臺灣博碩士論文加值系統

本篇論文探討的是以含浸法還原Pt、Ru、Ni前驅物分別為H2PtCl6、RuCl3、NiCl2，並用MWCNT做為金屬離子之載體。實驗中所使用的還原劑分別為乙二醇、甲酸、NaBH4。
在本實驗中，使用三種還原劑合成Pt-Ru/CNT，並利用循環伏安法(Cyclic Voltammetry,CV)測試評估二元各項數據最好之還原劑為甲酸和乙二醇，再成功使用此兩種還原劑合成Pt-Ru-Ni/CNT，先以循環伏安法各別測試出最佳還原比例之電極觸媒，再將測試結果進行CO毒化指標、峰值電位與峰值電流之判定，兩者還原劑在三元合金Pt：Ru：Ni比例都為4：2：4為最佳，塗佈於Nafion上之陽極觸媒Pt-Ru-Ni/CNT觸媒劑量約為0.387mg/cm2，而陰極以相同還原劑製成之觸媒Pt/CNT塗佈，最終製成MEA進行單電池測試。
單電池測試中，使用甲酸及乙二醇還原之觸媒，雖開路電壓低，但甲酸電流密度卻比乙二醇來的佳，測試結果分別為甲酸1.71mA/cm2與乙二醇1.39mA/cm2，推測原因為甲酸製備之觸媒氧化電位比乙二醇製備之觸媒來的低，致使甲酸還原之觸媒擁有較佳之活性。
熱壓溫度、壓力及時間都會對製備出的MEA效能有所影響。因此，有效控制上述變因，將是提升膜電極（MEA）效能的重要條件。

This study was to prepare the Pt-Ru-Ni alloy electrocatalyst for direct methanol fuel cells using Impregnation-reduction with three different reductants. The process of this work was divided into two steps. The first step was to use Enhylene glycol, Formic acid, NaBH4 ehthylene glycol as the reductants respectively to reduce hexachlorplatinic acid into Pt-Ru-Ni nanoparticles. Dispersion stability of the electrocatalyst nanoparticles on multi-walled carbon nanotube was examined respectively by changing the volumetric ratio of Pt-Ru-Ni and evaluated the catalytic activity of the catalysts by cyclic voltammetry (CV).
　　The second was to prepare Membrane and Electrode Assembly(MEA) with the best catalytic activity of the Pt:Ru:Ni(40:20:40) electrocatalyst under I-V characteristic curve for cyclic voltammetry. The catalysts used at the anode and cathode were applied on the membrane by a spraying method, sandwiched with carbon cloth, and hot pressed by changing temperature and pressure. The loading of the alloy electrocatalyst on electodes was 0.387mg/cm2. MEA performance was evaluated using a DMFC single cell with a 12.25 cm2 cross-section area and measured with a potentiometer which recorded the cell potential from the circuit voltage under constant current condition. The result indicated that the performance of MEA prepared by using Formic acid as the reductants was better than using the Enhylene glycol.

目錄
中文摘要 i
英文摘要 ii
致謝 iv
目錄 v
表目錄 ix
圖目錄 x
第一章 緒論 1
1-1 前言 1
1-2 文獻回顧 2
1-2-1 甲醇性能測試 2
1-2-2 觸媒製作 4
1-2-3 碳載體研究 8
1-2-4 疏水研究 11
1-2-5 nafion膜相關研究 11
1-2-6 觸媒塗佈研究 13
1-2-7 熱壓研究 14
1-3 研究目的 14
第二章 理論背景 16
2-1 燃料電池開發背景 16
2-2 燃料電池種類 17
2-3 直接醇類燃料電池（direct methanol fuel cell，DMFC）： 18
2-3-1 反應三相點 19
2-3-2 膜電極組內部元件 19
2-4 極化： 20
2-5 具載體型奈米金屬催化劑合成： 21
2-5-1 直接還原法： 21
2-5-2 含浸法： 22
2-5-3 浸漬法： 22
2-5-4 膠體法： 23
2-5-5 微波法： 23
2-5-6 醇類還原含浸法： 24
2-5-7 共沉澱法： 24
2-5-8 微細胞法： 25
2-5-9 UV輻射輔助晶化： 25
2-6 電化學反應簡介[39]： 26
2-6-1 電化學反應 26
2-6-2 電化學反應系統 27
2-6-3 電化學反應程序 27
2-7 循環伏安法(Cyclic Voltammetry,CV) 28
2-7-1 循環伏安法測試原理 30
第三章 實驗方法 32
3-1 實驗藥品與設備 32
3-2 實驗機台介紹 32
3-2-1 單電池測試機台 32
3-2-2 熱壓機台 32
3-2-3 電化學分析儀 33
3-2-4 掃瞄式電子顯微鏡(Scanning Electron Microscopy，SEM) 33
3-3 實驗流程 34
3-3-1 尋找電池性能測試參數 34
3-3-2 碳載體的前處理 35
3-3-3 Pt-Ru/CNT觸媒的製備 35
3-3-4 Pt-Ru-Ni/CNT觸媒的製備 36
3-3-5 半電池電極片製備 36
3-3-6 循環伏安法分析 37
3-3-7 MEA製作 37
3-3-8 MEA性能測試 38
第四章 結果與討論 39
4-1 電池性能測試參數探討 39
4-1-1 不同流率下DMFC的效能差異 39
4-1-2 不同甲醇進料溫度下對於DMFC的效能差異 39
4-1-3 不同電池溫度下對於DMFC的效能差異 40
4-1-4 不同甲醇進料濃度對於DMFC的效能差異 40
4-2 觸媒循環伏安法(CV)活性探討 41
4-2-1 觸媒有無熱壓之電性比較 41
4-2-2 Pt單觸媒和PtRu二元觸媒之CV 42
4-2-3 不同還原法製備二元觸媒之CV 43
4-2-4 甲酸還原劑製備三元觸媒Pt-Ru-Ni之CV 44
4-2-5 乙二醇還原劑製備三元觸媒Pt-Ru-Ni之CV 45
4-3 三元(Pt-Ru-Ni)&二元(Pt-Ru)觸媒之比較 46
4-3-1 三元(Pt-Ru-Ni)&二元(Pt-Ru)觸媒之成本 46
4-3-2 三元(Pt-Ru-Ni)&二元(Pt-Ru)觸媒之金屬附載量 47
4-4 不同還原劑製備觸媒之SEM比較 48
4-5 二元觸媒於DMFC電池性能測試比較 49
4-6 甲酸三元觸媒於DMFC電池性能測試比較 49
4-7 三元觸媒於DMFC電池性能測試比較 50
第五章 結論與建議 51
5-1 結論 51
5-2 建議 52
參考文獻 53
直接甲醇燃料電池應用三元觸媒Pt-Ru-Ni之甲醇電氧化性能 92
簡歷(CV) 100

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