获得高性能电致变色薄膜的ITO表面修饰方法

氧化铟锡玻璃(ITO)以其优良的导电性能和透过率以及相对低的反应活性使其在显示器和电致变色器件中有广泛的应用. 然而, ITO表面的金属氧化物基团也带来了一些问题, 如通过物理方法沉积的电致变色薄膜易从ITO基底上脱离, 从而降低器件寿命, 此种问题在使用液体电解质时显得尤为突出. 为此, 我们利用有机酸小分子对ITO基底表面进行修饰, 继而利用电化学沉积的方法制备聚3,4-(2,2-二甲基丙烯二氧基)噻吩电致变色薄膜. XPS结果表明基底与修饰物间以化学键结合, 超声波处理可以看出电致变色薄膜在修饰后的基底上有更好的稳定性. 本研究提供了一种简单易行的方法来获得高性能的高分子电致变色薄膜.     

磷钨酸盐修饰的氧化钨薄膜的制备与电致变色性质研究

为了提高WO_3纳米粒子薄膜的光学对比度,利用层接层自组装方法,将Keggin型结构的磷钨酸盐H_3[α-PW_(12)O_(40)]与WO_3纳米粒子复合,制备[PEI/PW_(12)/PEI/WO_3]_(20)复合膜.采用扫描电镜、紫外光谱和电化学工作站对复合膜的形貌及电致变色性能进行研究,结果表明:该复合膜与单纯的WO_3纳米粒子薄膜相比,光学对比度提高了117.28%,且这种复合膜提供了较大的H~+扩散系数,可以获得更好的电致变色性能.     

MoO_3电致变色薄膜的XPS研究

近年来 ,随着人们提倡节能和使用洁净能源 ,无机电致变色材料在建筑物采光控制系统和反射率可调表面的应用研究 ,已成为材料领域的一个新热点 .WO3、 MoO3等过渡金属氧化物薄膜具有良好的电致变色效应 ,是人们研究的重点 .其中 MoO3的电致变色效果要好于 IrO2、 TiOx、 CoO及 NiOx等电致变色材料 [1],而且它在可见光区有比 WO3更柔和的色彩 ,使人眼更易于适应其颜色变化 .着色态的 MoO3称为钼青铜 ,其开路记忆也好于钨青铜 [2].故 MoO3电致变色薄膜是极有潜力用于实用化的电致变色器件 .MoO3薄膜常用的制备方法有真空蒸 发、化学气…     

壳聚糖辅助制备WO_3薄膜材料及其电致变色性能

以壳聚糖(CS)为辅助材料,利用层层自组装方法(LbL)制备了WO3复合薄膜材料(CS/WO3).采用紫外-可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)和循环伏安扫描(CV)等手段对CS/WO3纳米复合材料的形貌和电化学性能进行了表征.利用电化学和UV-Vis联机技术研究了复合材料的电致变色性能.结果表明,该复合材料呈现出从无色到蓝色的颜色调变,其光反差可达48.0%,着色效率为58.5cm2/C,着色与褪色时间分别为9.5和1.8s.     

TiO2-PTPAT纳米核/壳结构复合膜的制备及电致变色性能

通过水热法在氟掺杂氧化锡(FTO)导电玻璃基底上制备了垂直生长的二氧化钛(TiO₂)纳米棒阵列, 以TiO₂纳米棒阵列为模板采用电化学聚合法, 原位制备了TiO₂-聚三[2-(4-噻吩)苯]胺(PTPAT)纳米核/壳结构的复合薄膜, 相比于纯PTPAT薄膜, TiO₂-PTPAT复合薄膜显示出更好的电致变色(EC)性能. PTPAT薄膜在600 nm波长下的对比度为28%, 在1100 nm波长下的对比度为60%, 其褪色时间为3.86 s, 着色时间为5.52 s; TiO₂- PTPAT复合薄膜在600 nm波长下的对比度为43%, 在1100 nm波长下的对比度为79%, 其褪色时间为3.35 s, 着色时间为4.43 s, 表明核/壳复合结构薄膜的光学对比度和响应时间性能更加优异. 将PTPAT薄膜和TiO₂-PTPAT复合薄膜作为电致变色层组装成固态EC器件, 基于复合薄膜的器件具有更好的循环稳定性和更高的耐受电压. 复合薄膜在保持PTPAT薄膜原有的EC性能的基础上, 由于有序生长的纳米阵列结构的引入增加了薄膜的比表面积, 为电致变色过程中离子的掺杂和脱掺杂提供了更多有序通道, 从而加快了离子扩散速度. TiO₂阵列的引入也改善了聚合物薄膜与透明导电电极之间的界面结合情况, 从而提升了器件的稳定性.     

