臺灣博碩士論文加值系統

本論文以硝酸與硫酸，將質子交換膜燃料電池之觸媒碳載體(XC-72)改質，酸處理後之碳載體再以含浸法被覆鉑觸媒，熱壓法製作膜電極組後組裝成單電池，探討不同酸處理對單電池電性影響。由傅立葉紅外線光譜儀(FT-IR)分析之結果顯示，未經酸洗改質前碳載體表面並無明顯的官能基存在，但經過硝酸改質碳載體表面後以FT-IR量測出其表面產生-OH官能基，有助於提升電性之效能，平緩電壓電流曲線下降之趨勢。但以混酸（硝酸/硫酸 = 3/1）改質碳載體表面後，其比表面積大幅下降，經過單電池組裝測試其電壓電流曲線圖顯示出電性曲線也明顯下降；以混酸（硝酸/硫酸 = 3/2）改質碳載體表面後，量測其比表面積下降幅度更大，電壓電流曲線下降也更明顯。結果顯示以硝酸於80℃經8小時酸洗後之碳載體以含浸法被覆鉑觸媒，再以熱壓法製做膜電極組後組裝成單電池測試其電性可得到最佳之效果。

In this thesis, we use nitric and sulfuric acid to treat the surface of the catalyst carbon support in PEMFC. The results of FT-IR analysis show that the surface of carbon support with pure nitric acid treatment does contain the –OH functional groups. The –OH functional groups make the platinum particles attached on the surface of carbon support more easily. By treatment of pure sulfuric acid or mixed acids with nitric acid, the surface area of carbon support decreases, and that is disadvantage for platinum particles attachment. The performances of the fuel cell fabricated with those treated carbons with acids show that the best is by using pure nitric acid in 80℃ for 8 hours, and sulfuric acid treatment showing negative effects.

摘要 ii
Abstract ii
致謝 iii
目錄 iv
圖目錄 vi
表目錄 viii
第一章 緒論 1
第一章 緒論 1
1-1前言 1
1-2 燃料電池的種類 2
1-3 質子交換膜燃料電池 6
第二章 文獻回顧 10
2-1 膜電極組(MEA) 10
2-1-1 觸媒層 10
2-1-2 氣體擴散層 14
2-1-3 質子交換膜 15
2-2 觸媒製備 16
2-3 流場板 17
2-4 研究動機 20
第三章 研究方法與步驟 23
3-1 實驗藥品 23
3-2 實驗儀器 23
3-3 實驗方法 24
3-4 實驗步驟 25
3-4-1 觸媒製備 25
3-4-2 MEA製備 27
3-4-3 單電池組裝 28
3-5 觸媒載體比表面積量測-氣體吸脫附法 29
3-6 紅外線光譜分析儀 33
3-7 電化學活性量測-循環伏安法 34
3-8 X光粉末繞射儀 36
3-9 燃料電池測試平台 37
第四章 結果與討論 39
4-1 碳載體酸洗後之特性影響 39
4-1-1 酸洗碳載體之比表面積變化 39
4-1-2 酸洗碳載體所產生出之官能基分析 40
4-2 含浸法被覆觸媒後之性質量測 43
4-2-1 X光粉末繞射儀測定分析 43
4-2-2 電化學測定儀分析 49
4.3 單電池電性量測 52
第五章 結論 58
參考文獻 59

[1] 翁鴻山、楊明長、紀景發，『以混合碳材為PtRu/C 觸媒擔體用於改良直接甲醇燃料電池中陽極觸媒層之效能』，國立成功大學化學工程學系碩士論文，2006
[2] 陳密、游宏偉，『以微波聚醇法被覆鉑觸媒在奈米碳管之特性分析與應用於直接甲醇燃料電池電極上之探討』，明新科技大學化學工程硏究所，2006
[3] 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, p.409, 1999
[4] 溫志湧、黃國瑋，『高熱傳導石墨膜應用於質子交換膜燃料電池之熱管理研究』，大葉大學機械工程研究所，2005
[5] Miachon S. and P. Aldebert, “Internal Hydration H2/O2 100 cm2 Polymer Electrolyte Membrane Fuel Cell,” J. Power Sources, Vol. 56, pp. 31-36, 1995
[6] Lee J.H., T.R. Lalk and A.J. Appleby, “Modeling Electrochemical Performance in Large Scale Proton Exchange Membrane Fuel Cell Stacks,” J. Power Sources, Vol. 70. pp.258-268, 1998
[7] Jalan V.M., “ Noble metal/vanadium alloy catalyst and method for making,” U. S. Patent, 4,202,934, 1980
[8] Jalan V.M. and D.A. Landsman,” Noble metal-refractory metal alloys as catalysts and method for making,” U.S. Patent, 4,186,110, 1980
[9] Landsman D.A., and F.J. Luczak, “Noble metal-chromium alloy catalysts and electrochemical cell,” U.S. Patent,”4,316,944, 1982
[10] Luczak F.J., and D.A. Landsman,” Ternary fuel cell catalysts containing platinum, cobalt and chromium,” U.S.Patent,4,447,506, 1984
[11] Luczak F.J., and D.A. Landsman,” Ordered ternary fuel cell catalysts containing platinum and cobalt and method for making the catalysts,” U.S. Patent, 4,677,092, 1987
[12] Murata, K., Kaneko, K., Kokai, F., Takahashi, K., Yudasaka, M., and Iijima, S., “Exploration of Carbon Nanocapsules “, Chem. Phys. Letters, 331, 14, 2000
