規則多孔碳應用在燃料電池陰極觸媒擔體之研究

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余政哲(Jheng-Jhe Yu) 查詢紙本館藏

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能源工程研究所

論文名稱

規則多孔碳應用在燃料電池陰極觸媒擔體之研究
(Ordered Porous Carbon as The Catalyst Support for Fuel cells)

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摘要(中)

目錄
本研究利用模板法製作出整齊的多孔碳並應用於燃料電池陰極觸媒擔體。首先以四種不同粒徑的矽微粒球做為模板，經由酚醛樹脂填入、碳化後可得四種不同孔徑的多孔洞碳。還原白金奈米粒於多孔洞碳上後探討不同孔徑的多孔洞碳對觸媒有哪些影響。
從SEM圖可發現多孔洞碳的孔徑及結構與模板形狀、尺寸大小及排列方式有關係，氣體吸附分析藉由BET公式可計算出多孔洞碳的比表面積，其結果皆比商用碳黑XC-72R高，且值隨著碳材孔徑變小有變大的趨勢。還原觸媒並確定擔載量皆在20wt%附近後，利用TEM影像進行觸媒粒徑統計，發現使用醇類還原法可成功製備出分散均勻且小顆的白金觸媒，其平均粒徑隨著碳材表面積變大有變小的趨勢，與XRD繞射峰半高寬逐漸變緩符合，CV的分析更能證明小顆粒觸媒能提供較多的活性表面積。此外，XPS分析的化學位移現象判斷為金屬氧化態含量較高所導致。LSV分析可比較觸媒在陰極的活性，發現ORR受到觸媒顆粒大小、活性表面積、金屬氧化物含量及碳材結構所共同影響。以CV長時間測試來觀察觸媒穩定性，發現比表面積較大的碳材其觸媒活性表面積變化較不大。

摘要(英)

Abstract
We used template transfer method to fabricate ordered porous carbons and used the porous carbon as the catalyst support for fuel cell application. At first, four different size silica spheres were synthesized as the templates and finally obtained ordered porous carbon with different pore size after the procedure of phenolic formaldehyde resin injection, carbonization and tamplate etching. In this study we mainly focus on the effects of different pore size porous carbons on the catalyst.
The SEM images showed that the pore size and structure of the porous carbon were affected by the shape, partical size and the arrangment of the template. ASAP analysis indicated that the ordered porous carbons had higher BET surface area than commercial carbon black and the value increased with decreasing pore size of porous carbon. Small Pt nanoparticles (NPs) with uniform dispersion were successfully grown on the orderd porous carbons by using polyol reducing method. Pt loadings for all samples were all close to 20wt%. Particle sizes of Pt were measured from TEM images. The mean particle size of Pt was found to be smaller when grown on higher surface area carbon. The same trend was also observed from the XRD results. CV analysis further proved that ECSA increased when the Pt NPs became smaller. In addition, the high percentage of Pt-oxides caused the chemical shift in XPS analysis. Therefore, the Pt NPs size, ECSA, Pt-oxide amount and support structure all can influence the oxygen reduction reaction (ORR) activity. The long term test was used to test the catalytic stability and we found that ECSA was much stable for Pt grown on the higher surface area porous carbon.

關鍵字(中)

★ 氧氣還原反應
★ 燃料電池
★ 觸媒擔體
★ 多孔洞碳

關鍵字(英)

