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研究生：	張軒誌 hsuan chih Chang
論文名稱：	三價離子摻雜於電解質BaZrO3的導電趨勢 Trends of the Ionic Conductivity of Cation-Doped Barium Zirconates
指導教授：	王禎翰 Wang, Jeng-Han
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	136
中文關鍵詞：	電解質、固態氧化物燃料電池、BaZrO3
英文關鍵詞：	electrolyte, SOFC, barium zircornate
論文種類：	學術論文
相關次數：	點閱：228 下載：4
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本實驗為探討BaZr1-xMxO3， (M = In3+、Y3+、 Yb3+、 Dy3+、 Gd3+、 Sm3+、 Nd3+、 La3+)不同摻雜金屬的導電趨勢，並利用計算的結果去解釋。實驗部分為使用燃燒法合成不同濃度的摻雜金屬，並使用XRD、SEM、EDX、ICP-MS來確認物理及化學性質。再把粉末壓錠，並燒結於1250、1450、1600 ℃，持溫5、10、40小時，形成BaZr1-xMxO3 試片，進行導電度測試，通入氣氛為濕-空氣、濕-氫氣、乾-氮氣、乾-氫氣。
　　計算部分為使用密度泛涵理論(DFT)計算摻雜於BaZrO3的氧空缺(V_o^(..))及氫缺陷的形成能以及氧空缺、氫缺陷、氫氧空缺移動的反應熱。
　　由實驗及計算的結果顯示，導電率會隨著摻雜的濃度增加或持溫時間降低而上升，燒結溫度對導電率的影響則不大。從化學的觀點來看，導電率會受到摻雜金屬的離子半徑所影響，較小的離子半徑，導電率佳，且計算出來的反應熱低。

Trends of the ionic conductivity of BaZr1-xMxO3, (M = In3+, Y3+, Yb3+, Dy3+, Gd3+, Sm3+, Nd3+, La3+) have been experimentally and computationally examined in this work. Experimentally, the powder with different dopant ratios , 2%, 5%, 10% and 20%, has been initially synthesized by GNP (glycine nitrate process) method, and it physical and chemical properties have been examined by XRD, SEM, EDX and ICP-Mass (Inductively coupled plasma mass spectrometry). The synthesized powder is further pressurized and sintered at different temperatures, 1250, 1450 and 1600 oC and heating period, 5, 10 and 40 hours, to form BaZr1-xMxO3 pellets for the conductivity tests in various atomspheres: dry N2, dry H2, wet air and wet H2. Computationally, formation energies of oxygen vacancy V_o^(..) and proton defect OH_o^' and enthalpy of V_o^(..) migration, proton hopping and OH_o^' diffusion of the doped BaZrO3 have been systematically examine by the means of density functional theory (DFT) calculation.
　　Based on the experimental and computational works, the results show that the ionic conductivity will increase as the dopant ratio raises and the sinter period decreases. The sinter temperature has limited effect on the conductivity. From the chemical aspect, the conductivity is systematically influenced by the ionic radius of the doped cation. The small radius of the dopant results a better conductivity from the experimental measurement and lower enthapy in the DFT calculation.

誌謝    2
中文摘要    3
英文摘要    4
目錄    6
圖表目錄    10

第一章    固態氧化物燃料電池介紹    14
    1-0 緒論    14
    1-1燃料電池    15
       1-1-1 燃料電池原理    15
       1-1-2 燃料電池種類    17
    1-2固態氧化物燃料電池(SOFC)    19
       1-2-1固態氧化物燃料電池簡介    19
       1-2-2固態氧化物燃料電池結構    19
    1-3固態電解質    21
       1-3-1 螢石結構    22
       1-3-2 鈣鈦礦結構    23
       1-3-3 電解質傳導機制    24
    1-4 文獻回顧    25
第二章    實驗與計算方法    28
    2-0實驗藥品列表    28
    2-1 粉末製備    29
       2-1-1 燃燒法    29
       2-1-2 溶膠-凝膠法(sol-gel)    32
       2-1-3 水熱法    34
    2-2 BaZr1-xMxO3-α試片與導電測量裝置    36
       2-2-1 試片成型與燒結條件    36
       2-2-2 導電度測量裝置    36
    2-3 儀器介紹    38
       2-3-1 X光繞射分析    38
       2-3-2 顯微結構分析(SEM)    38
       2-3-3 能量散射光譜儀(EDX)    39
       2-3-4 感應耦合電漿質譜儀(ICP-MS)    39
       2-3-5 導電率分析(conductivity)    40
       2-3-6 活化能分析(activity)    41
    2-4 計算方法介紹    42
       2-4-1 DFT原理    42
       2-4-2 計算方法    47
第三章    結果與討論    51
    3-1  實驗部分    51
    3-1-1合成粉末與燒結體的結構分析    51
       3-1-1-1以燃燒法合成BaZr1-xMxO3-α粉末結構分析    51
       3-1-1-2 燒結1450 ℃持溫5小時結構分析    53
    3-1-2 BaZr1-xMxO3-α粉末EDX分析及ICP-MS分析    54
       3-1-2-1 BaZr1-xMxO3-α粉末EDX分析    54
       3-1-2-2 BaZr1-xMxO3-α粉末ICP-MS分析    60
    3-1-3 BaZr1-xMxO3-α燒結前後的顯微結構分析    61
       3-1-3-1 比較以燃燒法及溶膠凝膠法的顯微結構差異    61
       3-1-3-2 BaZr1-xMxO3-α燒結後顯微結溝分析    62
    3-1-4導電性質分析    74
       3-1-4-1 1450℃下不同摻雜濃度對導電度影響    74
       3-1-4-2 不同溫度對導電度影響    84
       3-1-4-3持溫時間對導電度影響(1450 ℃)    94
       3-1-4-4同一條件不同摻雜離子比較    104
    3-1-5交流阻抗分析    113
    3-2 計算部分    116
       3-2-1 氧離子移動活化能，反應熱和氧空缺形成能    117
       3-2-2 氫離子移動活化能,反應熱和氧空缺形成能    119
       3-2-3 氫氧根離子移動活化能和反應熱    121
    3-3 實驗和計算的比較    123
第四章    結論    126
第五章    未來展望    127

文獻    128
                                

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