以奈米銅催化輔助控制多孔石墨烯之孔隙結構及其於超級電容之研究

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蔣建勇(JIAN-YONG JIANG) 查詢紙本館藏

畢業系所

能源工程研究所

論文名稱

以奈米銅催化輔助控制多孔石墨烯之孔隙結構及其於超級電容之研究
(Nano-catalyst assisted pore-structure tailoring of holey-graphene for high performance energy storage)

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摘要(中)

近年來奈米多孔石墨烯在許多重要技術領域中實現了廣泛的應用潛力，而在科學界以及工業界引起不小的關注，對於多功能性的多孔石墨烯來說，要能完全控制其整體孔洞結構和密度。對於高質量負載的電極來說，想要快速地儲存和傳輸能量，離子能有效地在電極材料內移動以及量身定製的多孔性是相當重要的。

本研究呈現一個獨特、簡單且低成本的技術，即是以奈米銅顆粒作為催化劑，由銅顆粒來決定所合成之多孔石墨烯的孔洞尺寸以及形狀，從而產生高孔洞密度(103/µm)。以電化學結果來看，電極材料於高質量負載時，多孔石墨烯的比電容值、能量以及功率密度皆比還原電化學剝離石墨烯(Reduced electorchemical exfoliation graphene, rECG)高出一個數量級，同時於循環15000次之後依然保有高於99%的電容維持率。在電極材料負載量15 mg/cm2時，多孔石墨烯的擴散係數比rECG高出約1.5倍，由於多孔的結構提供離子一個不曲折的貫通傳輸路徑，使多孔石墨烯具有較高之電化學表現。

此外，多孔石墨烯的振實密度(0.72 g/cm3)比rECG(0.0064 g/cm3)高出約兩個數量級，表示多孔石墨烯較不易因回疊而損耗電容量以及具有較高體積電容，本研究證實能夠控制多孔石墨烯的孔洞結構，使電極材料在高負載量時仍能確保離子傳輸的效率，同時也了解到孔洞結構的重要性，並為可控性多孔石墨烯為基礎的技術開啟新的應用道路。

摘要(英)

Nanoporous holey-graphene (HG) recently, made a sensation in scientific and industrial community because of its just actualized versatile potentials in several technologically important fields. The versatility of HG demands a complete control over its entire pore-architecture and density. Particularly, for ultra-high storage and rapid delivery of energy, along with well-tailored porosity, facile through-thickness ion-transport in a high-mass-loaded electrode is immensely important. Here we report, a unique, simple and cost effective copper nanocatalyst assisted predefined porosity tailoring of HG leading to extraordinary high pore-density exceeding 1103 per µm-2. Synchronizing the porosity with high-mass loading results in excellent supercapacitor performance of at least an order higher areal capacitance (~100% retention up to 15000 cycles), energy and power densities along with 90% retainment of gravimetric capacitance (as a function of mass loadings) than rECG. A rapid increase (1.5 fold higher than rECG) of diffusion coefficient (4.0102 fold) as a function of mass loading suggest excellent non-tortuous ion-transport in 15 mg cm-2 HG electrode. Further, two order higher tap-density of HG (0.72 g cm-3) as compared to rECG (0.0064 g cm-3) suggests lower restacking and higher volumetric capacitance of HG. As far our knowledge, this is the first report of complete tailoring of HG porosity blended to facile ion-transport in a high mass loaded electrode and opens new avenue for futuristic HG based technologies wherein pore architecture is significantly important.

關鍵字(中)

★ 多孔石墨烯
★ 銅
★ 奈米催化
★ 奈米孔洞
★ 超級電容

關鍵字(英)

★ holey-graphene
★ copper
★ nano-catalyst
★ nanopores
★ supercapcitor

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
第二章研究背景與文獻回顧 4
2-1 物理性方式製造多孔石墨烯 4
2-2 化學性方式製造多孔石墨烯 10
2-3 奈米多孔石墨烯之應用 16
2-4 研究動機 28
第三章實驗方法與步驟 30
3-1電化學剝離石墨烯之製備 30
3-2多孔石墨烯之製備 31
3-2-1銅/氧化銅-石墨烯(Cu/CuxO-ECG)複合物粉末製作： 31
3-2-2多孔石墨烯的形成： 32
3-3-3銅粒子移除： 35
3-3材料特性鑑定 37
3-3-1 形貌之分析 37
3-3-2 結晶結構分析 37
3-3-3 表面元素成分分析 37
3-3-4 孔洞尺寸分佈 38
3-4電化學量測之實驗流程 39
3-4-1電極製備 39
3-4-2循環伏安法 (cyclic voltammetry, CV) 39
3-4-3計時電位法 (chronopotentiometry, CP) 40
3-4-4交流阻抗分析(electrochemical impedance spectroscopy, EIS) 40
3-5樣品定義 41
第四章結果與討論 42
4-1材料特性分析 42
4-1-1 表面形貌觀察─ u-HG系列 42
4-1-2 表面形貌觀察─ HG-HT系列 48
4-1-3 表面形貌觀察─ h-HG 50
4-1-4 XPS分析結果與討論 52
4-1-5 XRD分析結果與討論 55
4-1-6 Raman分析結果與討論 56
4-1-7 BET分析結果與討論 58
4-2電化學特性分析 60
4-2-1 空白鎳網測試 60
4-2-2 討論無孔洞石墨烯之電化學特性 61
4-2-3 討論多孔石墨烯之電化學特性 65
4-2-4 比較多孔/無孔石墨烯之電化學特性 70
4-2-5 電化學特性綜合比較 74
第五章結論 77

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指導教授

蘇清源(Ching-Yuan Su)

審核日期

2019-6-4

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