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研究生: 吳琇媚
Wu, Hsiu-Mei
論文名稱: 表覆聚苯胺碳層奈米碳管之製備與其於氧氣還原反應之應用
Preparation of Controllable Nitrogen-Doped Carbon Layer Surrounding Carbon Nanotubes through Polyaniline for Oxygen Reduction Reaction
指導教授: 郭炳林
Kuo, Ping-Lin
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 93
中文關鍵詞: 氮摻雜奈米碳管電極觸媒直接甲醇燃料電池
外文關鍵詞: N-doped, carbon nanotube, electrocatalyst, direct methanol fuel cells
相關次數: 點閱:128下載:1
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  • 本研究利用苯胺覆蓋於碳管的表面並聚合,經高溫碳化後,成功於奈米碳管上製備出含氮碳層(N/C ratio 3.3-14.6%)的新式觸媒載體-含氮碳層碳管(NC-CNT)。
    使用不同Aniline/CNT比例以及不同碳化溫度皆會影響到NC-CNT的外觀形態。實驗中以四點碳針、Raman光譜、X光光電子能譜以及等溫物理吸脫附曲線等方法鑑定含氮碳層碳管之物理特性,發現NC-CNT在800℃碳化溫度下具有最佳導電度值,在900℃碳化溫度下具有最佳結晶性,並且NC-CNT本身對於氧氣還原具有催化活性。
    本研究利用含浸法製備白金奈米粒子並擔載於含氮碳管表面。透過穿透式電子顯微鏡發現白金奈米粒子粒徑均一(約1.5±0.5 nm)且平均分布於含氮碳管表面。與商用品E-TEK (55.3 m2/g)相比,更是具有相當顯著的電化學活性表面積 (111.4 m2 /g)。而在耐久性測試中,擔載白金粒子於NC-CNT上的耐久性遠高於擔載白金粒子於純碳管(Pt/CNT)上。
    於甲醇燃料電池(DMFC)測試後,以含氮碳管擔載白金觸媒 (Pt/NC-CNT)應用於陰極的效能約為44.4 mW/mgPt,高出E-TEK (27.2 mW/mgPt) 60%,更高出Pt/CNT (19.4 mW/mgPt)將近130%。綜合以上實驗結果,表示將NC-CNT應用於DMFC陰極觸媒層,將具有發展潛力。

    Novel nitrogen-containing carbon layer surrounding carbon nanotubes (NC-CNT) (N/C ratio 3.3-14.6%) as catalyst support have been successfully prepared using Aniline as a dispersant to CNT and as a source for both carbon and nitrogen coated on the surface of the CNT.
    The surface morphology of NC-CNT varied at different Aniline/CNT ratio and different carbonization temperature. In this study, four-point probes, Raman spectra, X-ray photoelectron spectroscopy and nitrogen adsorption-desorption isotherm curves used to examine the physical properties of NC-CNT. It showed best conductivity after 800℃ carbonization, best crystalline after 900℃carbonization and had activity toward ORR.
    Pt nanoparticles were load at NC-CNT surface and synthesized in-situ. From TEM image, it showed that Pt nanoparticles had average size about 1.5±0.5 nm and uniform dispersion. Pt/NC-CNT had a significantly higher electrochemically active surface area (111.4 m2 g-1) than E-TEK (55.3 m2 g-1). In durability test, Pt/NC-CNT was better than Pt/CNT.
    In single cell test, performance of Pt/NC-CNT (44.4 mW/mgPt) used at cathode was higher than that of commercial E-TEK catalyst (27.2 mW/mgPt) about 60%, and higher than that of Pt/CNT (19.4 mW/mgP) about 130%.

    摘要 I 英文摘要 II 致謝 III 目次 IV 表目錄 VIII 圖目錄 IX 第一章 緒論 1 1.2 燃料電池簡介 2 1.2.1 燃料電池發展背景 2 1.2.2 燃料電池種類 2 1.2.3 燃料電池優點與現今發展 7 1.3 直接甲醇燃料電池(DMFC) 8 1.3.1 工作原理 8 1.3.2 觸媒層 10 1.3.3 質子交換層 11 1.4 研究動機與目的 13 第二章 理論 14 2.1 碳材料簡介 14 2.1.1 碳黑 16 2.1.2 中孔碳 16 2.1.3 奈米碳管 18 2.2 電極觸媒 19 2.2.1 電極觸媒種類 20 2.2.2 氧氣還原之反應機構 22 2.3 氮原子添加材料 24 2.4 電化學測試 28 2.4.1 循環伏安法(Cyclic voltammograms) 28 2.4.2 活性表面積測試 33 2.1 膜電極組(Membrane Electrode Assembly , MEA) 38 2.4.3 極化現象 40 2.4.4 極化曲線 42 第三章 實驗 44 3.1 實驗藥品與材料 44 3.2 實驗分析儀器與裝置 45 3.2.1 掃描式電子顯微鏡(SEM) 45 3.2.2 穿透式電子顯微鏡(TEM) 45 3.2.3 四點探針(Four-Point Probes) 46 3.2.4 X光光電子能譜儀(XPS) 46 3.2.5 單電池設備(Single cell equipment) 47 3.3 樣品製備 48 3.3.1 含氮碳層碳管製備 48 3.3.2 金屬奈米觸媒製備 49 3.3.3 導電度測試樣品製備 51 3.3.4 製備電化學測試工作電極 51 3.3.5 製備膜電極組(MEA) 53 第四章 結果與討論 54 4.1 含氮碳層碳管分析 54 4.1.1 含氮碳層碳管(NC-CNT) 形態與結構分析 54 4.1.1.1 不同Aniline:CNT的影響 54 4.1.1.2 不同碳化溫度的影響 59 4.1.2 元素分析 60 4.1.3 等溫物理吸脫附 61 4.1.4 碳材料熱重分析儀測試,TGA 62 4.1.5 拉曼光譜及導電度分析 63 4.1.6 X射線電子光譜儀,XPS 66 4.1.7 碳材料氧氣還原反應測試,ORR 68 4.2 金屬觸媒特性分析 70 4.2.1 觸媒型態分析 70 4.3 金屬觸媒電化學分析 74 4.3.1 電化學活性表面積測試,EASA 74 4.3.2 氧氣還原反應測試,ORR 77 4.3.3 金屬觸媒耐久性測試 79 4.4 單電池組效能測試 82 第五章 結論 85 第六章 參考文獻 87

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