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中文論文名稱 Bi3(Nb1-xMx)O7-δ (M = Mg, Ho) 的製備與離子導電性研究
英文論文名稱 Preparation and ionic Conductivity of Bi3(Nb1-xMx)O7-δ (M = Mg, Ho)
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 100
學期 1
出版年 101
研究生中文姓名 施長志
研究生英文姓名 Chang-Chi Shih
學號 698160396
學位類別 碩士
語文別 中文
口試日期 2012-01-03
論文頁數 106頁
口試委員 指導教授-高惠春
委員-王錫福
委員-黃炳照
中文關鍵字 離子導體  固態電解質  螢石 
英文關鍵字 ionic conductivity  solid state electrolyte  fluorite  crystal structure  solid oxide fuel cell 
學科別分類 學科別自然科學化學
中文摘要 本實驗採用固態法製備Bi3(Nb1-xMgx)O7-1.5x (x = 0-0.70)和Bi3(Nb1-xHox)O7-x (x = 0-1.0)兩系列樣品,在空氣中熱處理溫度分別為900 和 1000C。所有的樣品皆為螢石結構,皆有95%以上的緻密度。樣品的單位晶胞a-軸遵守Vegard定律。Ho2O3可完全溶於Bi3NbO7,而MgO卻只能溶到0.70,推論維持單相螢石結構,氧原子數必須達6以上,當MgO取代到0.70時,氧原子計量只剩5.95。以3價的Ho3+或2價的Mg2+取代5價的Nb5+,隨著取代量的增加,使得氧空缺濃度增加,有利於氧離子導電。在Bi3(Nb1-xMgx)O7-1.5x系列中,700C時,Bi3(Nb0.3Mg0.6)O6.1樣品有最高的導電度,達1.13(3) × 10-1 S•cm-1,氧離子遷移率0.881(7),活化能0.682(7) eV。在Bi3(Nb1-xHox)O7-x系列中,700C時,Bi3HoO7樣品有最高的導電度,6.25(9) × 10-2 S•cm-1,氧離子遷移率0.872(2),活化能0.94(1) eV。氧離子遷移率隨著溫度的升高而增加,估計在900C左右,可以接近1。假使要將這些化合物放在SOFC中當作電解質使用,建議要在900C。
英文摘要 Two series of Bi3(Nb1-xMgx)O7-1.5x (x = 0-0.70) and Bi3(Nb1-xHox)O7-x (x = 0-1.0) samples were prepared by a solid state reaction method at 900 and 1000C, respectively under the static air atmosphere. The resulting samples have relative densities larger than 95% and a fluorite crystalline phase. Unit cell a-axis of them obeys Vegard’s law well. Solubility of Ho2O3 in the Bi3NbO7 is complete, but only 0.70 of the MgO can be dissolved into Bi3NbO7. It probably relates to the amount of oxygen vacancies. When x >0.70, the oxygen stoichiometry for the Bi3(Nb0.3Mg0.7)O5.95 is<5.95, which may be too less to keep a fluorite phase. Substitution of Nb by Mg or Ho, both oxygen vacancies and ionic conductivity of Bi3(Nb1-xMx)O7-x is increased with increasing the amount of x. For the Bi3(Nb1-xMgx)O7-1.5x series, at 700C, x = 0.60 has the highest conductivity, 1.13(3) × 10-1 S•cm-1 with a transference number of 0.881(7) and the least activation energy of 0.682(7) eV. For the Bi3(Nb1-xHox)O7-x series, at 700C, Bi3HoO7 has the highest conductivity 6.25(9) × 10-2 S•cm-1 with a transference number of 0.872(2) and the least activation energy of 0.94(1) eV. Transference number increases with increasing the measuring temperature, in order to obtain a transference number close to 1, for the pure ionic conduction as an electrolyte in the SOFC, these bismuthate may be used at temperature close to 900C.
論文目次 目 錄
目錄......................................... І
圖索引....................................... Ⅲ
表索引....................................... ⅩⅡ

第一章 緒論................................. 1
1-1 固體氧化物燃料電池(Solid Oxide Fuel Cell) ......... 1
1-2 氧離子導體..................................... 3
1-3 常用的電解質材料............................... 8
1-4 常用的電極材料................................. 10
1-5 研究動機及目的................................. 11
第二章 實驗................................. 13
2-1 藥品........................................... 13
2-2 實驗流程....................................... 13
2-3 樣品的物性分析................................. 14
2-3-1 X-光粉末繞射圖譜鑑定................... 14
2-3-2 Rietveld精算法.......................... 15
2-3-3 掃描式電子顯微鏡(SEM).................... 17
2-3-4 X光微區分析 (EDS)..................... 18
2-3-5 交流阻抗分析(AC Impedance).............. 18
2-3-6 變氧壓對導電度影響..................... 19
2-3-7 電動勢(EMF)分析........................ 20
2-3-8 X-光吸收近邊緣光譜(XANES)................. 21
第三章 結果與討論........................... 24
3-1 樣品單相鑑定.................................... 24
3-2 結構分析........................................ 26
3-3 樣品微結構分析.................................. 32
3-4 樣品緻密度測量.................................. 36
3-5 樣品元素分析(EDS)............................... 37
3-6 交流阻抗分析 (AC Impedance)...................... 39
3-7變氧壓導電度影響................................. 82
3-8 電動勢(EMF)分析................................. 92
3-9 X-光吸收近邊緣結構光譜......................... 96
第四章 結論與未來計畫........................ 99
4-1 結論........................................... 99
4-2 未來計畫....................................... 100
參考文獻..................................... 101
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