In-situ preparation and electrochromic properties of TiO2/PTPA-HTAN core-shell nanocomposite film

A new star-shaped structure conjugated microporous polymers, poly (2,8,14-tri[4-diphenyl-benzene]-hexaazatrinaphthylene) (PTPA-HATN), was designed and in-situ electrochemically polymerized on the surfaces of FTO electrodes with a directional alignment TiO₂ nanorod array to obtain TiO₂/PTPA-HATN core-shell nanocomposite films. Compared with the PTPA-HATN film, the TiO₂/PTPA-HATN composite film exhibits higher optical contrast and faster response time, with contrast of 57% at 783 nm, coloring time of 3.62 s and discoloring time of 2.55 s (43%, 4.63 s and 4.77 s for PTPA-HATN film, respectively). After 400 cycles, the contrast of nanocomposite film decreased by 28%, while the PTPA-HATN film basically lost its electrochromic properties. A simple three-layer EC prototype device based on TiO₂/PTPA-HATN nanocomposite film constructed with hydrogel electrolyte clearly shows color changes at different voltages. On the one hand, the formation of core-shell porous nanostructure of TiO₂/PTPA-HATN composite film provides a larger ion doping/de-doping interface, shortening the average diffusion length of ions. On the other hand, the large indented polymer-nanorods contact interface makes it difficult for the polymer to detach from the electrode, thus significantly improving the cyclic stability of the composite film.     

Low band‐gap diketopyrrolopyrrole‐containing polymers for near infrared electrochromic and photovoltaic applications

Donor–acceptor type polymers bearing diketopyrrolopyrrole and 3,4‐ethylenedioxythiophene units are reported. The polymers are green and exhibit very low band‐gaps (1.19 eV) with strong and broad absorption (maxima of about 830 nm) in the near infrared (NIR) region in their neutral film states. The polymers display color changes between dark green and light blue with exceptional optical contrasts in the NIR regions of up to 78 and 63% as thin films and single‐layer electrochromic devices, respectively. Fast switching, good stabilities as well as high coloration efficiencies (743–901 cm² C^?1) were also observed. The polymers could also be potentially used as photovoltaic material, with a power conversion efficiency of up to 1.68%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1287–1295     

导电聚合物基电致变色器件的研究进展

导电聚合物作为电致变色活性材料是目前最有应用前景的智能材料之一。本文概述了电致变色器件的基本结构和导电聚合物的电致变色机理,着重介绍了多种导电聚合物基电致变色器件的特点、组成及制备,并展望了未来电致变色器件的发展及应用趋势。     

有机噻吩类衍生物作为电致变色材料*

噻吩类衍生物包括聚噻吩衍生物和齐聚噻吩衍生物。本文从有目的地设计、合成噻吩类衍生物的角度出发,探索了其作为电致变色材料的应用,综述了噻吩类衍生物作为电致变色材料的最新研究进展。     

固态导电聚合物多色电致变色器件的制备

制备了基于聚3-甲基噻吩(P3MeT)和聚苯胺(PANI)的两种结构(侧面结构和垂直结构)固态导电聚合物多色电致变色器件(ECD). 采用电化学现场紫外-可见光谱法研究了侧面结构固态ECD的电致变色特性, P3MeT-ECD显示出蓝色和红色的可逆变化, PANI-ECD显示出墨绿色和黄绿色的可逆变化, 同时采用P3MeT和PANI作变色材料的P3MeT-PANI-ECD可以实现红、蓝、墨绿和草绿多色变化. 用激光雕刻微型化P3MeT-PANI变色层组装制得的侧面结构固态P3MeT-PANI-ECD控制合适电压也可多色变化. 另外, 用CeO₂-TiO₂作为P3MeT-PANI对电极的垂直结构固态P3MeT-PANI-ECD在实现红、蓝、墨绿和草绿多色变化的同时, 也可进行四色自由搭配选择.     

