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研究生: 饒展螢
Jhan-Ying Rao
論文名稱: 氮,硼和硼/氮摻雜對石墨烯對超級電容器的影響
Effect of Nitrogen-, Boron- and Boron/Nitrogen-doping on Graphene for Energy Storage Application
指導教授: 今榮東洋子
Toyoko Imae
口試委員: 氏原真樹
Masaki Ujihara
周宏隆
Hung-Lung Chou
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2018
畢業學年度: 106
語文別: 英文
論文頁數: 60
中文關鍵詞: 石墨烯
外文關鍵詞: Graphene
相關次數: 點閱:193下載:0
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氧化石墨烯片由石墨薄片合成藉由改良的Hummers法,氧化石墨稀分別與氮和硼混合,然後在180℃下水熱反應12小時。
熱差分析曲線表明,與rGO相比,NG,BG和BNG的碳分解溫度轉移到更高的溫度。比較三種電極系統下的電化學數據,NG,BG,BNG和GO在1M NaCl溶液中的CV電容分別為303,262,225和153 F/g。 NG的比電容值比其他的還要高。因此,acid-CNHox使用與NG相同的程序並與N-CNH反應。熱差分析曲線顯示acid-CNHox和N-CNH的碳分解溫度具有相同的溫度。比較5 mV/s時的CV電容,acid-CNHox和N-CNH分別為219和248 F/g。為了進一步研究NG和N-CNH,充電/放電顯示在1M NaCl溶液中0.8 A/g的比電容分別為128和95 F/g。為了進一步確認結果,NG和N-CNH的比電容由於物理結構,含氮和化學結構而受到影響。此外,在5000次循環後,NG和N-CNH的電容保持率仍分別保持97.9%和98.7%。


Graphene oxide sheets were synthesized from graphite flake by the modified Hummers method and it was doped by nitrogen, boron and both of them by mixing with nitrogen, boron and both of them, respectively and then used hydrothermal method at 180℃ for 12h.
The DTA curve showed that the carbon decomposition temperature of nitrogen-, boron- and boron/nitrogen-doping graphene (NG, BG and BNG) are shifted to more high temperature comparing with rGO. Comparing the electrochemical data under three electrodes system, the Cyclic voltammetry (CV) capacitance of NG, BG, BNG and GO at 5 mV/s in 1M NaCl solution were 303, 262, 225 and 153 F/g, respectively. The specific capacitance of NG was higher than others. Therefore, (acid treated carbon nanohorns) acid-CNHox was synthesized and (N-doped carbon nanohorns) N-CNH was prepared by using same procedure with NG. The DTA curve displayed that the carbon decomposition temperature of acid-CNHox and N-CNH have same temperature. Comparing CV capacitance at 5 mV/s, acid-CNHox and N-CNH were 219 and 248 F/g, respectively. To further investigate NG and N-CNH, galvanostatic charge/discharge showed the specific capacitance of 128 and 95 F/g, respectively, at 0.8 A/g in 1M NaCl solution. The specific capacitance of NG and N-CNH were influenced by the surface area, nitrogen-containing and chemical structure (pyridinic-N, pyrrolic-N and quaternary-N moieties). Furthermore, after 5000 cycles, the capacitance retention of NG and N-CNH still retained 97.9% and 98.7% respectively.

Abstract i 摘要 ii Acknowledgements iii Contents iv List of Figures vii List of Tables ix Chapter 1: Introduction and Motivation 1 1.1 Sort of Supercapacitors 1 1.2 Materials for Supercapacitors 3 1.3 Applications of Supercapacitors 5 1.4 Motivation 8 Chapter 2: Experimental Section 9 2.1 Materials 9 2.2 Synthesis of graphene oxide (GO) and nitrogen, boron and nitrogen/boron–doped graphene 10 2.2.1 Synthesis of nitrogen-doped graphene nanosheets (NG) and reduced graphene oxide 10 2.2.2 Synthesis of boron-doped graphene nanosheets (BG) 11 2.2.3 Synthesis of boron/nitrogen-doped graphene nanosheets (BNG) 11 2.3 Synthesis of oxidized single-wall carbon nanohorns (acid-CNHox) and nitrogen-doped carbon nanohorns (N-CNH) 13 2.4 Preparation of working electrode and electrochemical measurement 14 2.5 Instruments 15 Chapter 3: Results and Discussion 16 3.1 Characterization 16 3.1.1 FTIR (Fourier Transform infrared) adsorption spectra of nitrogen-, boron- and nitrogen/boron–doped graphene 16 3.1.2 The thermal behaviors of nitrogen-, boron- and nitrogen/boron–doped graphene 20 3.1.3 FTIR of carbon nanohorns, acid-treated single-wall carbon nanohorns and nitrogen-doped carbon nanohorns 22 3.1.4 The thermal behaviors of nitrogen-doped carbon nanohorns 24 3.2 Comparison of nitrogen-doped graphene and nitrogen-doped carbon nanohorns 25 3.2.1 Morphological comparison of nitrogen-doped graphene and nitrogen-doped carbon nanohorns 25 3.2.2 The comparison of surface characteristics nitrogen-doped graphene and nitrogen-doped carbon nanohorns 26 3.2.3 X-Ray Photoelectron Spectroscopy (XPS) of nitrogen-doped graphene and nitrogen-doped carbon nanohorns 29 3.3 Electrochemical properties of N-and/or B-doped carbons 34 3.3.1 Cyclic voltammetry result of nitrogen, boron and nitrogen/boron-doped graphene and nitrogen-doped carbon nanohorns 34 3.3.2 Galvanostatic charge/discharge and electrochemical impedance spectroscopy result for comparing nitrogen-doped graphene and nitrogen-doped carbon nanohorns 38 3.3.3 Cycle life of capacitance retention for nitrogen-doped graphene and nitrogen-doped carbon nanohorns 41 Chapter 4: Conclusion 43 References 45

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