高度有序氧化钨纳米棒的制备和表征

采用直流磁控溅射法结合阳极氧化法在铝基纳米点阵上制备氧化钨(WO3)纳米棒. 运用原子力学显微镜(AFM), 电子扫描显微镜(SEM), X射线衍射仪(XRD), 电化学工作站(EW)和紫外-可见分光光度计(UV)观察表征了WO3纳米棒的表面形貌、结构、光学性能和电致变色性能. 结果表明: 在溅射过程中, 溅射粒子优先沉积于铝基纳米点阵的凸点上, 然后成核并形成棒状; WO3纳米棒的直径约为200 nm, 与铝基纳米点阵的直径一致, 拥有一定的电致变色性能.     

水溶性共轭聚电解质的制备及在有机电致变色器件中的应用

制备了聚噻吩电解质聚[3-(1'-丙氧基-3'-磺酸)噻吩](PTH-n₃-SO₃H). 以铂线和ITO玻璃作为电极, PTH-n₃-SO₃H的水溶液作为支持电解质, 分别以齐聚噻吩衍生物5,5"'-双醛基-2,2': 5',2": 5",2"'-四噻吩(4T-2CHO)和5,5"'-双氰基-2,2': 5',2": 5",2"'-四噻吩(4T-2CN)薄膜作为电致变色活性层, 组装了有机电致变色器件. 研究了4T-2CHO和4T-2CN的电致变色性能, 同时考察了PTH-n₃-SO₃H水溶液作为支持电解质在有机电致变色器件中的应用. 研究发现, 当进行电化学掺杂和去掺杂时, 4T-2CHO膜发生从黄色到蓝绿色的可逆变化, 4T-2CN膜发生从淡黄色到蓝色的可逆变化. 结果表明, PTH-n₃-SO₃H水溶液可以作为支持电解质用于有机电致变色器件.     

固态聚苯胺电致变色器件的制备和性能

采用CeO2-TiO2复合物薄膜作为聚苯胺电致变色器件的对电极, 选用聚合物固态电解质(PE: PMMA-PC-EC-LiClO4), 构筑了新型双层结构(Dual-type)聚苯胺(PANI)固态电致变色(EC)器件. 用电化学现场紫外-可见光谱法表征了该EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的电致变色性能, 并与单层结构(Single-type)EC器件(ITO|PANI||PE|| ITO)进行了比较. 研究结果表明, 双层结构EC器件比单层结构EC器件的电致变色性能好, 如响应速度快, 循环寿命长. 同时, 考察了电解质组分对聚苯胺电致变色稳定性的影响. EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的颜色呈现由透明的黄色(-1.5 V, PANI vs. CeO2-TiO2)到蓝色(1.0 V)的可逆变化, 在700 nm处的透射率由42.19%变到13.35%, 经过150个循环, 其透射率差仍保持不变, 着色效率为152.1 cm2/C.     

热处理对WO3纳米薄膜结构及其气致变色性能的影响

以钨粉和过氧化氢溶液为原料, 采用溶胶凝胶法制备了WO3溶胶, 并结合提拉镀膜法, 分别在普通玻璃载玻片和抛光硅片上制备了掺钯气致变色WO3纳米结构薄膜; 并分别在50, 150, 250, 350和450 ℃的空气氛围中对薄膜进行了热处理. 采用IR、双椭圆偏振光谱仪、AFM和XRD分析了薄膜的性质和微观结构, 观察了薄膜的表面形貌, 根据所得数据讨论了不同热处理温度对薄膜的结构和气致变色性能的影响.     

石墨烯-ITO复合电极对聚苯胺薄膜电致变色性质的影响

采用改进的Hummers法制备氧化石墨烯(GO),首先,石墨与浓硫酸、过硫酸钾和五氧化二磷反应制得强氧化产物,随后将其与浓硫酸、硝酸钠、高锰酸钾反应,经双氧水发泡、酸洗、超声等合成氧化石墨烯水溶液,再通过金属箔还原和基底转移过程制备GO-氧化铟锡(ITO)复合电极材料.通过金属箔还原和基底转移过程制备GO-氧化铟锡(ITO)复合电极材料.利用电化学聚合法在GO-ITO复合电极上制备聚苯胺(PANI)薄膜,并对其形貌结构、电化学及电致变色性质进行表征.结果表明,与ITO电极相比,采用GO-ITO复合电极制备的PANI的成膜性得到明显改善,复合电极具有更加均匀细致的颗粒表面,增大了聚合物与电解液之间的接触面积,为电致变色过程中平衡离子的注入/脱出提供了更多的通道,因而PANI薄膜在700nm处的光学对比度提高了约13%,响应速度缩短了约2.6 s,着色效率高达169.6 cm2/C.GO的引入保持了PANI良好的电化学稳定性.GO-ITO复合电极有效改善了聚合物的综合性能,对于聚合物电致变色材料及器件的开发具有潜在的应用前景.     

