硫化鈷對電極與離子液體電解液應用於染敏太陽能電池之研究

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研究生：	蔡祐同
論文名稱：	硫化鈷對電極與離子液體電解液應用於染敏太陽能電池之研究 A Study of CoS Counter Electrode and Ionic Liquid Electrolyte for Dye-Sensitized Solar Cells
指導教授：	萬其超
口試委員:	林正裕童永樑吳曜杉
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2012
畢業學年度：	100
語文別：	英文
論文頁數：	102
中文關鍵詞：	染料敏化太陽能電池、硫化鈷、離子液體
相關次數：	點閱：2 下載：0
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近年來，染料敏化太陽能電池(Dye-sensitized solar cells, DSSC)因其高效率、低成本和簡單的製程而引起廣泛的注意。其中，白金電極在DSSC的對應電極上扮演減少電位損失和加速I3-還原速率的角色。然而，白金非常昂貴且當製造方法為熱還原法時，白金電極需要在高溫環境下完成，非常耗能且無法應用於軟性基板，或是當製造方法為濺鍍法時白金電極需要在真空下完成，因此上述常用的白金電極製備方法不利於大量製造。為了要大量製備染敏太陽能電池，學者們嘗試尋找能夠取代貴重金屬白金的材料和採用能夠大量製備的方法。近年來，硫化鈷被應用於染料敏化太陽能電池中當作對電極，因為硫化鈷擁有較好的催化性、便宜的價格、及充足的原料。在本研究，我們提供一個電鍍方法(potential reversal method, PR method)去製備硫化鈷電極。此方法可以在常溫常壓下應用，有利於大量製造。藉由此方法，在製備硫化鈷電極時可以有效地移除不具催化性的鈷金屬，可以製備催化性更好的硫化鈷電極並與採用直接電鍍方法製備的硫化鈷電極比較，此後還會將硫化鈷電極跟白金電極組成電池量測效率來做比較。
採用PR方法時，有許多因素會影響到硫化鈷電極的催化能力，例如:氧化電位和還原電位、電鍍液中的酸鹼度、還原時間佔總周期的比例(duty cycle)、頻率及鍍上導電玻璃基板的庫倫數。我們將探討這些因素對硫化鈷電極的催化性的影響，並藉由循環伏安法及交流阻抗分析量測來評估硫化鈷電極的催化性。另外，其它量測也會執行以鑑定硫化鈷電極，例如: 用EDX確認有硫跟鈷的元素及比例、用XRD來確認有硫化鈷、用FESEM來確認硫化鈷的表面形貌。根據表3-3，以硫化鈷電極(PR method)所組成的DSSC，其效率為5.39%，僅略低於以白金電極所組成的DSSC(5.42%)，遠高於硫化鈷電極(PS method, 直接電鍍法)所組成的DSSC(2.13%)，代表硫化鈷有取代白金的可行性且利用PR方法所得到的硫化鈷電極相較於用直接電鍍的方法效率來得更高。最後，我們使用離子液體電解液和robust電解液搭配硫化鈷對電極做DSSC的長效測試，以確認硫化鈷電極是否可以通過長效測試。我們發現在長效測試中，硫化鈷對電極有脫落的現象發生，推測原因可能是來自於空氣或水影響到硫化鈷膜的黏著能力，使得脫落的現象發生。

ABSTRACT    I
摘要    III
謝辭    V
Table of Contents    VI
List of Figures    VIII
List of Tables    XI
Chapter 1: Introduction and Literature review    1
1-1 Overview of Dye-Sensitized Solar Cells (DSSCs)    1
1-1.1 Introduction of DSSCs    1
1-1.2 Structures and Operational Principle of DSSC    2
1-1.3 The Counter Electrode (CE)-Electrochemical Catalyst    5
1-1.4 Platinum-Based Counter Electrode    6
1-1.5 Carbon-Based Counter Electrode    12
1-1.6 Conducting Polymer-Based Counter Electrode    14
1-2 Introduction of Cobalt Sulfide Counter Electrodes    16
1-2.1 Literature Review of Cobalt Sulfide Counter Electrodes    16
1-2.2 Deposition Mechanism of CoS by potentiodynamic method    20
1-3 Introduction of Pulse Method    23
1-3.1 Basic concept of Pulse Method    23
1-3.2 Application of Potential Reversal Method    25
1-4 Overview of Ionic Liquids    27
1-4.1 Introduction of Ionic Liquids    27
1-4.2 Viscosity of Ionic Liquids    28
1-4.3 Electrochemical Window of Ionic Liquids    29
1-4.4 Ionic Conductivity of Ionic Liquids    31
1-4.5 The Role of Ionic Liquid in The Electrolyte of DSSC    32
1-4.6 Purely Electroactive Ionic Liquid Electroytes    33
1-4.7 Binary Ionic Liquid Electrolytes    35
1-5 Motivation of This Study    38
Chapter 2: Experimental Section    39
2-1 Materials    39
2-2 Experimental Instrument    40
2-3 Principle and Measurement of Experiment instrument    41
2-3.1 Scanning Electron Micorscope (SEM)    41
2-3.2 Cell Efficiency Instrument    41
2-3.3 Cyclic Voltammetry (CV) Measurement    43
2-3.4 Electrochemical Impedance Spectroscopy(EIS) Measurement    44
2-4 Preparation of DSSC    47
2-4.1 Preparation of Photo-anode    47
2-4.2 Preparation of CoS CEs by potential reversal technique    47
2-4.3 DSSC Assembly    48
Chapter 3 Results and Discussion    50
3-1 Determination of Anodic and Cathodic Potential for PR method    50
3-2 PH Effect on The Electrocatalytic Ability of The CoS CEs    53
3-3 Duty Cycle Effect on The Electrocatalytic Ability of The CoS CEs    55
3-3.1 Surface Morphology of The CoS CEs at Different Duty Cycle    55
3-3.2 EDX Spectroscopy of The CoS CEs at Different Duty Cycle    59
3-3.3 XRD Pattern of The CoS CEs at Different Duty Cycle    60
3-3.4 Impedance Spectra of The CoS CEs at Different Duty Cycle    62
3-3.5 Cyclic Voltammogram of The CoS CEs at Different Duty Cycle    65
3-3.6 Cell Performance of The CoS CEs at Different Duty Cycle    67
3-4 Frequency Effect on The Electrocatalytic Ability of The CoS CEs    69
3-4.1 Surface Morphology of The CoS CEs at Different Frequency    69
3-4.2 XRD Pattern of The CoS CEs at Different Frequency    71
3-4.3 Impedance Spectra of The CoS CEs at Different Frequency    72
3-4.4 Cyclic Voltammograms of The CoS CEs at Different Frequency    74
3-4.5 Cell Performance of The CoS CEs at Different Frequency    76
3-5 Coulomb Effect on The Electrocatalytic Ability of The CoS CEs    78
3-5.1 Surface Morphology of The CoS CEs at Different Coulomb    78
3-5.2 Thickness of The CoS CEs at Different Coulomb    80
3-5.3 Impedance Spectra of The CoS CEs at Different Coulomb    81
3-5.4 CV Spectra of The CoS CEs at Different Coulomb    82
3-5.5 Cell Performance of The CoS CEs at Different Coulomb    83
3-6 Photocurrent Density-Voltage Performance about Different ILs    84
3-7 Long-Term Stability Test of DSSCs with The CoS CEs and ILs    88
Chapter 4 Conclusions    93
Chapter 5 Future Work    95
Chapter 6 Referecnce    96

                                

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