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研究生:李威龍
研究生(外文):Wei-Long Li
論文名稱:含二唑鈷錯合物氧化還原對的合成及其於染料敏化太陽能電池的應用
論文名稱(外文):ynthesis of Diazole-containing Cobalt-based Redox Couples and Their Application in Dye-sensitized Solar Cells
指導教授:吳春桂吳春桂引用關係
指導教授(外文):Chun-Guey Wu
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:183
中文關鍵詞:染料敏化太陽能電池電解質鈷錯合物釕金屬錯合物染料
外文關鍵詞:DSSCselectrolyteCobalt complexRuthenium-based dyes
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  染料敏化太陽能電池(Dye-sensitized solar cells,簡稱DSSCs)因成本低、製作簡易、質輕、多色彩、可製作成可撓曲式…等優點,在新興太陽能電池中具有發展潛力。在染料敏化太陽能電池的組成中,電解質扮演還原染料、傳遞電洞及決定元件之理論開路電壓(Voc)的重要角色。目前最常使用的碘系統電解質因無法藉由結構修飾而調變其氧化還原電位來提高元件之開路電壓,亦無法精準搭配不同HOMO能階的光敏劑。另一方面,鈷錯合物因金屬中心有多重且穩定的氧化態,並且可藉由配位基結構的改變來調控其氧化還原電位,因此具有很大的可行性,成為DSSCs用電解質的研究重點之一。本論文合成出三組鈷錯合物電解質CRC-1、CRC-2、CRC-3。鈷錯合物在450 nm至700 nm間無吸收,不與光敏劑(如:CYC-B11H、SJW-B17、SJW-B18)競爭吸光。CRC-1的氧化還原電位為0.40 V vs. NHE、CRC-2為0.74 V vs. NHE、 CRC-3為0.71 V vs. NHE,皆高於上述光敏劑的HOMO,CRC-2、CRC-3的氧化還原電位較碘系統電解質低,故使用CRC-2及CRC-3電解質之元件有較大的理論開路電壓。以CRC-1電解質搭配染料SJW-B18之元件的開路電壓為0.716 V,由於鈷錯合物電解質易與二氧化鈦上電子進行再結合,所以鈷系統元件之開路電壓略低於碘系統元件的0.749 V。CRC-2電解質可有效提升理論開路電壓,搭配尾端有較大基團的染料SJW-B17可增加TiO2表面覆蓋度,又由於SJW-B17在TiO2薄膜的吸附量較多,以SJW-B17所敏化之元件有高的光電表現:短路電流密度為10.63 mA/cm2、開路電壓為0.916 V、填充因子為0.660 ,光電轉換效率為6.42%。CRC-3電解質有最適當的氧化還原電位0.71 V,與CRC-2電解質比較,對再生染料CYC-B11H、SJW-B17、SJW-B18有較大的驅動力,其中搭配染料SJW-B17所組裝之元件,短路電流密度為13.36 mA/cm2、開路電壓為0.868 V、填充因子為0.619、光電轉換效率為7.19 %。
Dye-sensitized solar cells (DSSCs), is one of the hottest research topics in the new photovoltaic technology, due to its low production cost, simple fabrication process, semi-transparent, light weight, colorful, and can be flexible. In a DSSC device, electrolyte is one of the important components, which reduced the dye, carried the hole to the cathode and determined the theoratical open-circuit voltage (Voc). Iodide/triiodide system is the most commonly used electrolyte, however it’s redox potential can not be tuned to be compatible to sensitizers with various highest occupied molecular orbitals (HOMOs) or increase the Voc of devices by structure modification. On the other hand, cobalt complexes have multiple, reversible oxidation states metal center and their redox potentials can be tuned by the ligands. Therefore ccbalt electrolyte is also one of the important research topics in DSSC. In this study, we synthesis three cobalt-based redox couple coded CRC-1, CRC-2 and CRC-3. CRC-1, CRC-2 and CRC-3 don’t absorb any light from 450 nm to 700 nm, no competing absorption with ruthenium sensitizers (eg: CYC-B11H, SJW-B17 and SJW-B18 developed in our lab). The redox potentials of CRC-1, CRC-2 and CRC-3 are 0.40, 0.74, 0.71 V vs. NHE respectly, all higher than HOMOs of Ru-based sensitizers studied in this thesis. The redox potentials of CRC-2 and CRC-3 are lower than that of iodine-based electrolyte. Devices based on CRC-2 or CRC-3 electrolyte will have higher theoretical Voc. Device using CRC-1 electrolyte and SJW-B18 sensitizer achieves Voc of 0.716 V which is lower than that for the device baesd on iodide/iodine electrolyte, due to the electron in TiO2 recombined with cobalt-based electrolye rapidly. On the other hand, device using CRC-2 electrolyte and SJW-B17 sensitizer has good photovoltaic performance: Jsc: 10.63 mA/cm2, Voc: 0.916 V, FF: 0.660, PCE: 6.42%. CRC-3 electrolyte has a appropriate redox potential for CYC-B11H, SJW-B17 and SJW-B18 dyes due to it has a proper driving force to regenerate the dyes as well as provides high theoretical Voc. Device based SJW-B17 and CRC-3 electrolyte has the best photovoltaic performance amongst the devices studied in this thesis, Jsc: 13.36 mA/cm2, Voc: 0.868 V, FF : 0.619 and PCE : 7.19%.
中文摘要 i

