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研究生:鄭雁文
研究生(外文):Yen-Wen Cheng
論文名稱:磷鉬酸/碳黑觸媒載體於鋅-空氣燃料電池之電極特性分析
論文名稱(外文):Characteristics of Carbon-Based Air Electrodes Containing H3PMo12O40.xH2O for Zinc-Air Fuel Cells
指導教授:薛富盛薛富盛引用關係
指導教授(外文):Fuh-Sheng Shieu
學位類別:碩士
校院名稱:國立中興大學
系所名稱:材料科學與工程學系所
學門:工程學門
學類:綜合工程學類
論文種類:學術論文
論文出版年:2009
畢業學年度:97
語文別:中文
論文頁數:84
中文關鍵詞:鋅-空氣燃料電池磷鉬酸/碳黑
外文關鍵詞:Zinc-air fuel cellsH3PMo12O40/CB
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近年來,環保意識抬頭,全世界都投入於綠色能源的研究。由於對環境友善以及低汙染,使得太陽能、氫能與燃料電池為目前的三大研究主流。在燃料電池的研究中,鋅空氣燃料電池由於具有重量輕以及結構簡單等優點,為目前科學研究的重點之一。鋅空氣燃料電池之效能取決於其電極、電解液以及觸媒特性,因此觸媒反應效率的改善為鋅空氣燃料電池研究的重點。磷鉬酸觸媒(H3PMo12O40.xH2O;簡稱PMo12)為目前被廣泛研究的新型觸媒。目前已有相關研究發表將磷鉬酸觸媒(PMo12)應用於質子交換膜燃料電池(PEMFC)以及直接甲醇燃料電池(DMFC)之電極觸媒以提升電池效能。本論文將強氧化劑磷鉬酸觸媒(H3PMo12O40.xH2O;簡稱PMo12)應用於鋅空氣燃料電池之空氣陰極部份,探討其是否可達催化效果,進而改善鋅-空氣燃料電池之大電流放電效能、提升陰極氧氣還原速率。
本研究以含浸法將磷鉬酸/碳黑(PMo12/C)製成觸媒載體空氣陰極,並且為瞭解磷鉬酸觸媒於鋅-空氣燃料電池有否達至催化效應,將其與觸媒MnO2作一對比。接著探討其燒結溫度對於PMo12/C空氣陰極膜的影響、不同負載電流及不同電解液之下有何種性能表現。利用電化學分析儀於1大氣壓及室溫下,進行50 mA定電流放電與電池壽命測試,並以X光繞射儀(X-Ray Diffractometer, XRD)分析與場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FESEM)分析PMo12/C晶體結構及表面形貌。
研究結果發現,PMo12/C觸媒載體之空氣陰極與MnO2/C有相同的催化特性,皆可加速氧氣的還原反應,甚且有較佳的電池特性,因此證實PMo12觸媒可應用於鋅空氣燃料電池中以提升其效能。而電池測試時,供給之負載電流越大,其電池電位隨之下降,電池壽命亦變短;結果也顯示出燒結溫度會影響PMo12/C觸媒載體之結構及催化特性,由XRD及TGA/DTA分析結果得知,於375℃時結構開始逐漸變化產生另一相三氧化鉬(MoO3),而電池測試結果亦發現未熱處理有最佳的電化學行為。再者,於不同電解液下進行電池測試,結果顯示電解液為KOH時有最佳的電池電性。
In the past decades, since the rise of environmental consciousness around the world, many efforts have been devoted into the discovery and development of clean energy technologiesm. Within them, solar energy、hydrogen energy and fuel cell, which are environment-friendly and zero-polluted, are the three mainstreams. Zinc-air fuel cell is one of the focal point of fuel cell studies. The performance of zinc-air fuel cell significantly depends on the characteristic of electrode、electrolyte and catalyst. Hence, the investigation of improving the transformation rate of catalyst plays a significant role to decide the range of future application of zinc-air fuel cell. H3PMo12O40.xH2O (PMo12) catalyst was widely to be applied into various electrochemical applications. There are several references has been reported to reveal that adding phosphomolybdic acid hydrate PMo12 in the electrode of proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cell (DMFC) could promote performance. Under this concept, the study aims to add H3PMo12O40.xH2O (PMo12), a strong oxidizing agent, into the cathode of zinc-air fuel cell to serve as catalyst to improve the electrocatalytical efficiency by increasing the oxygen reduction rate that can increase the current density.
