- 學位論文
氧化鈷超電容電極製備與全印刷式超電容製作
Preparation of Cobalt Oxide Supercapacitor Electrode and Fabrication of All-printed Supercapacitor
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摘要
近年來，超電容的高功率密度、長期穩定性及廣泛的應用性等優勢逐漸受到注意，因此已被視為一種相當具有潛力且重要的儲能元件。本篇論文分為兩個部分，分別探討氧化鈷超電容電極的製備及全印刷式超電容的製作。 在偽電容材料中，氧化鈷（Co3O4）因其突出的理論比電容值，尤為受到重視。但在所有製備氧化鈷超電容電極的文獻中，通常都涉及高溫的操作環境及繁瑣的製備程序。犧牲陽極法為一種自發性的電化學沉積方法，在操作過程中不需從外施加電力為其主要優勢。事實上，目前也尚未有文獻提及以此自發性電化學方法製備氧化鈷超電容電極。因此，在本論文第一部分研究提出以低溫、低耗能的犧牲陽極法製備氧化鈷超電容電極，取代過往複雜的製備程序。除了基本材料鑑定，本論文亦藉由比較可能發生之還原半反應、配合其他實驗數據，對陰極表面的電化學沉積機制作了詳盡的探討。同時為了計算犧牲陽極法沉積過程的法拉第效率，亦對所製備之薄膜的詳細分子式及質量作了驗證與定量。此外，在本研究中觀察到，犧牲陽極法的沉積速率與鍍液的濃度、陰陽極面積比例皆有高度相關性，同時也探討了兩個參數對所製備之薄膜電容表現的影響。而在本實驗中所製備之氧化鈷修飾電極其比電容表現最高可達到326 F/g。 在本論文第二部分，研究重點進入超電容的製作。已知印刷技術的應用可讓超電容的組裝更為方便、快速，但目前所有有關將印刷技術應用至超電容組裝的文獻，皆僅將印刷技術用於電化學活性材料的塗佈。因此，第二部分的研究嘗試將印刷技術更全面的應用在超電容的所有組成，以期能開發出全印刷式超電容。在組裝過程中，點膠技術為主要的印刷方法，同時採用紫外光固化式電解液克服印刷電解液及封裝等問題。此外水性聚氨酯將被使用為印刷的基材，以達成圖形設計的效果。所製作之全印刷式超電容的比電容表現最高可達到23.5 F/g。同時，該元件亦具有良好的充放電倍率性能、機械彈性及循環充放電穩定性。另外，在電化學交流阻抗分析中，分析結果顯示紫外光固化並不會對所製作之超電容的電容表現或是電解液內的離子擴散造成影響。
並列摘要
Recently, supercapacitors have been considered as a promising energy storage device due to their high power density, long cycle life and wide applicability. The research presented in this thesis consists of two parts, namely, on the preparation of cobalt oxide supercapacitor electrode and fabrication of all-printed supercapacitor. Among the pseudocapacitive materials, Co3O4 is particularly attractive due to its high theoretical specific capacitance. However, in most of the literatures, preparation of Co3O4 usually involves high-temperature or laborious procedures. Sacrificial anode method is a spontaneous electrochemical deposition method which provides the advantage of operating without external power supply. In fact, there is no literature mentioning this method to prepare Co3O4 electrodes so far. Therefore, in the first part of the thesis, the low-temperature, low energy-consumption sacrificial anode method was applied for preparing Co3O4 supercapacitor electrodes in order to replace the commonly used complicated procedures. In addition to the materials characterization, the mechanism involved during the deposition was also studied by comparing the possible half-reactions with the experimental data. Meanwhile, the detailed chemical formula and the deposited mass of the prepared film were investigated in order to estimate the Faraday efficiency of the sacrificial anode deposition. It was observed that the deposition rate is highly dependent on both the concentration of the electrolyte and the accessible surface area ratio of anode to cathode. The effect of these two factors on the capacitive performance of the obtained films was also investigated. A high specific capacitance of 326 F/g was obtained in this study. In the second part of the thesis, the research focuses on the fabrication of supercapacitors. It is known that the application of printing technique helps in facilitating the fabrication of supercapacitors. However, in all the literatures concerning printed supercapacitors, the printing technique was only applied as the coating of active materials. Hence, the goal of this part is to extend the application of printing technique to all components of the device in order to fabricate an all-printed supercapacitor. In the fabrication process, the dispensing technique was employed, and an UV-curable electrolyte was introduced in order to overcome the difficulty in printing the electrolyte and the packaging problem. In addition, the water-based polyurethane was used as the substrate, so as to achieve the desired pattern design. The all-printed device showed a high specific capacitance of 23.5 F/g, meanwhile demonstrated reasonable rate capability, flexibility and cycling stability. Furthermore, the electrochemical impedance spectroscopy analysis suggested that the UV-induced solidification of the electrolyte has no significant influence on the capacitive behavior and the ionic diffusion of the studied supercapacitor.
並列關鍵字
All-printed ； Cobalt oxide ； Dispensing ； Sacrificial anode method ； Supercapacitors ； UV-curing參考文獻
[2] J. M. Tarascon and M. Armand, Issues and challenges facing rechargeable lithium batteries, Nature, 414 (2001) 359.
[3] P. Yang and W. Mai, Flexible solid-state electrochemical supercapacitors, Nano Energy, 8 (2014) 274.
[4] X. Wang, X. Lu, B. Liu, D. Chen, Y. Tong and G. Shen, Flexible energy-storage devices: design consideration and recent progress, Advanced Materials, 26 (2014) 4763.
[5] X. Lu, M. Yu, G. Wang, Y. Tong and Y. Li, Flexible solid-state supercapacitors: design, fabrication and applications, Energy & Environmental Science, 7 (2014) 2160.
[6] S. Zhang and N. Pan, Supercapacitors Performance Evaluation, Advanced Energy Materials, 5 (2014) 1401401.