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博碩士論文 etd-0906112-142754 詳細資訊
Title page for etd-0906112-142754
論文名稱
Title
利用甲醇水溶液系統的NMR光譜和微影像研究質子交換膜 Nafion 117的結構、動態與老化
Investigation of the structure, dynamics and degradation of proton exchange membrane Nafion 117 with NMR spectroscopy and micromaging of the aqueous solutions of methanol
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
91
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2012-06-15
繳交日期
Date of Submission
2012-09-06
關鍵字
Keywords
微影像、擴散、鬆弛、甲醇、老化、核磁共振
Diffusion, Relaxation, Methanol, Degradation, Nafion, NMR
統計
Statistics
本論文已被瀏覽 5654 次,被下載 1073
The thesis/dissertation has been browsed 5654 times, has been downloaded 1073 times.
中文摘要
全氟磺酸質子交換膜Nafion是燃料電池中使用最廣泛的離子交換膜。幾十年來對其不同尺度的結構、質子傳導機制、電化學性能、機械性能等進行了大量研究 1,但仍然有很多基本問題沒有明確答案,例如,質子傳導的圖像,劣化和老化、甚至孔洞的分佈等。其中老化問題與現實應用密切相關且與對開發新的交換膜有啟發作用,故近年來得到越來越多的關注 2,3。由於直接甲醇燃料電池中使用甲醇而且醇對Nafion的結構和動態較敏感且可能有介觀(mesoscopic)尺度上的特別結構 4,5,本論文工作以甲醇水溶液作為探針,利用固態NMR光譜、鬆弛、交換、擴散以及微影像,對Nafion 117的老化現像之物化機制進行研究。
本工作配置了一系列涵蓋全濃度範圍 (0% ~ 99%(w/w))的甲醇-水二元溶液體系,並且將Nafion 117置於這些不同濃度的醇水溶液中,利用液態及固態核磁共振,量測bulk溶液以及置於Nafion中的1H、17O光譜及其T1、T2鬆弛及交換參數。在bulk體系中,40%(w/w)濃度以上的甲醇水溶液其水的OH峰與甲醇的OH峰可被解析開。然後我們利用變溫以及擴散實驗進一步探討了甲醇水溶液的介觀/微觀結構及動態。利用量測Nafion內各濃度的甲醇水溶液的變溫1H、17O、T1、T2、擴散以及微影像實驗,比較bulk與受限環境下 (Nafion內)甲醇水溶液結構與動態的異同,藉此推測Nafion膜的結構、動態、與質子傳導和老化的關聯等。這些資料對進一步理解Nafion的結構、動態、質子傳導及老化等問題提供重要的參考。
Abstract
Perfluororated proton exchange membrane Nafion is the mostly used type of ion exchange membrane in fuel cells. Over the past decades, various studies have been carried out on their structures at different scales, proton conduction mechanism, electrochemical performance, thermal and mechanical properties etc, but many problems are still open, such as the precise picture of proton conduction, degradation and aging of the membrane, even the distribution of pores and channels etc. Because membrane degradation is crucial for practical operation of fuel cells and its understanding offers insights for developing new generation membranes, more and more attention is paid to this issue. Methanol is used in direct methanol fuel cells (DMFC) and alcohols are sensitive to the structure and dynamics of Nafion. In addition, aqueous solutions of alcohols are known to have special mesoscopic structures. Therefore, this thesis employs the aqueous solution of methanol as a probe and investigate the physicochemical mechanism of the degradation of Nafion 117 by means of solid state NMR spectra, relaxation, exchange, diffusion and micro-imaging.
A series of methanol-water binary solution samples covering the entire range of concentration (0% ~ 99%(w/w)) were prepared and the 1H,17O NMR spectra,T1、T2, exchange rate, diffusion coefficient of these samples in bulk and in Nafion were measured. In bulk samples, the OH peak of water and that of methanol could be resolved with concentration at or above 40% (w/w). The microscopic and mesoscopic structure and dynamics of methanol solutions (in bulk) were subsequently investigated with variable temperature and diffusion experiments. By measuring the variable temperature 1H and 17O spectra, T1, T2, diffusion and micro-images of the methanol solutions in Nafion 117, the structure and dynamics of methanol solutions in bulk and in Nafion 117 were then compared. Based on these data, the structure an dynamics of Nafion 117 and the correlations between methanol and proton conduction and membrane degradation are discussed. The results of this work provides valuable reference for further understanding the structure, dynamics and degradation of Nafion and their relationship with proton conduction.
目次 Table of Contents
摘要 i
Abstract ii
第一章 緒論 1
1.1 前言 1
1.2燃料電池簡介 3
1.3 Nafion薄膜的老化 9
1.4 研究動機 12
第二章 核磁共振簡介 13
2.1 核磁共振的發展 13
2.2 基本理論 26, 27 14
2.3 NMR鬆弛(Relaxation) 17
第三章 固態核磁共振原理 31 26
3.1偶極作用力 33
3.2化學位移各向異性 (Chemical Shielding Anisotropy) 35
3.3四級核種之固態NMR 37
3.4轉動活化能 41
3.5 擴散係數 42
第四章 核磁共振微影像原理 33 43
第五章 實驗部分 47
5.1實驗材料 47
5.2 樣品前處理及藥品配製 47
5.3 實驗儀器及裝置 47
5.4 實驗參數設置 47
第六章 結果與討論 50
6.1 Bulk甲醇水溶液1H、17O一維光譜測量 50
6.2 NMR 1H, 17O於酸性條件下研究 54
6.3甲醇水溶液 1H, 17O T1動態與變溫研究 57
6.4 Nafion 117膜內甲醇水溶液結構、動態、酸性與變溫研究 61
6.5 核磁共振微影像於Nafion 117老化研究 65
第七章 總結及展望 78
參考文獻 80
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