Abstract iii

謝誌 v

圖目錄 xii

表目錄 xvi

第一章、緒論 1
1-1、前言 1
1-2、染料敏化太陽能電池(DSSCs)的組成與工作原理 2
1-2-1、染料敏化太陽能電池的工作機制 3
1-3、染料敏化太陽能電池中所使用的電解質 4
1-3-1、應用於染料敏化太陽能電池的電解質之性質需求 5
1-3-2、染料敏化太陽能電池中電解質材料的介紹 6
1-4、鈷錯合物電解質的文獻回顧 13
1-4-1、鈷錯合物結構與染料結構對電池效率的影響 13
1-4-2、鈷錯合物結構與其氧化還原電位的影響 19
1-5、研究動機 23
第二章、實驗方法 25
2-1、實驗藥品及產物結構、名稱、分子量對照表 25
2-1-1、實驗藥品 25
2-1-2、結構、名稱、分子量對照表 27
2-2、測量儀器及樣品製備 32
2-2-1、紫外光/可見光/近紅外光吸收光譜儀 (UV/Vis/NIR spectroscope) 32
2-2-2、核磁共振光譜儀 (Nuclear Magnetic Resonance spectroscope) 33
2-2-3、電化學測量 (Electrochemical Measurement) 34
2-2-4、太陽光模擬器與光電轉換效率測試 (Solar Simulator and J-V measurement system) 35
2-2-5、太陽能電池外部量子效率量測系統 (Incident Photon to Current Conversion Efficieny, IPCE) 35
2-2-6、交流阻抗分析儀 ( AC-Impedance analysis,) 36
2-3、鈷錯合物的合成 39
2-3-1、Ligand-1的合成 39
2-3-1-1、[2,2'-bipyridine] 1-oxide (bpy N-oxide)的合成步驟[30] 40
2-3-1-2、6-isocyano-2,2'-bipyridine (6-CNbpy)的合成步驟[31] 41
2-3-1-3、6-(1H-imidazol-2-yl)-2,2'-bipyridine (6-Imbpy)的合成步驟 42
2-3-1-4、6-(1-methyl-1H-imidazol-2-yl)-2,2'-bipyridine (Ligand-1)的合成步驟 43
2-3-2、Ligand-2的合成 44
2-3-2-1、2-bromopyridine 1-oxide (2-Brpy N-oxide)的合成步驟 44
2-3-2-2、6-bromopicolinonitrile (2-CN-6-Brpy)的合成步驟 45
2-3-2-3、6-(1H-pyrazol-1-yl)picolinonitrile (2-CN-6-pzpy)的合成步驟 46
2-3-2-4、2-(1H-imidazol-2-yl)-6-(1H-pyrazol-1-yl)pyridine (2-im-6-pzpy)的合成步驟 47
2-3-2-5、2-(1-methyl-1H-imidazol-2-yl)-6-(1H-pyrazol-1-yl)pyridine (Ligand-2)的合成步驟 48
2-3-3、Ligand-3的合成 49
2-3-3-1、2-bromo-4-methylpyridine 1-oxide (2-Br-4-Mepy N-oxide)的合成步驟 49
2-3-3-2、6-bromo-4-methylpicolinonitrile (2-CN-4-Me-6-Brpy)的合成步驟 50
2-3-3-3、4-methyl-6-(1H-pyrazol-1-yl)picolinonitrile (2-CN-4-Me-6- pzpy)的合成步驟 50
2-3-3-4、2-(1H-imidazol-2-yl)-4-methyl-6-(1H-pyrazol-1-yl)pyridine (2-im-4-Me-6-pzpy)的合成步驟 52
