臺灣博碩士論文加值系統

　　直接甲醇燃料電池目前仍有（1）電極觸媒活性不夠高，（2）觸媒會被中間產物一氧化碳毒化及（3）甲醇會滲透過質子交換膜等三個問題亟待解決。若能研製出高活性之電極觸媒不僅可解決第一個問題，也可大幅降低甲醇滲透現象。我們選擇了多數文獻報導有抗一氧化碳毒化能力的鉑和釕雙金屬觸媒，並嘗試多種不同的製備條件，希望能改進觸媒的效能。在製備觸媒方面，我們是用含浸還原法來製備；而對於觸媒的特性分析我們採用XRD、SEM、TEM作特性分析，分析觸媒之結構與觸媒中金屬之粒徑和分散性。製成電極觸媒後，作電化學分析，在不同溫度下測試電極觸媒的甲醇電催化活性。

　　實驗的結果顯示：含浸溶液的濃度及體積皆有最適值。採用傳統一次含浸法時，以濃度約為0.06 M含浸碳黑時最適當。在相同的金屬含量的條件下，採用多次含浸所製得的觸媒電極的活性，明顯地比採用傳統一次含浸法所製成的觸媒電極的活性好（電流密度約高17-45%）。而以多次含浸來製備觸媒，因含浸濃度較小，所以Pt-Ru之分散性較好，其粒徑也較小，所以可以使觸媒的催化與電化學性能提升。在碳材的選擇上，以奈米碳管為擔體比以傳統碳黑為擔體性能好；若同時將奈米碳管與碳黑以各一半的比例同時含浸鉑與釕製備觸媒時，其性能更佳。實驗結果也顯示：隨著操作溫度上升，電流密度會提高。

　Up to the present, the direct methanol fuel cell still has the following drawbacks to be overcome:(1) the activity of electrocatalyst is low,(2) the electrocatalyst is susceptible to CO which is a byproduct, and (3) the methanol crossover is high. Note that the problem of methanol crossover can be mitigated if a highly active electrocatalyst can be developed. This study is for developing an electrocatalyst with a high performance. We chose the Pt-Ru bimetal catalyst which was generally accepted to have a high resistance to CO poisoning as a target. We prepared the catalysts by two different impregnation methods and under different conditions. The method XRD、SEM and TEM were employed to characterize the catalysts, including their structures and the particle size of metal on the catalysts. The electrocatalytic activities of the electrocatalyst prepared were tested in different temperatures.

　Experimental results reveal that there exist an optimal concentration and volume of the metallic salt solution for impregnation in the preparation of Pt-Ru/carbon catalyst. The optimal concentration is about 0.06 M. When the method of multiple impregnation was employed for preparing the catalyst, it was found that the catalyst thus prepared would give a better electrochemical performance than that by single impregnation. The reason that multiple impregnation gives a better result is attributed to a higher metal dispersion and a smaller metal grain size. In the selection of carbon materials, nano carbon tube was found to have a higher performance than carbon black. When the mixture of CNT and carbon black with a ratio of 1：1 was used of the support, the prepared electrocatalyst gave the highest electrocatalytic activity.

