博碩士論文 100223048 詳細資訊




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姓名 馬雷(Lei Ma)  查詢紙本館藏   畢業系所 化學學系
論文名稱 含甲酸吡啶輔助配位基之無硫氰酸釕金屬光敏劑的合成及其在染料敏化太陽能電池上的應用
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摘要(中) 由於全球暖化危機,尋找好的再生能源是目前非常重要的議題,而取之不盡、用之不竭,乾淨且少污染的太陽能是目前最被看好的能源。染料敏化太陽能電池(DSSCs)是被廣泛研究的新型式太陽能電池之一。此類型電池光電流的來源-染料,是影響電池光電轉換效率與元件長時間穩定性的重要關鍵。以釕金屬為中心的高效率錯合物染料通常是以兩個雙牙基(bipyridine)及兩個單牙基(Thiocyanate ligand﹙NCS﹚)所組成的六配位錯合物,但單牙基的NCS穩定度低。本論文研究重點即合成出一個新結構雙牙基輔助配位基Ligand-30,再使用Ligand-30取代兩個單牙基NCS利用“Two-step syntheses”合成法製備釕金屬錯合物 CYC-B30。合成CYC-B30有三種空間異構物:CYC-B30(P1)、CYC-B30(P2) 以及CYC-B30(P3),產率分別為 4.4 %、12.3 %以及 6.3 %。這三個染料分子的最大吸收波長與吸收係數分別為 526 nm (2.73×104 M-1 cm-1)、535 nm (3.69×104 M-1 cm-1)以及 534 nm (3.41×104 M-1 cm-1)。以CYC-B30(P1)、CYC-B30(P2)以及CYC-B30(P3)所敏化的電池元件,在AM 1.5 光源照射,光電轉換效率分別為 3.01 %、4.02 %以及 4.68 %。此外,由於CYC-B30(P2)的產率最高,因此選擇以CYC-B30(P2)所敏化的電池元件與本實驗室先前所合成的CYC-B29(P2)所敏化的電池元件的光電表現做比較,以瞭解釕錯合物染料結構與其光電表現的關係。
摘要(英) Renewable energy is an important and inexhaustible subject partly due to the global warming issue. Solar energy is one of the most promising source of energy. Dye-sensitized solar cells (DSSCs) are a new generation solar cell under widely studied. Dye molecule is the source for the photocurrent of DSSC and affect the conversion efficiency and stability of the corresponding devices. Ruthenium dye for DSSC usually contains two bipyridine bidentates and two thiocyanate (NCS) monodentate ligands to form a hexacoordinated complex. However the monodentates have low stability. In this thesis we focus on the synthesis of a new bidentate ancillary ligand, named Ligand-30. Then use Ligand-30 to synthesis CYC-B30 using a “Two-step” synthesis method. CYC-B30 has three spatial isomers: CYC-B30(P1), CYC-B30(P2) and CYC-B30(P3) with a respective yield of 4.4 %, 12.3 % and 6.3 %. The max (the corresponding absorption coefficient) of these three dye molecules were 526 nm (2.73x104 M-1 cm-1), 535 nm (3.69 x 104 M-1 cm-1) and 534 nm (3.41 x 104 M-1 cm-1), respectively. DSSCs based on CYC-B30(P1), CYC-B30(P2) and CYC-B30(P3) under AM 1.5 light source achieve the conversion efficiency of 3.01 %, 4.02 % and 4.68 %, respectively CYC-B30(P2) has the highest yield among three isomers, it was used to compare with CYC-B29(P2) dye to understand the relationship between the structure and photovoltaic performance of Ru based sensitizers.
關鍵字(中) ★ 太陽能電池 關鍵字(英)
論文目次 壹、序論 1
1- 1、前言 1
1- 2、太陽能電池的種類 2
1- 3、染料敏化太陽能電池(Dye-sensitized solar cells, DSSCs, 簡稱染敏電池)之介紹 2
1- 4、光電轉換效率(η)的量測 5
1-4-1、IPCE(Incident Photon to current Conversion Efficiency) 6
1-4-2、總光電轉換效率( η ) 6
1-5、光敏化劑(染料)概述 7
1-6、钌金屬光敏化劑 8
1-6-1、雙牙固著配位基之釕金屬錯合物染料: 8
1-6-1-1、對稱型(Homoleptic)與非對稱型(Heteroleptic)釕金屬錯合物染料 9
1-6-1-2、輔助配位基(Ancillary ligand)的修飾 11
1-6-1-3、固著配位基(Anchoring Ligand)的修飾 19
1-6-1-4、Thiocyanate Ligand 在釕金屬配位錯合物上的穩定性 22
1-6-1-5 不含Thiocyanate Ligand的釕金屬錯合物 23
1-6-2、三牙固著配位基之釕金屬錯合物染料: 26
1-7、研究動機: 32
貳、實驗部分 35