Electrochromic devices based on copolymers of 3-Trimethoxysilanylpropyl-N-aniline-2,5-Dimethoxyaniline

Electrochemical copolymerization of 3-trimethoxysilanyl-propyl-N-aniline (TMSPA) with 2,5-dimethoxyaniline (DMA) was performed in 1 M HCl aqueous solution for different feed ratios of TMSPA using cyclic voltammetry. The deposition rate of TMSPA–DMA copolymer is higher than that of PTMSPA but lower than that of PDMA. (TMSPA-co-DMA) film was deposited using electrochemical polymerization as conducting film on indium tin oxide (ITO) electrode and used as an electrode in an electrochromic device. Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) was spin-coated on ITO as the other electrode. Carboxyl-terminated- butadiene-acrylonitrile (CTBN) blended with LiClO₄ was used as solid polymer electrolyte. A total solid electrochromic device was assembled as follows: ITO|P(TMSPA-co-DMA)LiClO₄-CTBNPEDOT:PSS|ITO. The columbic efficiency of the devices reached to 104% for P(TMSPA-co-DMA) film with TMSPA feed ratio of 0.25. The optical contrast (ΔT, %) of the single electrode and the device were determined by UV–vis spectroelectrochemical studies. The stability of ΔT was improved during color switching from +1.5 to −1.5 V (vs. PEDOT) for this device. The device was pale yellow at −1.5 V and blue at +1.5 V.     

X-Ray Analysis of Multi-Films for Electrochromic Device Application

Multilayer films based on tungsten oxide (WO₃), ITO (indium tin oxide) and CdS were deposited mainly by reactive dc magnetron sputtering onto glass substrates for electrochromic application. The thin films were analyzed by means of XPS (X-ray photoelectron spectroscopy), GIXD (grazing incidence X-ray diffraction) and XRD (X-ray diffraction). XRD and XPS results confirmed that the films were WO₃, CdS and ITO, respectively. The surface and interface of the CdS/ITO bi-layered film was studied by GIXD in different incidence angles. Detailed results about the amorphous characterization of the films during room temperature growth and post annealing are given.     

Urea Biosensor Based on Electrochromic Properties of Prussian Blue

Prussian blue (PB) is an electrochromic material, which can be used as a signal transducer in the formation of optical urea biosensors. The previous researches in electrochromic properties of PB demonstrated the optical PB response to ammonium ions, which occurs when ammonium ions are interacting with PB layer at a constant 0.2 V vs Ag|AgCl|KCl_sat potential. In this work PB optical dependence on ammonium ions concentration was applied in the formation of electrochromic urea biosensor. Biosensor was formed by modifying the optically transparent indium tin oxide (ITO) coated glass electrode (glass/ITO) with Prussian blue layer and immobilizing urease (glass/ITO/PB‐urease). Calibration curve showed the linear dependency (R²=0.995) between the change of maximal absorbance (ΔA) and urea concentration in concentration range varying from 3 mM to 30 mM. The highest sensitivity (4 ΔA M^?1) of glass/ITO/PB‐urease biosensor is in the concentration range from 7 mM to 30 mM. It was determined that working principle of the glass/ITO/PB‐urease biosensor is not related to pH changes occurring during enzymatic hydrolysis of urea.     

离子液体中聚3-己基噻吩的制备及电致变色性质和器件的研究

以室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM]PF₆为溶剂及支持电解质,通过电化学方法制备聚(3-己基噻吩)(PHexT)膜。采用循环伏安法和扫描电子显微镜,对膜的电化学性质及形貌结构进行表征。同时通过紫外可见光谱、计时电流、计时库仑以及计时吸收曲线等方法研究聚合物膜的光谱电化学和电致变色特性,并在此基础上制备PHexT膜的电致变色器件。实验结果表明,在离子液体中制备的PHexT膜光滑致密,掺杂态时为蓝色,脱掺杂时为桔红色,并且具有高的颜色对比度 (40%),较短的响应时间 (2.5 s) 和高的电致变色着色效率 (230cm²/C),该膜制成的固态电致变色器件具有很好的电致变色性能和长的循环寿命。     

染料敏化TiO2/WO3薄膜电池的光电变色

The light-to-electricity conversion process of the TiO2 nanostructured electrode sensitized by a dye was investigated using the photoelectrochemical method in this paper. At the same time, the WO3 thin film was electrodeposited on conducting glass. The results showed that the dye-sensitized nanoporous TiO2 film has the properties of energy conversion, along with good electrochromic properties of electrodeposited MoO3 thin film. A self-powered smart window was achieved by combining a dye-sensitized nanoporous TiO2 film as the photovoltaic layer and an electrodeposited WO3 film as the electrochromic layer. This window changed from being almost transparent to blue spontaneously under illumination, and thus could modulate light transmittance.     