中文摘要-----------------------------------------------------I
英文摘要-----------------------------------------------------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---------------------------------------------1
1.2.1 燃料電池發展歷史-------------------------------1
1.2.2 燃料電池特點-----------------------------------2
1.2.3 燃料電池種類-----------------------------------3
1.3 直接甲醇燃料電池-------------------------------------8
1.3.1 質子交換膜------------------------------------10
1.3.2 陰極部分--------------------------------------14
1.3.3 陽極部分--------------------------------------14
1.3.4 陽極觸媒製備方式------------------------------19
1.4 研究動機與目的--------------------------------------21
第二章 原理-------------------------------------------------23
2.1 直接甲醇燃料電池工作原理----------------------------23
2.2 甲醇電催化氧化機制----------------------------------24
2.3 電池的極化現象--------------------------------------30
2.3.1 活性過電位------------------------------------30
2.3.2 濃度過電位------------------------------------31
2.3.3 歐姆過電位------------------------------------32
2.3.4 極化曲線--------------------------------------33
2.4 電化學原理------------------------------------------34
2.4.1 恆電位分析儀----------------------------------34
2.4.2 線性掃描伏安法--------------------------------36
第三章 實驗設備與步驟---------------------------------------39
3.1 藥品與材料------------------------------------------39
3.2 儀器設備--------------------------------------------40
3.3 實驗方法--------------------------------------------41
3.3.1 碳材之前處理----------------------------------41
3.3.2 Pt50-Ru50/C 觸媒製備--------------------------42
3.3.3 電極觸媒層製備--------------------------------46
3.3.4 觸媒特性分析----------------------------------46
3.3.4.1 X 光繞射分析(XRD)-----------------------46
3.3.4.2 掃瞄式電子顯微鏡(SEM)-------------------46
3.3.4.3 穿透式電子顯微鏡(TEM)分析---------------46
3.3.5 電化學分析------------------------------------47
第四章 結果與討論-------------------------------------------49
4.1 觸媒特性分析----------------------------------------49
4.1.1 XRD繞射分析-----------------------------------49
4.1.2 SEM分析---------------------------------------54
4.1.3 TEM分析---------------------------------------58
4.2 觸媒電極之電化學活性測試----------------------------64
4.2.1 單次含浸部分----------------------------------64
4.2.2 多次含浸--------------------------------------69
4.2.3 添加奈米碳管----------------------------------74
第五章 結論與未來研究方向----------------------------------79
參考文獻----------------------------------------------------82
附錄一 EDS分析結果-----------------------------------------86

