石墨烯之複合電極於全固態纖維式微型超電容的研究

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曾信尹(Sin-Yin Tseng) 查詢紙本館藏

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機械工程學系

論文名稱

石墨烯之複合電極於全固態纖維式微型超電容的研究
(Flexible all-solid-state Microsupercapacitors based on Carbon clothes fiber electrode coated with ECG via electrophoretic deposition (EPD))

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摘要(中)

微型超級電容器(micro-supercapacitors，MSCs)為一種新型電化學儲能元件，因為具有高功率密度、高充放電速率、體積小、使用壽命長、可彎折、綠色環保等特點，被視為現代儲能元件之一大選擇，然而，微型超級電容器現今面臨的最大挑戰為成本高、電解液洩漏、製程複雜等問題，因此如何解決這些問題並保持著高功率為本實驗的一大考驗。
本實驗選擇利用電泳沉積之方法來製備微電容，電極方面選擇使用碳布的纖維，而活性材料方面則是利用電化學剝離石墨烯(electorchemical exfoliation graphene, ECG)，此實驗可以製造出全固態（包含電解液）的柔性微電容，該方法顯示了一種簡單、快速且無汙染的製程，應用於生產及組裝具有成本效益且高功率的微型電容器。
本實驗結果顯示此微電容元件具有良好的單位面積電容179.9 mF/cm2，且在彎曲測試時，當彎曲角度達到0°時，電容幾乎無劣化，並且當彎曲角度回復至180°時，電容仍保有高於99%的電容維持率，這歸因於石墨烯電極所提供的高擴散路徑以及促進離子傳輸能力，與此同時，在15000次充放電循環後仍保持高達95％以上的循環穩定性，顯示此元件擁有卓越的操作穩定性以及機械柔韌性。
此外，此微電容元件在能量和功率密度分別為63.96 Wh/cm2以及23485.1 W/cm2。並且，元件的輸出電流與電壓可以利用並聯和串聯數個微電容元件來提升，去達到各種生活應用上的所需效能，也因為其纖維電容之特性，亦可以縫紉於衣物或不同基板材料上，成功演示穿戴式電子元件的展現，最重要的是，這項工作提供了一種具經濟效益的製程來生產高能量與功率密度的固態可撓式微電容，提供未來可穿戴式元件一個新里程碑。

摘要(英)

Micro-supercapacitors (MSCs) are a new type of electrochemical energy storage components that have a high power density, high charge/discharge rate, small size, long cycle life, flexible, environmentally friendly, etc. However, the biggest challenges of MSCs is the limitation of high cost, electrolyte leakage, and complicated manufacturing processes. Therefore, this study aim to solve the manufacturing process and maintaining a high power density of MSCs by using the electrophoretic deposition (EPD. Here, we reported an all solid state and flexible MSCs by comprising the electrochemically exfoliated graphene (ECG) as electrode with the solid-state electrolyte through the controllable EPD process on carbon fiber (F-MSCs). This method shows a scalable, rapid, and eco-friendly process to fabricate and assemble F-MSCs with cost-effective and high-power/energy density.
As a result, the F-MCSc exhibit a high area capacitance of 179.9 mF/ cm2, and maintenance performance of capacitance even under the bending test (from 180o to 0o and back to 0o) with the capacity retention higher than 99%. Also, F-MCSc demonstrates a high cycle stability of up to 95% after 15000 cycles, which was attributed to creating a high diffusion path, promoting ion transport capability, and excellent mechanical flexibility. In addition, the energy and power density of F-MSCs are 63.96 Wh / cm2 and 23485.1 W / cm2, respectively. Furthermore, the output current and voltage of the F-MSCs can be further improved by using several micro-capacitor components with parallel and series connections to fulfill the practical demands of various applications. Finally, we demonstrated the as-prepared F-MSCs could be integrated into with clothing or different substrate materials. This work provides a cost-effective process to produce high energy and power density as well as the all solid state and flexible MSCs, which provids a new milestone for wearable components in the future.

關鍵字(中)

★ 石墨烯
★ 微電容
★ 電泳

關鍵字(英)

論文目次

摘要 i
Abstract iiii
總目錄 iv
圖目錄 vi
表目錄
第一章緒論 1
1-1 前言 1
1-2 電容器介紹 2
第二章研究背景與文獻回顧 5
2-1 微型超級電容器介紹 5
2-2 微型超級電容器之儲能機制 6
2-2-1 電雙層電容器 6
2-2-2 擬電容器 7
2-2-3 混合電容器 8
2-3製備微型超級電容器之材料分類 10
2-3-1 碳材料(Carbon based material) 10
2-3-2 金屬氧化物(Metal oxide) 10
2-3-3 導電高分子(Conducting polymer) 11
2-4 電解液種類介紹 13
2-5 纖維微電容電極製備方法介紹 14
2-5-1 濕式紡絲 (Wet spinning) 15
2-5-2 浸泡塗佈 (Dip coating) 16
2-5-3 電泳沉積 (Electrophoretic deposition) 17
2-6 研究動機 19
第三章實驗方法與分析原理 21
3-1 實驗用品與儀器 21
3-1-1 實驗用品 21
3-1-2 實驗儀器 21
3-2 實驗架構 22
3-3 實驗流程 24
3-3-1 電化學剝離石墨烯製備 24
3-3-2 電泳沉積溶液配置 24
3-3-3 電解液製備 25
3-3-4 指叉結構設計 25
3-3-5 微電容置備 26
3-4 材料分析 27
3-4-1 光學顯微鏡 (Optical Microscopes, OM) 27
3-4-2 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 27
3-4-3 X光光電子能譜儀 (X-ray Photoelectron Spectroscopy，XPS) 27
3-4-4 拉曼光譜分析 (Raman Spectroscopy) 28
3-5 電化學分析 29
3-5-1 循環伏安法分析 (Cyclic Voltammetry，CV) 29
3-5-2 計時電位法分析 (Chronopotentiometry，CP) 29
3-5-3 交流阻抗分析 (Electrochemical Impedance Spectroscopy，EIS) 30
第四章結果與討論 31
4-1 電泳製備條件的優化 31
4-1-1電泳電壓之優化 31
4-1-2電泳時間之優化 38
4-1-3電泳溶液濃度之優化 43
4-2 不同電解液種類及濃度對微電容的影響 (The influence of electrolyte types and concentrations) 50
4-2-1 循環伏安法分析 50
4-2-2 計時電位法分析 52
4-2-3 交流阻抗分析 53
4-3微電容的整合與應用 (In-plane integration of MSCs device) 55
4-3-1微電容元件的穩定性與耐久度測試 55
4-3-2微電容器之平面整合 57
4-3-3元件應用測試 59
4-4各纖維微型電容器之比較 (Compare with previous works) 61
第五章結論 65
第六章未來工作 66
6-1 電解液優化 66
參考文獻 68

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指導教授

蘇清源

審核日期

2020-8-11

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