本文分為兩部分，第一部分，以簡易的水熱法合成MxNi1-xCo2O4 (M = Mn, Fe, Cu, Zn, x=0.1)尖晶石氧化物，標示為MNCO-01、FNCO-01、CNCO-01和ZNCO-01，利用X光繞射(XRD)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、感應耦合電漿質譜分析儀(ICP-MS)、電子能譜儀(XPS)、比表面積分析儀和電化學技術包含循環伏安法(CV)、線性伏安掃描(LSV)、塔弗曲線與定電流充放電分析，探討四種不同金屬部分取代尖晶石氧化物中的鎳離子，對外觀形貌和氧氣產生與還原的電化學特性之影響，結果顯示，鐵離子添加的鎳鈷系氧化物(FNCO-01)對氧氣產生與氧氣還原有最佳的電催化活性。第二部分，比較不同比例鐵離子添加的三成份尖晶石氧化(FexNi1-xCo2O4, 0≤x≤1)，對ORR與OER電催化活性的影響，經由氧化物的結構、表面形貌與電化學表現的分析，部分的鐵離子取代鎳離子可大幅提升氧化物的電催化活性，當FexNi1-xCo2O4的鐵離子比例在0.1≤x≤0.3的範圍時，有最高的ORR和OER催化活性。將催化劑實際用於可充式鋅空氣電池，並在一般大氣下操作，FexNi1-xCo2O4(x=0.3)展現卓越的充放電電位與長效的循環壽命，幾乎無電位損耗。本研究認為FexNi1-xCo2O4兼具高效益與商業可行性，能成為可充式金屬空氣電池的的雙效催化劑。

There are two parts in this research. In the first part, partially substituted MxNi1-xCo2O4 (M = Mn, Fe, Cu, and Zn, x=0.1) spinel oxides, labeled as MNCO-01, FNCO-01, CNCO-01, and ZNCO-01, were synthesized via a facilely hydrothermal method. The effects of the metal partially substitution in the Ni site of the spinel oxide on the morphology and electrocatalytic properties of the materials toward the ORR and OER were investigated and compared by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma-mass spectrometer (ICP-MS), X-ray photoelectron spectroscopy (XPS), surface area analyzer and electrochemical techniques including cyclic voltammetry (CV), linear sweep voltammetry (LSV), tafel plot, and galvanodynamic charge-discharging. As a result, the iron-substituted nickel-cobalt based oxides (FNCO-01) displayed a significant electrocatalytic activity towards both the ORR and OER in comparison with the Mn-substituted, Cu-substituted, and Zn-substituted nickel-cobalt based oxides.
In the second part, the spinel-type ternary transition metal oxides of nickel, cobalt, and iron with the composition FexNi1-xCo2O4 (0 ≤ x ≤ 1) were prepared and tested as promising electrocatalysts for the ORR and OER in alkaline solution. The structural, morphological and electrocatalytic performances confirmed that substitution of Ni by Fe increases the electrocatalytic activity of the resulting material significantly. The highest activity was achieved for FexNi1-xCo2O4 with 0.1 ≤ x ≤ 0.3. The practicality of the catalyst were corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where FexNi1-xCo2O4 (x=0.3) demonstrated superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. The excellent electrochemical results presented in this study highlight the FexNi1-xCo2O4 as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery application.

中文摘要 I
Abstract II
目錄 IV
圖目錄 VIII
表目錄 XIV
第一章 緒論及文獻回顧 1
1-1鋅空氣電池 1
1-1-1前言 1
1-1-2鋅空氣電池歷史[4, 5] 3
1-1-3鋅空氣電池簡介 4
1-2可充式空氣極的化學反應 6
1-2-1可充式空氣極氧氣還原反應(Oxygen Reduction Reaction, ORR) 6
1-2-2可充式空氣極氧氣產生反應(Oxygen Evolution Reaction, OER) 7
1-3 可充式空氣極催化劑與碳材 8
1-3-1 可充式空氣極雙效催化劑(Bifunctional Air Electrocatalysts) 8
1-3-2 碳材 11
1-4鎳鈷系尖晶石氧化物電極 12
1-4-1 尖晶石氧化物簡介 12
1-4-2 鎳鈷氧化物 15
1-5流動系統分析技術 17
1-5-1旋轉圓盤電極的基本原理 17
1-5-2旋轉環-盤電極的基本原理 19
1-6研究動機與本文大綱 21
第二章實驗方法、步驟與儀器介紹 22
2-1 儀器與藥品 22
2-2 水熱法製備催化劑 24
2-2-1 MxNi1-xCo2O4 (M=Mn, Fe, Cu, Zn)的製備 24
2-2-2 FexNi1-xCo2O4的製備 24
2-3 電化學分析 25
2-3-1旋轉環－盤電極(RRDE)塗布與前處理 25
2-3-2循環伏安法(Cyclic Voltammetry, CV) 25
2-3-3線性伏安掃描(Linear Sweep Voltammetry, LSV) 26
2-3-4塔弗曲線(Tafel curve) 26
2-3-5鋅空氣電池空氣極的塗布與量測分析 27
2-4 材料分析儀器與原理簡介 28
2-4-1 X光繞射分析(X-ray diffraction analysis, XRD) 28
2-4-2掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 28
2-4-3穿透式電子顯微鏡(Transmission Electron Microscopy, TEM) 29
2-4-4比表面積與孔徑分析儀 (Surface Area and Porosity Analyzer) 29
2-4-5感應耦合電漿質譜儀(Inductively Coupled Plasma-Mass Spectrometer, ICP-MS) 30
2-4-6電子能譜儀(X-ray Photoelectron Spectroscopy, XPS) 30
第三章 MxNi1-xCo2O4 (M=Mn, Fe, Cu 和Zn)對氧氣產生(OER)與還原(ORR)電觸媒特性之影響 32
3-1材料分析 32
3-1-1 XRD結果分析 32
3-1-2 SEM結果分析 34
3-1-3 TEM結果分析 34
3-1-4 BET結果分析 35
3-1-5 ICP-MS結果分析 37
3-1-5 XPS結果分析 38
3-2氧氣產生與還原之電化學分析 47
3-2-1循環伏安(CV)行為 47
3-2-2線性掃描伏安(LSV)法分析ORR行為 49
3-2-3線性掃描伏安法(LSV)與塔弗曲線(Tafel slope)分析OER行為 52
3-3 鋅空氣電池電化學行為 55
3-3-1 鋅空氣電池空氣極之極化曲線( polarization ) 55
3-3-2 催化劑於空氣陰極之充放電行為分析 58
3-4結果與討論 62
第四章　FexNi1-xCo2O4對氧氣產生(OER)與還原(ORR)電觸媒特性之影響 64
4-1材料分析 64
4-1-1 XRD結果分析 64
4-1-2 SEM結果分析 66
4-1-3 TEM結果分析 67
4-1-4 BET結果分析 68
4-1-4 ICP-MS結果分析 71
4-1-5 XPS結果分析 72
4-2 氧氣產生與還原之電化學分析 80
4-2-1循環伏安(CV)行為 80
4-2-2線性掃描伏安(LSV)法分析ORR行為 82
4-2-3線性掃描伏安法(LSV)與塔弗曲線(Tafel slope)分析OER行為 85
4-3 鋅空氣電池電化學行為 88
4-3-1 鋅空氣電池空氣陰極極化曲線( polarization ) 88
4-3-2 催化劑於空氣陰極之充放電行為分析 92
4-4 結果與討論 97
第五章 總結與展望 99
5-1 總結 99
5-2 展望 101
參考文獻 102

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