研究生: |
洪卿雲 Hung, Ching-Yun |
---|---|
論文名稱: |
以脈衝-休止法製備錳氧化物奈米線應用於超級電容器 Manganese Oxide Nanowire Prepared by Pulse-Rest Method for Supercapacitors |
指導教授: |
胡啟章
Hu, Chi-Chang |
口試委員: | |
學位類別: |
碩士 Master |
系所名稱: |
工學院 - 化學工程學系 Department of Chemical Engineering |
論文出版年: | 2009 |
畢業學年度: | 97 |
語文別: | 中文 |
論文頁數: | 135 |
中文關鍵詞: | 超電容 、錳氧化物 、陽離子 |
外文關鍵詞: | supercapacitor, manganese oxide, cation |
相關次數: | 點閱:2 下載:0 |
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錳金屬的奈米線氧化物可以成功地利用脈衝-休止法來製備在石墨電極上,可藉由控制實驗的脈衝時間、休止時間改變氧化物的特性。製備出的所有氧化物經由循環伏安法在鹼金、鹼土族水溶液中進行電化學測試,都具有良好的電容器行為,其電容量介於41-157 F/g。根據本研究,在1.1V脈衝電壓、0.5 s休止時間、0.5 s脈衝時間、工作於0.5 M的氯化鈣溶液中可以得到最大的電容量。
表面的結構由掃描式電子顯微鏡(FE-SEM, field emission scanning electron microscope)觀察;細微的結構、特徵長度以及晶相則由高解析穿透式電子顯微(HR-TEM, high resolution transmission electron microscope)鏡觀察;氧化數分析則是藉由X光光電子光譜儀(XPS, X-ray photoelectron spectroscope)和拉曼光譜儀(Raman spectrum)來獲得;微震盪電子石英天秤(EQCM, electrochemistry quartz crystal microbalance)則是用來觀察不同陽離子電解液間的差異。
另一方面,脈衝的參數同時影響著帶單電荷離子和帶雙電荷離子電解液對電化學行為的影響,由實驗結果,推斷可能和ton/toff 的比例有關。其充放電的電化學反應可被歸納為:
MnO2 + δM+ + δe− □ MnO2−δ (OM)δ
最後,分別以脈衝休止法所製備出的錳氧化物、純Mn3O4結晶以及多層奈米碳管做為基材,再以定電流的方式成長錳氧化物於以上基材上,這些錳氧化物的混合物都表現出良好的電化學行為。此外,這些氧化物的穩定性相當的好:在10000圈的掃描中,僅僅只有5~15 %的電容損失,而實驗中得到最大的比電容值為390.8 F/g。
Manganese oxide nanowire mixture is successfully prepared by two electrode pulse-rest method with different pulse time and rest time. All of conditions show good capacitor behavior by cyclic voltammetry in both monovalent and bivalent mild solution, and the specific capacitance is between 41~157 F/g. The largest data from this study is obtained in 1.1V pulse voltage, 0.5s pulse time, 0.5s rest time, and working in 0.5M calcium chloride solution.
The surface morphology was obtained by field emission scanning electron microscope (FE-SEM), which aspect ratio was affected by the pulse parameter, and the detail morphology and crystalline species are confirmed by high resolution transmission electron microscope (HR-TEM). Finally, the oxidation state is obtained by X-ray photoelectron spectroscope (XPS) and Raman spectrum. The cation effect is observed by electrochemistry quartz crystal microbalance (EQCM).
On the other hand, the pulse parameters also affected the different capacitor behavior in monovalent and bivalent electrolyte. In our study, we assume that the ton/toff ratio, could affect the capacitor behavior in monovalent and bivalent electrolyte. The charge/discharge reaction can be summarized as:
MnO2+δM+ + δe− □ MnO2−δ (OM)δ
Finally, we deposited manganese oxide by galvanostatics by using the pulse oxide, pure Mn3O4 crystalline, and MWCNT (multiwall carbon nanotube) as the substrate. The manganese oxide mixture also shows good capacitance, power density, and reversibility. Moreover, the mixture shows excellent stability in 0.5M Na2SO4 electrolyte: only 5~15% decay during 10000 cycling, and the maximum specific capacitance value is 390.8F/g.
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