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研究生： 邱家豪
Hao, Chiu-Chia
論文名稱： PtSnRu/C 陽極觸媒在直接乙醇燃料電池之電化學行為
The Electrochemical Behaviors of PtSnRu/C in Ethanol Fuel Cell
指導教授： 楊明長
Yang, Ming-Chang
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： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 149
中文關鍵詞： 直接乙醇燃料電池 、白金三元合金 、白金錫釕合金 、乙醇燃氧化產物分析
外文關鍵詞： direct ethanol fuel cell, platinum ternary alloy, platinum-tin-ruthenium alloy, ethanol product analysis
相關次數： 點閱：68  下載：3 
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    • 本研究主要提升直接乙醇燃料電池的陽極觸媒的活性。目前對乙醇氧化活性最高的觸媒為白金錫合金，本實驗探討白金錫雙元合金中的原子比例、合成方法、適合的第三金屬及三元合金各成分比例對氧化乙醇的影響來尋找適合乙醇燃料電池的陽極觸媒。
    雙元合金中，只有Pt-Sn/C在循環伏安法觀察到在0.4V (vs. Ag/AgCl) 下有明顯的峰電流，其餘金屬的第一峰電流主要都在0.7V (vs. Ag/AgCl)，而本實驗也藉由紅外光譜證實Pt-Sn/C在0.4V (vs. Ag/AgCl) 下的反應為乙醇氧化成乙醛。其中白金錫的原子比在1:1時的活性最佳(37.2 mA/mg-Pt)。
    本研究除了採用含浸還原法也探討了以金屬置換法，以錫金屬當作還原劑，直接將白金還原在錫表面上，讓白金有更大的表面積。結果顯示在半電池測試下以金屬置換法得到的白金錫觸媒活性高於含浸還原法，但全電池分析時，金屬置換法提升活性的效果有限。
    比較釕、鈀、鎳當作三元合金觸媒的第三金屬，釕較適合，主因是白金釕合金的If/Ib值較大，顯示釕的加入可增強觸媒抗毒化的能力。研究三元合金不同比例下的活性後發現，Pt:Sn:Ru = 1:1:0.5時對乙醇氧化的活性最大，且全電池產物分析中也證明三元合金可略為提升乙醇氧化到二氧化碳的比例。

    This study focuses on activity improvement for the anode catalysts in direct ethanol fuel cells. According to literatures, the catalyst with the highest activity for ethanol oxidation is platinum-tin alloy. This research investigated the effects of atomic ratio of platinum to tin, synthesis methods, appropriate third metal and atomic ratio for ternary alloy on the catalyst activity which was used to determine. the best anode catalyst for direct ethanol fuel cell.
    For the binary alloy catalysts,only Pt-Sn/C gave a clear peak current at 0.4V (vs. Ag / AgCl) in a cyclic voltammogram, and the other metals only gave the peak current in 0.7V (vs. Ag / AgCl). The infrared spectrum confirmed that the reaction of Pt-Sn/C at 0.4V (vs. Ag / AgCl) is due to the oxidation of ethanol to acetaldehyde . The atomic ratio of Pt/Sn 1:1 had the highest activity.
    This study not only focused on the impregnation reduction method but also utilized displacement method. Tin reduced platinum precursor on the tin surface to provide greater surface area on platinum , as confirmed in half cell test. The catalysts formed by displacement method have higher activity(39.4 mA/mg Pt) than impregnation reduction method. But in single cell test, the enhancement of catalysts activity was not significant.
    Comparing to palladium and nickel, ruthenium is more suitable as the third metal for ternary alloy catalysts, because the If/Ib of the platinum-ruthenium alloy was larger than those of others, due to the enhancement of anti-poisoning of the catalyst. And this study found that the ternary alloy with atomic ratio of Pt: Sn: Ru = 1:1:0.5 gavethe highest activity. The product analysis from a single cell also proved that ternary alloy increased the oxidation of ethanol to carbon dioxide.

    目錄 摘要 I Abstract III 致謝 V 目錄 VI 圖目錄 XI 表目錄 XXI 第一章 緒論 1 1.1前言 1 1.2燃料電池簡介 1 1.2.1燃料電池的起源 1 1.2.2燃料電池的種類 4 1.2.3 燃料電池的應用與發展 10 1.3 直接乙醇燃料電池 13 1.3.1 直接乙醇燃料電池的特性 13 1.3.2 陽極觸媒 16 1.3.3 陰極觸媒 24 1.3.4 乙醇燃料電池的挑戰 26 1.4 研究動機 29 第二章 原理 31 2.1 乙醇燃料電池氧化機制 31 2.2電池放電極化現象 34 2.2.1活性過電位 36 2.2.2歐姆過電位 38 2.2.3質傳過電位 38 2.2.4 電池阻抗的計算 39 2.3 參考電極 40 2.4 循環伏安法 44 2.5 線性掃描法 45 2.6 交流阻抗分析 46 2.6.1交流阻抗分析原理 46 2.6.2電化學系統之交流阻抗分析 49 第三章 實驗步驟與儀器 56 3.1藥品與材料 56 3.2 儀器設備 58 3.3 觸媒製備 59 3.3.1 雙元合金觸媒製備 59 3.3.2 三元合金觸媒製備 63 3.3.3 金屬置換法觸媒製備 64 3.4 電極漿料製備 65 3.4.1半電池電極製備 65 3.4.2單電池電極製備 66 3.5 觸媒電化學測試觸 66 3.6 單電池放電測試 68 3.7 觸媒特性分析 71 3.7.1 穿透式電子顯微鏡圖譜 71 3.7.2誘導耦合電漿原子放射光譜儀 72 3.7.3 X射線繞射分析圖譜 72 3.7.4熱重分析 73 3.8　產物分析 73 3.8.1 全反射-傅立葉轉換紅外線光譜分析 73 3.8.2 氣相層析儀分析 73 第四章 結果與討論 75 4.1 PtSn組成分析 75 4.1.1 X光繞射儀與穿透式電子顯微鏡結構分析 75 4.1.2 熱重分析儀與誘導耦合電漿原子放射光譜儀組成分析 81 4.1.3 電化學活性測試 83 4.2 PtRu組成分析 90 4.2.1 X光繞射儀與穿透式電子顯微鏡結構分析 90 4.2.2 熱重分析儀與誘導耦合電漿原子放射光譜儀組成分析 95 4.2.3 電化學活性測試 97 4.3 不同第二金屬對觸媒活性的影響 101 4.3.1 X光繞射儀與穿透式電子顯微鏡結構分析 101 4.3.2 熱重分析儀與誘導耦合電漿原子放射光譜儀組成分析 106 4.3.3 電化學活性測試 106 4.3.4 紅外線光譜中間產物分析 110 4.4 三元合金組成分析 116 4.4.1 X光繞射分析儀與穿透式電子顯微鏡結構分析 116 4.4.2熱重分析儀與誘導耦合電漿原子放射光譜儀組成分析 123 4.4.3 電化學測試 124 4.5 含浸還原法與金屬置換法比較 131 4.5.1 X光繞射分析儀與穿透式電子顯微鏡結構分析 132 4.5.2熱重分析儀與誘導耦合電漿原子放射光譜儀組成分析 135 4.6 綜合比較 135 4.6.1 電化學活性測試 136 4.6.2 全電池測試 138 4.6.3 氣相層析產物分析 140 第五章 結論 144 參考文獻 146

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