【作者】 李梅；

【导师】 徐春叶；

【作者基本信息】 中国科学技术大学 ， 高分子化学与物理， 2014， 博士

【摘要】 电致变色器件是一类具有响应性变色功能的器件,在适当的电压驱动下可改变自身颜色。选择不同材料,可使器件调节紫外、可见光区域甚至是红外区域的光学性质,甚至可使器件具有多级变色的功能。这类器件可应用于建筑、交通工具上,改善工作和生活环境,调光节能,也可用于显示装置。作为有机小分子材料,紫精化合物具有良好的氧化还原性质和相对稳定的变色过程,拥有广泛的应用背景,是目前国内被广泛研究的电致变色材料之一本博士论文围绕如何提高紫精系电致变色器件综合性能的这一研究目标展开了系统论述,分别介绍了就固态和全液态两种不同形态的电致变色器件进行的探索性研究,依照新型紫精材料设计与合成,电极制备与匹配,器件结构与优化,性能寿命测试与评估这一路线,分别研制出了三种不同性质的电致变色器件。具体研究内容包括：快速响应电致变色器件：设计可吸附紫精材料,优化器件性质。利用富电子的三苯胺基团与膦酸基对紫精化合物的修饰作用,使紫精材料与疏松多孔的二氧化钛通过化学吸附作用固定于导电基板上制得固态电极。将其与普鲁士蓝电极配对制得器件,三苯胺基团带来的低电压变色效果以及膦酸基团提供的吸附作用赋予了该器件以快速的响应时间和较好的稳定性。高寿命电致变色器件：通过优化电极制备方法,确保电极的匹配性,以提高器件使用寿命。按照匹配性原则,对阴极变色材料紫精化合物和阳极变色材料三苯胺同时以膦酸基团修饰,采用化学吸附法分别制备成固态电极。相似的表面形貌、分子存在方式以及分子浓度使得该电极在颜色变化、变色电压以及电荷容量上有很高的匹配性。所组装的器件在可见光和红外区域有着卓越的变色性质,使用寿命也有了很大的提高。全液态电致变色器件：通过器件的结构的改变而改变其变色性质。寻找溶解性好的阳极变色小分子,与对称紫精化合物配对以溶液状态制备成器件,获得了一系列颜色丰富,制备工艺简单,且具有自擦写功能的全液态电致变色器件。通过综合性能对比,以二茂铁为配对电极材料组装的大面积器件具有良好的颜色变化和变色均匀性。本文通过对紫精化合物分子的设计与合成制备出一系列新型紫精化合物,针对不同结构选用不同的制备方法制作电极,组装出了变色速度最快小于1s,寿命高达15万次的固态或液态电致变色器件,实现了紫精基电致变色器件的多功能化。更多还原

【Abstract】 Electrochromic device (ECD) is a kind of device with functions of responsive discoloration and coloration through oxidation-reduction reactions by an appropriate driving voltage. ECD could adjust optical properties of the ultraviolet, visible or infrared region, and some can even show multi-level color through different voltages, which can be realized by selecting different electrochromic materials. Such devices can be used in building windows, the transport dimming devices or displays, in order to improve the working and living environment, to save energy. The small organic viologens were extensively researched, because of their good redox properties and stable color change process.This dissertation focused on how to improve properties of electrohromic devices based on viologens, and explore solid and liquid eletrochromic devices. Here, we designed and systhesised novel viologens, prepared matching electrodes, optimized structures of devices and measured the cycle life to prepare three kinds of electrochomic devices. And the contents include:Fast color changing ECD:We used electron-rich triphenylamine and phosphonate groups to modify viologen, thus the viologen molecule could be fixed on conductive glass substrate to form film electrodes through chemisorption between phosphonate groups and titanium dioxide. The as-prepared film electrode was applied to assemble a device with Prussian blue film. The device show fast color changing speed and good stability as a result of the modification and triphenylamine and phosphonate groups.Stable ECD:We used phosphonic acid to modify both asymmetric viologen triphenylamine materials, and prepared electrodes through chemisorption method. The similar morphology, molecule form and molecular concentration make that the electrodes can match with each other on color change, color change voltage and charge capacity. Using the above two electrodes an ECD was assembled, which exhibit the switching effect in the visible and infrared region, and high stable life.Liquid ECD:We searched for anion electrochromic materials as pairs with symmetric viologens dissolved in the solvent to assemble liquid ECD. The results showed that soluble electrochromic devices had vivid color changes. By comprehensive performance comparison, ferrocene was chosen as the counter material to assemble large area electrochromic device which showed good color change and uniformity color.In this paper, we designed and synthesized series of novel viologens, and prepared different electrodes through different methods for different structures, and assembled the solid and liquid viologen-based electrochromic devices with color changing speed less than1s or cycle life reach up to15,0000, thus to achieve its developments in multi-functions.更多还原