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研究生： 張雲傑
Chang, Yun-Jie
論文名稱： 以PS微球製備巨孔LSM/YSB複合陰極之研究
Fabrication of Macroporous LSM/YSB Composite Cathode Derived from PS Microspheres
指導教授： 方冠榮
Fung, Kuan-Zong
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 87
中文關鍵詞： PS微球 、三維規則巨孔結構 、鑭鍶錳氧化物 、氧化鉍 、中溫固態氧化物燃料電池
外文關鍵詞： PS microspheres, 3DOM, LSM, bismuth oxide, IT-SOFC
相關次數： 點閱：126  下載：0 
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    • 固態氧化物燃料電池(Solid Oxide Fuel Cell, SOFC)與其他發電技術相比，有低汙染、無噪音、維護簡單、長期供電穩定等優點，然而中溫燃料電池(Intermediate Temperature Solid Oxide Fuel Cell, IT-SOFC)在600-800 oC範圍操作時，效率會因極化阻抗的增加而降低，其中以陰極所造成的極化阻抗最為顯著，而具有規則性的孔洞有助於氣體傳送及提升其反應速率，以降低陰極界面極化阻抗來達到效率的提升。
    傳統燃料電池透過粉末與漿料製備出的陰極結構，其孔隙率約為30-60%，且比表面積通常低於10 m2/g，故本研究透過改善微結構的方式來達到孔隙率與比表面積的提升，利用無乳化劑乳化聚合法，製備不同粒徑之單分散聚苯乙烯(PS)球，並將PS微球做規則排列形成模板，利用浸漬法與高溫煅燒的方式，製備氣孔連通的高比表面積之三維規則巨孔(3-dimensionally ordered macroporous，3DOM)結構，並選用高電子導性LSM與高離子導性YSB為其複合材料。
    本研究結果分為兩部分，第一部分為規則排列PS模板的製備，首先以無乳化劑乳化聚合法，製備粒徑分佈集中的聚苯乙烯微球，經由SEM觀察與粒徑分析，成功製備出粒徑250-900 nm的次微米級PS微球。接著將不同粒徑的PS微球，經重力沉積乾燥後，成功製備出規則排列的PS微球模板。
    第二部分為LSM/YSB複合粉末的製備，結果顯示，利用各別螯合的LSM與YSB溶膠做混合，經過加熱乾燥後，形成凝膠，再經過煅燒500-1000 oC，成功獲得LSM/YSB雙相結構，證明LSM與YSB在此溫度區間為相穩定，雙相不會互相反應。
    經由PS球的DTA/TG分析結果，在500 oC達100%的熱重損失，即經過熱處理500 oC以上可完全移除PS球模板，因此本研究透過浸漬法與熱處理的方式來製備LSM/YSB複合巨孔材料，由SEM的觀察，成功製備出三維規則巨孔結構，其孔隙率約為72-77%，比表面積約為5-24 m2/g，綜合以上結果，顯示無論在微結構、孔隙率與比表面積等性質上，皆比傳統陰極材料還要優越，預期將來可以應用在中溫燃料電池上。

    The intermediate temperature solid oxide fuel cells (IT-SOFC) have many advantages such as, high efficiency, no low pollution, no noise, etc among several advanced energy technologies. However, the performance of IT-SOFC is highly dependent on the polarization resistance of cathode. In the structure of SOFC, ordered porous structure will enhance the transport of gas and then facilitate the electrochemical reaction to improve the resistance of cathode.
    In this study, polystyrene (PS) microspheres have been used as templates to obtain desired 3-dimensionally ordered macroporous (3DOM) structure which has the high porosity and high surface area. In order to obtain various diameters of PS microspheres, the PS microsphere were prepared by emulsion-free polymerization method. The monodisperse PS microsphereswith diameters of 250-900 nm werepreparedsuccessfully.According to the analysis of TG/DTA, The loss of weight reached 100% at 500 oC. In other words, the PS templates wereentirely removed after heat treatment at 500 oC.
    In order to obtain 3DOM structure, the precursors of La0.8Sr0.2MnO3 (LSM) and Bi1.5Y0.5O3 (YSB) immersed into interstices between ordered microspheres. According to the XRD pattern, the LSM and YSB phases coexist in the structure without impurity phase. The SEM image showed the 3DOM structure, and the porosity was about 72-77%. The BET-specific surface area tends to increase with decrease of pore size (5 - 24 m2/g).

