臺灣博碩士論文加值系統

本研究以有機官能基改質之石墨烯（FGO）與鄰甲氧基苯胺單體，利用原位聚合法製備出聚鄰甲氧基苯胺-石墨烯奈米複合材料，所製備出的奈米複合材料利用傅利葉轉換紅外線光譜（FTIR）、X光繞射儀（XRD）、X光電子能譜儀（XPS）、穿透射電子顯微鏡（TEM）等儀器鑑定。由XRD分析顯示，所製備的奈米複合材料隨著改質石墨烯比例增加產生新的結晶面，從穿透式電子顯微鏡觀察插層分散之改質石墨烯呈現平行的規則性排列，其原因是導電高分子與所設計的改質石墨烯存在著化學鍵結，高分子鏈成長過程因為苯環結構彼此有π-π交互作用，而使得石墨烯與高分子間形成較為平行的排列，以層狀型態形成奈米複合材料。
本研究在應用方面分為兩部份，包括電化學電容及染料敏化太陽能電池的應用。經由循環伏安法(CV)與電化學阻抗頻譜(EIS)分析發現，添加FGO後電容量增加(由75 F/g 提升至117.7 F/g) ， 電荷轉移電阻(Rct)下降(由13.23 Ω下降至8.89 Ω)，表示FGO可以有效提升奈米複合材料之電化學行為。
而應用於染料敏化太陽能電池背電極部份，目的希望取代昂貴的白金電極，研究結果證實本研究以聚鄰甲基苯胺導電高分子取代白金電極之元件效率最高達8.29％，有機會應用在於染料敏化太陽能電池。在提升元件效率方分別嘗試有機酸摻雜及石墨烯添加策略。結果顯示有機酸摻雜後催化能力大幅提升，符合預期效益。然而添加FGO元件效率卻下降，由CV量測結果得知其電化學行為氧化還原電位差較大，推測其原因可能是FGO本身共軛結構較不完整，使得POMA/FGO奈米複合材料作為背電極時，元件之內電阻較大，造成染料敏化太陽能電池效率不好。

In this study, an organic functionalized graphene oxide (FGO) was modified with an o-methoxyaniline monomer, and then a series of poly(o-methoxyaniline) (POMA)/graphene-based nanocomposites were prepared by using an in situ oxidative polymerization method. The FGO and as-prepared nanocomposits were characterized by Fourier transform infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The intercalated layers of FGO appeared with parallel orientation in the polymer matrix were observed in TEM images. The results are in consistent with XRD analysis, which increasing in diffraction intensity for the as-prepared POMA/FGO nanocomposites. Multiple interactions include chemical bonding and aromatic - interaction might attribute to the orientated morphology.
We also investigated the applications for the as-prepared nanocomposits in two fields include electrochemical capacitors and dye-sensitized solar cells (DSSCs). Electrochemical capacitor studies show that POMA/FGO nanocomposite exhibited a higher capacitance compared with pure POMA, in which the capacitance increased from 75 F/g to 117.7 F/g with the incorporation of 0.5 wt% FGO in the POMA polymer matrix. The electrochemical impedance spectrum (EIS) analysis showed decreasing of diameter for the semi-circle in Nyquist plot; and the charge transfer resistance (Rct) decreased from 13.23 to 8.89 Ω. The results indicate that the electrochemical behaviors of nanocompositescould be enhanced by the incorporation of FGO.
In DSSCs studies, we used pure POMA, organic acid doped POMA, and POMA/FGO nanocomposites employed as the counter electrodes (CEs) in DSSCs. The DSSC based on the organic acid doped POMA CE achieves a remarkable power conversion efficiency of 8.29%. The result indicates that the doped-POMA may have potential to replace the expensive Pt CE for DSSCs application. However, the power conversion efficiency of doped-POMA/FGO nanocomposites CEs was lower than that of doped-POMA. This may be attributed to a higher internal resistance was observed by the cyclic voltammetry studies for the doped-POMA/FGO nanocomposites as compared to the doped-POMA.

