臺灣博碩士論文加值系統

本研究將商售活性碳藉添加多孔石墨烯並在有機電解液系統下封裝成鈕扣型超級電容（Coin-SCs）探討其電容特性，研究主要分為三大部分：第一部分，吾人將多孔石墨烯經由改變退火溫度，控制石墨烯表面上的含氧量，並測試其電化學特性之影響。由XPS及EA分析顯示隨著退火溫度提高，多孔石墨烯表面的殘留含氧官能基越少，因含氧官能基在有機電解液下會增加內阻抗，反而降低其電容特性。
第二部分中，吾人改變多孔石墨烯與活性碳的混拌比例，由SEM觀察極片表面可發現當多孔石墨烯與活性碳之重量比為1：10時，能均勻塗佈表面。由電化學分析結果顯示，因多孔石墨烯表面上有許多孔洞，使電解液能較快速擴散至內部孔隙，在高電流密度下能有較高的維持率。另交流阻抗EIS測試中，添加多孔石墨烯的活性碳相較於純活性碳有較低的內阻抗，內阻抗從約40Ω降至10Ω，此結果更加證明多孔石墨烯因表面上的多孔結構，能縮短離子擴散的路徑，提升高速充放電時的電容維持率。
最後，第三部分，進一步將多孔石墨烯進行氮摻雜改質，藉由石墨烯表面含有氮官能基提高電容量。在能量密度及功率密度方面，氮摻雜多孔石墨烯與活性碳混拌之超級電容，其能量密度大約提高5倍，循環壽命在經一萬次循環後能有70%的維持率，未來將有機會解決目前商售之活性碳超級電容市場上高功率、高能量、長使用壽命與低成本無法兼備之困境。

In this study, the commercial activated carbon was added with holey graphene and encapsulated into a coin supercapacitor (Coin-SCs) under the organic electrolyte system. The study was mainly divided into three parts. First part, we control the oxygen content on the surface of graphene by changing the different annealing temperatures and tests the effect of electrochemical properties. The analysis of XPS and EA shows that the residual oxygen-containing functional groups on the holey graphene are smaller along with the annealing temperature increasing. The internal resistance is increased by the oxygen-containing functional groups under the organic electrolyte.
In the second part, we change the ratio of holey graphene and activated carbon. It can be found that the surface of the pole piece can be uniformly coated when the weight ratio of holey graphene and activated carbon is 1:10. Electrochemical analysis showed that it has a high maintenance rate at high current density because there are many pores on the surface of the holey graphene, so that the electrolyte can diffuse more rapidly into the internal pores. In the EIS analysis, the activated carbon with the holey graphene has a lower internal impedance compared with that the pure activated carbon, and the internal impedance decreased from 40 Ω to 10 Ω. This results further demonstrate the porous structure on the surface of the holey graphene, it can shorten the ion diffusion path, and enhance the capacitance retention under the high-speed charge and discharge.
Finally, in the third part, the holey graphene is further modified by nitrogen doping, and the capacity is increased by the presence of nitrogen functional groups on the surface of the graphene. In terms of energy density and power density, the energy density of nitrogen-doped holey graphene and activated carbon is about 5 times higher than the activated carbon. The cycle life can be 70 % after 10,000 cycles. In the future, it has the opportunity to solve the problems of the current commercial activated carbon supercapacitor that can not both with the high power, high energy, long life and low cost.

誌謝 ii
摘要 iii
Abstract iv
表目錄 viii
圖目錄 ix
1.緒論 1
1.1前言 1
1.2研究動機 3
2.文獻回顧 5
2.1超級電容 5
2.1.1超級電容簡介 5
2.1.2超級電容儲能機制 8
2.2石墨烯 11
2.2.1石墨烯之發現 11
2.2.2石墨烯之性質與應用 12
2.2.3石墨烯製備方法 16
2.3超級電容 27
2.3.1多孔碳/活性碳超級電容 27
2.3.2石墨烯超級電容 30
3.研究方法與設備 49
3.1 實驗流程圖 49
3.2 多孔石墨烯製備 50
3.2.1 氧化石墨之製備 50
3.2.2多孔石墨烯之製備 51
3.3多孔石墨烯之退火處理 51
3.4多孔洞石墨烯混拌活性碳之製備 51
3.5氮摻雜多孔石墨烯之製備 51
3.6電化學分析 52
3.6.1循環伏安法(Cyclic voltammetry, CV) 52
3.6.2定電流充放電測試(Galvanostatic charge/discharge, GCD) 53
3.7實驗藥品與儀器 54
4.結果與討論 56
4.1退火溫度對多孔石墨烯之結構特性與全電容特性之影響 56
4.1.1退火溫度對於多孔石墨烯結構特性之影響 56
4.1.2退火溫度對於多孔石墨烯全電容特性之影響 65
4.2多孔石墨烯/活性碳複合物之製備與全電容特性 70
4.2.1多孔石墨烯/活性碳複合物之結構特性 70
4.2.2多孔石墨烯/活性碳複合物之全電容特性 75
4.3氮摻雜多孔石墨烯/活性碳結構特性及全電容特性之影響 82
4.3.1氮摻雜對於多孔石墨烯結構特性之影響 82
4.3.2氮摻雜多孔石墨烯/活性碳之全電容特性 88
5.結論 97
參考文獻 99
未來規劃 108
自傳 110

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