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標題: | 以奈米結構普魯士藍類似物提升窗戶型及顯示型電致色變元件性能之研究 A Study on the Performance Enhancement of Window-oriented and Display-oriented Electrochromic Devices Using Nanostructured Prussian Blue Analogues |
作者: | Siang-Fu Hong 洪祥富 |
指導教授: | 陳林祈 |
關鍵字: | 電致色變,普魯士藍類似物,三氧化鎢,智慧窗戶,鐵氰化銦,鐵氰化鋅,顯示器, Electrochromic,Prussian blue analogues,WO3,Smart windows,Indium hexacyanoferrate,Zinc hexacyanoferrate,Displays, |
出版年 : | 2011 |
學位: | 博士 |
摘要: | 本論文主要以奈米普魯士藍類似物材料為研究核心,藉由奈米結構、光學及電化學的分析、鍍膜製程的改良以及新系統的開發等方向,來提升智慧窗戶型以及顯示應用型電致色變元件之性能。期望能加速電致色變節能窗戶以及低耗能反射式電致色變顯示器的普及,進一步提升居住生活以及閱讀品質並達到節能減碳的目的。
第一部分,我們首先以普魯士藍類似物發展兩種電致色變透明輔助電極系統,其一為電鍍製備鐵氰化銦薄膜,我們藉由電鍍液的改進以及電解液的最佳化,使鐵氰化銦薄膜達到良好的電化學活性及穩定性,可進一步作為透明輔助電極應用於電致色變系統。接著我們繼續發展另一普魯士藍類似物-鐵氰化鋅,鐵氰化鋅在氧化還原過程中,相對於鐵氰化銦有更良好的透明度,但由於在導電玻璃上難以達到良好的電鍍效率,我們轉而使用化學方法製備鐵氰化鋅奈米粒子,再結合溼式製程進行鍍膜。我們發現利用導電高分子作為鍍液添加物不僅可提升其穩定性,並可大幅提升電化學性質。為了能分析複合薄膜介面間的反應機制,我們提出一個新的電化學阻抗分析的模型,藉此定量比較導電高分子添加比例以及不同奈米結構如何影響鐵氰化鋅薄膜之介面電化學現象。 第二部分,我們將高穩定性鐵氰化銦及鐵氰化鋅透明輔助電極整合融膠凝膠法製備的三氧化鎢薄膜,發展兩款節能窗戶型應用之電致色變系統。由於透明輔助電極的使用可免去與電致色變工作電極之間的光學匹配問題,並且不需使三氧化鎢預先著色可減小因電極反應電量衰退造成的元件光學表現。鐵氰化銦-三氧化鎢以及鐵氰化鋅-三氧化鎢電致色變元件系統,透過碳酸丙烯電解液的使用以及輔助電解質的最適化,兩系統皆可達到良好的光學調幅及元件穩定性,單一波長最大光學調幅皆接近60%,經過加速循環操作測試,預期元件可達到10萬次以上的操作壽命。除此之外,由於鐵氰化鋅及三氧化鎢皆使用低成本的溼式製程製備,亦較不易受到導電玻璃導電度的限制而達到大面積的鍍膜,我們進一步使用旋轉塗佈法成功製作出具有10x10平方公分反應面積的三氧化鎢電致色變窗戶原型。經過近三年的靜置,相對於初始狀態仍保有約75%之最大電致色變調幅的表現,良好的靜態元件壽命亦在此被證實。 第三部分,我們利用普魯士藍類似物的材料發展顯示型電致色變應用,首先我們使用普魯士藍結合另一有機電致色變高分子-聚苯胺製作出多顏色之電致色變複合膜,透過電子顯微鏡、電化學及石英震盪微量天平的分析,我們發現普魯士藍及聚苯胺的鍍膜順序會明顯影響電致色變及電化學性質,由於聚苯胺具有導電高分子性質且普魯士藍薄膜具有明顯裂痕及孔隙可作為離子通道,先鍍聚苯胺於導電玻璃再鍍上普魯士藍可達到較理想的穩定性及電致色變表現,呈現出透明、淺綠、藍綠、藍色的可逆顏色變化。此外,由於紅色電致色變系統目前相對較少,且有機電致色變材料一般而言擁有較高著色效率及亮眼的顏色表現,我們希望使用我們的高透明度鐵氰化鋅輔助電極結合有較鮮豔電致色變表現的共軛高分子材料組成有機/無機混合元件以作為顯示方面的應用,首先我們結合聚-3-甲基噻吩發展出可由鮮豔紅色至灰色的電致色變元件,我們亦透過鍍膜製程的改進提升元件穩定性,經過10,000圈的連續操作元件仍保有95%的電化學活性,且由灰色轉紅色的反應時間可達到0.6秒( 2x2平方公分),深具有作為顯示元件的潛力。進一步我們整合三種電致色變共軛高分子-聚3-甲基噻吩、聚苯胺以及聚二氧乙基噻吩,分別作為紅色、綠色、藍色電致色變材料,成功製作出一個類似液晶顯示器三原色的三段顯示器,可分別由紅、綠、藍色的狀態著色成黑色、暗藍、暗紫色的深色狀態,除了證明了鐵氰化鋅透明輔助電極的良好適用性,也展現電致色變顯示器的未來可能。 Material study of Prussian blue analogues (PBA) is the core theme of this dissertation. We aim to enhance the performances of both window-oriented and display-oriented electrochromic devices by analyzing nanostructural, optical and electrochemical properties, improving film processes and developing of new systems. The main prospect in this study is to speed up the popularization of electrochromic power-saving windows and low-power electrochromic displays, and further to improve the living environment and to save energy. In the first part, we have developed two kinds of transparent counterelectrode systems based-on PBA. The first one is electrodeposited indium hexacyanoferrate (InHCF), we improved the electroplating solution and also optimized the electrolyte, thus a better electrochemical activity and stability of non-aqueous InHCF system could be achieved successfully. Then we further developed another PBA, which is zinc hexacyanoferrate (ZnHCF). Comparing with InHCF, ZnHCF exhibits higher transparency during redox reaction. but due to the low electrodeposition efficiency of ZnHCF on transparent conductive oxide (TCO) glasses, we turned an alternative way to prepare ZnHCF nanoparticle by chemical synthesis and coat the thin film by wet process. And we also find that the conducting polymer assistance method can not only help the stability but also greatly enhance the electrochemical properties. A new model for electrochemical impedance spectroscopy is also proposed here for