臺灣博碩士論文加值系統

離子與電子混合傳導體的鈦酸鍶是可以取代鎳添加之釔穩定氧化鋯的固態氧化物燃料電池之陽極材料，因其擁有高的化學與熱穩定性，然而鈦酸鍶的離子導電度仍較釔穩定氧化鋯來的低。一般來講，晶界處空間電荷的累積會導致氧空缺的傳導受到阻礙並使離子導電度下降，而根據前人的研究，無法證明低能量的共位晶界Σ3有空間電荷的累積。而目前Σ3晶界難以提升的原因有兩個，一是異常晶粒成長會消耗Σ3晶界，二是陶瓷太脆弱不能滾軋，因此此實驗的目的即在於增加多晶鈦酸鍶的Σ3晶界以提升離子導電度，方法是藉由適合的添加物之作用，在起始粉體的表面形成較多的(111)平面（Σ3晶界）。本實驗以硝酸鍶與異丙醇氧鈦作為前驅物，並添加硝酸與及不同濃度的雙氧水，利用噴霧熱裂解法製備鈦酸鍶粉體，並以X光繞射儀與拉曼光譜鑑定結晶結構，以掃描式電子顯微鏡與穿透式電子顯微鏡觀察粉體的形貌、大小與晶界的形貌，以氮氣吸/脫附儀量測其比表面積，以背向散射電子繞射儀分析晶界資訊，以直流與交流阻抗分析儀量測其導電度。本實驗利用前驅物添加硝酸及雙氧水製備出擁有更多(111)表面的圓弧粉體，發現其Σ3晶界最多且導電度最高。

Strontium titanate (SrTiO3), has been reported as the candidate of solid-oxide-fuel-cell anode materials to substitute the conventional materials of Ni-doped yttria-stabilized zirconia (YSZ) cermets because of its high chemical and thermal stability. However, the ionic conductivity of SrTiO3 is low comparing to YSZ. In general, space charge of grain boundaries (GBs) trapped oxygen ion to result low ionic conductivity. Based on previous studies, there is no evidence of space charge layers in low energy coincidence-site lattice ?? GBs which do not impede the transport of charge. So far, the reasons of low ?? GBs are abnormal grain growth (losing of low energy GBs) and difficult to orientate because ceramic is too brittle. This study attempts to increase the population of ?? GBs in polycrystalline SrTiO3 for high ionic conductivities. The strategy is to form more (111) faces (?? GB plane) on the surface starting powder by chosen suitable precursor additives. Four types of SrTiO3 powders have been synthesized using spray pyrolysis with strontium nitrate, titanium isopropoxide and additives of nitric acid (HNO3) and the mixtures of HNO3 and hydrogen peroxide (H2O2) with different concentrations. The crystalline structures of SrTiO3 particles were characterized by X-ray diffractometer and Raman spectra. The morphology and size of SrTiO3 particles were observed by using scanning electron microscope (SEM) and transmission electron microscope. And, the microstructures of sintered SrTiO3 bulks were observed by using SEM. The GB orientations were characterized by electron back-scattered diffraction (EBSD). The conductivities were measured by electrochemical impedance spectroscopy and DC method. The microstructural results suggest that the SrTiO3 particles prepared from the additive mixture of HNO3 and H2O2 have a rough surface which contains more (111) surfaces than that of the SrTiO3 particles prepared from HNO3 only. In addition, EBSD and DC measurements show that the SrTiO3 from HNO3 and H2O2 (highest population of ?? GBs) exhibit highest conductivity, which supports our microstructural observations.

Abstract i
摘要 iv
致謝 v
目錄 vi
圖目錄 xi
表目錄 xv
第1章 緒論 1
第2章 文獻回顧 2
2.1 固態氧化物燃料電池 2
2.1.1 工作原理 2
2.1.2 陽極材料 5
2.2 鈦酸鍶的性質 10
2.2.1 晶體結構 10
2.2.2 相圖 14
2.2.3 電性 17
2.2.3.1 溫度 18
2.2.3.2 氣氛 19
2.2.3.3 摻雜 21
2.2.3.4 微結構 22
2.3 晶界 25
2.3.1 一般晶界 26
2.3.1.1 表面能 28
2.3.1.2 鈦酸鍶的表面能與晶界形貌 31
2.3.2 共位晶界 35
2.3.2.1 共位晶界的定義 35
2.3.2.2 共位晶界的Σ3晶界 36
2.3.2.3 鈦酸鍶的Σ3晶界 40
2.4 噴霧熱裂解製備鈦酸鍶粉體 43
2.5 研究目的 46
第3章 實驗方法 50
3.1 實驗設計 50
3.2 實驗藥品與儀器 52
3.3 試片製備 53
3.3.1 鈦酸鍶粉體製備 53
3.3.2 壓碇與燒結 54
3.4 粉體與塊材的特性量測 55
3.4.1 X光繞射儀分析 (X-Ray diffraction analysis, XRD) 55
3.4.2 拉曼光譜儀 (Raman spectra) 55
3.4.3 氮氣吸/脫附分析儀 (Brunauer-emmett-teller, BET) 56
3.4.4 場發射掃描式電子顯微鏡 (Field-emission scanning electron microscope, FE-SEM) 56
3.4.5 場發射穿透式電子顯微鏡 (Field-emission transmission electron microscope, FE-TEM) 57
3.4.6 塊材的密度分析 58
3.4.7 背向散射電子繞射 (Electron back-scattered diffraction, EBSD) 60
3.4.7.1 背向散射電子繞射的裝置 60
3.4.7.2 背向散射電子繞射的原理 61
3.4.7.3 背向散射電子繞射儀的試片製備 63
3.4.8 電化學交流阻抗圖譜 (Electrochemical impedance spectroscopy) 65
3.4.8.1 電化學交流阻抗圖譜的原理 65
3.4.8.2 交流與直流阻抗分析儀的試片製備 68
第4章 結果與討論 71
4.1 鈦酸鍶粉體的性質分析 71
4.1.1 X光繞射晶相分析 71
4.1.2 拉曼光譜相分析 73
4.1.3 場發射掃描式電子顯微鏡表面形貌分析與粒徑分布 75
4.1.4 穿透式電子顯微鏡顆粒形貌分析與粒徑分布 80
4.1.5 氮氣吸/脫附分析 83
4.2 鈦酸鍶燒結後塊材的性質分析 85
4.2.1 X光繞射晶相分析 85
4.2.2 阿基米德密度分析 87
4.2.3 拉曼光譜相分析 89
4.2.4 場發射掃描式電子顯微鏡晶粒形貌分析與粒徑分布 91
4.2.5 背向散射電子繞射圖譜晶界分析 93
4.2.6 交流與直流阻抗的電性分析 102
4.3 綜合討論 108
第5章 結論 111
第6章 未來工作 112
第7章 參考文獻 113

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