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研究生: 李依文
Lee, Yi Wen
論文名稱: 應用於質子交換膜燃料電池陰極端之奈米碳管支撐鉑鎳二元觸媒對於氧氣還原之效能研究
Efficiency of Carbon-Nanotube-Supported Pt-Ni Binary Catalysts on Oxygen Reduction Reaction at the Cathode of a Proton Exchange Membrane Fuel Cell
指導教授: 葉宗洸
Yeh, Tsung Kuang
口試委員: 薛康琳
Hsueh, Kan Lin
陳燦耀
Chen, Tsan Yao
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: 2015
畢業學年度: 103
語文別: 中文
論文頁數: 73
中文關鍵詞: 二元觸媒氧氣還原反應質子交換膜燃料電池
外文關鍵詞: Platinum, Nickel, Binary Catalyst, ORR, PEMFC
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  • 本研究於奈米碳管上製備PtNi二元觸媒並應用於質子交換膜燃料電池中之陰極。奈米碳管是藉由化學氣相沉積法直接成長於碳布上以增加電極表面積,經由親水處理後,先以脈衝式電鍍法於奈米碳管上沉積金屬鎳顆粒,而後將試片浸於攝氏80度含有氯鉑酸及乙二醇之溶液中沉積鉑奈米顆粒;純鉑之單元觸媒亦會製備做為對照組。
    測試方面,經由循環伏安法於0.1 M過氯酸溶液中進行電化學測試,並利用X光粉末繞射儀(XRD)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)以及電感耦合等離子體質譜(ICP-MS)對試片做進一步的分析。經由TEM觀測發現觸媒形貌為5 nm之Pt顆粒包覆在50 nm之Ni顆粒上。透過電化學結果顯示,PtNi二元觸媒較Pt單元觸媒活性高,並反應在CV及LSV之測試曲線中,包含CV氫氧吸脫附區域及LSV測得的反應起始電位及電流密度大小,都顯示Ni的存在確實優化觸媒之催化效果。
    半電池立體化成全電池時三相介面為重要考量,於自製陰極電極噴塗0.8 mg/cm2 Nafion與商用觸媒作組裝再經由氫氣單電池測試,此效率表現最佳,功率密度可達611 mW/cm2,比商用觸媒之329 mW/cm2高出許多,顯示出透過本研究手法製備之PtNi電極其催化效果優良。


    In this study, Pt-Ni binary alloy catalysts supported on carbon nanotubes (PtNi/CNTs) were developed for enhancing the oxygen reduction reaction (ORR) efficiency for proton exchange membrane fuel cell (PEMFC) application. The CNTs were directly grown on carbon cloths by chemical vapor deposition method and then treated with hydrophilic process. The nickel nanoparticles were deposited on CNTs by pulse electro-planting, and then the platinum particles were reduced on them in a chloroplatinic acid solution containing platinum precursor and ethylene glycol at 80 ℃ for different hours. The sample with Pt/CNTs was also prepared for comparison. Electrochemical characteristics of the PtNi/CNTs catalyst were investigated via cyclic voltammetry analysis and rotating disk electrode test in 0.1 M perchloric acid. Structure and elementary composition were measured by SEM, EDX and ICP-MS. In ORR test, it was found that the limiting current density and onset potential of PtNi/CNTs specimen were better than those of Pt/CNTs specimen. The outcome signified better PtNi binary catalysts in adsorption and desorption behavior of oxygen to increase the ORR rate.

    摘要 i Abstract ii 致謝 iii 總目錄 iv 表目錄 vii 圖目錄 viii 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質子交換膜燃料電池結構 7 2.2.1氣體擴散層 7 2.2.2觸媒層 8 2.2.3觸媒載體 8 2.2.4質子交換膜 10 2.2.5雙極板 11 2.3質子交換膜燃料電池工作原理 12 2.4全電池極化損失 13 2.4.1活性極化 14 2.4.2歐姆極化 15 2.4.3濃度極化 15 2.4.4燃料穿透 16 2.5電化學分析 16 2.5.1循環伏安法(Cyclic Voltammetry) 16 2.5.2極化曲線(Linear Sweep Voltammetry) 17 2.5.3旋轉盤電極(Rotating Disc Electrode, RDE) 18 2.6陰極氧氣還原反應 20 2.6.1氧氣還原反應機制 20 2.6.2氧氣還原反應觸媒 23 第三章 實驗方法 26 3.1實驗流程 26 3.2實驗藥品與設備 27 3.2.1實驗藥品 27 3.2.2實驗用氣體 28 3.2.3實驗設備 28 3.2.4分析儀器 28 3.3觸媒載體之製備 29 3.4奈米碳管親水化處理 30 3.5半電池-陰極電極之製備 31 3.6觸媒電化學特性分析 34 3.6.1循環伏安法測試(CV) 34 3.6.2線性掃描伏安法測試(LSV) 35 3.7觸媒形態分析 37 3.7.1場發射掃瞄式電子顯微鏡(Field Emission Gun Scanning Electron Microscopy,FEG-SEM) 37 3.7.2穿透式電子顯微鏡(Transmission Electron Microscopy,TEM) 37 3.7.3 X光粉末繞射(X-ray Powder Diffraction,XPRD) 38 3.8組成比例分析 39 3.8.1感應耦合電漿質譜分析儀(Inductively Coupled Plasma-Mass Spectrometer,ICP-MS) 39 3.9單電池測試 (Single Cell Test) 40 3.9.1膜電極組(Membrane Electrode Assembly,MEA)製備 40 3.9.2漿料配製與噴塗 41 3.9.3 MEA組裝 41 3.9.4單電池極化掃描測試 42 第四章 結果與討論 44 4.1奈米碳管載體 44 4.1.1 奈米碳管形貌 44 4.1.2 奈米碳管親水化處理 45 4.2場發射掃描式電子顯微鏡之觸媒形貌分析(SEM) 46 4.2.1 電鍍法製備之鎳金屬顆粒 46 4.2.2 PtNi二元觸媒 47 4.2.3 Pt單元觸媒 50 4.3穿透式電子顯微鏡之觸媒微影圖像分析(TEM) 51 4.4 X光粉末繞射法分析(XPRD) 52 4.5感應耦合電漿質譜分析儀分析(ICP-MS) 53 4.6半電池電化學分析結果 54 4.7單電池測試分析結果 64 第五章 結論 69 參考文獻 70

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