Characterization of an all Sol-Gel Electrochromic Device WO3/Ormolyte/CeO2-TiO2

Electrochemical lithium intercalation in thin films of CeO₂-TiO₂ and WO₃, prepared by the sol-gel technique was investigated with cyclic voltammetry and spectroelectrochemical techniques in propylene carbonate solutions. A solid state system having the configuration WO₃/Ormolyte/CeO₂-TiO₂ has been assembled. The solid electrolyte, an organically modified electrolyte (ormolyte), was prepared with different [O]/[Li] ratios. The transmittance variation of this system during a potentiostatic step from –0.7 V to 0.8 V was about 35% at 550 nm.     

硫钒铜矿化合物电子结构和电致变色特性的第一原理研究

基于密度泛函的第一原理赝势平面波方法,计算晶体结构、电子结构和光学性质,研究硫钒铜矿化合物Cu₃VS₄、Cu₃NbS₄和Cu₃TaS₄的电子输运及电致变色特性,探讨作为透明半导体材料应用于太阳能电池和电致变色器件的可能性.电子结构的计算表明这类化合物是间接带隙半导体,其电子能带的导带底和价带顶分别位于布里渊区的X点和R点.价带顶的电子本征态主要来自于Cu原子的d电子轨道,而导带底电子态主要来源于VB族元素原子的d电子轨道.能带结构、电荷布居分析、电子局域化函数和光吸收及反射谱的计算表明这些硫钒铜矿化合物属于极性共价半导体,具有较高的电荷迁移率和优良的电致变色特性,可应用于高效电致变色器件.     

高分子凝胶电解质及其在电色Smart窗中的应用

研究了高分子凝胶电解质高氯酸锂－碳酸丙烯酯－聚甲基丙烯酸甲酯体系（ＬｉＣｌＯ４－ＰＣ－ＰＭＭＡ）的离子导电性、导电机理以及在电色Ｓｍａｒｔ窗中的应用．其离子电导率与温度的关系服从Ｖｏｇｅｌ－Ｔａｍｍａｎｎ－Ｆｕｌｃｈｅｒ方程，并与体系的ＰＭＭＡ质量百分数、玻璃化温度（Ｔｇ）、碱金属盐的浓度等有关．当ＬｉＣｌＯ４浓度为０．５ｍｏｌ／Ｌ，ＰＭＭＡ＝３５％时，电解质具有良好的粘附性、光学透明度及较高的室温离子电导率（σ＝８．７５×１０－４Ｓ／ｃｍ）．由其组装成的全固态电色Ｓｍａｒｔ窗具有良好的光谱特性，可见光调制范围为４０％～６０％；具有良好的光开关特性，响应时间仅为５ｓ．     

电致变色薄膜锂化技术的研究

提出了一种新的电致变色薄膜的锂化方法，通过电子枪蒸镀锂单质，提高了锂的离化率，从而提高了锂化效果，采用此技术研制的全固态电致变色薄膜器件获得了较好的变色特性，透射式和反射式全固态电致变色薄膜器件的变色性能分别为５０％￣５％和７０％￣２０％。     

Chromogenic WPA/TiO 2 Hybrid Gels and Films

A novel low-temperature electrochromic and photochromic material in the form of gels and thin solid films composed of H₃PW₁₂O₄₀·nH₂O (WPA) incorporated in titanium oxide gel issued of Ti(OPr ⁱ )₄ with addition of acetic acid were made via the sol-gel route by the dip-coating technique. Gels in bulk and thin film forms have been studied with the help of FT-IR transmission, reflection absorption and Raman spectroscopy. Similarity of the characteristic band frequencies with pure WPA confirmed that entrapped Keggin salt is well preserved inside the gel. Photochromism of WPA/TiO₂ gels which appears after short exposure to UV (λ=366 nm) radiation is related to the excitation effect of branched alcohol leading to formation of carbonyl modes due to the alcohol transformation to aldehyde. Electrochromic properties of WPA/TiO₂ gel films were tested in aqueous 0.001M HClO₄ and 0.1M LiClO₄ electrolytes as well as in the sol-gel electrochromic device (ECD) composed of LiClO₄ doped ormolyte and Sb:Mo:SnO₂ counter electrode film with optically passive response. Slight improvement of the WPA/TiO₂ intercalation/deintercalation kinetics was obtained with the films exhibiting one order of magnitude higher electronic conductivity which were made with addition of in situ polymerized pyrrole with Fe(NO₃)₃.