多孔石墨烯邊界態之氮改質於超級電容的效能研究

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姓名

黃俊偉(Chun-Wei Huang) 查詢紙本館藏

畢業系所

能源工程研究所

論文名稱

多孔石墨烯邊界態之氮改質於超級電容的效能研究
(Study on Edge-Nitrogen Doped Graphene for High Performance Supercapacitors)

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摘要(中)

近年來氮摻雜石墨烯在諸多領域的研究中展現了比本質石墨烯更優異的電化學特性，石墨烯的氮摻雜可分為三種主要型態，其中對於電化學增益最大的屬於邊界態的氮改質(吡啶(pyridinic)和吡咯(pyrrolic))，透過多孔石墨烯大量裸露的邊界缺陷，促使氮摻雜的過程中石墨烯的邊界缺陷能成為摻雜的優選位置，進而比較出邊界態氮摻雜對電化學及儲能應用上的增益。

本研究利用奈米銅粒子和電化學剝離石墨烯複合物(Cu-ECG)合成氮摻雜多孔石墨烯，奈米銅粒子可以在石墨烯片層上蝕刻出不同大小的孔洞(階層孔洞)，進而利用氨氣熱退火(Ammonia annealing)實現氮摻雜的效果。透過XPS和EDS元素分析可得知，氮摻雜後的多孔石墨烯可同時擁有三種氮摻雜型態，且透過對多孔石墨烯的氮摻雜不僅可以提升氮摻雜率，甚至可有效提升邊界態氮摻雜的比例。

相較於多孔石墨烯，邊界態氮摻雜的多孔石墨烯在高質量負載時的比電容值可增加49.0%且擴散係數也提升了44.4%，且經過15000次的循環測試之後仍可保有高於99%的電容維持率，另外在BET分析中氮摻雜石墨烯的比表面積提升了兩倍以上，且孔隙的尺寸分布也較氮摻雜前更廣。本研究證實氮摻雜可以在不破壞原有特性的情況下有效的提升多孔石墨烯的電化學表現，同時也探討了邊界態氮改質的多寡對氮摻雜多孔石墨烯儲能表現的影響。

摘要(英)

N-doped holey graphene is promoted to solve the main issue of graphene for supercapacitor such as volumetric and gravimetric also the ion-transport mobility. This work proposed two strategies to synthesis N-doped holey graphene with ammonia (NH3) as N-doped precursor. This first strategy, the holey graphene (HG) synthesized by rationally design of the Cu nano catalyst in the annealing method, then the N-doped holey graphene (N-EHG) is produced by post annealing HG in NH3 gas. The second strategy is proposed by post-annealing treatment of Cu nano catalyst/graphene (Cu-Graphene) in NH3 gas to produced N-doped graphene (N-BHG).
Both N-EHG and N-BHG resulted the holey graphene, the edge N-doping (pyridinic and pyrrolic) graphene and graphitic type of N-doping. However, the N-EHG achieved higher surface are up to 509.03 m2/g (2-fold higher than HG) than N-BHG 264.65 m2/g. Also the pore size distribution of N-HG is larger than HG and N-BHG. In the electrochemical application, the N-EHG demonstrated higher specific capacity up to 449.2 mF/cm2 that 49.0% higher than HG (404.2 mF/cm2). In the stability test, the N-EHG could maintain 99% capacity after more than 15,000 cycles retention testing. The diffusion coefficient of N-EHG is increased 44.4% then HG in the high mass loading (15 mg/cm2) that indicate excellent ionic transport. Finally, our method was effectively to synergetic holey and N-doped graphene that a low-cost, highly efficient for supercapacitor application.

關鍵字(中)

★ 氮摻雜石墨烯
★ 多孔石墨烯
★ 超級電容

關鍵字(英)

論文目次

摘要 i
Abstract ii
誌謝 iii
總目錄 iv
圖目錄 vi
表目錄 ix
第一章緒論 1
1-1 石墨烯 1
1-2 氮摻雜石墨烯 3
第二章研究背景與文獻回顧 5
2-1 多孔石墨烯的製造與應用 5
2-1-1 物理方法 5
2-1-2 化學方法 8
2-1-3 多孔石墨烯應用 13
2-2 氮摻雜石墨烯的製備方法及應用 17
2-2-1化學氣相沉積(Chemical vapor deposition, CVD) 17
2-2-2 熱退火(Thermal annealing) 19
2-2-3 水熱法(Hydrothermal method) 22
2-2-4 氮摻雜石墨烯在儲能材料的效能提升與機制 23
2-2-5 研究動機 27
第三章實驗方法與分析 29
3-1 實驗用品與儀器 29
3-2 氮摻雜多孔石墨烯之製備流程 32
3-2-1 電化學剝離石墨烯之製備 32
3-2-2 奈米銅粒子催化劑-石墨烯(Cu-ECG)複合物粉體製作： 32
3-2-3 多孔石墨烯及氮摻雜多孔石墨烯的形成： 33
3-2-4 氨氣熱處理形成氮摻雜多孔石墨烯 36
3-3 試片名稱定義 37
3-4 電化學量測之實驗流程 38
3-4-1 電極製備 38
3-4-2 循環伏安法 (Cyclic voltammetry, CV) 40
3-4-3 計時電位法 (Chronopotentiometry, CP) 40
3-4-4 交流阻抗分析(Electrochemical impedance spectroscopy, EIS) 41
第四章結果與討論 42
4-1 材料特性分析 42
4-1-1 TEM表面形貌觀察 42
4-1-4 XPS分析結果與討論 45
4-1-5 EDS 元素線分析結果與討論 47
4-1-6 接觸角測量 49
4-1-7 Raman 光譜分析結果與討論 49
4-1-8 BET分析結果與討論 51
4-2電化學特性分析 53
4-2-1 討論多孔石墨烯(HG)之電化學特性 53
4-2-2 討論氮摻雜多孔石墨烯(N-EHG)之電化學特性 56
4-2-3 討論氨氣蝕刻之多孔石墨烯(N-BHG)電化學特性 57
4-2-4 三極式電化學特性綜合比較 59
4-2-5 二極式電化學特性比較 66
第五章結論 69

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指導教授

蘇清源(Ching-Yuan Su)

審核日期

2020-7-29

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