[13] Yoshitake T., Y. Shimakawa, S. Kuroshima, H. Kimura, T. Ichihashi, Y. Kudo, D. Kasuya, K. Takahashi, F. Kokai, M. Yudasaka, and S. Iijima, Physica B.,” The Synthesis and Characterization Pt/C Cathode Catalysts for PEMFC ”, 323, 124, 2002
[14] Liang, Li, W., C., Qiu, J., Zhou, W., Han, H., Wei, Z., Sun, G., and Xin, Q., Carbon, “Vapor-Grown Carbon nano-Fiber as electrocatalyst support for Proton Exchange Membrane Fuel Cell “, 40, pp.791,2002. Angew. Chem. Int. Ed. 42, pp.4352, 2003
[15] Hyeon, T.; Han, S.; Sung, Y. E.; Park, K. W.; Kim, Y. W. Angew. Chem. Int. Ed., “Pt and Pt-Ru Nanoparticles Dispersed on Ethylenediamine Grafted Carbon Nanotubes as New Electrocatalysts: Preparation and Electrocatalytic Properties for Ethanol “, 42, 4352, 2003
[16] Pinna F., Catal. Today, 41 (1998) 129 and C. Perego, and P. Villa, Catal., “Synthesis of supported palladium catalysts“, Today, 34, pp.281, 1997
[17] Jackson S.D., J. Willis, G.D. Mclellan, G. Webb, M.B. Keegan, T. Moyes, S. Simpson, P.B. Wells, and R. Whyman, J. Catal., “Hydrogenation of Alkadienes and Poly-Enes”, 139, pp.191, 1993
[18] Perego C., and P. Villa, Catal., “Catalyst Preparation Methods ”, Today, 34, pp.281, 1997
[19] Rodriguez F., “The role of carbon materials in heterogeneous catalysis,” Carbon, 36, pp.159, 1998
[20] Starz K.A., E. Auer, Th. Lehmann, and R. Zuber, “Characteristics of platinum-based electrocatalysts for mobile PEMFC applications ”, J. Power Sources, 84, pp.167, 1999
[21] Takasu Y., W. Sugimoto, and Y. Murakami, “Electrocatalytic Oxidation of Methanol and Related Chemical Species on Ultrafine Pt and PtRu Particles Supported on Carbon”, Catal. Surveys from Asia, 7, pp.21, 2003
[22] Antolini E., Mat., “Carbon aerogel supported Pt–Ru catalysts for using as the anode of direct methanol fuel cells”, Chem. Phys., 28, pp.563, 2003
[23] Han S., Y. Yun, K.W. Park, Y.E. Sung, T. Hyeon,”Simple Solid-Phase Synthesis of Hollow Graphitic Nanoparticles and their Application to Direct Methanol Fuel Cell Electrodes”, Adv. Mater., 15, pp.1922, 2003
[24] Hyeon T., S. Han, Y.E. Sung, K.W. Park, Y.W. Kim, “High-Performance Direct Methanol Fuel Cell Electrodes using Solid-Phase-Synthesized Carbon Nanocoils”, Ange. Chem. Int. Edit., 42, pp.4352, 2000
[25] Liu C., H.T.Cong, F. Li , “Semi-continuous synthesis of single-walled Carbon nanotubes by a hydrogen arc discharge method”, Carbon, 37, pp.1865, 1999
[26] Liu C., Hui-Ming Cheng, H. T. Cong, F. Li, G. Su, B. L. Zhou, and M. S., “Dresselhaus Synthesis of Macroscopically Long Ropes of Well-Aligned Single-Walled Carbon Nanotubes”, Adv. Mater., 12, pp.1190, 2000
[27] Endo M., C. Kim, K. Nishimura, T. Fujino, K. Miyashita, ”Recent development of carbon materials for Li ion batteries” , Carbon, 38, pp.183, 2000
[28] Hayward Ryan C, Peter Alberius-Henning, Bradley F. Chmelka and Galen D. Stucky “The current role of mesostructures in composite materials and device fabrication,” Micropor. Mesopor. Mater., 44, pp.619, 2001
[29] 陳士堃、林信全，『使用磁控濺鍍法製備燃料電池金屬雙極板鎳鋁鍍層之研究』，逢甲大學材料科學與工程學系碩士論文，2005年
[30] Ogumi Z., T. Kuroe, Z.I. Takehara, J. Electrochem. Soc., 132, pp.2601, 1985
[31] Kim H., J.N. Park, W.H. Lee, ”Preparation of platinum-based electrode catalysts for low temperature fuel cell”, Catalysis Today., 87, pp.237 , 2003
