本篇論文以高溫與冷凍交互作用法，成功還原出具有高比表面積、高電子傳導率之三維結構氧化石墨烯(reduced Graphene Oxide, rGO)。並因為冰晶的作用下使GO在孔洞間有多層堆疊而增強其機械強度。利用微波還原法，沉積奈米顆粒於前述碳材之上，以提高觸媒承載量，利用石墨烯之材料特性提高白金觸媒高承載表面積，亦可提高觸媒分散性，目前已經可以沉積3~5奈米之白金觸媒於載體的表面及內部，且觸媒乘載量可達0.43mg/cm2。從其半電池循環伏安法性質可看出，白金氧化峰單位質量電流密度達到217.3 A/g，電化學活性面積（ECSA）達到25.87 m2/g，全電池結果在70℃之下，功率密度來到53.96 mW/cm2，此時電流密度為130.14 mA/cm2。並在增加rGO三維載體孔徑後，發現比起最小孔洞的效能提升約兩倍。未來期望利用氫氣將PtrGO電極進行熱退火，以提升電極導電性，進而提升整體全電池效能。應用於直接甲醇燃料電池中做為高效能、高反應面積、低成本之白金觸媒或多元材料觸媒。

In this paper, we successfully produced three-dimensional reduced Graphene Oxide (rGO) with high specific area and high electron conductivity by the method which combined heating and freezing, as the anode electrode for micro Direct Methanol Fuel Cells (μDMFC). And we deposit Pt catalyst on the rGO substrate by microwave reduction, which can produce 3~5 nm nanoparticles on the rGO substrate and loading weight has reached 0.43 mg/cm2. The mass current density has reached 217.3 A/g and electrochemical active surface area (ECSA) value 25.87 m2/g. The best fuel cell performance of PtrGO was 53.96 mW/cm2 for the power density and 130.14 mA/cm2 for the current density. And found that when we increase the pore size of PtrGO, the performance of power density increased 2 times with respect to the smallest pore size sample. For further experiment, the H2 annealing for the PtrGO should be operated to improve the conductivity.

誌謝 I
摘要 II
Abstract III
目錄 IV
第1章 緒論 1
1.1 前言 1
1.2 燃料電池的發展 2
1.3 直接甲醇燃料電池 5
1.4 燃料電池工作原理 6
1.5 陽極觸媒原理及所遇到的問題 8
1.6 研究動機與目標 12
第2章 文獻回顧 13
2.1 碳載體的運用 13
2.2 碳纖維親水化 14
2.3 製備高表面積Graphene/CNT結構 18
2.4 水熱法還原氧化石墨烯 22
2.5 利用冰晶增進rGO機械強度 23
2.6 氮參雜技術應用於化學還原石墨烯 25
2.7 開放式直流還原系統的建立 28
2.8 微波法成長白金觸媒於GO載體上 32
2.9 乙二醇的作用和機制 33
2.10 PtRu製程與參數探討 35
第3章 實驗設計、設備與方法 40
3.1 水熱法還原水溶液中之氧化石墨烯 40
3.2 實驗原理及流程 40
3.3 利用冷凍法在rGO載體產生均勻孔洞 42
3.4 開放式直流還原製程參數 42
3.4.1 碳載體親水化： 42
3.4.2還原溶液的配製及試片檢測方式： 42
3.5 微波法還原參數 43
3.5.1 碳載體親水化： 43
3.5.2 還原溶液的配製及試片檢測方式： 43
3.6 冷凍乾燥系統 43
3.7 高溫熱還原…………. 44
3.8 電化學量測系統 44
3.9 全電池量測系統 46
3.10 FTIR試片的製備 47
3.11 TEM試片的製備 47
第4章 結果與討論 48
4.1 比較有無加入 1,12-diaminododecane脫水接合之電性 48
4.2 分析有無加入 1,12-diaminododecane脫水接合之微觀結構 49
4.3 比較有無加入 1,12-diaminododecane脫水接合之觸媒性能 49
4.4 Linker鍵結狀況探討 51
4.5 不同冷凍方法與碳載體孔洞大小之關係 52
4.6 N-dope與否對於觸媒載體的影響 54
4.7 不同觸媒還原方式對於觸媒形貌與電化學性質之影響 57
4.8 載體還原對於效能之影響 60
4.9 全電池測試 61
第5章 結論 65
第6章 未來工作 66
參考文獻及附錄 67

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