analyzing the interfacial electrochemistry of ZnHCF under the different additive amount and the different nanostructures. And we believe it can also be applied extensively to other nanoparticulate or composite thin films.under the different additive amount and the different nanostructures. And we believe it can also be applied extensively to other nanoparticulate or composite thin films. In the second part, we integrated two PBA-based transparent counterelectrode systems with sol-gel WO3 electrochromic films to fabricate energy-saving window-type electrochromic systems. Using the transparent counterelectrode can get rid of the color matching problems and also can reduce the degradation of optical properties of a device caused by the loss of charge capacity of electrodes. By optimizing the electrolytes of the WO3-InHCF and WO3-ZnHCF systems, they both exhibit good capability of transmittance modulation and enhanced stability. The maximum transmittance change of them are both about 60%. And after the accelerated aging tests, the devices are expected to have a long cycle life of up to 100k cycles. Furthermore, due to superiority of the facile wet process of PEDOT:PSS-assisted ZnHCF and WO3 and the lack of the plating problems caused by TCO glass’s conductivity, we successfully develop a 10x10 cm2 WO3 smart window prototype by spin coating. And it can remain about 75% of its origin transmittance modulation at 700 nm after about 3 years, the practical at-rest stability is well-proved. In the third part, we also aim to develop display-oriented electrochromism based on PBA. First, we integrate PB with another organic electrochromic polymer-polyaniline (PANI) to fabricate a multicolor electrochromic bilayer system. And we find the deposition order would affect the electrochemical and electrochromic properties of the bilayer obviously. Moreover, due to the conductive character of PANI and the PB’s ion channels resulted from PB structural cracks, coating PANI as the first layer can achieve better stability and more vivid electrochromism, which exhibit colorless, light green, blue green and blue colors reversibly. On the other hand, because red color electrochromism is relatively rare in this field, we intend to integrate our highly transparent ZnHCF/PEDOT:PSS counterelectrode with other kinds of conjugated polymers with vivid electrochromism to fabricate organic/inorganic hybrid system. First we integrated ZnHCF/PEDOT:PSS with poly(3-methylthiophene) (PMeT) and fabricated a vivid red-to-gray electrochromic device with a fast gray-to-red switching speed of 0.6 sec for a 2x2 cm2 device, and it can retain about 74.5% of its initial charge capacity after 10,000 cycle of aging test. The potential on display purposes of this system is shown. In addition, we further integrated the PEDOT:PSS-assisted ZnHCF counterelectrode system with 3 kinds of electrochromic conjugated polymers, which are PMeT, polyaniline (PANI) and poly(3,4-ethylenedioxythiophene) (PEDOT), and a red, green and blue color 3-segment demo device was successfully fabricated. It can switch the red, green and blue colors to darkened states with the color of black, dark purple and dark blue respectively. The great applicability of the transparent PBA-based counterelectrode was proved, and the possibility of electrochromic displays can also been seen here. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/16589 |
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