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研究生:黃俊瑋
研究生(外文):Chun-Wei Huang
論文名稱:以二階段燒結控制氧化鈰固態氧化物燃料電池電解質之微結構與電性研究
論文名稱(外文):Electrical properties and microstructure of cerium oxide electrolytes produced by two-step sintering
指導教授:施劭儒
指導教授(外文):Shao-Ju Shih
口試委員:施劭儒
口試委員(外文):Shao-Ju Shih
口試日期:2013-07-15
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:113
中文關鍵詞:固態氧化物電解質二階段燒結微結構交流阻抗圖譜
外文關鍵詞:SOFCTwo-step sinteringmicrostructureAC-impedance spectroscopy
相關次數:
  • 被引用被引用:0
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  • 下載下載:53
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以傳統的球磨法製備出摻雜稀土元素氧化釤的二氧化鈰基固態電解質Ce1-xSmxO2-x/2 (x=0, 0.2, 0.4)粉末,經二階段燒結後,具有高氧離子傳導的能力。
以(X-ray diffraction analysis, XRD)鑑定二氧化鈰之相結構(Fluorite structure),並利用(Scanning electron microscopy, SEM)觀察比較傳統的一階段燒結與二階段燒結下在不同的燒結溫度下(1500~1600oC),其微結構之緻密程度與晶粒大小分佈的變化,與(Electron back-scattered diffraction, EBSD)分析其晶界之能量分佈,為了掌握晶界在不同燒結溫度下之變化,利用(Transmission electron microscopy, TEM)觀察傳統的一階段燒與二階段燒結下晶界形貌的變化,最後以交流阻抗量測儀(AC-impedance)量測在不同的環境溫度下(600~800oC),不同微結構之阻抗性質,並計算不同微結構下晶粒與晶界離子導電性之變化,與活化能的大小。
其中電性表現最好的為二階段燒結的試樣0SDC-1600-1500-20h,在環境溫度800oC下其晶界導電度為1.38×10-3、晶粒導電度為1.41×10-2、整體導電度為1.26×10-2、活化能為0.89 eV。
Samarium doped ceria (SDC) is good candidate for application in intermediate temperature solid oxide fuel cells (IT-SOFC) due to the ability of high oxygen ionic conductivity.
SDC powders Ce1-xSmxO2-x/2 (x=0, 0.2, 0.4) is synthesized by traditional solid state reaction method and sintered to densify in conventional sintering and two-step sintering. The sample were characterized by XRD, SEM, EBSD, TEM and AC-impedance in the temperature range of 500~700oC.
The uniformly particle size (1~4?慆) of the SDC mixed powders allows the sintering of the samples into highly dense (≅95%) pellet at 1600oC. All powders and pellet were found to be pure CeO2 or ceria-based solutions with fluorite-type structure in X-ray diffractometer. The microstructure of grain size (≅ 8~15?慆) and grain boundaries in sintered pellets was observed under the SEM and EBSD. The morphology of grain boundaries were defined by high resolution transmission electron microscopy. All the solid oxide electrolytes were characterized by impedance spectroscopy to distinguish the grain and grain boundary electrical properties. The sample 0SDC-1600-1500-20h has the best electrical properties under 800 oC (σgb =1.38×10-3 S/cm, σg =1.41×10-2 S/cm, σeff =1.26×10-2 S/cm, Q =0.89 eV).
摘要 I
關鍵字 : 固態氧化物電解質、二階段燒結、微結構、交流阻抗圖譜 I
ABSTRACT II
目錄 III
圖目錄 VI
表目錄 XII
第1章 緒論 1
1.1 研究動機與目的 1
第2章 文獻回顧 2
2.1 二氧化鈰之特性及應用 2
2.1.1 物理性質 2
2.1.2 化學性質 4
2.2 燃料電池之重要性 4
2.3 燃料電池之類型 5
2.4 固態氧化物燃料電池原理與組成 7
2.4.1 固態氧化物燃料電池工作原理 7
2.4.2 固態氧化物燃料電池組成 9
2.5 固態電解質的選用及微結構 11
2.5.1 鈣鈦礦結構 (Pervoskite structure, ABO3) 11
2.5.2 螢石結構 (Fluorite structure CaF2) 13
2.6 固態電解質導電機制的變因 16
2.6.1 環境因素 19
2.6.2 微結構控制 26
2.7 電化學交流阻抗分析簡介 (AC-IMPEDANCE) 32
2.7.1 電化學交流阻抗圖譜與基礎理論 33
2.7.2 等效電子元件訊號 34
2.8 背向散射電子繞射 (ELECTRON BACK-SCATTERED DIFFRACTION, EBSD)圖譜分析 38
2.8.1 EBSD分析技術原理 38
2.8.2 晶界分類 40
2.8.3 共位晶界 41
第3章 實驗方法 44
3.1 實驗藥品與儀器 44
3.2 實驗流程 45
3.3 試片製備 47
3.3.1 Ce1-xSmxO2-x/2粉末合成 47
3.3.2 Ce1-xSmxO2-x/2壓碇與燒結 47
3.4 粉體與塊材之特性量測 48
3.4.1 X光繞射分析 (X-ray diffraction analysis, XRD) 48
3.4.2 場發射掃描式電子顯微鏡 (Field-emission scanning electron microscope, FE-SEM) 49
3.4.3 燒結體密度分析 49
3.4.4 EBSD晶界能量與晶粒取向分析 50
3.4.5 場發射穿透式電子顯微鏡 (Transmission electron microscopy, TEM)試片製備 51
3.4.6 交流組沆量測 51
第4章 結果討論 53
4.1 初始粉末CEO2與SM2O3性質分析 53
4.1.1 初始粉末粒徑分佈 53
4.1.2 初始粉末相鑑定 60
4.2 CE1-XSMXO2-X/2 一階段燒結後之塊材性質分析 61
4.2.1 一階段燒結塊材之XRD結晶相與密度分析 61
4.2.2 微結構與晶相分析 65
4.3 CE1-XSMXO2-X/2二階段燒結後之塊材性質分析 73
4.3.1 微結構與晶相分析 73
4.3.2 EBSD晶界分析 77
4.3.3 TEM晶界微結構觀察 81
4.3.4 交流阻抗圖譜分析與計算 90
第5章 結論 107
第6章 參考文獻 109
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