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研究生:楊凱博
研究生(外文):Kai-PoYang
論文名稱:具高長寬比與光散射強化性質之氧化鎢奈米材料及其電致變色元件
論文名稱(外文):Tungsten Oxide Based Electrochromic Devices with High-Aspect-Ratio Nanostructure and Light Scattering Enhancement
指導教授:郭昌恕
指導教授(外文):Chang-Shu Kuo
學位類別:碩士
校院名稱:國立成功大學
系所名稱:材料科學及工程學系碩博士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:英文
論文頁數:129
中文關鍵詞:電致變色電化學沉積電紡絲二氧化鈦氧化鎢聚苯胺光散射
外文關鍵詞:ElectrochromicElectrodepositionElectrospinningNanofibersTitanium oxideTungsten oxidePolyanilineLight scattering
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氧化鎢薄膜已經成功地利用電化學沉積方法均勻地沉積於二氧化鈦的奈米電紡絲上。藉由高分子輔助配方製備的二氧化鈦奈米纖維具有隨機分佈,奈米尺度下的光散射行為。氧化鎢鍍膜層可作為陰極的電致變色材料,經過電化學反應的還原過程產生顏色上的變化。核殼結構狀的二氧化鈦-氧化鎢奈米複合纖維展示出由光散射特性而提升的高光學對比的性質。而預期中光散射特性能夠延伸光線的行走路徑,增強材料對光的吸收量和著色效率,並且纖維之間的開放區域能提升鋰離子載體在電解液中的擴散效率。電紡絲中,散射峰值和纖維的直徑大小有很強的相關性,將二氧化鈦-氧化鎢奈米纖維直徑控制在300至700 nm左右在可見光區域有最大的散射效果。以奈米纖維為基礎的電致變色元件,其相對應的散射峰強度和對應直徑分佈經過仔細的研究。為了組合出合適的互補式電致變色元件,此研究中另外展示聚苯胺作為陽極層的變色材料。本研究中,同時也仔細地審視了各種材料的相關結構特性,電致變色性質以及光散射行為提升的變色效應。
Homogeneous tungsten oxide were successfully electrodeposited on the electrospun titania nanofibers as the conformal outer layers. Randomly deposited titania nanofibers from the polymer-assisted electrospinning were utilized as the nano-scaled scaffolds with light scattering behavior. Tungsten oxide outer layers were introduced as the cathodic electrochromic material that undergoes the color change by an electrochemical redox reaction. Obtained TiO2/WO3 core-sheath nanofibers exhibited the high optical density as a result from the intensive light scattering. While the light scattering prolongs the light path length, the enhanced absorption and the coloration efficiency were expected. Moreover, the open spacing among nanofibers encouraged the diffusion of Lithium ion carriers in the electrolyte. Preferred scattering bands revealed the strong correlation with the nanofiber diameter. And, TiO2/WO3 core-sheath nanofibers with diameters of 300 to 700 nm were found to have the maximized scattering in the visible region. Nanofiber-based electrochromic devices were carefully investigated in terms of the preferred scattering wavelength and the fiber deposition thickness. Nanostructured polyaniline was also introduced as the anodic electrochromic materials in order to assemble the complementary electrochromic device. Material characterizations, preferred scattering behavior, and the enhanced elctrochromic performance were investigated in this research work.
Abstract II
摘要 III
Acknowledgement IV
Contents V
List of Tables VIII
List of Illustrations IX
Chapter 1. Introduction 1
1-1. Electrochromism 1
1-1-1. Chromism 1
1-1-2. Electrochromic Materials 2
1-1-3. Electrochromic Device (ECDs) 8
1-1-4. Complemantary Electrochoromic Device 10
1-2 . Tungsten oxide 11
1-2-1. Introduction and Preparation Methods 11
1-2-2. Structure of Tungsten Oxide 12
1-2-2. Electrochromic Properties of Tungsten Oxide 15
1-2-3. Electrochromism of Amorphous Tungsten Oxide 16
1-2-4. Electrochromism of Crystalline Tungsten Oxide 18
1-2-5. Low Dimensional Structure 18
1-4. Polyaniline 20
1-4-1. Polymerization of PANI 20
1-4-2. Structure of PANI 21
1-4-3. Electrochemical characterizations 24
1-5. Titanium Dioxide 26
1-5-1. Crystal Structure and Properties . 26
1-5-2. TiO2 Layer. 28
1-5-3. Sol-Gel Method. 29
1-5-4. Electrospinning 31
1-5-5. One-Dimensional Nanostructures 32
1-5-6. Light Scattering and Propagation. 33
1-6. Tungsten oxide - Titanium dioxide 36
1-7. Motivation 37
Chapter 2. Experimental 38
2-1. Materials and Experimental Instruments 38
2-1-1. Materials 38
2-1-2. Experimental Instruments 39
2-1-3. Electrospinning Apparatus 39
2-2. Analytical Instruments 41
2-2-1. Scanning Electron Microscopy (SEM) 41
2-2-2. UV-vis Spectrometer (UV-vis) 42
2-2-3. X-ray Diffraction (XRD) 43
2-2-4. Transmission Electron Microscopy (TEM) 43
2-2-5. Potentiostat (Autolab 128N) 45
2-3. TiO2 Nanofibers. 46
2-3-1. TiO2 Thin Blocking Layers. 46
2-3-2. Prefabricated Layers. 48
2-3-3. Electrospinning of TiO2 Nanofibers. 48
2-3-4. Hot Pressing Process. 50
2-3-5. Calcination. 50
2-3-6. Surface Modification by TiCl4 51
2-4. Electrodeposition of WO3 films and WO3-coated TiO2 nanofibers 52
2-5. Electropolymerization of Polyaniline 54
2-6. Assembly of the Eelectrochromic Devices 54
Chapter3. Results and Discussion 55
3-1. Material Preparations 55
3-1-1. Electrospun Titanium Nanofibers 55
3-1-2. Electrodeposition of Tungsten Oxide Coatings 58
3-1-3. Electrodeposition of WO3-coated TiO2 nanofibers 60
3-1-4. Electropolymerization of Polyaniline 62
3-2. Material Characterizations 64
3-2-1. Morphologies of TiO2 Nanofibers 64
3-2-2. Crystal Structure of TiO2 nanofibers 67
3-2-3. Specific Surface Areas and Pore Sizes 69
3-2-4. UV-vis Absorption Spectra in Transmission Mode 71
3-2-5 . X-ray Diffraction Analysis of WO3 film 74
3-2-6. SEM Images and analysis of WO3-Coated TiO2 Nanofibers 75
3-2-7. XRD Analysis of WO3-Coated TiO2 Nanofibers 79
3-2-8. TEM Analysis of WO3-Coated TiO2 Nanofibers 83
3-2-9. Microstructure of PANI Nanorods 90
3-2-10. UV-vis spectra of WO3-coated TiO2 nanofibers 92
3-3. Electrochromic Performances 96
3-3-1. Electrochromic Properties of Tungsten Oxide Film 96
3-3-2. Cyclic Voltammetric Analysis of WO3-coated TiO2 nanofibers 99
3-3-3. Coloration Analysis of WO3-coated TiO2 Nanofibers 102
3-3-4. Cyclic Voltammetric Analysis at Different Scanning Rates 106
3-3-5. Cycling Stability 108
3-3-6. Coloration Enhancement of WO3-coated TiO2 Nanobers 110
3-3-7. Cyclic Voltammetry and Optical Properties of PANI 114
3-3-9. Complementary Electrochromic Devices 116
Chpater 4. Conclusion 121
Chapter 5. Reference 123

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