電化學法所製備石墨烯及其硼摻雜改質之 超級電容特性分析

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李馳(LI CHI) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

電化學法所製備石墨烯及其硼摻雜改質之超級電容特性分析
(Supercapacitor Properties of Electrochemical Exfoliation Graphene and Boron doping effect in Ionic Liquid Electrolytes)

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摘要(中)

摘要
本研究主要是利用電化學電解方法法剝離製備石墨烯，用來做為超高電容器的電極，電解液則是選用擁有廣大電位窗的離子液體，藉以得到高的能量密度以及功率密度。
目前超高電容電極材料多以石墨烯方向發展，但製程皆過於繁複，本研究期望利用簡便的電化學電解的方法，利用不同電解電流製造不同石墨烯并探討其對於超高電容電化學性質之影響。本研究選用三種不同電解電流下之石墨烯在離子液體BMP-DCA中進行比較，分別是3 A電流下電解之石墨烯 (3 A)、4.5 A電流下電解之石墨烯 (4.5 A)以及6 A電流下電解之石墨烯 (6 A)，根據結果顯示，3 A石墨烯的比電容值高於其他兩者，並且擁有高的比電容值 (198 F/g)、能量密度 (74.9 Wh/kg)以及高的功率密度 (18.6 kW/kg)，五百圈後維持率仍有86 %。目前超高電容普遍是以rGO在為主軸，本研究比較高溫熱還原之石墨烯以及電化學電解石墨烯在離子液體BMP-DCA的超高電容行為，由結果得知電化學電解石墨烯在離子液體BMP-DCA中有較好的超高電容性能。
本研究嘗試通過摻雜硼原子來對電化學石墨烯進行改質，透過對電化學石墨烯與硼酸之高溫燒結，可以得到最高硼含量為7.5%之石墨烯，因而作為電極材料應用于超高電容中，其中可以得到可以得到最佳硼摻雜條件為硼酸與石墨烯質量比為3:7時，其擁有最高的比能量密度46.9 Wh/kg，以及比功率密度8.6 kW/kg，五百圈後維持率為183%。
關鍵詞：超高電容器、離子液體、石墨烯、電化學電解、B-doping

摘要(英)

ABSTRACT
The graphene sheets were prepared by Electrochemical Exfoliation method in this study, and were used for the electrode in supercapacitor. We chose ionic liquids as electrolyte for their wide potential window to get better energy density and power density.
Currently, most of supercapacitor electrodes are graphene sheets, but the processes are too complicated, so this study expects to use a simple electrochemical method to get graphene. We choose different electrolytic currents to manufacture different kind of graphene and then discuss the influences of the electrochemical properties in supercapacitor. In our study, three different electrolysis currents of graphene are choosen to be compared in the ionic liquid BMP-DCA. According to the results, it showed that the current of 3A graphene has a specific capacitance which is higher than the other two. The 3A graphene has a high specific capacitance (198 F / g), which gets better energy density for 74.9 Wh/kg and power density for 18.6 kW/kg, and the retention after five hundred cycles is still 86%. In general, the main manufacture of capacitors electrode is reduced graphene oxide (rGO). So in this study, we also compare the behaviors of the rGO which use the thermal reduction and the electrochemical exfoliation graphene in ionic liquids BMP-DCA. From the results, it shows that the electrochemical exfoliation graphene has the better performance in BMPDCA.
In our study, we attempt to make the electrochemical graphene modified by doping boron atoms through mixing the graphene and boric acid in boiler tube. Then we can get the graphene which the content of boron can be up to 7.5%, and thus use it in supercapacitors as electrode, When the mass ratio of boric acid and graphene is 3:7, we obtain the optimum conditions, which has the highest energy density of 46.9 Wh/kg, and a specific power density of 8.6 kW/kg, and 183% retention after five hundreds cycle.

Key Word: Supercapacitor, Ionic liquid, Graphene, Electrochemical exfoliation, Boron-doping.

關鍵字(中)

★ 超高電容器
★ 離子液體
★ 石墨烯
★ 電化學電解
★ B-doping

關鍵字(英)

論文目次

目錄
第一章、前言 1
第二章、文獻回顧 3
2-1能源儲存裝置概述 3
2-2 超高電容器簡介 5
2-2-1電雙層電容器 (EDLC) 6
2-2-2擬電容器 (pseudo-capacitors) 7
2-3超高電容器之電解質 11
2-4電雙層電容器之材料分類 19
2-5石墨烯之製備方法 22
2-6石墨烯之摻硼改質方法 33
第三章、實驗步驟 37
3-1 碳材之準備 37
3-1-1石墨烯之製備 37
3-1-2摻雜石墨烯之製備 38
3-2電解液之製備 39
3-3 材料特性分析 40
3-3-1表面形貌之觀察 40
3-3-2表面組成以及缺陷結構 40
3-3-3結晶結構分析 40
3-4 碳材於離子液體內電化學性質之評估 41
3-4-1電極之製備 41
3-4-2電化學裝置 41
3-4-3電化學性質之評估 41
第四章、結果與討論 44
4-1不同電流下得到之電化學剝離石墨烯於離子液體內之比較 44
4-1-1不同電流下石墨烯表面形貌之觀察 44
4-1-2電化學剝離石墨烯表面組成以及缺陷結構 45
4-1-3電化學剝離石墨烯結晶結構分析 47
4-1-4離子液體BMP-DCA 47
4-1-5電化學剝離石墨烯於離子液體BMP-DCA中之儲電性能 48
4-1-6電化學剝離石墨烯之小結 51
4-2電化學法剝離石墨烯與熱還原法石墨烯於離子液體之比較 52
4-2-1不同碳材表面形貌之觀察 52
4-2-2不同碳材表面組成以及缺陷結構 53
4-2-3不同碳材結晶結構分析以及比表面積分析 54
4-2-4不同碳材於離子液體BMP-DCA中之儲電性能 54
4-2-5不同製程之石墨烯之小結 56
4-3 B doping之電化學剝離石墨烯於離子液體內之比較 57
4-3-1不同B doping下石墨烯表面形貌之觀察 57
4-3-2不同B doping下石墨烯表面組成以及缺陷結構 58

4-3-3電化學剝離之B doping石墨烯於離子液體BMP-DCA中之儲電性能 59
4-3-4電化學剝離石墨烯之小結 62
第五章、結論 95
參考文獻 97

參考文獻

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指導教授

張仍奎

審核日期

2016-7-25

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