用於氧氣還原反應觸媒的貴金屬，例如Pt、Pd等…，因成本過高和稀少並限制質子交換膜燃料電池的大規模商業化，非貴重金屬觸媒(NPMCs)的目標是取代昂貴鉑金屬觸媒，NPMCs不僅有高氧氣還原反應(ORR)催化活性而且價格便宜，以碳基材非貴重金屬ORR觸媒的開發已成為燃料電池的重要課題之一。
本研究利用三聚氰胺，其中高氮含量作為氮元素來源以外，亦可做碳元素來源，戊二醛可與三聚氰胺進行交聯形成架橋物，並加入過渡金屬鐵化合物，將其合成後進行鍛燒，而使鐵、氮以及碳將在煅燒之後形成活性位點成為非貴重金屬觸媒。
藉由X-光繞射儀(XRD)、拉曼光譜儀(Raman)、功能性穿透式電子顯微鏡(cryo-TEM)、場放射型掃描式電子顯微鏡(FE-SEM)、恆電位電流儀、燃料電池測試設備進行觸媒性能分析。

Precious metals acted as a catalyst in oxygen reduction, such as Pt, Pd, etc., they are expensive and rare, which would affect the efficiency in proton exchange membrane fuel cell s. Non-precious metal catalysts (NPMCs) are used to replace expensive or precious platinum. NPMCs not only have high catalytic activity for oxygen reduction reaction (ORR) but also an economic option in the case. The development of carbon substrate non-precious metal ORR catalyst has became one of the important topics of fuel cells.
Regarding to the high nitrogen and carbon content in Melamine, it was utilized for providing amount of nitrogen and carbon in the study. Glutaraldehyde can be linked with melamine to form a network, and a transition metal iron compound can be trapped inside. When finish the preparation of them, it would make iron, nitrogen and carbon will form an active site after calcination to convert into the non-precious metal catalyst.
Characterized by X-ray diffractometer (XRD), Raman spectrometer (Raman), functional penetrating electrons Catalyst performance analysis was performed by a microscope (cryo-TEM), a field emission type scanning electron microscope (FE-SEM), a potentiostat current meter, and a fuel cell test equipment.

目錄

摘要 I頁
Abstract II頁
誌謝 III頁
目錄 IV頁
表目錄 VIII頁
圖目錄 IX頁
第一章 緒論 1
1.1 前言 1
1.2 研究動機 6
1.3 研究架構 8
第二章 文獻回顧 9
2.1燃料電池的發展 9
2.2燃料電池的發電原理 11
2.3燃料電池的優點 16
2.4燃料電池的種類與應用 18
2.5質子交換膜燃料電池(PEMFC) 21
2.5.1 PEMFC之原理 22
2.5.2 質子交換膜燃料電池之構造及關鍵元件 23
2.5.3 質子交換膜 24
2.5.4 觸媒層(Catalyst Layer; CL) 26
2.5.5 氣體擴散層(Gas Diffusion Layer; GDL) 27
2.5.6 雙極板(Bipolar Plates; BP) 29
2.5.7 膜電極組(Membrane Electrode Assembly; MEA) 31
2.6氧氣還原反應(Oxygen Reduction Reaction; ORR) 32
2.7非貴重金屬觸媒 36
2.7.1 非貴重金屬之ORR反應機制 37
2.7.2 氮摻雜於碳材料(Nitrogen-doped carbon materials) 38
2.8三聚氰胺應用於觸媒 39
2.9 沸石咪唑酯骨架(Zeolitic imidazolate frameworks; ZIFs) 40
第三章 實驗 41
3.1實驗藥品 41
3.2儀器設備 42
3.3實驗步驟 45
3.3.1 觸媒製備 45
3.3.2 線性掃描伏安法(LSV)測定 48
3.3.3 膜電極組(MEA)製作 50
3.3.4 MEA之單電池效率分析 52
第四章 結果與討論 54
4.1鐵氮碳純水系列觸媒(MGFe-PW) 54
4.1.1 結晶性分析(XRD) 54
4.1.2 表面型態分析(TEM) 55
4.1.3 有序性分析(Raman) 57
4.1.4 表面性質分析(BET) 58
4.1.5 電化學分析(Linear Sweep Voltammetrys; LSVs) 61
4.1.6 單電池分析 63
4.2鐵氮碳乙二醇系列觸媒(MGFe-EG) 64
4.2.1 結晶性分析(XRD) 64
4.2.2 表面型態分析(TEM) 65
4.2.3 有序性分析(Raman) 66
4.2.4 表面性質分析(BET) 68
4.2.5 電化學分析(Linear Sweep Voltammetrys; LSVs) 70
4.2.6 束縛能分析(XPS) 73
4.2.7 單電池分析 80
第五章 結論 81
參考文獻 82

表目錄

Table 1.1-1 燃料電池的種類 4
Table 2.4-1 各燃料電池類型 20
Table 2.5.6-1雙極板材料的物理和化學特性 30
Table 2.5.7-1 MEA組件及其主要性質 32
Table 2.6-1 電化學O2還原的熱力學電極電位 33
Table 2.6-2 Pt觸媒ORR機制表 34
Table 4.1.3-1 MGFe-PW系列觸媒之ID/IG統計表 59
Table 4.1.5-1 MGFe-PW系列觸媒LSV的電化學參數 63
Table 4.2.3-1 MGFe-EG系列觸媒之ID/IG統計表 68
Table 4.2.5-1 MGFe-EG系列觸媒LSV的電化學參數 72
Table 4.2.6-2 MGFe-EG系列觸媒之不同型態碳含量 78
Table 4.2.6-3 MGFe-EG系列觸媒之不同型態氮含量 80