摘要 I
Abstract III
目錄 IV
圖目錄 VII
表目錄 XIV
第一章 緒論 1
1-1 前言 1
1-2 石墨烯介紹及製備 3
1-2-2 石墨烯的化學與物理性質 6
1-2-3 石墨烯的製備方法 7
1-3 導電高分子介紹 16
1-3-1 導電高分子的起源 16
1-3-2 基本能帶理論與摻雜理論 17
1-3-3 共軛高分子導電理論 19
1-3-4 主要共軛高分子結構 20
1-3-5 聚苯胺(Polyaniline) 21
1-3-6 聚苯胺的聚合 24
1-3-7 聚苯胺之結晶形分析 25
1-4奈米複合材料介紹 27
1-4-1奈米複合材料種類 27
1-4-2 石墨烯/高分子奈米複合材料的合成方法 28
1-5 染料敏化太陽能電池 31
1-6 聚苯胺/石墨烯奈米複合材料 35
1-6 研究動機與目的 42
第二章 實驗部份 43
2-1 實驗藥品 43
2-2 鑑定及分析儀器 46
2-3 實驗儀器介紹 48
2-3-1循環伏安法(Cycle Voltammetry) 48
2-3-2電化學分析儀(EIS) 50
2-4 材料合成步驟 52
2-4-1 改質 Hummers`method製備氧化石墨烯之合成 53
2-4-2鄰甲氧基苯胺修飾氧化石墨烯(GO)之製備方法 55
2-4-3 原位聚合法FGO/POMA奈米複合材料 57
第三章 結果與討論 65
3-1結構形貌鑑定 65
3-1-1 傅立葉轉換紅外線光譜儀(FT-IR) 65
3-1-2化學分析電子光譜(XPS) 69
3-1-3 拉曼光譜(Raman spectroscopy)鍵定 75
3-1-4 X射線粉末繞射儀(XRD)分析 76
3-1-5 穿透式電子顯微鏡(TEM)之鑑定 79
3-2熱性質分析 82
3-2-1 熱重力分析 (TGA) 82
3-3石墨烯/聚鄰甲氧基苯胺奈米複合材料的電化學電容應用研究 85
3-3-1 循環伏安法 85
3-3-2交流阻抗圖譜(EIS)分析 86
3-3-3充放電圖分析 88
3-4聚鄰甲基氧苯胺染料敏化太陽能電池 89
3-4-1 有機酸摻雜POMA在染料敏化太陽能電池的應用研究。 90
3-4-1-1循環伏安法 90
3-4-1-2 IPCE 91
3-4-1-3 J-V curve 92
3-4-2 POMA/FGO 奈米複合材料在染料敏化太陽能電池的應用研究 94
3-4-2-1 循環伏安法 94
3-4-1-2 IPCE 95
3-4-2 J-V curve 96
第四章 總結 102
第五章 參考文獻 104

圖目錄
圖1-1 Ruoff 團隊於2006年發表以phenyl isocyanate改質，及1,1-dimethylhydrazine還原的graphene oxide 至倍之0.48 vol. % graphene/polystyrenes 複合材料；其導電性隨graphene添加量增加而提升 2
圖1-2 2010年諾貝爾物理獎得主Andre Geim(左)及Konstantin Novoselov(右) 3
圖1-3 C60、奈米碳管及石墨烯等碳家族之基本構造 5
圖1-4 James M. Tour的研究團隊等人報導之GO的合成方法 (Improved Method)之流程示意圖 9
圖1-5 GO之結構示意圖 10
圖1-6 2009年Air Ivaska研究團隊利用3-丙胺三乙氧基矽烷(3-Aminopropyltriethoxysilane, APTS)的胺基(Amine Group)與石墨烯氧化物(GO)上的環氧基(Epoxide Group)進行親電子基取代反應 11
圖1-7 2008年James M. Tour的研究團隊等人利用聯胺(Hydrazine)與界面活性劑十二基烷基苯磺酸鈉(Surfactant Dodecyl Benzonium Salt,SDBS)進行還原，形成化學轉換的石墨烯(Chemical Converted Graphene, CCG)，再與親電子取代的芳基重氮鹽(Aryl Diazonium Salt)反應最後形成能高度分散於有機溶劑中的石墨烯 11
圖1-8 2006年Rodney S. Ruoff的研究團隊等人先製備石墨烯氧化物，然後利用異氰酸酯化合物( Isocyanate Compound) 與氧化石墨烯上的羧基(Carboxylic Group)和烴基(Hydroxyl Group)行縮合反應，得到一系列異氰酸之酯功能化石墨烯(i-GO) 12
