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研究生： 張凱興
Chang, Kai-Hsing
論文名稱： 以規則性排列PMMA微米球為模板製備巨孔結構Ni/YSZ複合材料之研究
Fabrication of Macroporous Ni/YSZ Compound Derived From Ordered PMMA Microspheres as Template
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： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 88
中文關鍵詞： 固態氧化物燃料電池 、高分子球合成
外文關鍵詞： SOFC, Porous composites
相關次數： 點閱：64  下載：1 
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    • 本研究和其他發電技術相比較，在固態氧化物燃料電池上具有更高效率、無噪音、低汙染等優點。在固態氧化物燃料電池之電性微結構中，具有規則性的孔洞會有助於氣體的傳送及提升其反應速率。本研究利用PMMA 微米球當作陽極之巨孔結構Ni/YSZ 模板，而Ni(CH3COO)2前驅物溶液為鎳金屬之來源。單分散之PMMA球在沉積時利用重力沉澱的方式規則排列後，以沉浸法在孔隙內填入NiO/YSZ前驅物溶液，再經過熱處理從800oC至1100oC移除PMMA球以得到規則性之巨孔結構。同時探討PMMA球之尺寸大小、溫度和還原氣氛對於結構之影響。
    實驗結果顯示，可以無乳化劑乳化聚合法可成功的製備出規則排列0.15μm、0.3μm、0.5μm以及1μm尺寸大小PMMA球來當作巨孔結構之模板。由熱差(DTA)結果可知，在260℃至380℃之間有強烈的放熱峰存在。對應熱重分析(TG)結果，也可發現PMMA球約在260℃開始有明顯的熱重損失，隨溫度持續上升，熱重損失也逐漸增加，至約380℃時熱重損失幾乎已達100％， PMMA球模板在加熱到380℃時即完全分解，符合DTA分析之結果。
    在1100oC持溫4小時之後，以PMMA球為模板所製備之NiO/YSZ巨孔結構已完全消失，然而在1000oC之溫度下，NiO/YSZ仍可維持其巨孔結構。另外當氧化鎳在還原氣氛下還原成鎳金屬，由於氧分子消失產生空孔而有壓應力，造成Ni/YSZ之機械強度較NiO/YSZ明顯降低。而以直徑0.3μm與0.5μm之PMMA球為模板時可製備出三維規則性之巨孔結構，孔徑分別為0.15μm與0.37μm，利用氮氣等溫吸附/脫附分析孔徑為0.15μm與0.37μm之巨孔結構得知其BET比表面積為21.64m2/g與15.32m2/g。
    由甲烷催化結果可知，陽極材料Ni/YSZ之甲烷催化效能，隨著孔洞越小與測試溫度(600oC至900oC)越高，其催化效能越好。原因在於Ni/YSZ孔徑越小相對地表面積越大，具催化能力之鎳金屬晶粒擁有較快之反應速率進行甲烷之催化反應，而得到較高之催化效率。由300nm PMMA球所製備之Ni/YSZ，在測試溫度為900oC時，陽極材料Ni/YSZ之甲烷催化轉化效率達79%。
    陽極材料Ni/YSZ導電性隨著NiO:YSZ體積比增加而上升。結果顯示，NiO:YSZ體積比為100% (1:0)時，陽極材料Ni/YSZ之導電率為55.94(S/cm)，而當NiO:YSZ體積比為90% (9:1)導電率下降為0.44S/cm。表示當金屬鎳含量增加有助於提昇陽極材料Ni/YSZ金屬鎳與鎳晶粒之間之相互接觸點與連接處而增加其導電率。因此巨孔結構中， PMMA球以外的孔隙為Ni/YSZ之分佈，而Ni為NiO所還原而成，因此實際Ni體積在整體孔洞材料中體積佔20%，因此電子傳輸的路徑較傳統Ni/YSZ受到限制。

