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研究生： 張亘佑
Chang, Hsuan-Yu
論文名稱： 利用恆電位沉積法製備高活性鉑觸媒應用於磷酸燃料電池電極之製程優化
Optimized Fabrication Process for High Catalytic Activity Platinum Prepared by Electrodeposition Technique for PAFC Electrodes
指導教授： 葉宗洸
Yeh, Tsung-Kuang
口試委員: 曾繁根
Tseng, Fan-Gang
薛康琳
Hsueh, Kan-Lin
王美雅
Wang, Mei-Ya
學位類別： 碩士
Master
系所名稱： 原子科學院 - 工程與系統科學系
Department of Engineering and System Science
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 94
中文關鍵詞： 磷酸燃料電池 、鉑 、觸媒 、恆電位沉積法 、電化學沉積
外文關鍵詞： PAFC, platinum, catalyst, potentiostatic deposition, electrodeposition
相關次數： 點閱：4  下載：0 
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    • 磷酸燃料電池（Phosphoric acid fuel cells, PAFC）相比於一般質子交換膜燃料電池，其操作溫度較高，約為150°C–220°C，有利於提高反應速率、簡化水管理系統和降低一氧化碳毒化觸媒效應；相比於相似操作溫度的鹼性燃料電池，磷酸作為電解質亦可耐受燃料中的二氧化碳影響，是未來具發展潛力的電池之一。在燃料電池中，電極觸媒為影響效率的關鍵，其中鉑為目前研究發現最佳的觸媒材料，因此，本研究利用電化學沉積法於碳布上製備高活性鉑觸媒，應用於磷酸燃料電池電極。
    實驗步驟方面，由於碳布為疏水性材質，因此試片先浸泡異丙醇進行親水處理後，再使用恆電位電鍍法在1.5mM氯鉑酸溶液中，直接沉積鉑於碳布上，並改變電鍍時的電位參數，利用循環伏安法（Cyclic voltammetry, CV）進行電化學分析，並透過掃描式電子顯微鏡（Scanning electron microscopy, SEM）、感應耦合電漿分析儀（Inductivity Coupled Plasma-Mass Spectrometer, ICP-MS）和X光粉末繞射儀（X-ray Powder Diffraction, XRD）分別對試片進行鉑觸媒形貌、含量和結晶性之分析，尋找適合的電鍍條件。
    在本研究中，選用3D結構均勻與高電化學活性表面積（Electrochemical surface area, ECSA）之觸媒，進行全電池測試。由於膜電極組（Membrane Electrode Assembly, MEA）進行熱壓組合時，溫度、壓力與時間參數相互影響，因此，在將熱壓製備時的參數與PBI膜的選用優化後，可在1cm2的電極面積下，得到最佳電池輸出功率974mW/cm2，相比於陰陽極都選用商用觸媒的對照組（643 mW/cm2），效能提升了51％。此外，以前述結果為基礎，進一步優化電鍍時的時間參數，可在1cm2的電極面積下，得到單位白金loading量電池輸出功率753mW/cm2-mgPt，優於商用觸媒的對照組17％。

    Phosphoric acid fuel cells (PAFC) is a high-temperature fuel cell with an operating temperature of 150°C–220°C. This high temperature not only can improve the reaction and simplify water management but also has a high tolerance to carbon monoxide poisoning. Besides, PAFC can also tolerate the influence of carbon dioxide in the fuel, comparing to alkaline electrolyte fuel cells with similar operating temperatures. Catalysts on the electrodes are critical to the efficiency of PAFC. In this study, Pt catalysts supported on 1×1 cm2 carbon cloth based microporous layer were developed by electrodeposition.
    The MPL was first treated with a hydrophilic process to make conduction with plating solution (1.5mM chloroplatinic acid solution). Different electric potentials were applied when electrodepositing. Morphology, particle size, loading, crystallinity, and electrochemical surface area (ECSA) were characterized by SEM, ICP-MS, XRD, and CV. Moreover, the temperature, pressure, and time of the hot-pressing process applied in MEA were also optimized in this study. In single cell tests, the maximum peak power density of PAFC with homemade Pt catalyst acted as the anode reached 974 mW/cm2, which was better than commercial Pt/C by 51%. Moreover, the electrodeposition time was optimized based on the previous experiments. The result showed that power per unit Pt loading could reach 753 mW/cm2-mgPt, better than the commercial PAFC by 17%.

