臺灣博碩士論文加值系統

為了探討晶粒尺寸對氧化物中離子導電率之影響，本研究將不同尺寸之CeO2粉末利用火花電漿燒結製備成二氧化鈰奈米塊材。以X光粉末繞射儀(XRD)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM),拉曼光譜(Raman Spectroscopy)及X光吸收光譜分析塊材中晶粒大小及缺陷，所得到的結果與量測到的導電率變化作連結。
　　研究結果顯示，火花電漿燒結進行塊材製備確實能得到較小的晶粒尺寸，但塊材的相對密度與所使用的起始粉末之團聚程度及粒徑分布有密切關係。在導電性方面，當塊材的相對密度夠高時，導電率與晶粒尺寸的關係較為明顯，且塊材中若存在著部分奈米晶粒時導電率較佳，最後，為了進一步提高奈米塊材之導電率，在起始粉末中摻雜15% Sm所得到的奈米塊材之導電率較未摻雜樣品提高兩個數量級，但仍然比傳統燒結法製備之塊材差，推測原因與塊材之相對密度有關，此部分有待後續做進一步的製程參數調整。

In order to unravel the effect of grain size on the ion conductivity of the oxide, In this study, CeO2 nano bulks were prepared by Spark Plasma Sintering (SPS). The raw powders were of different particle size.X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray Absorption Spectroscopy (XAS) and Raman Spectroscopy were utilized to investigate the grain size and defects of the bulks.Then the conductivity was correlated to the change of microstructures.
Our results showed that smaller grain size could be obtained by using SPS. However, the relative density of bulk closely depends on the aggregation of raw powders. Next, it is demonstrated that the relative density is critical in bulk conductivity. Conductivity is rather low in bulks with relative density lower than 85%. As for the bulks of higher relative density, conductivity can be enhanced by introducing nano-grains. At last, nanoparticles with doping of 15% Sm were used as raw powders. Conductivity of the bulk was improved by two orders of magnitude as compared to undoped ones. However, the value of conductivity was lower than bulks prepared by conventional sintering process, implying the requirement of further adjusting of process.

摘要 I
Abstract II
圖目錄 VII
表目錄 XI
第一章 緒論 1
1.1前言 1
1.2研究背景 2
1.3 研究動機與目的 5
第二章 文獻回顧與理論介紹 7
2.1燃料電池的簡介 7
2.1.1 燃料電池的歷史 7
2.1.2 燃料電池的特點 8
2.1.3 燃料電池的分類及應用範圍 9
2.2固體氧化物燃料電池 (SOFC) 11
2.2.1固體氧化物燃料電池的優點 11
2.2.2 SOFC之基本原理 11
2.2.3 SOFC的材料 13
2.3 二氧化鈰的基本性質 16
2.3.1 物理性質及晶體結構 16
2.3.2 光學性質 17
2.3.3化學性質 17
2.4 二氧化鈰粉末製備方式 19
2.4.1 沉澱法 19
2.4.2 噴霧裂解法 23
2.5 塊材燒結方法 25
2.5.1火花電漿燒結概要 25
2.5.2火花電漿燒結概要系統 26
2.5.3 DC脈衝電流的供應效應 27
2.5.4 火花電漿燒結機制 28
2.6 粉末的燒結性 30
2.6.1 粉體的性質 30
2.6.2 成形體的性質 31
2.7 晶粒及晶界導電度影響 33
2.7.1 晶粒尺寸之影響 33
2.7.2 晶界導電度 33
2.8 阻抗基本介紹 35
第三章 實驗方法 39
3.1 藥品及氣體 39
3.2 二氧化鈰奈米顆粒之製備 40
3.2.1 未摻雜之二氧化鈰奈米顆粒 40
3.2.2 摻雜釤之二氧化鈰奈米顆粒 41
3.3 二氧化鈰奈米顆粒之熱處理 42
3.4 熱處理後二氧化鈰奈米顆粒之燒結過程 43
3.5粉體之製程及來源簡介 44
3.6 樣品分析方法 45
3.6.1 XRD分析 45
3.6.2 SEM分析 45
3.6.3 TEM分析 46
3.6.4 XAS分析 47
3.6.5 Raman分析 50
3.6.6 導電率分析 51
3.6.7 相對密度量測 52
第四章 結果與討論 54
4.1起始粉末尺寸對二氧化鈰塊材之導電性與缺陷結構影響 54
4.1.1 XRD分析 54
4.1.2 SEM 分析 56
4.1.3 TEM 分析 58
4.1.4 XAS分析 64
4.1.4.1 Ce L3-edge 64
4.1.5 相對密度分析 67
4.1.6 離子導電率分析 69
4.2釤摻雜對二氧化鈰塊材之導電性與缺陷結構影響 72
4.2.1 XRD分析 72
4.2.2 TEM分析 73
4.2.3 SEM 分析 74
4.2.4 XAS分析 75
4.2.4.1 Ce L3-edge 75
4.2.4.2 Ce M4,5-edge 76
4.2.4.3 O K-edge 77
4.2.4.4 Sm M5,4-edge 79
4.2.5 Raman分析 81
4.2.6 相對密度及導電性分析 83
4.3 綜合討論 85
第五章 結論 87
參考文獻 88

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