臺灣博碩士論文加值系統

本研究利用模板法研發一個製作具孔洞規則性碳材薄膜的方法，並探討以鉑奈米溶膠(Pt sols)製作電極中，具孔洞規則性碳材對電極性能的影響，以了解此種碳材在燃料電池的應用。
在碳材薄膜合成方面，以AAO (anodic aluminum oxide，陽極處理鋁)薄膜為模板，以含浸法將epoxy resin碳源填入AAO孔洞中，當採用兩步驟製程，分次洗除AAO，並重複填入碳源的作法，可以合成出具有類似AAO孔洞特性之連續碳材薄膜。漿液調配方面，以溶劑與添加劑(Nafion與Carbon)為調配參數，以接觸角、沉降時間、粒徑分佈與界達電位(Zeta Potential)分析溶膠沾溼性與穩定性，溶劑選擇上添加醇類(MeOH與IPA) 能幫助漿液沾溼碳紙但會聚集導致溶膠沉澱，因此塗覆時間需在兩小時內完成。添加劑選擇上添加Nafion與Carbon等添加劑，溶膠仍維持良好穩定性。隨後，將調配好之漿液塗覆成電極，利用I-V極化曲線與交流阻抗分析電化學反應特性，實驗結果發現Pt sol-C電極，其電化學反應特性隨著溫度上升性能隨之下降，與擔載型Pt/C觸媒隨著溫度升高，反應速率加快導致效能上升之趨勢相反，當以孔洞規則碳膜碎片取代碳黑，其孔洞特性使得質傳極化區域限制條件有所改善，而於0.6V工作電壓下可獲得1.5kW/gPt效能。

In this research, a carbon membrane with well-aligned pore structure is synthesized by template method. This carbon membrane is used together with Pt sols for improving performance of PEMFCs.

Epoxy solution is deposited into pore of a commercially available AAO (anodic aluminum oxide) membrane. After carbonization under N2 environment at elevated temperature, the carbon-AAO composite is subjected to a 2-step AAO removal procedure. By controlling the extent of AAO removal in the first step, and the use of a second carbon-filling-and-carbonization procedure, we achieve a continuous carbon membrane with pore structure replicating that of AAO template.

In this study, we use different solvents and additivies (involved Nafion and Carbon) over Pt sols to compare the ink stability. We use Contact angle, precipitation, Particle size distribution and Zata potential to analyze the stability of ink. The result shows that the addition of IPA and MeOH over Pt sols forces quick precipitation. We prepared thinner electrode made of Pt sols, but its performance decreases quickly from 35 to 70oC.However, the trend is reverse compared to Pt/C. The preparation of the electrode in combination with Pt sols and One-dimensional carbon material improves mass transport limitation.

摘要.....................................................III
Abstract..................................................IV
誌謝.......................................................V
目錄......................................................VI
圖索引..................................................VIII
表索引...................................................VII
第一章 緒論................................................1
1.1 前言...................................................1
1.2 PEFC工作原理...........................................4
1.3 文獻回顧...............................................6
1.3.1 PEFC電極簡介.........................................6
1.3.2 影響電極效能因素.....................................7
1.3.3 理想電極之結構設計..................................11
1.3.4 一維碳材在燃料電池電極之應用簡介....................15
1.3.5 一維碳材的合成與特性分析............................17
1.4 碳材陣列結構電化學特性分析............................21
1.4.1 極化現象............................................21
1.4.2 交流阻抗分析........................................24
1.5 研究目的..............................................26
第二章 實驗設備與方法.....................................27
2.1 研究架構與研究方法....................................27
2.2 藥品與儀器設備........................................30
2.2.1 藥品部分............................................30
2.2.2 氣體部分............................................31
2.2.3 儀器部分............................................32
2.3 一維碳材製備方法......................................33
2.4 奈米溶膠製備方法......................................34
2.4.1 鉑奈米顆粒製備方法..................................34
2.4.2 奈米溶膠漿液調配....................................34
2.5 單電池測試............................................34
2.5.1 Nafion membrane 前處理..............................34
2.5.2 MEA的製作...........................................35
2.5.3 單電池組裝..........................................35
2.5.4 交流阻抗分析........................................37
2.5.5 單電池性能測試......................................38
第三章 結果與討論.........................................39
3.1 碳材薄膜製備及鑑定....................................39
3.1.1 碳源填入與碳化分析..................................39
3.1.2 AAO的鹼液蝕除分析...................................44
3.1.3 二階段式碳膜製備....................................53
3.1.4 碳材薄膜碎片特性分析................................56
3.2 鉑奈米溶膠製作觸媒漿料的分析..........................63
3.2.1 溶劑種類對漿液在碳紙上沾溼程度的影響................63
3.2.2 溶劑添加對漿液穩定性的影響..........................66
3.2.3 添加劑添加對漿液穩定性的影響........................71
3.3 單電池效能測試與分析..................................76
3.3.1 ionmer添加量對電極效能的影響........................76
3.3.2 Carbon添加量對電極效能的影響........................78
3.3.3 碳材結構對電極效能之影響............................80
第四章 結論...............................................91
參考文獻..................................................93
附錄A Pt sols與商購Etek 觸媒之粒徑分佈....................96
附錄B 以溶劑DMAc改善Pt sols於碳材上的分佈.................98
附錄C 碳材孔洞親疏水性與泛溢行為分析......................99

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