[32] Sarma L.S., T. D. Lin, Y.W. Tsai, J. M. Chen, B. J. Hwang, “Carbon-supported Pt-Ru catalysts prepared by the Nafion stabilized alcohol-reduction method for application in direct methanol fuel cells”, J. Power Sources., 139, pp.44 ,2005
[33] Lizcano-Valbuena W.H., V. A. Paganin, E. R. Gonzalez , “Methanol electro-oxidation on gas diffusion electrodes prepared with Pt-Ru/C catalysts”, Electrochimica Acta., 47, pp.3715 ,2002
[34] Lizcano-Valbuena W.H., V. A. Paganin , Carlos A.P. Leite ,F. Galembeck , E. R. Gonzalez , ”Catalysts for DMFC: relation between morphology and electrochemical performance”, Electrochimica Acta., 48, pp.3869 ,2003
[35] Lizcano-Valbuena W.H., D. C. de Azevedo, E. R.Gonzalez, ”Supported metal nanoparticles as electrocatalysts for low-temperature fuel cells, Electrochimica Acta., 49, pp.1289 ,2004
[36] Deivaraj T.C. and Jim Yang Lee, “Preparation of carbon-supported PtRu nanoparticles for direct methanol fuel cell applications – a comparative study”, J. Power Sources., 142, pp.43 ,2005
[37] Zhou Z., W. Zhou, S. Wang , G. Wang , L. Jiang, H.Li, G. Sun, Q. Xin, “Preparation of highly active 40 wt% Pt/C cathode electrocatalysts for DMFC via different routes”, Catalysis Today., 93–95, pp.523 ,2004
[38] Roth C., N. Martz, H. Fuess,” Characterization of different Pt–Ru catalysts by X-ray diffraction and transmission electron microscopy”, Phys. Chem. Chem. Phys., 3, pp.315 ,2001
[39] Takasu Y., T. Kawaguchi, W. Sugimoto, Y. Murakami, “Effects of the surface area of carbon support on the characteristics of highly-dispersed Pt-Ru particles as catalysts for methanol oxidation”, Electrochimica Acta., 48, pp.3861 ,2003
[40] Liu Z., L. M. Gan, L. Hong, W. Chen, J. Y. Lee,“Carbon-supported Pt nanoparticles as catalysts for proton exchange membrane fuel cells”, J. Power Sources., 139, pp.73 ,2005
[41] Philip Hentall L., J. Barry Lakeman, O. Gary Mepsted, and L. Paul Adock, ”New materials for polymer electrolyte membrane fuel cell current collectors”, Journal of Power Source, 80, pp.235-241, 1999
[42] Coloma F., A. Sepulveda-Escribano, F. Rodriguez-Reinoso, J. Catal., 154, pp.299, 1995
[43] Kyotani T., S. Nakazaki, W.H. Xu, and A. Tomita, Carbon, pp.771, 2001
[44] Yasuda K., and Y. Nishimura, “The deposition of ultrafine platinum particles on carbon black by surface ion exchange - increase in loading amount,” Materials Chem. and Phys. pp.921, 2003
[45] Zhang Jian, Ge-Ping Yin , Zhen-Bo Wang, Qin-Zhi Lai, Ke-Di Cai,” Effects of hot pressing conditions on the performances of MEAs for direct methanol fuel cells”, Journal of Power Sources 165, pp.73–81, 2007
[46] Lizcano-Valbuena W.H., V.A. Paganin , Carlos A.P. Leite ,F.Galembeck , E. R. Gonzalez, ”Catalysts for DMFC: relationbetween morphology and electrochemical performance”, Electrochimica Acta., 48, pp.3869, 2003
[47] Ko Tse-Hao, Yuan-Kai Liao, and Ching-Han Liu, “Effects of Fabricated Gas Diffusion Layers with Different Reinforce Materials in Proton Exchange Membrane Fuel Cell (PEMFC)”, Energy & Fuels, 2008
[48] 李明三、呂俊逸，『質子交換膜燃料電池研究-MEA的製造和性能分析』，國立中山大學機械工程研究所碩士論文，2000
[49] “Nova 4200 Operation Manual”, Quantachrome, 2003
[50] Xing Yangchuan, “Synthesis and Electrochemical Characterization of Uniformly Dispersed High Loading Pt Nanoparticles on Sonochemically-Treated Carbon Nanotubes, J. Phys. Chem. B 108, pp.19255-19259, 2004