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研究生： 陳娸玫
Chen, Chi-Mei
論文名稱： 以(La,Ag)(Co,Fe)O3-δ為固態氧化物燃料電池陽極行煤合成氣反應之研究
On the performance of (La, Ag)(Co, Fe)O3-δ as solid oxide fuel cell anode material reacting with coal syngas
指導教授： 黃大仁
Huang, Ta-Jen
口試委員:
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： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 117
中文關鍵詞： 鈣鈦礦結構 、煤合成氣 、固態氧化物燃料電池
外文關鍵詞： perovskite, coal syngas, solid oxide fuel cell
相關次數： 點閱：2  下載：0 
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    • 煤合成氣(Coal syngas)為氫氣與一氧化碳之混合氣，具有製程簡單、價格低廉等優點，且氫氣與一氧化碳兩者皆為最容易被還原之氣體，在通入陽極端前不需再經過氣體重組之步驟，而可直接反應生成水氣與二氧化碳，於應用上頗具潛力。
    在陽極材料的選擇上，傳統的鎳觸媒如60Ni-YSZ，易於表面生成積碳，對於一氧化碳之活性較差。本研究選用具有混合導體特性之鈣鈦礦結構材料LSCF (La0.58Sr0.4Co0.2Fe0.8O3) 及LACF (La0.7Ag0.3Co0.2Fe0.8O3) 為陽極材料，並含浸不同活性金屬Cu、Ag，期能提升對水煤氣之反應性，並避免積碳，以改善此問題。
    將LSCF及LACF混合導氧離子性較佳的GDC，並含浸2 wt% Cu或2 wt% Ag，配製成LSCF-50GDC-2Cu、LSCF-50GDC-2Ag、LACF73-50GDC三種陽極漿料，塗佈於YSZ電解質生胚上，陰極端使用活性極好的LSCF-50GDC-2Cu，通入100 mL/min煤合成氣為燃料，測得最大功率密度分別為22.658、37.537與23.496 mW•cm-2。
    觀察陽極端通入煤合成氣之電流表現，可發現因CO之擴散及電化學反應速率較慢，因此H2之效能較CO為佳，在某些混合比例下，電池擁有相似之混合效能，推測陽極端有水氣轉移反應的發生，令CO與H2比例維持平衡關係。
    使用煤合成氣為陽極燃料時，Ag觸媒比Cu觸媒之表現來得優越，推測以Ag為活性金屬時，氧於Ag上移動較快，可提升燃料催化效果。然而，含Ag量不能太多，否則將會覆蓋氧空缺，不利O2-之擴散。
    由定電壓實驗可看出，電池效能受燃料比例與積碳所構成之電流收集層相互影響；而電池於陽極端之反應機制，推測與被吸附之H原子與O2-形成之OH基團相當重要，可促進形成COOH反應中間體，以利CO之氧化成CO2。
    由此可知，鈣鈦礦材料對於煤合成氣具有一定之催化活性，以其為陽極材料，可提升電池效能，且在操作過程中並無失活現象。

    第一章 緒論 1 第二章 文獻回顧 5 2-1 固態氧化物燃料電池 5 2-1-1 簡介 5 2-1-2 原理 7 2-2 電池組成 8 2-2-1 陽極 8 2-2-2 陰極 10 2-2-3 電解質 12 2-3 鈣鈦礦型氧化物陽極材料 16 2-3-1 鈣鈦礦型結構 16 2-3-2 鈣鈦礦氧化物應用於陽極材料 18 2-4 燃料的選擇 23 2-4-1 煤合成氣 23 2-4-2 CO氧化觸媒 27 第三章 研究構想 32 第四章 實驗方法 35 4-1 實驗藥品與氣體 35 4-1-1 實驗藥品 35 4-1-2 實驗氣體 36 4-2 材料製備方法 37 4-2-1 La0.58Sr0.4Co0.2Fe0.8O3(LSCF) 37 4-2-2 La0.7Ag0.3Co0.2Fe0.8O3(LACF) 38 4-2-3 Ce0.9Gd0.1O1.95 (GDC) 39 4-2-4 陽極複合材料 40 4-3 電池單元製作 41 4-3-1 旋轉塗佈漿料製備 41 4-3-2 電池製作 42 4-4 分析儀器與實驗裝置 44 4-4-1 儀器 44 4-4-2 實驗裝置 45 4-5 實驗步驟與流程 46 4-5-1 定溫還原反應實驗 46 4-5-2 電池封裝 47 4-4-2 電池效能測試 48 第五章 實驗結果與討論 50 5-1 X光繞射分析(XRD) 50 5-1-1 GDC 50 5-1-2 La0.58Sr0.4Co0.2Fe0.8 O3-δ 52 5-1-2 (La,Ag)Co0.2Fe0.8O3-δ 53 5-2 鈣鈦礦粉體定溫還原反應 56 5-2-1 氫氣定溫反應 56 5-2-2 一氧化碳定溫反應 59 5-2-3 水煤氣定溫反應 61 5-3 鈣鈦礦混合GDC粉體定溫還原反應 65 5-3-1 氫氣定溫反應 65 5-3-2 一氧化碳定溫反應 67 5-3-3 水煤氣定溫反應 69 5-4 電池性能測試 72 5-4-1 電池之SEM微結構圖 72 5-4-2 不同燃料比例所造成之影響 75 5-4-2 不同陽極材料之比較 83 5-4-3 拉電過程紀錄 89 5-5 定溫定電壓測試 91 5-5-1 水煤氣之開路與閉路反應 91 5-5-2 合成氣之定電壓反應分析 95 5-5-3 反應機構推導 106 第六章 結論 110 第七章 未來方向 112 第八章 參考資料 113

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