三成份鎳-鈷系尖晶石氧化物於可充式 鋅空氣電池之空氣極的研究

Ternary Spinel Nickel-Cobalt-Based Oxides for the Air Electrode of Rechargeable Zinc-Air Batteries

簡佑如

鋅空氣電池 ； 氧氣產生 ； 氧氣還原 ； 鎳鈷氧化物 ； 尖晶石氧化物 ； zinc air battery ； OER ； ORR ； nickel cobalt oxide ； spinel oxide

清華大學化學工程學系學位論文

2016年

碩士

胡啟章

繁體中文

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.

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