圖1-9 2011年Xianbao Wang的研究團隊等人利用甲殼素(Chitosan, CS)上的胺基(Amine Group)與氧化石墨烯上的羧基反應，進行縮合反應，形成醯胺鍵結(Amide linkages) 12
圖1-10 2010年Vasilios Georgakilas利用1,3-偶極子(Azomethine Ylid)與無缺陷的石墨烯(Defect-free Graphene)進行1,3-偶極環加成反應(1,3-Dipolar Cycloaddition) 13
圖1-11 2009年Thomas P. Davis研究團隊等人利用石墨烯的π軌域和聚(N-丙烯醯胺)(Poly(N-Isopropylacrylamide, PNIPAAM)的π軌域形成π-πInteraction 14
圖1-12 2008年Rodney S. Ruoff的研究團隊等人利用氫氧化鉀水溶液(KOH Aqueous)的鉀離子(K+)與石墨烯氧化物(GO)的羧基離子(COO-)形成離子鍵結，再利用聯胺(Hydrazine)還原形成hKMG 15
圖1-13 不同材料的導電度及材料屬性分界 18
圖1-14 極子(polaron)與雙極子(bipolaron)能階圖 20
圖1-17 m-toluidine、o-toluidine及o-methoxyanilne的結構式 23
圖1-18 (a)中間氧化態(Emeraldine Base) (b) 經鹽酸摻雜之導電中間氧化鹽態(Emeraldine Salt)之XRD圖。 25
圖1-19 TPU/TRG奈米複合材料合成及TEM比較 30
圖1-20 染料敏化太陽能電池基本架構及工作原理 33
圖1-21 PANI-G-rGO 合成步驟 35
圖1-22 PANI-G-RGO於1M 硫酸溶液偵測循環伏安法 36
(掃描速率100 mV/S). 36
圖1-23 左圖為 PaniNF/G 複合材料薄膜，右圖為其 37
應力應變(Stress – strain)曲線 37
圖1-24 sGNS、PANI以及sGNS/PANI奈米複合材料的循環伏安圖 (掃描速率:1 mV s-1) 38
圖1-25 sGNS、PANI以及sGNS/PANI奈米複合材料的充放電圖 (電流: 0.2 A g-1) 38
圖1-26 Pt、PANI-N以及PANI-SDS/白金元件的J-V曲線圖 39
圖1-27 Pt、PANI-N以及PANI-SDS/白金元件的阻抗頻譜圖 39
圖1-28 PANI、PANI-1wt‰ graphene complex、PANI-4wt‰ graphene complex
以及PANI-8wt‰ graphene complex白金元件的JV阻抗頻譜圖 40
圖1-29 Pt、PEDOT-10s、PEDOT-20s、PEDOT-40s以及PEDOT-60s白金元件的JV阻抗頻譜圖 41
圖2-1 玻璃碳電極偵測5 mM K4Fe(CN)6 in 0.1 M KCl水溶液CV圖 49
圖2-2 阻抗示意圖 51
圖2-3 阻抗頻譜分析圖 51
圖2-4 POMA/FGO奈米複合材料製備示意圖 52
圖2-5 Improved Hummers` method方法製備氧化的石墨烯之流程 54
圖2-6 鄰甲氧基苯胺修飾氧化石墨烯製備流程圖 56
圖2-7 FGO/POMA奈米複合材料之製備流程 58
圖2-8 循環伏安法模具製備流程 59
圖2-9 三電極示意圖 60
圖2-10敏化太陽能電池測試三電極示意圖 62
圖2-11敏化太陽能電池測試三電極示意圖 63
圖3-1材料鑑定應用之實驗流程圖 65
圖3-2 材料之傅立葉轉換紅外線光譜圖(a) Graphite, (b) GO, (c) FGO, (d) OMA 68
圖3-3 C1s的化學分析電子光譜(a) GO (b) FGO 71
圖3-4 O1s的化學分析電子光譜 (a) GO (b) FGO 72
圖3-5 N1s的化學分析電子光譜 FGO 73
圖3-6 ESCA之全能譜 (a) Graphite (b) GO (c) FGO 74
圖3-7 石墨改質前後之Raman圖 75
