臺灣博碩士論文加值系統

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。
本研究利用過渡金屬鐵化合物為常見的非貴重金屬觸媒，對苯二胺作為氮元素來源以外，經過高溫碳化後，亦可用來當作導電載體，戊二醛可聚合對苯二胺呈網狀固體以及作另一氮元素來源。
在本研究中，藉由使用不同方法及調控不同鍛燒溫度，對苯二胺-戊二醛碳化程度會有所不同，載體含氮量也會有所不同，而使鐵、氮以及碳將在煅燒之後形成活性位點，並以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)、比表面積與孔隙度分析儀(BET)、X-光電子光譜儀(XPS)、恆電位電流儀等測試設備進行觸媒性能分析，以氯化鐵加入對苯二胺並含戊二醛，再進行鍛燒，鍛燒溫度為700°C、1 hr、Ar，成功合成出此觸媒命名為FeNC-T-700，在與商用20% Pt/C觸媒進行電化學分析 (Linear Sweep Voltammetrys; LSVs)比較，所分析出的極限電流密度較商用20% Pt/C觸媒低，ORR氧氣還原效果較好，鐵/氮/碳觸媒顯現出氧氣還原反應性能和穩定性，此結果顯示鐵/氮/碳所形成的觸媒有機會發展成為質子交換膜燃料電池的陰極觸媒。

The prohibitive cost and scarcity of the precious metals used for oxygen reduction reaction (ORR) catalysts limit the large-scale commercialization of proton exchange membrane fuel cells (PEMFCs). Non-precious metal catalysts are suitable candidates to replace Pt catalysts.
The aim of non-precious metal catalysts (NPMCs) is to replace expensive Pt-based catalysts. NPMCs require not only high oxygen reduction reaction (ORR) catalytic activity but also cheap ingredients. The development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in field of fuel cell.
In this study, transition metal iron compounds are used as common non-precious metal catalysts. Phenylenediamine is used as a source of nitrogen. After high-temperature carbonization, it can also be used as a conductive carrier. Glutaraldehyde can be polymerized with p-phenylenediamine. A solid as well as another source of nitrogen.
This research, by using different methods and controlling different calcination temperatures, the degree of carbonation of p-phenylenediamine-glutaraldehyde will be different, and the nitrogen content of the carrier will be different, so that iron, nitrogen and carbon will be active site after calcination. The morphology was analyzed by X-Ray Diffractometer (XRD), Raman spectroscopy, Fourier Transform Infrared Spectrometer (FT-IR), cryo-Transmission Electron Microscopy (cryo-TEM), Field Emission Scanning Electron Microscope (FE-SEM), Specific Surface Area and Porosimetry Analyzer (BET), X-ray photoelectron spectroscopy (XPS), Potentiostat/Galvanostat, Fuel Cell Test Equipment, respectively. Therefore, adding p-phenylenediamine and glutaraldehyde to ferric chloride, and then calcining, the calcination temperature is 700°C, 1 hr, Ar. We denote the catalyst as FeNC-T-700. The Fe-N/C series catalysts showed excellent performance and stability for oxygen reduction reaction, which implies that it is a promising candidate as an electrocatalyst in PEMFC.

目錄
摘要 I頁
Abstract III頁
誌謝 V頁
目錄 VI頁
表目錄 IX頁
圖目錄 X頁
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 文獻回顧 3
2.1 燃料電池簡介 3
2.2 燃料電池原理 6
2.3 燃料電池系統 9
2.4 燃料電池種類 11
2.5 質子交換膜燃料電池 13
2.5.1 運作原理及特點 13
2.5.2 質子交換膜燃料電池構造及元件 17
2.5.3 質子交換膜性能 18
2.5.4 觸媒層 24
2.5.5 氣體擴散層 25
2.5.6 雙極板 27
2.5.7 膜電極組 28
2.6 非貴重金屬觸媒 29
2.6.1 氮摻雜至碳材料 29
2.6.2 氧氣還原反應 32
第三章 實驗 35
3.1 實驗藥品 35
3.2 儀器設備 38
3.3 實驗步驟 41
3.3.1 各種方法製備FeNC之觸媒製備 41
3.3.2 FeNC-T之觸媒進行鍛燒溫度比較製備 46
3.4 樣品命名 47
第四章 結果與討論 48
4.1 各種方法製備FeNC之觸媒分析 48
4.1.1 X光繞射光譜分析 (XRD) 48
4.1.2 拉曼光譜分析 (Raman) 49
4.1.3 表面型態分析 (TEM) 51
4.1.4 表面型態分析 (SEM) 53
4.1.5 電化學分析 (Linear Sweep Voltammetrys; LSVs) 54
4.2 各種溫度製備FeNC之觸媒分析 57
4.2.1 X光繞射光譜分析 (XRD) 57
4.2.2 有序性分析 (Raman) 58
4.2.3 表面性質分析 (BET) 59
4.2.4 表面型態分析 (TEM) 61
4.2.5 表面型態分析 (SEM) 62
4.2.6 束縛能分析 (XPS) 63
4.2.7 電化學分析 (Linear Sweep Voltammetrys; LSVs) 67
4.3 與商用20% Pt/C觸媒進行比較 69
4.3.1 電化學分析 (Linear Sweep Voltammetrys; LSVs) 69
4.3.2 電化學分析(電子轉移數、K-L曲線分析) 70
第五章 結論 72
參考文獻 74

