臺灣博碩士論文加值系統

本研究是使用含浸法(Impregnation Method)製備Pt/CNT和Ni/CNT及使用奈米鎳粉(Nickel Powder)做為直接甲醇燃料電池(DMFC)的陰陽極觸媒。將常使用的觸媒載體碳黑（Vulcan XC-72）以奈米碳管取代，此因奈米碳管擁有比碳黑更高的比表面積（specific surface area），範圍約在50~1315m2/g之間變化，而碳黑（Vulcan XC-72）約250m2/g。白金觸媒的製備是使用三次含浸法及乙二醇還原法，以乙二醇還原法所製備之白金觸媒較好，其平均粒徑為8.9 nm，且依此法所製備之觸媒重現性佳。對乙二醇還原法所製備之白金觸媒數量及粒徑尺寸進行統計及分析，可得知碳管管徑大上的觸媒其粒徑大小分布較廣,且各個碳管上之觸媒平均粒徑隨著管徑變大而變大。鎳觸媒部分則是購買平均粒徑35 nm的鎳粉，與奈米碳管混合作為電極觸媒用。當陽極為鎳，陰極為白金時，無穩定電流產生。當陽極為白金，陰極為鎳時，在0.1 V時有0.125 mA/cm2的穩定電流產生。在鎳觸媒部分加入Au做改善，結果在0.1 V時，電流密度提昇至0.375 mA/cm2，在電位部分也提昇至0.3 V，電流密度為0.025 mA/cm2，在量測電池性能的過程中發現，電池效能會隨著量測的次數增加而有一個最佳值，之後電池效能又會隨著量測次數的增加而遞減，所以我做了一次連續量測60次的實驗，每10次取一個平均值來觀察及比較，結果發現，在31~40次的平均值中，其電池效能最好，所以若要得知自製之MEA的真正效能，可使用多次量測法找出最好且真正的I-V性能曲線圖。

This research is based on Impregnation Method which applies Pt/CNT、Ni/CNT and apply nickel powder as catalyst for anode/cathode. By substitute CNTs for Vulcan XC-72 for it has a higher specific surface area which ranges from 50~1315 m2/g. However, for Vulcan XC-72 is only about 250 m2/g. we use Three times impregnation and the polyol reduction process to prepare Platinum catalyst. For the preparation of the polyol reduction process can reach a better efficient which has the average particle diameter about 8.9 nm. Beside, the ability of preparation to reach the same result is very high. To analysis the particle size and the amount of platinum catalyst, we can acknowledge that the dispersion of catalyst on the CNTs diameter is very wide. Futhermore, the average catalyst particle on each CNTs is getting larger as the diameter goes up. Ni catalyst is the nickel powder which has the average particle diameter of 35 nm which is used to mix with CNTs as electrode catalyst. When we apply Ni as anode platinum as cathode, there is no stable current occur. On the other hand, when we apply platinum as anode and Ni as cathode, there is a stable current which is about 0.125 mA/cm2 occurs at 0.1 V. when we add Au to improve, the current density raise up to 0.375 mA/cm2 at 0.1 V. For the voltage is rising up to 0.3 V, the current density reaches0.025 mA/cm2. During the process of measuring the ability of battery, the battery efficient reaches a best value as the measuring time increase. Afterwards, the battery efficient reduces as the measuring time increases. For a 60times measuring, the average value of battery reaches a best result at measuring times of 31-40. If we really need to know the true efficient of MEA, we can find the I-V curve through rising up the times measurement.

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 序論 1
1.1 前言 1
1.2 燃料電池的歷史 1
1.3 燃料電池的種類 2
1.3-1鹼性燃料電池(AFC) 3
1.3-2磷酸燃料電池(PAFC) 3
1.3-3熔融碳酸鹽燃料電池(MCFC) 3
1.3-4固態氧化物燃料電池(SOFC) 4
1.3-5質子交換膜燃料電池(PEMFC) 4
1.3-6直接甲醇燃料電池(DMFC) 5
1.4 電池的構造及關鍵元件 8
1.4-1 質子交換膜 8
1.4-2 陰極觸媒部分 11
1.4-3 陽極觸媒部分 11
1.5 研究動機與目的 12
第二章 原理與文獻回顧 14
2.1直接甲醇燃料電池工作原理 14
2.1-1 甲醇電催化氧化機制 17
2.2 電池的極化現象 19
2.3 相關文獻探討 22
2.3-1 觸媒的製備 22
2.3-2 氯離子的影響 24
2.3-3 觸媒載體 24
2.3-4奈米碳管 25
2.3-5 觸媒漿料製作 29
2.3-6 膜電極組(MEA)的製備 29
2.3-7 質子交換膜與觸媒結合的方式 29
2.3-8氣體擴散層和觸媒之結合技術 30
2.3-9 奈米碳管表面改質 32
2.3-10 鎳觸媒 33
2.3-11 金觸媒 35
第三章 實驗方法與步驟 36
3.1 藥品與材料 36
3.2 實驗設備 37
3.3 實驗方法及流程 38
3.3-1 質子交換膜Nafion®117前處理 39
3.3-2 觸媒製備 40
3.3-3 觸媒漿料及氣體擴散層電極製備 41
3.3-4 熱壓法製備膜電極組(MEA) 42
3.4 電池放電測試 42
3.5 分析檢測之方式 46
3.5-1 X光繞射分析（X-ray Differaction，XRD） 46
3.5-2穿透式電子顯微鏡（Transmission Microscope，TEM） 47
3.5-3 掃瞄式電子顯微鏡 (SEM) 48
3.5-4 X光光電子能譜儀 (XPS) 51
3.5-4 能譜儀分析(EDS) 52
第四章 結果與討論 53
4.1 觸媒載體之選擇 53
4.2 比較不同製備方式之觸媒分析 59
4.2-1 白金觸媒製備方式 59
4.2-2 奈米碳管管徑對觸媒粒徑尺寸之分析 60
4.2-3 鎳觸媒製備方式 61
4.3 電池放電性能測試 77
4.3-1 不同觸媒製備方式之性能比較 77
4.3-2 觸媒漿料改質之比較 82
第五章 結論 84
參考文獻 85

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