2-1、實驗藥品 35
2-2、儀器分析與樣品製備 39
2-2-1、紫外光/可見光吸收光譜儀﹙UV/Vis. Spectrometer﹚ 39
儀器型號:Cary 300 Bio 39
2-2-2、核磁共振光譜儀 ﹙NMR﹚ 40
儀器型號:Bruker300&Bruker500 40
2-2-3、電化學測量裝置 ﹙Electrochemical Measurement﹚; 40
儀器型號:AUTOLABPGSTAT30 電位/電位儀 40
2-2-4、交流阻抗分析﹙AC-Impedance analysis﹚; 41
儀器型號:ECO CHEMIE Autolab PGSTAT30 Potential/Galvanostate with FRA 2 41
2-2-5、太陽光模擬器與元件I-V效率量測系統 (Solar Simulator and I-V measurement system) 44
儀器型號:YSS-50A 44
2-2-6、太陽能電池外部量子效率量測系統 (Incident Photon to Current Conversion Efficieny, IPCE) 44
儀器型號:Enti-Tech QE-R3011 44
2-2-7、光強度調制光電流/光電壓分析儀 (intensity modulated photocurrent spectroscopy , IMPS / intensity modulated photovoltage spectroscopy, IMVS) 45
儀器型號:Zahner CIMPS-1 45
2-2-8、瞬態吸收光譜 (Transient Absorption Spectroscopy,TAS) 46
儀器型號:Ultrafast Proteus 46
2-2-9、長時間加速老化測試 (longterm accelerated aging test) 48
儀器型號:KD-SALC-0404 48
2-3、合成輔助配位基﹙Ligand 29 & Ligand 30﹚ 49
2-3-1、Ligand 29的合成步驟 49
2-3-2、Ligand 30的合成步驟 50
2-3-2-1、4-Bromopyridine(簡稱4-BrPy) 以及4-Bromopyridine N-oxide(簡稱4-BrPy-N-oxo)的合成 50
2-3-2-2、4-Bromo-2-pyridine-carbonitrile(簡稱4-Br-2-CNPy)的合成 52
2-3-2-3、5-Thiohexyl-(3,4-ethylenedioxy)thiophene(簡稱EDOT-SR)的合成 52
2-3-2-4、(5-Thiohexyl-(3,4-ethylenedioxythiophene-2-yl)) Trimethylstannane(簡稱EDOT-SR-5-tin)的合成 53
2-3-2-5、4-(5-Thiohexyl-(3,4-ethylenedioxy)thiophene-2-yl)) picolinonitrile(簡稱EDOT-SR-2-CNPy)的合成 54
2-3-2-6、4-(5-Thiohexyl-(3,4-ethylenedioxy)thiophene-2-yl)) 55
picolinic acid(Ligand 30, 簡稱L30)的合成 55
2-4、合成釕金屬錯合物﹙CYC-B30﹚ 57
2-4-1、[Ru(diethyl 2,2’-bipyridine-4,4’-dicarboxylate)](p-cymene) (Cl)]+ (簡稱AnRu)的合成 57
2-4-2、Ru(Ligand 30)2(diethyl 2,2’-bipyridine-4,4’-dicarboxylate)] (簡稱CYC-B30-OEt)的合成 59
2-4-3-1、CYC-B30 (P1)的合成 61
2-4-3-2、CYC-B30 (P2)的合成 62
2-4-3-3、CYC-B30 (P3)的合成 63
叁、結果與討論 64
3-1、CYC-B30染料的合成,性質探討及其光電表現 64
3-1-1、Ligand 30與CYC-B30系列合成探討 64
3-1-2、CYC-B30染料分子邊界軌域 (frontier orbitals)的理論計算: semi-empirial Method 67
3-1-3、CYC-B30染料光學性質探討 70
3-1-4、CYC-B30染料能階結構探討 72
3-1-5、以CYC-B30染料所敏化之DSSC元件的效能探討 75
3-1-6、以CYC-B30染料所敏化之電池元件的電化學阻抗 (Electrochemical impedance spectroscopy,EIS)分析 80
3-2、CYC-B30(P2)與CYC-B29(P2)之染料結構對其所敏化之DSSC元件光電表現的影響 82
3-2-1、Ligand 29的合成探討 82
3-2-2、CYC-B29(P2)染料及CYC-B30(P2)染料的分子邊界軌域與吸收光譜的理論計算: TDDFT 82
3-2-3、CYC-B29(P2)染料及CYC-B30(P2)染料的光學性質比較 87
3-2-4、 CYC-B29(P2)染料及CYC-B30(P2)染料的前置軌域的能階比較 89
3-2-5、以CYC-B29(P2)染料及CYC-B30(P2)染料所敏化之DSSC元件的效能比較 90
3-2-6、以CYC-B29(P2)染料及CYC-B30(P2)染料所敏化之電池元件的電化學阻抗 (Electrochemical impedance spectroscopy,EIS)分析 96
3-2-7、CYC-B30(P2)染料及CYC-B29(P2)染料所敏化之電池元件的瞬態吸收光譜(Transient Absorption Spectroscopy, TAS)分析 97
3-2-8、CYC-B29(P2)染料及CYC-B30(P2)染料所敏化之電池元件的光強度調製光電流/光電壓譜(Intensity Modulated Photocurrent / Photovoltage Spectroscopy,IMPS/IMVS)分析 99
3-2-9、CYC-B29(P2)染料及CYC-B30(P2)染料所敏化之電池元件的長時間穩定性(Long Term Stability)的測試 105
肆、結論 107
伍、參考文獻 109
附錄 …………………………………………………………………. 114
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指導教授 吳春桂(Chun-Guey Wu) 審核日期 2013-7-24
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