钒钨酸盐/刚果红电致变色复合膜及器件研究

应用Layer-by-Layer自组装技术,采用聚乙烯亚胺(PEI)阳离子将无机电致变色材料[P2W15V3O62]8-(P2W15V3)阴离子与刚果红(CR)阴离子通过静电引力复合,构筑了复合膜[PEI/P2W15V3/PEI/CR]20及对比膜[PEI/P2W15V3]20.利用扫描电子显微镜、紫外-可见吸收光谱和电化学工作站研究了复合膜的形貌与电致变色性能.对比研究表明,复合膜可实现浅红色-蓝紫色-浅红色的可逆颜色调变,且保持了[P2W15V3O62]8-阴离子的电致变色性能,光反差22.55%,着色效率122.67 cm2/C.复合膜循环测试400圈后透过率(500 nm)处损耗仅为6.94%,稳定性良好;由复合膜组装的电致变色器件也实现了由浅红色到蓝紫色的颜色变化.本研究可为解决多酸电致变色材料颜色变化单一的问题提供参考.     

Time-resolved electrochromic properties of MoO<Subscript>3</Subscript> thin films electrodeposited on a flexible substrate

In this paper, a MoO₃ thin film was firstly electrodeposited on flexible ITO/PET substrates. Its electrochromic properties were examined using an electrochemical workstation coupled in situ with a charge-coupled device (CCD) spectrophotometer. The film was characterized by XRD and AFM. The electrodeposited MoO₃ thin film on the ITO/PET substrate showed a large transmittance contrast between the colored and bleached states, a quick response, and good durability and reversibility. The low working potential range, –0.5 to 1.6 V (vs. Ag/AgCl), for the MoO₃/ITO/PET film prepared in this work makes it a good candidate for flexible smart windows, as well as other plastic electrochromic devices. Electronic Publication     

Electrochromic properties of novel strictly alternating poly(amine-amide-imide)s with electroactive triphenylamine moieties

A series of novel triphenylamine-containing aromatic poly(amine-amide-imide)s (PAAIs) were prepared by the phosphorylation polyamidation reactions from the diamine, N,N′-bis(4-aminophenyl)-N,N′-diphenyl-1,4-phenylenediamine, and various imide ring-preformed dicarboxylic acids. All the PAAIs were amorphous, had good solubility in many polar aprotic solvents, and exhibited excellent thin film forming capability with good mechanical properties. They displayed relatively high glass-transition temperatures (220-306 °C) and good thermal stability, with 10% weight-loss temperatures in excess of 522 °C in air or nitrogen and char yields at 800 °C in nitrogen higher than 66%. The solutions of polymers in NMP exhibited strong UV-vis absorption bands with a maximum around 315 nm. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the PAAIs prepared by casting polymer solution onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.63 and 1.01 V vs. Ag/AgCl in acetonitrile solution. All the PAAIs revealed very stable electrochromic characteristics, changing color from original pale brownish to green, and then to blue at 0.67 and 1.08 V, respectively.     

纳米纤维素/聚3,4-乙撑二氧噻吩复合薄膜的制备及电致变色性能

以棉浆粕为原料,采用硫酸溶胀结合超声波处理的方法制备了纳米纤维素(NC).在纳米纤维素的水分散液中加入3,4-乙撑二氧噻吩单体,以过硫酸铵为氧化剂,采用原位化学氧化法制得了纳米纤维素/聚3,4-乙撑二氧噻吩(NC/PEDOT)纳米复合物.对NC和NC/PEDOT复合物进行扫描电镜、透射电镜和红外光谱分析.将纳米复合物的水分散液滴涂在氧化铟锡(ITO)玻璃表面形成复合薄膜,考察不同纳米纤维素含量对NC/PEDOT复合薄膜电致变色性能的影响.结果表明,NC呈棒状,平均直径为20 nm,长度为100~300nm;NC/PEDOT复合物中PEDOT均匀包覆在NC表面形成核壳结构,平均直径为30 nm;复合薄膜中当NC含量为60%时,其电致变色性能最好,具有最高的对比度(24.4%),最短的响应时间(1 s),最高的着色效率(51.8 cm~2/C).