圖3-8 材料X-ray繞射儀圖譜(a) Graphite (b) GO (c) FGO 77
圖3-9 POMA/FGO奈米複合材料之X-ray繞射儀圖譜 (a) FGO(b) POMA/0.25％FGO, (c) POMA/0.50％FGO, (d) POMA/0.75％FGO, (e) POMA/1.00％FGO and (f) POMA 78
圖3-10 氧化石墨烯 (GO) 的TEM圖 80
圖3-11 改質氧化石墨烯 (FGO) 的TEM圖 80
圖3-12 POMA/FGO之TEM分析圖 81
圖3-13 POMA/FGO 鍵結示意圖 82
圖3-14 材料之熱重力分析圖 (a) Graphite (b) GO (c) FGO 83
圖3-15 不同比例組成的POMA/FGO奈米複合材料之TGA (a) POMA (b) POMA/0.50％FGO, (c) POMA/1.00％FGO 84
圖3-16 材料於1 M硫酸溶液的循環伏安圖 (a)POMA, 86
(b) POMA/0.50％FGO, (c) POMA/1％FGO 86
表3-6 POMA, POMA/0.50％FGO,POMA/1％FGO之比電容比較 86
圖3-17 材料於1 M硫酸溶液的交流阻抗圖譜 (a)POMA, (b) POMA/0.50％FGO, (c) POMA/1％FGO 87
表3-7 POMA, POMA/0.50％FGO,POMA/1％FGO阻抗值 87
圖3-18 材料於1M硫酸溶液的充放電圖譜 88
(a)POMA, (b) POMA/0.50％FGO, (c) POMA/1％FGO 88
表3-8 POMA, POMA/0.50％FGO,POMA/1％FGO充放電值 89
圖3-19 POMA及POMA-doping的循環伏安法圖 91
圖3-20 POMA及POMA-doping元件之外部量子效率圖 92
圖3-21 POMA及、POMA-doping元件的J-V曲線圖。 93
圖3-22 POMA、POMA/0.5％FGO 95
及POMA/1％FGO的循環伏安法圖 95
圖3-23 POMA、POMA/0.5％FGO、 96
POMA/1％FGO元件的外部量子效率圖 96
圖3-24 POMA、POMA/0.5％FGO、 97
及POMA/1％FGO的J-V曲線圖 97
圖3-25 POMA-doping、POMA/0.5％FGO-doping 98
及POMA/1％FGO-doping的循環伏安法圖 98
圖3-26 POMA-doping、POMA/0.5％FGO-doping及POMA/1％FGO-doping元件之外部量子效率圖 99
圖3-27 POMA-doping、POMA/0.5％FGO-doping及POMA/1％FGO-doping的J-V曲線圖 100

表目錄
表1-1 氧化鹽態(Emeraldine Salt) XRD圖之訊號 26
表1-2 PANI、PANI-1wt ‰ graphene complex、PANI-4wt ‰ graphene complex以及PANI-8wt ‰ 的EIS及J-V數值 40
表1-3 Pt、PEDOT-10s、PEDOT-20s、PEDOT-40s及PEDOT-60s白金元件的EIS及J-V數值 41
表2-1 不同比例的奈米複合材料 57
表3-1 Graphene oxide、FGO與o-methoxyaniline之FT-IR數值表 67
表3-2 化學分析電子能譜之原子組成含量彙整 74
表3-3 Graphite、GO、FGO的Raman 光譜圖之數據 76
表3-4 XRD數據表 78
表 3-5 POMA與不同FGO之熱裂解溫度 85
表3-6 POMA, POMA/0.50％FGO,POMA/1％FGO之比電容比較 86
表3-7 POMA, POMA/0.50％FGO,POMA/1％FGO阻抗值 87
表3-8 POMA, POMA/0.50％FGO,POMA/1％FGO充放電值 89
表3-9 POMA、POMA-doping及Pt的J-V數值 93
表3-10 POMA、POMA/FGO摻雜與否及Pt的J-V數值 101

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