臺灣博碩士論文加值系統

本研究主要是研究以甲烷或丙烷直接當做陽極支撐型固態氧化物燃料電池(SOFC)的陽極進料，探討燃料於陽極支撐層的反應機制。本實驗以Ni/YSZ當陽極支撐層，發現以甲烷為燃料時，電流的生成反應主要是來自氧離子是與甲烷解離後所產生碳，且可穩定輸出無衰退現象。當以丙烷為進料時，依然可以產生穩定的電流輸出，即無衰退現象，而主要出口產物為氫氣、一氧化碳和甲烷。由EDX分析發現積碳量隨著愈靠近電解質愈少，當小於80 μm時已無積碳生成。
當電池經過活化程序後，電池性能會有提升的現象，而在陽極會有奈米鎳的生成。由於陽極在電化學反應時，會將原本較大顆粒的氧化鎳細化成許多奈米級的鎳，導致三相點增多，以至於活性會提升，但是電池活性提升會有一極限值，即鎳的細化程度會達到平衡值，而相關的奈米增生效應循環反應方程式為: (1) NiO + H2 → Ni + H2O ; (2) Ni + O2- → NiO + 2e-。由無燃料電流實驗證實鎳在陽極的角色不在只是觸媒，而還可以當反應物參與反應，這也直接證明了上式(2)在電化學反應中的存在。若停止了電化學的反應，陽極增生的奈米鎳在800oC下會聚集成海綿狀結構，由高倍率的SEM分析可以看出此海綿狀結構是由許多奈米顆粒所組成，這代表了停止了電化學反應的供輸，即破壞了奈米鎳在陽極的穩定機制。當再一次的在1400 oC燒結，海綿狀結構內的晶界會融合長大成一體，即可以將海綿狀結構回復成原本剛製作成的陽極結構，然而因為晶格的遷移成長，會造成陽極有許多的大洞和裂縫生成。
CO2於SOFC陰極的直接解離反應於900 oC可有27 %的轉化率，且同時可輸出3.1 mW/cm2的電功率。陰極流速對CO2解離的轉化率存有一最佳值。電化學促進效應於SOFC上同時包含了電壓和電流效應。法拉第效率隨著溫度升高而降低，且隨著操作電壓提高而變大。於高溫和低電壓下，電流效應對於電化學促進的影響將會大於電壓效應。SOFC的開路電壓(OCV)應與陰極氧氣氛濃度有關，且氧氣的添加會抑制CO2的解離。
NO於SOFC陰極可行直接解離反應，並生成N2和O2。而用於產生氧離子的氧物種遠小於生成的氧氣，即法拉第效率大於1，這表示有電化學促進的效果。反應溫度愈低，電化學使用效率愈高。氧氣的添加於800 oC時會抑制NO的解離，然而氧濃度對於NO的轉化率影響會有一轉折點。560 ppm NO2或9000 ppm NO以流速200 ml/min於GDC-LSM陰極700 oC反應下可達100%。
SOFC應用於模擬廢氣反應裡，NO轉化率對會隨著NO濃度分佈存有一V形反轉的趨勢，即轉化率皆會隨著濃度降低或濃度提高而變高。以LSM-GDC為陰極時，NO解離於400~550oC溫度區間因為受動力學控制，所以轉化率會隨著溫度提高而提高；550~700oC溫度區間因為轉為熱力學控制，轉化率會隨著溫度提高而降低；而700~800 oC溫度區間因為晶格氧會往內部補充，所以轉化率反而會隨著溫度提高而提高。氮氣生成速率隨著NOx濃度增加而變高，主要是因為反應速率會隨濃度變高；而於低NOx濃度下，氮氣生成速率幾乎為定值，代表此時為表面擴散控制所致。以LSCC-GDC為陰極時，SO2的添加會降低NOx轉化率，可能是因為SO2會毒化Cu所致，而在較低NOx濃度反應裡的影響程度較高，於高濃度NOx的影響反而較有限。SOFC電池堆應用於汽車廢氣的減排，將可達到氮氧化物的零排放。

第一章 緒論 1
第二章 文獻回顧 5
2-1. 固態氧化物燃料電池 5
2-1-1. 歷史簡介 5
2-1-2. 工作原理 6
2-2. SOFC材料組成 12
2-2-1. 電解質 12
2-2-2. 陽極 15
2-2-3. 陰極 16
2-3. 燃料於陽極內部重組之研究 18
2-4. 丙烷燃料重組反應 23
2-4-1. 陽極支撐SOFC之丙烷燃料重組反應 23
2-4-2. 丙烷乾重組之反應機構 25
2-5. 電化學促進 26
2-6. 二氧化碳之減碳處理技術簡介 32
2-7. 氮氧化物之減量處理技術 34
2-7-1. 氮氧化物之來源 34
2-7-2. 觸媒催化氮氧化物之方法 36
第三章 實驗方法與步驟 48
3-1. 實驗藥品 48
3-2. 粉體合成 49
3-2-1. YSZ粉體合成 49
3-2-2. NiO/YSZ陽極粉體合成 49
3-2-3. GDC粉體合成 49
3-2-4. NixFe粉體合成 50
3-2-5. La0.6Sr0.4Co0.8Cu0.2O3合成 50
3-3. 塗佈漿料和成 51
3-3-1. 電解質漿料 51
3-3-2. 陰極漿料 51
3-4. 陽極支撐形電池製作 52
3-5. 實驗儀器 53
3-6. 反應器裝置 54
3-7. 實驗流程 55
3-7-1. 觸媒之丙烷乾重組 55
3-7-2. SOFC電池性能測試 56
3-7-3. CO2電化學還原測試 57
3-7-4. NOx電化學還原測試 57
第四章 實驗結果與討論 58
4-1. 陽極燃料處理 58
4-1-1. 陽極支撐型SOFC之微觀圖 58
4-1-2. 直接甲烷SOFC 60
4-1-3. 直接丙烷SOFC 65
4-1-4. 鎳鐵支撐型SOFC丙烷重組模擬 73
4-2. 陽極奈米鎳增生機制探討 77
4-2-1. 電池經活化後的效能測試 77
4-2-2. 電池陽極在不同狀態下的微結構分析 82
4-2-3. 陽極於再氧化處裡的微結構變化 88
4-2-4. 無燃料電流(non-fuel current)實驗 93
4-2-5. 電化學反應生成奈米鎳機制探討 97
4-2-6. 不同定電流操作下的電性影響 101
4-3. 二氧化碳於陰極上的電化學還原研究 103
4-3-1. 二氧化碳電化學還原機制 103
4-3-2. 溫度與電壓對於二氧化碳轉化率的影響 107
4-3-3. 電化學促進於二氧化碳轉化率的影響 110
4-3-4. 電壓和電流效應的探討 114
4-3-5. 氧濃度對於電壓和二氧化碳解離的影響 117
4-4. 氮氧化物於固態氧化物陰極上的電化學還原 121
4-4-1. 電性測試 121
4-4-2. 一氧化氮解離於不同操作電壓下的影響 123
4-4-3. 氧濃度的影響 132
4-4-4. 二氧化氮的電化學還原 137
4-4-5. 模擬廢氣於LSM-GDC陰極上的電化學還原研究 141
4-4-6. 模擬廢氣於LSCC-GDC陰極上的電化學還原研究 160
第五章 結論 167
參考文獻 172

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