    摘要 i Abstract ii 致謝 iii 總目錄 v 圖目錄 ix 表目錄 xiii 第一章 緒論 1 1.1 前言 1 1.2 研究動機 2 第二章 基本原理與文獻回顧 4 2.1 燃料電池簡介 4 2.2 磷酸燃料電池結構 6 2.2.1 氣體擴散層（Gas Diffusion Layer, GDL） 6 2.2.2 微孔層（Microporous Layer, MPL） 8 2.2.3 觸媒層（Catalyst Layer, CL） 9 2.2.4 觸媒載體（Catalyst Carrier） 10 2.2.5 質子交換膜（Proton Exchange Membrane） 11 2.2.6 雙極板（Bipolar Plate） 14 2.3 磷酸燃料電池工作原理 14 2.4 全電池極化損失 16 2.4.1. 燃料穿透（Fuel Crossover） 17 2.4.2. 活性極化（Activation Losses） 17 2.4.3. 歐姆極化（Ohmic Losses） 18 2.4.4. 濃度極化（Mass Transport） 19 2.4.5. 操作電壓 19 2.5 電化學分析 19 2.5.1 循環伏安法（Cyclic Voltammetry, CV） 19 2.6 質子交換膜燃料電池半反應 21 2.6.1 陽極氧化反應 21 2.6.2 陰極還原反應 23 2.6.3 氧化還原反應觸媒 25 2.6.4 觸媒與電解質含量 26 第三章 實驗方法 28 3.1 實驗流程 28 3.2 實驗藥品與設備 30 3.2.1 實驗藥品 30 3.2.2 實驗用氣體 31 3.2.3 實驗設備 31 3.2.4 分析用儀器 32 3.3 觸媒載體電沉積前處理 32 3.4 觸媒製備參數 34 3.5 觸媒電化學特性分析 35 3.5.1. 循環伏安法測試（CV） 35 3.6 觸媒檢測與形貌分析 37 3.6.1 熱場發射掃描式電子顯微鏡（Thermal Field Emission Scanning Electron Microscope, FEG-SEM） 37 3.6.2 感應耦合電漿分析儀（Inductivity Coupled Plasma-Mass Spectrometer, ICP-MS） 38 3.6.3 X光粉末繞射儀（X-ray Powder Diffraction，XRD） 39 3.7 全電池測試（Single Cell Test） 41 3.7.1 商用觸媒漿料配製與滴塗 41 3.7.2 膜電極組製備與組裝 42 3.7.3 全電池極化掃描測試 46 第四章 結果與討論 47 4.1 含有微孔層之商用碳布 47 4.1.1 微孔層形貌 47 4.1.2 商用觸媒Pt/C形貌 48 4.2 實驗A：調整恆電位沉積法之電位 48 4.2.1 場發射掃描式電子顯微鏡之觸媒形貌分析（SEM） 49 4.2.2 感應耦合電漿質譜分析儀分析（ICP-MS） 55 4.2.3 半電池電化學測試分析（CV） 56 4.2.4 X光粉末繞射法分析（XRD） 57 4.2.5 全電池測試分析 58 4.2.6 小結 60 4.3 實驗B和實驗B’：調整MEA熱壓之溫度、壓力和時間 60 4.3.1 全電池測試分析 61 4.4 實驗C和實驗C’：在相同恆電位沉積電位下調整電鍍時間 67 4.4.1 場發射掃描式電子顯微鏡之觸媒形貌分析（SEM） 68 4.4.2 感應耦合電漿質譜分析儀分析（ICP-MS） 73 4.4.3 半電池電化學測試分析（CV） 73 4.4.4 全電池測試分析 76 4.5 實驗D：使用PA-doped PBI並微調MEA組合參數 78 4.5.1 全電池測試分析 79 4.6 全電池再現性與長效性測試 81 4.7 自製電池與商用觸媒製備電池之效能比較 83 第五章 結論 86 參考文獻 88

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