2-3-3-5、 4-methyl-2-(1-methyl-1H-imidazol-2-yl)-6-(1H-pyrazol- 53
2-3-4、鈷錯合物的合成 54
2-3-4-1、二價鈷錯合物[Co(Ligand-1)2](PF6)2(CRC-1-II)的合成步驟 54
2-3-4-2、三價鈷錯合物[Co(Ligand-1)2](PF6)3(CRC-1-III)的合成步驟 55
2-3-4-3、二價鈷錯合物[Co(Ligand-2)2](PF6)2(CRC-2-II)的合成步驟 56
2-3-4-4、三價鈷錯合物[Co(Ligand-2)2](PF6)3(CRC-2-III)的合成步驟 58
2-3-4-5、二價鈷錯合物[Co(Ligand-3)2](PF6)2(CRC-3-II)的合成步驟 59
2-3-4-6、三價鈷錯合物[Co(Ligand-3)2](PF6)3(CRC-3-III)的合成步驟 60
2-4、光敏劑的合成 62
2-4-1、CYC-B11H的合成 62
2-4-2、SJW-B18的合成 63
2-4-3、SJW-B17的合成 64
2-4-3-1、Ligand-B17的合成 64
2-4-3-1-1、5-(3-bromopropyl)-2,2'-bithiophene(3BrPBT)的合成 65
2-4-3-1-2、3,6-di-tert-butyl-9-(3-(5-(thiophen-2-yl)thiophen-2 -yl)propyl)-9H-carbazole (BTPDTBC)的合成 66
2-4-3-1-3、3,6-di-tert-butyl-9-(3-(5-(5-(trimethylstannyl)thiophen -2-yl)thiophen-2-yl)propyl)-9H-carbazole(TMeSn-BTPDTBC)的合成 67
2-4-3-1-4、4,4'-bis(5'-(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl)- [2,2'-bithiophen]-5-yl)-2,2'-bipyridine(Ligand-B17)的合成 68
2-4-3-2、SJW-B17的合成 69
2-5、染料敏化太陽能電池元件製備與組裝 72
2-5-1、二氧化鈦漿料的製備 72
2-5-2、二氧化鈦陽極的製備 72
2-5-3、Pt對電極的製備 73
2-5-4、染料敏化太陽能電池元件的組裝 73
2-5-5、染料敏化太陽能電池元件內各組成條件 73
第三章、結果與討論 76
3-1、鈷金屬錯合物CRC-1、CRC-2及CRC-3的合成與鑑定 76
3-1-1、含有diazole取代之鈷金屬錯合物的合成方法探討 76
3-1-2、鈷金屬錯合物的NMR鑑定 78
3-2、鈷金屬錯合物CRC-1、CRC-2及CRC-3的光電特性探討 80
3-2-1、CRC-1、CRC-2及CRC-3氧化還原對的吸光特性 80
3-2-2、CRC-1、CRC-2及CRC-3氧化還原對的電化學特性 83
3-3、鈷金屬錯合物CRC-2-II之單晶結構 87
3-3-1、鈷金屬錯合物CRC-2-II的養晶方法 87
3-3-2、鈷金屬錯合物CRC-2-II的結構數據 87
3-4、使用鈷金屬錯合物為電解質之DSSC元件的光電性質探討 90
3-4-1、以CRC-1鈷金屬錯合物為電解質之元件的光電性質 90
3-4-2、以CRC-2鈷金屬錯合物為電解質之元件的光電性質 94
3-4-3、以CRC-3鈷金屬錯合物為電解質之元件的光電性質 99

第四章、結論 107

第五章、參考文獻 108

附錄一、化合物之1H NMR與13C NMR光譜 113

附錄二、元件測試結果 125

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