甘胺酸-硝酸燃燒合成法製備固態氧化物燃料電池陰極材料La0.8Sr0.2MnO3、La0.6Sr0.4Co0.2Fe0.8O3與其電化學性質之研究

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論文名稱

甘胺酸-硝酸燃燒合成法製備固態氧化物燃料電池陰極材料La0.8Sr0.2MnO3、La0.6Sr0.4Co0.2Fe0.8O3與其電化學性質之研究
(Synthesis and electrochemical properties of La0.8Sr0.2MnO3 and La0.6Sr0.4Co0.2Fe0.8O3 by glycine-nitrate combustion method)

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摘要(中)

本論文以甘胺酸-硝酸燃燒合成法(Glycine-nitrate combustion method)製備鑭、鍶、錳氧化物(La0.8Sr0.2MnO3；LSM)與鑭、鍶、鈷、鐵氧化物(La0.6Sr0.4Co0.2Fe0.8O3；LSCF)陰極材料，並探討前驅溶液在不同pH值、甘胺酸與硝酸之比例(g/n比)與粉體在不同煆燒溫度下之結晶結構、表面形貌、組成、熱性質等，並製成固態氧化物燃料電池(SOFC)全電池，進行電化學測試，以評估作為燃料電池陰極的可行性。
本研究利用X光繞射分析儀（XRD）探討合成出之陰極材料粉體結晶結構；使用掃描式電子顯微鏡（SEM）來觀察其微結構、表面形貌；能量散佈分析儀(EDS)進行元素半定量分析；利用熱重分析儀（TGA）來分析陰極粉體在高溫下之變化，最後再將陰極粉體製成全電池，以直流電極化曲線（I-V curve）和電化學交流阻抗頻譜圖（EIS）來測試電池的性能。
研究結果顯示，前驅溶液經過適當的pH值控制後，能夠增加金屬陽離子的錯合能力，使材料合成時生成之雜相(Impurity phase)減少。且g/n比為1.0以及1.5時，能夠形成純相之LSM與LSCF結構，經過1000oC的煆燒後得到奈米等級(約200nm)與具備多孔性(Porous)之陰極材料粉體。全電池性能測試結果顯示，LSM在g/n比1.0、操作溫度850oC具有最高輸出電流密度：469.474mA/cm2與最高功率密度：209.850mW/cm2。LSCF在高溫燒結下易與電解質材料(YSZ)發生反應，形成SrZrO3絕緣相，導致電池輸出性能大幅下降。

摘要(英)

Glycine-nitrate combustion method was used to prepare the precursor which could be calcined to form La0.8Sr0.2MnO3 (LSM) and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) as the cathode catalyst materials of the solid oxide fuel cell(SOFC). The effect of pH value from precursor, glycine to nitrate ratio(g/n ratio) and calcination temperature on the crystalline structure, morphology, composition, thermal and electrochemical properties were of interest.
The crystal structure was determined by X-ray diffractmeter (XRD)The surface morphology of the oxide powders was examined through field emission scanning electron microscope (FE-SEM) and their composition was analyzed by the equipped energy dispersive spectrophotometer (EDS). The thermal property was determined by the thermal gravimetric analysis (TGA). After makng the calcined oxides as the cathode catalysts in a single cell. I-V polarization test and the electrochemical impedance were conducted to evaluate the electrochemical performance.
LSM and LSCF have successfully been developed after the specific pH value and g/n ratio controlled. All the powders prepared by glycine-nitrate combustion method were nanosized. The electrochemical test showed the LSM with maximum current density: 469.474mA/cm2 and the maximum power density: 209.850mW/cm2 when the g/n ratio was equal to 1.0. Additional diffraction peaks assigned to SrZrO3 phase were found after firing the LSCF-YSZ mixture at 900 and 1000ºC indicating a reaction between LSCF and YSZ which is stronger as the temperature increases.

關鍵字(中)

★ 固態氧化物燃料電池
★ 陰極材料
★ 燃燒合成法
★ 電化學

關鍵字(英)

★ SOFC
★ cathode
★ combustion
★ electrochemistry

論文目次

摘要 i
Abstract iii
表目錄 vi
圖目錄 viii
第一章簡介 1
1.1 前言 1
1.2 研究動機與目的 3
第二章理論基礎與文獻回顧 5
2.1 燃料電池簡介 5
2.1.1 固態氧化物燃料電池原理與簡介 6
2.1.2 固態氧化物燃料電池元件材料 7
2.1.3 固態氧化物燃料電池之支撐結構 10
2.2 陰極材料之性質 11
2.2.1 鈣鈦礦結構( Pervoskite )[14] 11
2.2.2 三相界（TPB）[17] 13
2.3 陰極材料常用之合成法 14
2.3.1 固態反應法[18] 14
2.3.2 共同沉澱法[19] 14
2.3.3水熱法[20] 15
2.3.4 溶膠凝膠法[18] [21] 16
2.3.5 燃燒合成法[22] 16
2.4電化學原理-直流電極化曲線（I-V Curve）原理 17
2.5電化學原理-電化學交流阻抗(EIS)基本原理 20
2.6文獻回顧 24
2.6.1 固態氧化物燃料電池陰極文獻回顧 24
2.6.2 燃燒合成法對於材料結構文獻回顧 26
2.6.3 燃燒合成法對於材料電性與電化學交流阻抗文獻回顧 29
第三章實驗方法 30
3.1 實驗藥品與材料 30
3.2 實驗製備 30
3.2.1 陰極材料合成與分析 30
3.2.2 陰極膏製備 31
3.2.3 全電池製備 32
3.3 實驗儀器與設備 33
3.3.1 X光繞射儀 (X-Ray Diffractormeter XRD) 33
3.3.2 掃描式電子顯微鏡(FE-SEM)與能量散射光譜儀（EDS） 34
3.3.3 熱重分析儀(TGA) 35
3.3.4直流極化分析(I-V Curve) 36
3.3.5 交流阻抗頻譜分析(EIS) 36
第四章實驗結果 36
4.1 粉體之XRD分析結果 37
4.2 粉體之SEM表面形貌分析結果 40
4.3 粉體之EDS半定量分析結果 43
4.4 粉體TGA熱分析結果 44
4.5 直流電極化曲線(I-V curve)分析結果 45
4.6 直流極化曲線(I-P curve)分析結果 46
4.7 電化學交流阻抗(EIS)分析結果 47
4.8 等效電路圖模型(ECM)模擬 48
第五章實驗討論 49
5.1 不同pH值之影響討論 49
5.2 不同g/n比之影響討論 50
5.3 材料熱分析討論 52
5.4 全電池性能討論 53
5.4.1 LSM陰極材料之全電池性能討論 53
5.4.2 LSCF陰極材料之全電池性能討論 55
第六章結論與未來展望 57
6.1 結論 57
6.2 未來展望 58
第七章參考文獻 59

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指導教授

林景崎(Lin, Jing-Chie)

審核日期

2014-8-13

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