    摘要 I 英文延伸摘要(Extended Abstract) III 致謝 IX 總目錄 X 圖目錄 XV 表目錄 XIX 第一章 緒論 1 第二章 理論基礎與文獻回顧 3 2-1 單分散聚苯乙烯膠體粒子的合成 3 2-1-1 單分散聚苯乙烯簡介 3 2-1-2 乳化聚合法的優勢 3 2-1-3 乳化聚合法的缺點 5 2-1-4 無乳化劑乳化聚合法的優點 5 2-1-5 無乳化劑乳化聚合法的反應機構 6 2-1-6 無乳化劑乳化聚合法的動力學簡介 7 2-2 膠體晶體製備巨孔結構 8 2-2-1 多孔材料簡介 8 2-2-2 膠體晶體簡介 9 2-2-3 膠體粒子排列三維有序結構 9 2-2-4 膠體晶體模板的填充 11 2-2-5 膠體晶體模板的移除 12 2-2-6 巨孔結構電極之燒結 13 2-3 燃料電池陰極的工作原理 14 2-3-1 燃料電池簡介 14 2-3-2 陰極的反應途徑 16 2-4 燃料電池陰極材料簡介 17 2-4-1 鈣鈦礦陰極材料之錳酸鍶鑭 17 2-4-2 複合陰極的優勢 19 2-5 氧化鉍複合陰極簡介 21 2-5-1 氧化鉍簡介 21 2-5-2 氧化鉍系複合陰極的發展 25 第三章 研究動機與目的 27 第四章 研究方法及步驟 28 4-1 實驗藥品 28 4-2 單分散PS微球的合成 28 4-2-1 反應時間 30 4-2-2 起始劑濃度 30 4-2-3 單體濃度 30 4-2-4 等比例改變起始劑與單體濃度 30 4-3 LSM/YSB前驅液的配製 31 4-4 巨孔結構之製備 32 4-5 材料特性分析 32 4-5-1 X光繞射(XRD)分析 32 4-5-2 掃描式電子顯微鏡(SEM)分析 33 4-5-3 熱重(TG)分析及熱差(DTA)分析 33 4-5-4 傅氏轉換紅外線光譜分析 33 4-5-5 比表面積量測 34 4-5-6 孔隙率量測 34 4-5-7 粒徑分佈與表面電位分析 34 第五章 結果與討論 35 5-1 單分散聚苯乙烯膠體模板的製備 35 5-1-1 單分散聚苯乙烯微球之合成與性質分析 35 5-1-2 反應時間對PS球粒徑之影響 41 5-1-3 起始劑濃度對PS球粒徑之影響 44 5-1-4 單體濃度對PS球粒徑之影響 49 5-1-5 等比例改變單體與起始劑濃度對PS球粒徑之影響 53 5-1-6 環境溫度與濕度對PS球自然沉降排列之影響 59 5-2 PS球之熱分解行為 61 5-2-1 固定PS微球模板之預熱前處理 61 5-2-2 PS球之差熱與熱重分析 63 5-3 LSM/YSB複合陰極的製備 65 5-3-1 LSM與YSB複合結構的形成 65 5-4 具巨孔結構之LSM/YSB複合陰極 67 5-4-1 三維有序之巨孔結構 67 5-4-2 熱處理對巨孔結構的相與微觀結構之影響 69 5-4-3 LSM/YSB巨孔結構在不同操作溫度區間之穩定性探討 72 5-4-4 3DOM結構與傳統陰極孔隙率之比較 75 5-4-5 不同粒徑微球對巨孔結構的比表面積(BET)之影響 77 第六章 結論 80 參考文獻 82

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