本研究嘗試於BMP-NTf2室溫離子液體中利用電鍍法製備錳金屬薄膜電極，並探討不同還原電位以及鍍液溫度對於所製備錳薄膜電極電化學性質之影響。另外，再探討經不同電化學方式氧化後的氧化錳電極之材料與擬電容特性。

由於BMP-NTf2室溫離子液體有很寬廣的電位穩定範圍(大於4.5 V)並足以涵蓋Mn/Mn+2的電化學反應平衡電位，因此可利用其作為溶劑以進行金屬錳的電鍍。實驗結果顯示，在含兩價錳的離子液體中可將錳金屬薄膜析鍍於鎳箔基材上，其電流效率接近100%。改變還原電位(-1.8、-2.0、-2.2 VFc/Fc+)和鍍液溫度(50℃、70℃、90℃、110℃)，並不影響電鍍的電流效率。由表面形貌觀察可知，以較低的還原電位(-1.8 VFc/Fc+)與電鍍溫度(50℃)所製備之錳薄膜電極表面最為平整且均勻。由低掠角X光繞射圖譜得知，提高鍍液溫度並不會改變所製備之錳薄膜結晶性，且皆以非晶質錳呈現。

於50℃之BMP-NTf2室溫離子液體中，以-1.8 VFc/Fc+所製備之錳薄膜電極分別再以三種不同電化學方式(定電位、定電流，以及循環伏安法)氧化。以掃瞄式電子顯微鏡觀察定電位氧化之氧化錳電極，其表面形貌呈現團聚的表徵；以定電流法之氧化錳電極表面呈現團聚且有些許絲狀物的形貌；而循環伏安氧化之氧化錳電極表面為纖維狀的層狀結構。由低掠角X光繞射圖譜得知經三種不同電化學方式氧化之氧化錳皆為非晶質的。以X光光電子能譜儀分析結果可知，定電位氧化之氧化錳電極為含較多四價錳的氧化物且含水合物較少；循環伏安氧化之氧化錳電極為含較多三價錳的氧化物且含水合物較多；而定電流氧化之氧化錳電極則介於兩者之間。以循環伏安法量測電化學性質，結果顯示當還原電位為-1.8 VFc/Fc+且鍍液溫度為50℃時，所製備之錳薄膜電極經過循環伏安氧化後，在電位掃瞄速率為5 mV/sec的條件下可得到最高的比電容值402 F/g，且在500次循環伏安測試之後的電容衰退率約為6 %，顯示其應用在超高電容器中的發展潛力。

This study attempted to prepare Metallic Mn thin film electrodes by electro-deposition in BMP-NTf2 ionic liquid. Effects of reducing potential and temperature in electrochemical properties of the Mn thin film electrodes were investigated. In addition, the material characteristics and pseudo-capacitive properties of manganese oxide after different electrochemical oxidation were investigated, too.

The BMP-NTf2 ionic liquid was found to have a very wide potential window of 4.5 V, therefore, was capable of being a novel medium for electro-depositing metallic Mn thin film. By using an electrochemical process, block manganese counter electrode was dissolved in the ionic liquid to generate divalent Mn, which was subsequently cathodically deposited on the nickel substrate. The current efficiency of this process was confirmed to be extremely high (close to 100%). When changing reducing potential (-1.8、-2.0、-2.2 VFc/Fc+) and temperature (50℃、70℃、90℃、110℃), the current efficiency of deposited process was the same. The surface morphologies of Mn thin films indicated that the films were getting smoother when decreasing reducing potential and temperature. Glancing angle X-ray diffraction patterns indicated that metallic Mn thin films deposited at different temperatures were all amorphous.

The Mn thin film electrodes prepared at -1.8 VFc/Fc+ in 50℃ BMP-NTf2 ionic liquid oxidized by three different electrochemical methods (Potentiostatic, galvanostatic, and cyclic voltammetric methods). The surface morphology of the oxides prepared by different methods was observed by SEM. It showed that the particles of MnO-P and MnO-CV electrodes were lumping together and fully covered by a fiber-like layer, respectively. MnO-G electrodes were lumping together and partially coverd by fiber-like layer. Glancing angle X-ray diffraction pattern indicated that all oxides are amorphous. Moreover, their chemical states were analyzed with an X-ray photoelectron spectroscope. The analytic results indicated that MnO-P electrode was composed of more tetravalent and less hydrous Manganese oxides. Therefore, MnO-CV electrode was composed of more trivalent and more hydrous Manganese oxides. XPS analytic results of MnO-G electrides were between MnO-P and MnO-CV electrodes. Mn thin film deposited at -1.8 VFc/Fc+ in 50℃ BMP-NTf2 ionic liquid and then anodized by the cyclic voltammetric method showed a promising specific capacitance of 402 F/g (measured in 0.1 M Na2SO4 solution at a potential scan rate of 5 mV/s).

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