表目錄

Table 2.4-1 燃料電池種類 12
Table 4.1.2-1 不同鍛燒溫度下觸媒之紊亂程度表 50
Table 4.1.5-1 不同方法下觸媒之起始電位、半波電位、極限電流密度數值表 56
Table 4.2.2-1 不同鍛燒溫度下觸媒之紊亂程度表 58
Table 4.2.3-1 FeNC-T-700和FeNC-T-800的結構性質 60
Table 4.2.6-1 不同鍛燒溫度下所製備出觸媒之XPS元素分析 64
Table 4.2.6-2 不同鍛燒溫度下所製備出觸媒之不同型態氮含量 66
Table 4.2.7-1 不同溫度下觸媒之起始電位、半波電位、極限電流密度數值表 68

圖目錄

Figure 2.3-1 燃料電池系統的示意圖。 10
Figure 2.5.1-1 聚合物電解質膜燃料電池（PEMFC） 14
Figure 2.5.2-1 碳紙氣體擴散層 17
Figure 2.5.3-1每年全球專利申請累積率(涉及Nafion和燃料電池) 23
Figure 2.5.5-1 碳紙氣體擴散層 26
Figure 2.5.6-1 分隔板 27
Figure 2.5.7-1 碳紙氣體擴散層示意圖 28
Figure 3.3.1.1-1 FeNC-MT-900觸媒製備流程圖 41
Figure 3.3.1.3-1 FeNC-T-900觸媒製備流程圖 43
Figure 3.3.1.4-1 FeNC-900觸媒製備流程圖 44
Figure 3.3.1.5-1 NC-900觸媒製備流程圖 45
Figure 3.3.2-1 FeNC-T觸媒進行各溫度鍛燒製備流程圖 46
Figure 4.1.1 不同方法製備下觸媒之XRD 48
Figure 4.1.2-1 不同方法製備下觸媒之拉曼光譜圖 49
Figure 4.1.3-1 不同方法製備(a) NC-T-900 (b) FeNC-900(c) FeNC-H-T-900 (d) FeNC-M-T-900 (e) FeNC-T-900 × 12 K觸媒之TEM型態分析圖 51
Figure 4.1.3-2 不同方法製備(a) NC-T-900 (b) FeNC-900(c) FeNC-H-T-900 (d) FeNC-M-T-900 (e) FeNC-T-900 × 30 K觸媒之TEM型態分析圖 52
Figure 4.1.4-1 不同方法製備(a) FeNC-T-900 (b) FeNC-900 (c) FeNC-HT-900 (d) FeNC-MT-900 (e) NC-T-900 觸媒之SEM型態分析圖 53
Figure 4.1.5-1 不同方法製備下觸媒與商用20% Pt/C觸媒在0.5 M H2SO4之ORR極化曲線圖，掃描速率:10 mV/s、轉速:1600 rpm、O2 56
Figure 4.2.1-1 不同鍛燒溫度下之XRD分析圖 57
Figure 4.2.2-1 不同鍛燒溫度下觸媒之拉曼光譜圖 58
Figure 4.2.3-1鍛燒700度與800度觸媒之(a) N2吸脫附等溫線圖 (b)孔徑分布圖 60
Figure 4.2.4-1 不同鍛燒溫度下(a) FeNC-T-600 (b) FeNC-T-700 (c) FeNC-T-800 (d) FeNC-T-900 (e) FeNC-T-1000 × 30 K觸媒之TEM型態分析圖 61
Figure 4.2.5-1 不同鍛燒溫度製備下 (a) FeNC-T-600 (b) FeNC-T-700 (c) FeNC-T-800 (d) FeNC-T-900 (e) FeNC-T-1000觸媒之SEM型態分析圖 62
Figure 4.2.6-1 不同鍛燒溫度下(a) FeNC-T-600、(b) FeNC-T-700、(c) FeNC-T-800、(d)FeNC-T-900、(e)FeNC-T-1000 觸媒之 XPS束縛能分析 65
Figure 4.2.6-2 不同鍛燒溫度下所製備出觸媒之不同型態氮含量 66
Figure 4.2.7-1 FeNC以各種鍛燒溫度製備觸媒與商用20% Pt/C觸媒在0.5 M H2SO4之ORR極化曲線圖，掃描速率:10 mV/s、轉速:1600 rpm、O2 68
Figure 4.3.1-1 FeNC-T-700與商用20% Pt/C觸媒在0.5 M H2SO4之ORR極化曲線圖，掃描速率:10 mV/s、轉速:1600 rpm、O2 69
Figure 4.3.2-1 商用20% Pt/C觸媒在0.5 M H2SO4 中(a) FeNC-T-700不同轉速之LSVs，掃描速率:10 mV/s、轉速: 900, 1200, 1600, 2500, 3600 rpm、O2 (b) K-L曲線 71

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