    SOFC have many advantages such as higher efficiency, low pollution, no noise, etc among several advanced energy technologies. In the structure of SOFC, ordered porous structure will enhance the transport of gas and then facilitate the electrochemical reaction. In this study, the macroporous Ni/YSZ cermet were fabricated by using PMMA microspheres as a template and Ni(CH3COO)2 methanol solution as a nickel source. The monodisperse PMMA spheres were filled with NiO/YSZ precursor solution by impregnation method. Subsequently, NiO/YSZ with ordered and porous structure was obtained by removing the PMMA spheres followed heat treatment from 800oC to 1100oC. In this study, the effect of heat-treatment temperature and the reducing atmosphere on the macroporous structure of NiO/YSZ was discussed.
    The result shows that the diameter of PMMA spheres were 0.15μm、0.3μm、0.5μm and 1μm which were fabricated successfully using emulsifier-free emulsion polymerization method. PMMA microspheres were used as the template of macroporous structure. According to the analysis of TG/DTA. The PMMA spheres had significant exothermic curve from 260oC to 380oC and apparent loss of weight at about 260oC. The loss of weight reached 100% at 380oC matched the results of DTA.
    After calcining at 1100oC for 4 hours, the macroporous structure of NiO/YSZ collapsed due to the minimization of surface tension. However, the macroporous structure of NiO/YSZ remained stable at 1000oC. Due to the volume reduction accompanied the reduction of NiO into metallic Ni, the strength of macroporous Ni/YSZ is lower than its oxide counterpart. When using the PMMA spheres with diameter of 0.3μm and 0.5μm spheres as template, the 3-D ordered macroporoud structure with diameters of 0.15μm and 0.37μm was obtained. The BET specific surface area of macroporous Ni/YSZ with pore diameter of 0.15μm and 0.37μm was found to be 21.64m2/g and 15.32 m2/g.
    Results of the methane reforming over the catalyst showed that the conversion increased with the operating temperature from 600oC to 900oC. The Ni/YSZ with the smaller pore size had the excellent methane conversion rate due to the catalyst on the support with the smaller pore size and large surface area. Thus, macroporous Ni/YSZ catalyst possessed higher activity. The methane conversion of anode Ni/YSZ fabricated from 300nm PMMA spheres achieved 79% at 900oC.
    The metallic conductivity in Ni/YSZ cermet was increased with the vol.% of NiO to YSZ. From the results could observed that the vol.% of NiO to YSZ equal to 100%, the Ni/YSZ specimen exhibited a conductivity value 55.94 Scm-1 at room temperature improved the electrical property of 90vol.% NiO to YSZ was 0.44Scm-1. The nickel content in Ni/YSZ increased the contact point between the two neighboring grains or interconnectivity between the grains increased and it resulted in highering in the conductivity of the specimen. The pore occupied the space where actually nickel particles would have been to provide electron connection.

    中文摘要                Ι 英文摘要               ΙII 致謝                 V 總目錄                 VΙ 表目錄                 X 圖目錄                 XI 第一章 緒論 1 1.1 前言 1 1.2 研究動機與目的 3 第二章 理論基礎與文獻回顧 4 2.1 乳化聚合法 4 2.1.1乳化聚合法之優點 9 2.1.2乳化聚合法之缺點 11 2.1.3無乳化劑乳化聚合法 12 2.2 孔洞材料之原理介紹與應用 13 2.3 燃料電池簡介 17 2.3.1 燃料電池原理 17 2.3.2 燃料電池之優點 20 2.3.3 燃料電池的種類與應用 21 2.4 固態氧化物燃料電池 22 2.4.1固態氧化物燃料電池之操作原理 22 2.4.2固態氧化物燃料電池之結構 23 2.4.3固態氧化物燃料電池之型態 25 2.5 燃料電池之燃料選擇 27 2.5.1 固態燃料電池碳沉積之抑制 27 2.6 甲烷氫氣的還原和催化 28 2.6.1甲烷氫氣還原之催化 28 2.6.2甲烷混合氣體之還原 29 第三章 實驗方法與步驟 32 3.1 實驗藥品 32 3.2 微米級粒徑PMMA球之製備 32 3.3 巨孔結構之製備 36 3.4 實驗條件 38 3.5 材料特性分析 39 3.5.1 X射線繞射(XRD)分析 39 3.5.2 掃瞄式電子顯微鏡(SEM)分析 40 3.5.3 熱重(TG)分析及熱差(DTA)分析 40 3.5.4 比表面積量測 42 3.5.5 孔隙率量測 43 3.5.6 粒徑分佈分析及表面電位量測 43 3.5.7 催化效能之測試與氣體成份檢驗 44 第四章 實驗結果與討論 45 4.1 單分散PMMA球之探討 45 4.1.1 溶液反應前後之外觀變化 45 4.1.2 反應時間對PMMA球粒徑之影響 48 4.1.3 起始劑K2S2O8濃度對PMMA球粒徑之影響 51 4.1.4 MMA單體濃度對PMMA球粒徑之影響 54 4.1.5 PMMA球之表面電位分析 58 4.1.6 PMMA球之粒徑大小對熱分析之影響 60 4.2 巨孔結構之探討 62 4.2.1 熱處理對巨孔結構之影響 62 4.2.2 巨孔結構之比表面積(BET)及開孔孔隙率(Porosity)分析 68 4.3 巨孔結構Ni/YSZ催化效能之探討 71 4.3.1 孔洞大小對Ni/YSZ催化效能之探討 71 4.3.2 反應溫度對Ni/YSZ催化效能之探討 71 4.4巨孔結構Ni/YSZ導電性之探討 73 4.4.1 Ni/YSZ試片製作流程 73 4.4.2 Ni:YSZ體積比對Ni/YSZ陽極材料導電性之探討 76 第五章 結論 81 參考文獻 84

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