臺灣博碩士論文加值系統

本研究以430不�袗�(430SS)為底材，並塗覆La0.7Sr0.3Mn3O (LSMO73)以及在塗覆LSMO73之前於430SS底材預濺鍍銀及銅銀，探討LSMO73燒結後於800℃之高溫氧化行為及導電性。實驗結果顯示，LSMO73於1200℃氮氣氣氛之燒結會發生分解，若燒結溫度降低至1100℃，則LSMO73已充分燒結且未發生分解。LSMO73經過1100℃氮氣燒結過後，於800℃空氣氣氛，具有高溫化學安定性並對430SS具保護性。LSMO73與合金界面處所產生的氧化層種類與厚度，取決於燒結過程中LSMO73與合金的反應。電性量測方面，於500℃〜800℃，430SS原材具有最高的導電性，其次依序為430塗覆LSMO73、800℃空氣預氧化48小時、800℃空氣預氧化120小時。主要影響ASR值的因素為金屬底材在高溫氧化環境下所產生的氧化層厚度及氧化物的種類。參雜低價Ag+於氧化層，可以約略降低氧化層的氧化速率，並在高溫時明顯提升氧化層的導電性。於塗覆LSMO73前的銅銀預鍍層，由於銅在高溫燒結過程中發生氧化，不僅會降低導電性，且銅會與LSMO73中的La反應，生成LaCuO4導致LSMO73分解，對導電性有不良的作用。

This study investigates the sintering phenomenon under N2 atmosphere at 1100℃ and 1200℃ for La0.7Sr0.3Mn3O (LSMO73) screen-printed by 430 Stainless Steel (430SS), meanwhile, the behavior and conductive characteristic of high temperature oxidation at 800℃ for LSMO73 after sintering is also investigated too. The experimental results shows that for 430SS and for sintering at 1200℃ under N2 atmosphere, LSMO73 will decompose, however, when the temperature is reduced to 1100℃, LSMO73 will be sintered completely and no decomposition will occur. After 1100℃ sintering under N2 atmosphere and then put it at 800℃ under air environment, LSMO73 will possess high temperature chemical stability and protective characteristic, therefore, the oxide type and thickness generated at the interface between LSMO73 and alloy is decided by the reaction between LSMO73 and alloy during the sintering process. In the electrical property measurement aspect, the major factor which affects ASR (Area specific resistance) value is the oxide thickness and oxide type (conductivity) generated under high temperature environment by metallic double electrode plate. As the oxide layer gets thicker, ASR value will get increased. Dope low valence Ag+ into oxide layer will slightly decrease the oxidation rate of the oxide layer and, under high temperature environment, obviously increase the conductivity of the oxide layer, In the aspect of increasing the wetting characteristic by using Cu, Cu will get oxidized during high temperature sintering process and the conductivity will thus be reduced, meanwhile, Cu will react with La of LSMO73 to form LaCuO4 which will in turn leads to the decomposition of LSMO73.

第一章 前言 1
第二章 文獻回顧 4
　2.1 燃料電池簡介與種類 4
　　2.1.1 燃料電池的簡介 4
　　2.1.2 燃料電池的種類 5
　2.2 固態氧化物燃料電池簡介與操作原理 7
　　2.2.1 SOFC基本元件 7
　　　2.2.1.1 電解質 7
　　　2.2.1.2 陽極 8
　　　2.2.1.3 陰極 8
　　　2.2.1.4 雙極板(Interconnect) 9
　　2.2.2 SOFC的操作原理 9
　2.3 高溫氧化 13
　　2.3.1 氧化機制 13
　　　2.3.1.1 化學計量氧化物 13
　　　2.3.1.2 非化學計量氧化物 14
　　2.3.2 參雜對氧化物缺陷結構的影響 15
　2.4 SOFC雙極板 17
　　2.4.1 LaCrO3基陶瓷材料雙極板 18
　　2.4.2 耐高溫金屬材料雙極板 20
　　　2.4.2.1 Ni基材料 21
　　　2.4.2.2 Cr基材料 22
　　　2.4.2.3 Fe基材料 23
　2.5 陰極端金屬雙極板與保護塗層界面反應 33
　　2.5.1 LaCrO3基 33
　　2.5.2 La1-XSrXMnO3 33
第三章 實驗方法 40
　3.1 實驗流程 40
　3.2 試片的製備 41
　　3.2.1 合金成份分析 41
　　3.2.2 材料準備及表面清洗 41
　　3.2.3 試片的製作 42
　　　3.2.3.1 預氧化試片 42
　　　3.2.3.2 濺鍍銀試片 42
　　　3.2.3.3 濺鍍銅銀複合層 43
　3.3 LSMO73膠體製作及網印 44
　　3.3.1 LSMO73粉末的製作 44
　　3.3.2 LSMO73膠體的製作 45
　　3.3.2 LSMO73網印與燒結 45
　3.4 高溫氧化實驗 48
　3.5 電性量測 48
　　3.5.1 電極製作 49
　　3.5.2 電性量測 49
　3.6 實驗設備 54
第四章 實驗結果與討論 55
　4.1 430SS 55
　　4.1.1 LSMO73的燒結 55
　　4.1.2 高溫氧化 57
　　　4.1.2.1 430SS原材 57
　　　4.1.2.2 430-LSMO73 58
　　4.1.3 電性量測 59
　4.2 披覆銀對於不鏽鋼雙極板之效果 71
　　4.2.1 430-A 71
　　4.2.2 430-A的LSMO73燒結 71
　　4.2.3 430-A-LSMO73的高溫氧化 73
　　4.2.3 電性量測 73
　4.3 披覆銅銀對於不�袗�雙極板之效果 80
　　4.3.1 430-CA-LSMO73的燒結 80
　　4.3.2 430-CA-LSMO73的高溫氧化 81
　　4.3.3 電性量測 82
　4.4 導電電極的影響 90
第五章 結論 92
參考文獻 93
未來研究之建議 100
附錄A 101
作者簡介 102

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