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研究生： 韋玟卉
Wen-Hui Wei
論文名稱： 鐵基奈米核殼結構之觸媒應用於陰離子交換膜燃料電池
Fe-based Core-Shell Nanostructure Catalyst in Anion Exchange Membrane Fuel Cell Application
指導教授： 王丞浩
Chen-Hao Wang
口試委員: 王冠文
Kuan-Wen Wang
陳燦耀
Tsan-Yao Chen
葉禮賢
Li-Hsien Yeh
黃信智
Hsin-Chih Huang
學位類別： 碩士
Master
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2022
畢業學年度： 110
語文別： 中文
論文頁數： 90
中文關鍵詞： 氧氣還原反應 、燃料電池 、非貴金屬觸媒 、核殼結構觸媒 、鐵-氮結構
外文關鍵詞： Oxygen Reduction Reaction, Fuel cell, Non-precious metal catalysts, core-shell structure, Fe-N structure
相關次數： 點閱：245  下載：1 
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    • 陰離子交換膜燃料電池為一種低汙染、高持久性之綠色能源裝置。其主要的產物為水，且不會產生大量的廢氣或廢熱，可不斷從氫、氧燃料中的化學能直接轉換成電能與熱能，使燃料電池不間斷的發電。為了減少觸媒成本、延長燃料電池的使用壽命，因此希望研究出高效能且穩定的非貴金屬觸媒。
    本研究選用普魯士藍作為觸媒前驅物，經蝕刻後形成中空立方體結構，並加入適當比例之多巴胺與BP2000碳材，最後以化學氣相沉積儀在5% NH3/Ar環境下進行快速熱處理，即可製備出最佳條件之觸媒（Fast HT-NH3）。經電化學量測後，此觸媒有最佳的氧氣還原活性，且電子轉移數可達3.98，與理想電子轉移數4.00相當接近，在30,000圈穩定性測試後，半波電位僅衰退24 mV。將觸媒於鹼性陰離子交換膜燃料電池下進行全電池測試，可展現出263.9 mW/cm2之高輸出功率，由此可知此觸媒在鹼性環境中具備極佳之穩定性與效能。
    材料的結構分析可由穿透式電子顯微鏡（TEM）影像分析中看出觸媒呈現核殼結構，而X光繞射分析儀（XRD）可發現觸媒具有Fe4N之結晶結構，進一步以X光吸收光譜（XAS）證實Fe-N結構之存在，在X射線光電子能譜（XPS）的分析中發現觸媒還擁有高比例的Pyridinic-N與Pyrrolic-N官能基。因Fe3C、Fe4N與Fe2O3之間產生的協同效應，以及含有高比例的含氮官能基與Fe-N基團，使此觸媒（Fast HT-NH3）在氧氣還原反應中具有優異的表現。

    The use of stable non-metallic catalysts in Anion Exchange Membrane Fuel Cells (AEMFCs) will allow for a reduction in its manufacturing cost and increase its lifespan while still maintaining its hallmark efficiency and durability. AEMFCs, like most conventional fuel cells, generate electricity continuously using hydrogen and oxygen as their fuel and producing water and heat as their by-product. The use of more common materials in the construction of such fuel cells will allow for a more widespread deployment of this green technology.
    In this research, Prussian blue is used as the catalyst precursor. After the etching of the sample material, a hollow cube structure was formed to which BP2000 and dopamine were added. The mixture was pyrolyzed rapidly under a 5% NH3/Ar atmosphere to obtain the desired catalyst, labeled as “Fast HT-NH3”. After electrochemical measurement, a significant oxygen reduction activity was observed, with a direct four-electron transfer pathway for the AEMFC application. After 30,000 cycles, “Fast HT-NH3” showed only a 24 mV decrease in half-wave potential. It also showed a good cell performance with a maximum power density of 263.9 mW/cm2 which was very close to Pt/C performance under the same conditions.
    The structural analysis of the material shows that the catalyst has a core-shell structure and confirms the existence of Fe4N. Due to the synergistic effect between Fe3C, Fe4N, Fe2O3, high proportion of nitrogen functional groups, and Fe-N groups, the “Fast HT-NH3” catalyst has an excellent performance in the oxygen reduction reaction.

    中文摘要 Abstract 致謝 目錄 圖目錄 表目錄 第一章 緒論 1.1 研究背景 1.2 綠色能源之燃料電池介紹 1.2.1 燃料電池的種類 1.2.2 陰離子交換膜燃料電池（AEMFC）介紹 1.2.3 陰離子交換膜燃料電池結構介紹 1.2.4 燃料電池的極化現象 第二章 電化學原理與文獻探討 2.1 電化學原理 2.1.1 氧化還原反應 2.1.2 氧氣還原途徑 2.1.3 氧氣還原反應機制 2.1.4 氧氣還原反應之電化學催化 2.2 文獻探討 2.2.1 氮參雜之非貴金屬觸媒 2.2.2 普魯士藍應用於陰極觸媒 2.2.3 蝕刻製備中空奈米結構 2.2.4 中空普魯士藍結構 2.2.5 氮參雜之核-殼結構觸媒 2.3 研究動機 第三章 實驗步驟與研究方法 3.1 實驗規劃 3.2 實驗材料及藥品 3.3 實驗流程 3.4 實驗儀器與設備 3.5 實驗步驟 3.5.1 陰極觸媒製備 3.5.2 半電池觸媒工作電極製備 3.6 儀器分析原理 3.6.1 X光繞射分析儀（X-ray diffraction Spectrometer，XRD） 3.6.2場發射掃描式電子顯微鏡（Field Emission Scanning Electron Microscope，FSEM） 3.6.3 X射線光電子能譜（X-ray Photoelectron Spectroscopy，XPS） 3.6.4 X光吸收光譜（X-ray Absorption Spectroscopy，XAS） 3.6.5穿透式電子顯微鏡（Transmission Electron Microscope） 3.6.6比表面積及孔徑分析儀（Surface Area & Mesopore Analyzer） 3.6.7 電化學分析儀 3.6.8 燃料電池分析儀 第四章 結果與討論 4.1 蝕刻普魯士藍 4.1.1 蝕刻普魯士藍之形貌分析 4.1.2 蝕刻普魯士藍之X光繞射分析 4.1.3 蝕刻普魯士藍之氧氣還原反應活性比較 4.2 不同熱處理方式觸媒 4.2.1 不同熱處理方式觸媒之X光繞射圖譜分析 4.2.2 不同熱處理方式觸媒之形貌分析 4.2.3 不同熱處理方式觸媒之X光電子能譜分析 4.2.4 不同熱處理方式觸媒之X光吸收光譜分析 4.2.5 不同熱處理方式觸媒之氧氣還原反應活性比較 4.2.6 Fast HT-NH3觸媒之穩定性測試 4.2.7 Fast HT-NH3觸媒之單電池測試 第五章 結論 第六章 參考文獻

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