圖目錄

Figure 1.1-1全球石油需求 4
Figure 1.1-2全球石油供應 5
Figure 1.1-3 與氫能技術應用相關的各種特性和可能性 5
Figure 1.1-4燃料電池示意圖 6
Figure 2.1-1 William Robert Grove(1811-1896)的肖像 10
Figure 2.1-2 William Grove 1839年燃料電池的草圖 10
Figure 2.1-3 燃料電池技術的歷史發展 11
Figure 2.2-1 (A)陽離子(B)陰離子型燃料電池示意圖 14
Figure 2.2-2 單個燃料電池的示意圖 15
Figure 2.5-1 單組成PEMFCs的構造 22
Figure 2.5.1-1 PEM燃料電池中的現象:二維截面圖 23
Figure 2.5.2-1 PEMFC結構和運輸過程 24
Figure 2.5.3-1 Nafion和磺化聚醚酮(源自SAXS實驗)的微觀結構的示意圖 25
Figure 2.5.4-1 白金觸媒應用於PEMFC系統之示意圖 27
Figure 2.5.5-1 碳纖維紙 28
Figure 2.5.5-2 碳纖維布 29
Figure 2.5.5-3 碳纖維板 29
Figure 2.5.6-1 雙極板 30
Figure 2.5.7-1 MEA構造 31
Figure 2.6-1 Pt上的氧還原反應機理 33
Figure 2.6-2 Pt氧還原 (a) bridge model, (b) Griffiths model and (c) Pauling model 35
Figure 2.7-1 燃料電池系統成本 38
Figure 2.7.1-1 非貴重金屬之電催化ORR的反應機制 38
Figure 2.7.2-1 氮參雜示意圖 40
Figure 3.3.1-1 本研究觸媒製備流程圖 47
Figure 3.3.1-2 三聚氰胺與戊二醛架橋反應機制 48
Figure 3.3.1-3 本研究觸媒合成示意圖 48
Figure 3.3.1-3本研究之觸媒標記 49
Figure 3.3.2-1用於測量線性掃描伏安法(LSV)觸媒製備流程圖 50
Figure 3.3.2-2用於測量線性掃描伏安法(LSV)的Autolab電化學測試系統的示意圖 50
Figure 3.3.3.1-1漿料製備流程圖 51
Figure 3.3.3.2-1 MEA塗佈、組裝及單電池測試流程圖 52
Figure 3.3.4-1 單電池模組 53
Figure 3.3.4-2 燃料電池測試平台 54
Figure 4.1.1-1 MGFe-PW系列觸媒之XRD圖 56
Figure 4.1.2-1 (a, b) M2G3Fe25-PW-H-900 (c, d) M2G3Fe25-PW-H-900-A (e, f) M2G3Fe25-PW-H-800 (g, h) M4G3Fe10-PW-H-900觸媒之TEM型態分析圖 57
Figure 4.1.3-1 MGFe-PW系列觸媒之拉曼光譜圖 58
Figure 4.1.3-2 MGFe-PW系列觸媒之ID/IG比較圖 59
Figure 4.2.4-1 MGFe-PW系列觸媒(a)吸收脫附等溫線圖, (b)孔徑分布 61
Figure 4.1.5-1 MGFe-PW系列觸媒在0.5M H2SO4中之ORR極化曲線圖，掃描速率:10 mV/s、轉速:1600 rpm、O2 63
Figure 4.1.6-1 M2G3Fe25-PW-H-800和M4G3Fe10-PW-H-900陰極觸媒之單電池 (a) Polarization (b) Power density曲線圖 64
Figure 4.2.1-1 MGFe-EG系列觸媒之XRD圖 65
Figure 4.2.2-1 (a, b) M4G6-EG-900 (c, d) M4G6Fe5-EG-900 (e, f) M4G6Fe10-EG-900 (g, h) M4G6Fe20-EG-900 (i, j) M4G6Fe30-EG-900 (k, l) M4G6Fe40-EG-900 觸媒之TEM型態分析圖 66
Figure 4.2.3-1 MGFe-EG系列觸媒之拉曼光譜圖 67
Figure 4.2.3-2 MGFe-EG系列觸媒之ID/IG比較圖 68
Figure 4.2.4-1 MGFe-EG系列觸媒(a)吸收脫附等溫線圖, (b) M4G6Fe5-EG-900 (c) M4G6Fe10-EG-900、(d) M4G6Fe20-EG-900孔徑分布 70
Figure 4.2.5-1 MGFe-EG系列觸媒在0.5M H2SO4中之ORR極化曲線圖，掃描速率:10 mV/s、轉速:1600rpm、O2 72
Figure 4.2.5-2 (a)在O2飽和的0.5 M H2SO4水溶液中以10 mV/s的掃描速率對M4G6Fe10-EG-900進行RDE測量，旋轉速率為900至3600rpm (b)不同電位下的K-L圖(c)不同電位下電子轉移數 73
Figure 4.2.6-1 MGFe-EG系列觸媒之XPS光譜圖 75
Figure 4.2.6-2 MGFe-EG系列觸媒之C1s XPS束縛能分析 77
Figure 4.2.6-3 MGFe-EG系列觸媒之不同型態碳含量比較 78
Figure 4.2.6-4 MGFe-EG系列觸媒之N1s XPS束縛能分析 79
Figure 4.2.6-5 MGFe-EG系列觸媒之不同型態氮含量比較 80
Figure 4.2.7-1 M4G6Fe10-EG-900觸媒之單電池極化曲線圖 81

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