臺灣博碩士論文加值系統

本研究探討改變鈰與鋯的比例，以研究不同鋯摻雜比例之鋇鈰釔氧化物微觀結構與電學特性之間的關係。本研究利用固相反應法成功製備BaCe0.8-xZrxY0.2O3-δ (BCZYx, x=0.1~0.5)電解質粉末，隨著Zr摻雜比例增加，鈣鈦礦主峰的XRD衍射角度增加，表明Zr成功摻雜至BaCeYO3樣品中。由SEM微觀結構顯示隨著鋯摻雜比例的增加，晶粒大小會隨之減小，此結果會造成鋇鈰氧化物之晶界長度增長，導致晶界阻抗增加。在質子傳導率的結果表明，隨著Zr比例的提升而增加，當Zr摻雜比例為0.3時，在700 oC會有最高之質子傳導率0.010 S/cm，但是當鋯摻雜比例為0.4之後傳導率則開始減少，此原因是由於載子濃度、晶體結構隨著Zr摻雜比例的不同，而有所變化。於加濕氫氣下傳導率結果表明，其趨勢與未加濕時一致，BCZY0.3在700 oC亦有最高之質子傳導率0.014 S/cm，此結果亦證明加濕氣氛可有助提升質子傳導率。本研究亦使用Electron back scattered diffraction (EBSD)鑑定其不同樣品之晶體結構，映像圖結果表明所有樣品皆顯示正交晶體具有最高之比例。此外，本研究利用不同粒徑粉末制備BCZY0.3電解質，從性能結果表明，隨著使用鋯珠尺寸減小，有助於提升電解質緻密性，並且使用1 mm鋯珠所製備之單電池於700 oC時量測到最高功率密度84 mW/cm2。

This study explores the relationship between the ratio of cerium and zirconium to study the relationship between the microstructure and electrical properties of barium cerium oxide with different zirconium doping ratios. In this study, BaCe0.8-xZrxY0.2O3-δ (BCZYx, x=0.1~0.5) electrolyte powder was successfully prepared by solid state reaction method. As the increase of Zr doping ratio, the XRD diffraction angle of the main peak of perovskite increased, indicating Zr successfully doped into the BaCeYO3. The SEM microstructure shows that as the Zr doping ratio increases, the grain size decreases, causing increase the grain boundary length of the barium cerium oxide, resulting in increase grain boundary impedance. The proton conductivity results show that as the Zr ratio increases, the highest proton conductivity is 0.010 S/cm at 700 °C when the Zr doping ratio is 0.3. But when the zirconium doping ratio increase to 0.4, the conductivity begins to decrease. The reason for this is because the carrier concentration and crystal structure vary with the Zr doping ratio. The conductivity results under humidified hydrogen show that the trend is consistent with that of non-humidification. BCZY0.3 also has the highest proton conductivity of 0.014 S/cm at 700 °C. This result also proves that the humidified atmosphere can enhance the proton conduction. In this study, Electron back scattered diffraction (EBSD) was also used to identify the crystal structure of different samples. The results of the mapping showed that all samples had the highest proportion of orthorhombic crystals. In addition, in this study, BCZY0.3 electrolyte was prepared by using different particle size powders. The performance results show that as the size of the zirconium beads used is reduced, it contributes to the improvement of electrolyte density, and the use of 1 mm zirconium beads of the electrolyte has a maximum power density of 84 mW/cm2 at 700 oC.

摘要 i
Abstract ii
致謝 iv
目錄 v
圖目錄 viii
表目錄 x
第一章、緒論 1
1.1前言 1
1.2文獻回顧與研究目的 3
第二章、實驗原理 9
2-1 固態氧化物燃料電池(SOFC) 9
2-1-1 固態氧化物燃料電池之原理及介紹 9
2-1-2 固態氧化物燃料電池之優點 12
2-1-3 固態氧化物燃料電池之結構 12
2-2 固態氧化物燃料電池電解質材料 16
2-2-1 螢石(Fluorite)結構 16
2-2-2 鈣鈦礦(Perovskite)結構與性質 18
2-2-3 質子傳輸型電解質材料 19
2-2-4 質子傳輸機制 21
2-3 電解質粉末合成方法 22
2-3-1 燃燒法(Combustion) 22
2-3-2 固態反應法(Solid state reaction, SSR) 22
2-3-3 水熱法(Hydrothermal method) 23
2-3-4 溶膠-凝膠法(Sol-gel method) 23
2-3-5 共沉澱法(Co-precipitation method) 24
2-4 粉末燒結理論 24
2-4-1 燒結之擴散機制 25
2-4-2 燒結之過程 25
2-5 電化學分析原理 28
2-5-1 電化學之直流電極化曲線(I-V curve)原理 28
第三章、實驗方法 32
3-1 實驗藥品 32
3-2 實驗步驟 32
3-2-1 BaCe0.8-XZrXY0.2O3-δ粉末合成 34
3-2-2 單電池樣品製備 34
3-3 實驗架設與儀器 36
3-3-1 X光粉末繞射儀(X-ray diffraction, XRD) 36
3-3-2 掃描式電子顯微鏡(Scanning electron microscope, SEM) 37
3-3-3 導電性量測(Conductivity) 37
3-3-4 電子背向散射繞射儀(Electron back scatter diffraction, EBSD) 38
3-3-5 電化學性能及阻抗測試平台 39
第四章、實驗結果與討論 40
4-1 材料性質分析 40
4-1-1 BCZY電解質之XRD形貌及微觀結構之分析 40
4-1-2 BCZY電解質之表面形貌 41
4-1-3 不同氣氛下之導電性 42
4-2 晶體結構對傳導性之影響 47
4-2-1 晶體結構與質子導電性之探討 49
4-3 不同粒徑與電池性能之關係 52
4-3-1 不同粉末粒徑與樣品晶粒之關係 52
4-3-2 單電池I-V性能量測與傳導率量測 57
第五章、結論 61
第六章、未來規劃 62
參考文獻 63

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