★ porous carbon
★ catalyst support
★ fuel cell
★ ORR

論文目次

目錄
摘要.............................................i
Abstract.........................................ii
誌謝.............................................iv
目錄.............................................v
表目錄...........................................viii
圖目錄...........................................ix
第一章緒論.....................................1
1-1 前言...........................................1
1-2 燃料電池簡介...................................2
1-3 質子交換膜燃料電池構造及原理...................3
1-4 研究目的.......................................5
第二章文獻回顧.......................................6
2-1 觸媒層介紹及反應機制...........................6
2-1-1. 觸媒層結構.....................................6
2-1-2. 陽極觸媒.......................................6
2-1-3. 陰極觸媒.......................................7
2-1-4. 目前陰極觸媒遭遇的問題.........................8
2-2 中孔洞碳.......................................9
2-3 多孔洞碳應用在燃料電池.........................10
2-3-1. 碳擔體的比較...................................10
2-3-2. 多孔洞碳材用於燃料電池.........................11
2-4 多孔洞碳製作...................................12
2-4-1. 矽微粒球製作...................................13
2-4-2. 碳前驅物的填入.................................15
2-5 觸媒製備方式...................................16
第三章研究方法與進行步驟.............................19
3-1 研究方法.......................................19
3-2 實驗步驟.......................................19
3-3-1. 模板製作.......................................19
3-3-2. 填料及碳化.....................................20
3-3-3. 模板移除.......................................20
3-3 鉑顆粒合成.....................................20
3-4 分析儀器.......................................21
3-5-1. 掃描式電子顯微鏡(SEM)..........................22
3-5-2. 比表面積及孔洞結構分析.........................23
3-5-3. X-ray 繞射分析(XRD)............................27
3-5-4. 穿透式顯微鏡(TEM)..............................29
3-5-5. 熱重損失儀(TGA)................................29
3-5-6. X光光電子能譜儀(XPS)...........................30
3-5-7. 電性分析.......................................30
第四章結果與討論.....................................34
4-1 多孔洞碳的製備及結果...........................34
4-1-1. 矽球粒徑的影響.................................34
4-1-2. 不同孔徑的多孔洞碳比較.........................35
4-2 觸媒還原在多孔洞碳的結果.......................38
4-3 XPS分析........................................40
4-4 觸媒還原在多孔洞碳的性能表現...................41
4-4-1. CV分析結果.....................................41
4-4-2. LSV分析結果....................................42
4-5 長時間測試.....................................44
第五章結論與未來方向.................................46
參考文獻...............................................48
表目錄
表2-1. 鉑顆粒在不同碳材上的表面積.....................59
表2-2. 還原在不同擔體上的鉑顆粒大小比較...............59
表2-3. 使用不同擔體的鉑氧化電流密度...................59
表4-1. 不同尺寸的矽微粒製備參數.......................62
表4-2. 不同樣品的孔徑大小及比表面積比較...............62
表4-3. 不同樣品的活性表面積及觸媒粒徑關係.............63
表4-4. 不同樣品Pt4f7/2能階峰位置及價態組成比例比較....63
圖目錄
圖2-1. 表面積比較圖...................................65
圖3-1. 矽球模板製作流程圖.............................66
圖3-2. 碳化流程圖.....................................66
圖3-3. 乙二醇的氧化反應路徑...........................67
圖3-4. 觸媒還原流程圖.................................67
圖3-5. 樣品製備及測試流程圖...........................68
圖3-6. 電子束與試片作用示意圖.........................68
圖3-7. 等溫吸附曲線...................................69
圖3-8. 不同孔徑形狀的吸附曲線.........................69
圖3-9. X-ray射入晶體中反射造成波程差示意圖............70
圖3-10. 循環伏安法裝置圖...............................70
圖3-11. Pt/C在0.1M過氯酸電解液中的CV曲線...............71
圖4-1. 矽微粒SEM圖，順序同樣品編號....................72
圖4-2-1. A樣品小、大倍率SEM圖(孔洞約320nm).............73
圖4-2-2. B樣品小、大倍率SEM圖(孔洞約280nm).............74
圖4-2-3. C樣品小、大倍率SEM圖(孔洞約180nm).............75
圖4-2-4. D樣品小、大倍率SEM圖(孔洞約60nm)..............76
圖4-3. 等溫吸脫附曲線................................77
圖4-4. 多孔洞碳與商用碳黑NLDFT孔徑分佈圖.............78
圖4-5. 使用不同還原劑還原Pt在AB碳上的CV結果比較......79
圖4-6. 各樣品在熱重分析儀觀察碳燒掉後的殘重量........79
圖4-7. 使用甲醛還原觸媒於各種碳XRD圖.................80
圖4-8-1. AB樣品低、高倍率TEM影像圖.....................81
圖4-8-2. A樣品低、高倍率TEM影像圖......................82
圖4-8-3. B樣品低、高倍率TEM影像圖......................83
圖4-8-4. C樣品低、高倍率TEM影像圖......................84
圖4-8-5. D樣品低、高倍率TEM影像圖......................85
圖4-8-6. ETEK樣品高倍率TEM影像圖.......................86
圖4-9. TEM晶格相影像，順序如樣品編號(scale bar=5 nm).87
圖4-10. 各樣品觸媒顆粒尺寸統計結果，順序如樣品編號....88
圖4-11. 各樣品在C1s軌域上的束縛能比較圖...............89
圖4-12. 各樣品在Pt4f軌域上的束縛能比較圖..............89
圖4-13. 各觸媒樣品的Pt4f光電子能譜分峰比較圖..........90
圖4-14. 各樣品的CV性能圖比較圖........................91
圖4-15. 各樣品LSV-ORR性能比較圖.......................91
圖4-16. 反應物濃度變化示意圖..........................92
圖4-17. 各樣品LSV-ORR性能局部比較圖...................92
圖4-18. CV長時間測試ECSA變化圖........................93
圖4-19. CV長時間測試ECSA衰退變化圖(百分比)............93
圖4-20. CV長時間測試後ETEK於高倍率TEM影像圖...........94
圖4-21. CV長時間測試後A樣品於高倍率TEM影像圖..........94
圖4-22. CV長時間測試後B樣品於高倍率TEM影像圖..........95
圖4-23. CV長時間測試後C樣品於高倍率TEM影像圖..........95
圖4-24. CV長時間測試後D樣品於高倍率TEM影像圖..........96
圖4-25. 樣品CV長時間測試後顆粒尺寸統計結果............97
圖4-26. CV長時間測試後自製樣品於低倍率TEM影像圖.......98

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指導教授

曾重仁(Chung-jen Tseng)

審核日期

2011-7-26

推文