The PMo12/C cathodes are prepared by liquid impregnation method and then compared with MnO2/C cathodes for analyzing the effects of PMo12/C. Thereafter, the efficiency of PMo12/C cathodes for zinc-air fuel cell in different annealing temperatures、different loading currents and different electrolytes is investigated. The discharging behavior under the steady current of 50 mA and the life time properties were measured by the Galvanostat system at 1 atm and 27 ℃. The structure and surface morphologies of PMo12/C cathodes were characterized by using X-ray diffractometer (XRD) and field emission scanning electron microscopy (FE-SEM).
According to the results, PMo12/C cathodes show the same catalysis ability as MnO2/C cathodes, but PMo12/C cathodes reveal better efficiency. Therefore, the result proves the idea that PMo12/C serves as the cathode catalyst in zinc-air fuel cell is practical. In the single cell test, the potential is going down with increasing loading current, and the life time is becoming shorter. Specifically, form the results evidences, the annealing temperature is a factor of structure and catalysis of PMo12/C. From the XRD and TGA/DTA results, we know the PMo12 structure changes into molybedenum oxide (MoO3) at 375℃. And from the single test results, it is found the best electrochemical performance on unannealing PMo12/C cathode. Moreover, in single cell test with different electrolytes, it is also found the best cell behavior with potassium hydroxide (KOH) electrolyte.
中文摘要……………………………………………………………………………I
Abstract……………………………………………………………………………II
總目錄………………………………………………………………………………IV
圖目錄………………………………………………………………………………VI
表目錄……………………………………………………………………………VIII
第一章 緒論…………………………………………………………………………1
1-1前言………………………………………………………….………………1
1-2 研究動機……………………………………………………………………4
第二章 文獻回顧……………………………………………………………………6
2-1 鋅-空氣燃料電池之簡介……………………………………………………6
2-1-1鋅空氣電池之總類……………………………………………………7
2-1-2鋅空氣燃料電池的特性與優缺點……………………………………7
2-2 鋅-空氣燃料電池的結構……………………………………………………8
2-2-1鋅電極………..………………………………………………………8
2-2-2 空氣電極…………..…………………………………………………11
2-2-3電解質…………….…………………………………………………16
2-3 鋅-空氣燃料電池的電化學反應..…………………………………………17
2-3-1鋅極之氧化與還原……..……….……………………………….17
2-3-2空氣陰極的反應機制………………………………………………17
2-3-3影響電池性能的因素……..……………………………………….21
2-4雜多酸-十二磷鉬酸……………………………………………………….23
2-4-1 磷鉬酸之物化性質………….……….…………….……………….23
2-4-2 雜多酸-磷鉬酸之簡介…….………….…………….……………….25
2-4-3 雜多酸-磷鉬酸之催化機制.………….…………….……………….28
第三章 實驗方法及步驟……………………………………………………………33
3-1 藥品與材料………………………………………………………………..33
3-2 實驗儀器與設備………………………………………………………….34
3-3 實驗步驟………………………………………………………………….35
3-3-1實驗前準備….……………………………………………………36
3-3-2空氣陰極之製備………………………………..…………………37
3-3-3組裝成單電池模組.………….……………………………………42
3-4 實驗分析……………………………………………………………….44
3-4-1實驗方法……………………………………………………………44
3-4-2實驗分析儀器……………………………………………………….44
第四章 結果與討論…………………………………………………………………46
4-1 載體(C)與磷鉬酸(H3PMo12O40.xH2O)之特性分析………….………….46
4-1-1 熱重分析……..…..………….……….…………….……………….46
4-1-2 X光繞射分析………….….………….…………….……………….50
4-2觸媒的影響……………………………………………………………53
4-2-1 單電池測試……..…………….…….…………….……………….53
4-3 燒結溫度的影響………………………………………………………….57
4-3-1 單電池測試……..…………..….……….………….……………….57
4-3-2 表面形貌分析………….….………….…………….……………….63
4-3-3 能量分散光譜儀分析……..…….…..…………….……………….68
4-4 電解液的影響…………………………………………………………….69
4-4-1單電池測試……..………….….……….………….……………….69
4-4-2表面形貌分析………….….………….…………….……………….73
4-4-3 X光繞射分析……………..….…..…………….……………….77
4-4-4 能量分散光譜儀分析………..….…..…………….……………….77
4-5 負載電流的影響………………………………………………………….78
第五章 結論…………………………………………………………………………79
參考文獻…………………………………………………………………………….80
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