1. 鄭耀宗, 徐耀昇, 燃料電池技術進展的現況分析, 節約能源論文發表會論文專輯, pp.409-422, 1999年.
2. J. Giner, C. Hunter, J. Electrochem. Soc., 116(1969), 1124.
3. E. A. Ticianelli, C. R. Derouin, A. Redondo, and S. Srinivasan, J. Electrochemical. Soc., 135(1988), 2209.
4. A. J. Appleby, F. R. Folkes, Fuel Cell Handbook, Van Nostrand Reinhold, New York,1989.
5. 盧敏彥, 黃俊傑, 化工技術, 第十卷(2000),第六期.
6. Z. Ogumi, T. Kuroe, Z.I. Takehara, J. Electrochem. Soc., 132(1985), 2601.
7. A. Kuver, K. Potje-Kaamloth, Electrochim. Acta, 43(1998), 2527.
8. J. S. Wainright, J. T. Wang, D. Weng, R. F. Savinell, M. Litt, J. Electrochem. Soc., 142(1995), 121.
9. D. Weng, J. S. Wainright, U. Landau, R. F. Savinell, J. Electrochem. Soc., 143(1996), 1260.
10. J. Shim, D. Y. Yoo, J. S. Lee, Electrochim. Acta, 45(2000), 1943.
11. A. Hamnett, Catal. Today, 38(1997), 445.
12. N.M. Markovic, P. N. Ross Jr., Surface Science Reports, 45(2002), 117.
13. L. Carrette, K. A. Friedrich, U. Stimming, Chemphyschem, 1(2000), 162.
14. K. Ledjeff-Hey, A. Heinzel, J. Power Sources, 61(1996), 125.
15. M. Watanabe, Y. Furuuchi, S. Motoo, J. Electrochem. Chem., 191(1985), 367.
16. T. Iwasita, Electrochim. Acta, 47(2002), 3663.
17. W. F. Lin, M. S. Zei, M. Eiswirth, G. Ertl, T. Iwasita, W. J. Vielstich, Phys. Chem. B, 103(1999), 6968.
18. J. W. Long, R. M. Strou, K. E. Swider-Lyons, D. R. Rolison, J. Phys. Chem. B, 104(2000), 9772.
19. Z. Liu, J. Y. Lee, M. Han, W. Chen, L. M. Gan, J. Mater. Chem., 12(2002), 2453.
20. M. Watanabe, M. Uchida, S. Motoo, J. Electroanal. Chem., 29(1987), 395.
21. Y. Takasu, W. Sugimoto, Y. Murakami, Catal. Surveys, 7(2003), 21.
22. M. P. Hogarth, T. R. Ralph, Platinum Met. Rev., 46(2002), 146.
23. A. Hamnett, Catal. Today, 38(1997), 445.
24. B. Gurau, R. Viswanathan, R. Liu, T. J. Lafrenz, K. L. Ley, E. S. Smotkin, J. Phys. Chem. B, 102(1998), 9997.
25. A. S. Arico, Z. Poltarzewski, H. Kim, A. Morana, N. Giordano, V. Antonucci, J. Power Sources, 55(1995), 159.
26. K. L. Ley, R. liu, C. Pu, Q. Fan, N. Leyarovska, C. Segre, E. S. Smotkin, J. Electrochem. Soc., 144(1997), 1543.
27. A. S. Arico, A. Morana, N. Giordano, Z. Poltarzewski, H. Kim, J. A. Electrochem., 26(1996), 959.
28. J. H. Choi, K. W. Park, B. K. Kwon, Y. E. Sung, J. Electrochem. Soc., 150(2003), A973.
29. K. W. Park, Y. E. Sung, S. Han, Y. K. Yun, T. Hyeon, J. Phy. Chem. B, 108(2004), 939.
30. K. Kinoshita, P. Stonehart, Modern Aspect of Electrochem., 12, Plenum Press: New York(1996).
31. T. Yoshitake, Y. Shimakawa, S. Kuroshima, H. Kimura,; T. Ichihashi, Y. Kubo, D. Kasuya, K. Takahashi, Physica B, 323(2002), 124.
32. W. Li, C. Liang, W. Zhou, J. Qiu, Z. H. Zhou, G. Sun, Q. Xin, J. Phy. Chem. B, 107(2003), 6292.
33. Y. C. Liu, X. P. Qiu, Y. Q. Huang, W. T. Zhu, J. Power Sources, 111(2002), 160.
34. J. M. Petroski, Z. L. Wang, T.C. Green, M. A. El-Sayed, J. Phys. Chem., 102(1998), 3316.
35. M. Watanabe, M. Uchida, S. Motoo, J. Electroanal. Chem., 29(1987), 395.
36. A. S. Arico, Z. Poltarzewski, H. Kim, A. Morana, N. Giordano, V. Antonucci, J. Power Sources, 55(1995), 159.
37. S. A. Lee, K. W. Park, J. H. Choi, B. K. Kwon, and Y. E. Sung, J. Electrochem. Soc., 149(2002), A1299.
38. M. Gotz, H. Wendt, Electrochim. Acta, 43(1998), 3637.
39. M. J. Escudero, E. Hontanon, S. Schwartz, M. Boutonnet, L. Daza, J. Power Sources, 106(2002), 206.
40. M. Kishida, K. Umakoshi, J. I. Ishiyama, H. Nagata, K. Wakabayashi, Catalysis Today, 29(1996), 355.
41. T. Freelink, W. Visscher, J. A. R. Van Veen, Surf. Sci., 335(1995), 353.
42. Y. Zhu, H. Uchida, T. Yajima, M. Watanabe, Langmuir, 17(2001), 146.
43. T. Yajima, H. Uchida, M. Watanabe, J. Phys. Chem. B, 108(2004), 2654.
44. T. E. Springer, D. Raistrick, J. Electrohem. Soc. 136(1989), 1594.
45. K. W. Park, B. K. Kwon, J. H. Choi, Y. M. Kim, Y. E. Sung, J. Power Sources, 109(2002), 439.
46. T. Bewer, T. Beckmann, H. Dohle, J. Mergel, D. Stolten, J. Power Sources, 125(2004), 1.
47. J. Kim, S. M. Lee, S. Srinivasan, J. Electrochem. Soc., 142(1995), 2670.
48. M. D. Bernardi, M. W. Verbrugge, J. Electrochem. Soc., 139(1992), 2477.
49. 胡啟章, 電化學原理與方法, 五南書局, 台北, 2002年.
50. 陳慕辰, 直接甲醇燃料電池陰陽兩極阻抗分析, 國立成功大學化工系碩士論文, 2004年.
51. 張書銘, 支撐在鉑釕雙金屬觸媒的製備與鑑定, 國立清華大學化學系碩士論文, 2004年.
52. 林賜岱, 直接甲醇燃料電池陽極反應機制之研究, 國立台灣科技大學化工系碩士論文, 2002年.
53. 黃鎮江, 燃料電池, 全華科技圖書公司, 台北, 2003年.