本實驗使用脈衝電化學沉積技術，利用脈衝電場來控制液相金屬離子與碳纖維表面間固液界面的異質成核速率，並同時抑制金屬核的成長，如此可獲得奈米尺度之微粒貴金屬觸媒。
於脈衝電化學沉積時，同步的工作電極開路電位與脈衝電化學沉積次數，可被視為金屬觸媒沉積總量的指標。除碳纖維外，本實驗中亦採用新型碳素材料，其是將奈米碳纖維直接成長於碳纖維布上，稱之為奈米碳纖維布。利用直徑僅數奈米的碳纖維表面，可更近一步的抑制觸媒成核的大小。掃描式電子顯微鏡的觀察，脈衝電化學沉積技術能成功的將觸媒尺寸減少至數奈米，由高解析穿透式電子顯微鏡也觀察到，數奈米的鈀晶格影像。根據X光的繞射分析，依脈衝沉積的累積，鈀觸媒的平均結晶尺寸分佈於13~14 nm之間，而感應耦合電漿光譜定量鈀觸媒時，總量佔奈米碳纖維布總重約0.029到0.093 w t%之間。本實驗採用燃料半電池來進行電化學分析，循環伏安測試中，可觀察氫燃料與鈀觸媒進行反應的峰值，實驗中經2400次鈀觸媒沉積之奈米碳纖維布(CNFs/CFs-Pd 2400 cyc.)，其最大電流密度可達2.5 mA/cm2。而將CNFs/CFs-Pd 2400 cyc.與質導膜Nafion® 117熱壓成半電池膜極組，在電位0.1 V (vs. Ag/AgCl)時的半電池測試所得的比電流密度(mA/cm2)為10.3 mA/cm2。

This experiment is a successful debut of the pulse electrochemical deposition method for decorating ultra fine particle noble metal on carbon fabrics. These ultra fine particle noble metal, acting as catalysts in PEMFC, was heterogeneously nucleated on the interphase between solid surfaces of carbon fabrics and liquid electrolyte. By imposing the pulse potential energy, the method provides an energy barrier to limit the grain growth of clusters nuclei, while it has catalyst nucleation promoted.
A new carbonaceous material, carbon nanofiber fabrics (CNFs/CFs), carbon nanofibers directly grown upon carbon fabrics, was also used as one of catalyst supporters in the experiment. Carbon nanofibers have few nano-meters in mean diameter and the cylindrical graphite walls can reduce more critical nucleation size for catalysts. Observed by field-emission scanning electron microscopy, palladium catalysts did have nano-size morphologies on carbon nanofibers (CNFs). Palladium catalysts had clear lattice images with mean spacing of d(111) about 0.22 nm observed by HR-TEM. X-ray powder diffraction analyses showed that the average crystal size of palladium was between 13 to 14 nm, and it varied according to cyclic counts (cyc.) of deposition. Amounts of catalysts loading could be evaluated via open circuit potential of carbon fabric working electrodes versus cyclic counts of deposition, and be referred with quantity analyses via an inductively coupled plasma optima optical emission spectrometer. In the experiment, a three electrodes assembly half-cell was both used in pulse electrochemical deposition and electrochemical reaction analyses. Adsorption and desorption reactions of hydrogen with palladium catalysts were analyzed via cyclic voltammetry. After 2400 cyc. deposition, palladium coated carbon nanofiber fabrics (CNFs/CFs-Pd 2400 cyc.) had a highest current density 2.5 mA/cm2 in hydrogen adsorption/desorption reaction. When catalytic carbon nanofiber fabrics were assembled with Nafion® 117 as half-cell modules, electrochemical half-cell analyses showed that the half-cell module had 10.3 mA/cm2 in value.

中文摘要 I
英文摘要 II
目錄 IV
圖目錄 VII
表目錄 X
第一章 緒論 - 1 -
1.1 燃料電池 - 2 -
1.2 碳材料在燃料電池之應用 - 5 -
1.3 實驗動機 - 7 -
第二章 理論依據與文獻回顧 - 9 -
2.1 燃料電池效能 - 9 -
2.1.1 燃料電池熱力學 - 9 -
2.1.2 燃料電池極化現象 - 11 -
2.1.3 質子交換膜燃料電池與其關鍵元件 - 14 -
2.1.4.1 質子交換膜 - 16 -
2.1.4.2 觸媒層 - 18 -
2.1.4.3 氣體擴散層 - 19 -
2.1.4.4 雙極板 - 19 -
2.2 電化學沉積 - 20 -
2.2.1 電化學沉積理論 - 20 -
2.2.2 脈衝式電化學沉積理論 - 26 -
2.2 觸媒及其效率分析 - 28 -
2.2.1 鈀之基本性質 - 28 -
2.2.2觸媒載體 - 29 -
2.2.3 鈀載於碳上之電化學分析 - 33 -
第三章 實驗 - 39 -
3.1 實驗流程 - 39 -
3.2 實驗材料 - 40 -
3.3 實驗步驟 - 40 -
3.3.1 奈米碳纖維布製備 - 40 -
3.3.2 脈衝電化學沉積 - 42 -
3.3.3 電鍍碳纖維布基材 - 45 -
3.3.3 電鍍奈米碳纖維布基材 - 45 -
3.3.4 半電池組裝 - 46 -
3.4 分析測試 - 47 -
3.4.1 冷場發射掃描式電子顯微鏡照片分析 - 47 -
3.4.2 X光繞射分析 - 47 -
3.4.3 感應耦合電漿原子發射光譜分析儀 - 48 -
3.4.4穿透式電子顯微鏡 - 48 -
3.4.5 比表面積測試 - 49 -
3.4.6 循環伏特安培法 - 49 -
3.4.7 半電池測試 - 50 -
第四章 結果與討論 - 51 -
4.1 電化學曲線分析 - 51 -
4.1.1電鍍碳纖維布基材 - 51 -
4.1.2電鍍奈米碳纖維布基材 - 54 -
4.2 掃描式電子顯微鏡 - 56 -
4.2.1碳纖維布基材 - 57 -
4.2.2 奈米碳纖維布基材 - 59 -
4.3 穿透式電子顯微鏡 - 62 -
4.4 XRD繞射分析 - 66 -
4.5 感應耦合電漿光譜分析 - 71 -
4.6 比表面積分析 - 75 -
4.7 循環伏安測試 - 78 -
4.8 半電池測試 - 85 -
第五章 結論 - 87 -
第六章 參考文獻 - 89 -
附錄 - 96 -
致謝 - 97 -

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