臺灣博碩士論文加值系統

在本篇研究中，試圖製備一種新型的Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2)三金屬複合陽極材料並應用於中溫型固態氧化物燃料電池(SOFCs)。本論文分為三部份，第一部分為探討如何製備出單一相陽極材料，第二部分為不同組成對 Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2) 陽極燒結體之影響，第三部份為單電池組的製備並分析其單電池電性效能。
陽極粉體經XRD分析發現，Ni0.8Fe0.2-xCuxO陽極粉體當銅組成大於0.15後即可形成NiO的單一相結構，另外將不同組成比之複合陽極粉體壓碇燒結並進行還原煅燒則發現各組成比皆能形成單一相結構。Ni0.8Fe0.2-xCuxO-SDC陽極型態中當Fe含量較多時其孔隙型態分布較為均勻，不同組成比陽極燒結體孔隙率介於45.1~49.2%之間。將半電池進行阻抗測試時其總阻值隨溫度升高而降低，於不同組成比中Cu含量較低時具有較低的極化阻抗，當操作溫度在800℃時Cu含量為x=0.05與0.1時其陽極阻值分別為1.15與1.79 Ω˙cm2。開環電路測試方面，單電池其開環電壓達到0.78V，穩定性能維持至1200秒，其最大功率密度為3.5 mWcm-2。

In this studied, we would be prepared a novel composite anode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). We also changed the calcination temperature and metal composition ratio in order to prepare single crystalline phase, good porosity, good dispersion and low polarization resistance of composite anode. This studied was divided into three parts. The first part, had been investigated that how to prepare a single phase anode material. The second part, investigated on the influence of different anode composition. The final part, had been investigated preparation and electrical performance of the single cell.
From X-ray diffraction (XRD) analysis, the Ni0.8Fe0.2-xCuxO(x= 0.15, 0.175, 0.2) anode powder exhibited single phase structure. And composite anode exhibited a single crystalline phase as reduction at 600℃ in H2 for 2h. Field-emission scanning electron microscope (FE-SEM) imaged showed that the porous microstructures were uniform distribution with increasing the amount of Fe. Porosity of different composition anodes were from 45.1% to 49.2%. The AC-Impedance (EIS) analysis showed that the resistance values were decreased with increasing the operation temperature and decreasing the amount of Cu. The resistance values were 1.15 and 1.79 Ω × cm2 for the x= 0.15 and x= 0.1, respectively. From OCV analysis, the open-circuit voltage was 0.78V and stabled to 1200 second. It confirmed that the single cell was a potential material. I-V curve test showed that the power density was 3.5 mW/cm2.

Abstract i
摘要 i
致謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
一、序論 1
1.1燃料電池的起源 1
1.2 SOFC之應用及優缺點 6
1.3 SOFC陽極材料之選擇 7
1.3.1 Ni-YSZ金屬陶瓷陽極 7
1.3.2 Ni-SDC金屬陶瓷陽極 8
1.4 SOFC陽極材料之製備 9
1.5 SOFC陰極材料之選擇與製備 10
1.6 SOFC電解質材料之選擇 11
1.7 SOFC電解質材料之製備 15
1.8 文獻回顧 16
1.9 研究動機 19
二、原理 20
2.1 SOFC之基本原理 20
2.2 SOFC電解質的基本傳導原理 22
2.3 甘胺酸法簡介 24
2.4 水熱法簡介 25
2.5 燒結理論 27
三、實驗裝置與步驟 29
3.1 實驗藥品 29
3.2 儀器設備 30
3.3 實驗方法 31
3.3.1 複合陽極材料製備 31
3.3.2 電解質材料製備 31
3.3.3 複合陰極材料製備 32
3.3.4 單電池製備 32
3.4 材料特性分析 36
3.4.1 SEM燒結體形態分析 36
3.4.2 燒結體相對密度與開放孔隙度量測 36
3.4.3 TG/DTA熱重分析 37
3.4.4 X-ray繞射量測 38
3.4.4.1 晶形變化量測 38
3.4.4.2 晶格常數變化量測 39
3.4.5 AC-Impedance交流阻抗電化學特性測試 39
3.4.6 開路電位(OCV)測試 43
3.4.7 極化曲線測試 43
四、結果與討論 44
4.1 單一相陽極材料製備 44
4.1.1 甘胺酸法之優勢 44
4.1.2 不同煅燒溫度對形成單一相粉體之影響 44
4.1.3 不同組成對形成單一相Ni0.8Fe0.2-xCuxO (x=0, 0.05, 0.1, 0.15, 0.175, 0.2)粉體之影響 48
4.1.4 單一相Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2)複合陽極材料製備與分析 53
4.1.4.1 SDC陶瓷粉體合成分析 53
4.1.4.2單一相 Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2)複合陽極燒結體製備 54
4.1.4.3單一相 Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2)複合陽極燒結體X-ray繞射分析 55
4.2 不同組成對 Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2)燒結體微結構與電性之影響 60
4.2.1 不同組成對 Ni0.8Fe0.2-xCuxO-SDC(x=0, 0.05, 0.1, 0.15, 0.175, 0.2) 燒結體型態與孔隙率之影響 60
4.2.2 半電池製備與微結構分析 66
4.2.2.1 Ni0.8Fe0.2-xCuxO-SDC陽極燒結體與SDC電解質收縮率分析 66
4.2.2.2半電池製備 69
4.2.2.3半電池SEM型態分析 71
4.2.3 半電池交流阻抗分析 74
4.2.4 不同金屬組成對陽極阻抗影響 82
4.3 單電池組製備與分析 87
4.3.1 陰極材料分析 87
4.3.1.1 SSC(Sm0.5Sr0.5CoO3)粉體熱重分析 87
4.3.1.2 SSC(Sm0.5Sr0.5CoO3)粉體X-ray分析 88
4.3.1.3 SSC(Sm0.5Sr0.5CoO3)型態分析 88
4.3.2 單電池結構分析 90
4.3.3 單電池電性測試分析 91
五、結論 94
六、參考文獻 96

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