1-3 薄膜拉伸測試 63
4-1-4 SEM表面微結構分析 65
4-2 光聚合燃料電池薄膜的效能與性質分析 73
4-2-1 TGA熱穩定性測試 73
4-2-2 變溫導電度測試 74
4-2-3 化學穩定性測試 77
第五章未來展望 78
5-1 結論 78
5-2 未來展望與研究方向建議 79
1. 材料結構的挑選: 79
2. 光起始劑的挑選: 79
3. 主材料與導電材料的混合均勻性 79
參考文獻 81

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指導教授

諸柏仁

審核日期

2023-7-25

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