聚(3,4-乙撑二氧噻吩)导电织物的制备、结构及其电致变色性能

本文采用原位聚合法, 以耐酸性好的涤纶为基底, 制得了聚(3,4-乙撑二氧噻吩)/涤纶复合导电织物[Poly(3,4-ethylenedioxythiophene)/conducting terylene textile, PEDOT/CTT], 分析了该导电织物的形貌、导电性能及结构, 并对其电致变色性能进行了初步测试. 实验结果表明, 所得到的PEDOT/CTT具有良好的导电性和一定的电致变色性能, 有望在全固态电致变色织物的制备中获得应用.     

All-in-one,reversible yellow-green color switching tungsten oxide electrochromic devices

Tungsten oxide (WO₃) sol doped with carbon nanodots (CDs) was utilized for constructing an electrolyte-free, all-in-one electrochromic device (ECD). Different from the traditional WO₃-based ECDs, showing the color transition between colorless and blue, the demonstrated device could realize reversible color changes between yellow and green due to the intrinsic color of CDs. The optical contrast of the optimized ECD was up to 53.6% at 650 nm and the coloration response time was 27 s. It could also be automatically bleached under 0 V with the bleaching response time of 80 s. In addition, attributing to the unique photoluminescence (PL) characteristics of CDs, the ECD could also present tunable PL under various excitation wavelengths, which potentially broadens the applications of ECDs in multiple anti-counterfeiting. These results provide simple and effective guidelines for constructing high-performance ECDs with simple architecture and extended color palette.     

苯胺四聚体合成及电致变色器件制备——一个大学化学综合性实验

介绍一个研究探索型大学化学综合性实验——苯胺四聚体合成及其电致变色器件制备。内容包括苯胺四聚体的合成及简单的电致变色器件的制备和相关性能的测试。通过本实验的实践,可以让学生拓宽相关化学专业知识,提高学生综合实验操作技能和专业素质,让学生接触所学领域的前沿技术,激发学生对科学研究的兴趣,培养科研探究能力。     

P(VAc-MA)/PMMA为基体的聚合物电解质制备及其在电致变色器件中的应用

以醋酸乙烯酯(VAc)和丙烯酸甲酯(MA)为单体, 采用半连续种子乳液聚合法制备了无规共聚物P(VAc-MA), 以PMMA与P(VAc-MA)的共混物为基体制备了聚合物电解质. 用红外光谱(FTIR)、X射线衍射(XRD)、热重分析(TG)、紫外光谱(UV)、力学性能测试及电化学交流阻抗等方法研究了聚合物、聚合物膜和聚合物电解质的性质. 结果表明, VAc与MA通过打开各自的CC键聚合生成P(VAc-MA); P(VAc-MA)与PMMA共混后结晶状态发生了变化, 增加了无定形相区, 降低了链段运动的能量壁垒, 提高了热稳定性和拉伸强度. 以P(VAc-MA)/PMMA为基体的聚合物电解质膜具有很高的透明性, 最大室温电导率达到1.17×10-3 S/cm; 离子电导率随着温度的升高而迅速增加, 电导率-温度曲线符合Arrhenius方程; 将此电解质用于全固态电致变色显示器件显示出优良的性能.     

Electrochromic responses of low-temperature-annealed tungsten oxide thin films in contact with a liquid and a polymeric gel electrolyte

Thin films of tungsten trioxide (WO₃) for electrochromic application were synthesized by potentiostatic method by using a peroxytungstic acid as a solution precursor. The morphology of the films with and without postthermal annealing was analyzed by atomic force microscopy. When they were in contact with the liquid electrolyte (LiI in propylene carbonate, PC) and under alternatively applied negative (−1.5 V) and positive (+1.0 V) potentials, the transient optical transmittance modulations at wavelength of 650 nm of the as-deposited and 60 °C annealed WO₃ samples were higher than that of 100 °C annealed WO₃ films, and the switching times between the colored and bleached states were related to the surface morphology of the WO₃ films. In polymeric gel electrolyte (LiI and polymethyl methacrylate in PC) devices, longer time was required for complete coloration as well as bleaching process compared with the liquid one. A parametric analysis was made for each of the transient optical transmittance curves of WO₃-based electrochromic devices to extract the values of the response time in coloration (reduction) and bleaching (oxidation) processes. It concludes that the coloration process was determined by the exchange of current density at the electrolyte–WO₃ interface and a possible inhomogeneous interfacial potential for ion intercalation retards the effective coloration time. The bleaching process seems to be controlled by the space charge-limited lithium ion diffusion in WO₃ electrode and the ionic conductivity of the electrolyte as well.     

甲基丙烯酸乙基联吡啶共聚物的电化学性能研究

本文通过先共聚、后季铵化于共聚物侧链上接入单封端联吡啶的方法,合成了三种含有不同第二共聚单体的侧链型甲基丙烯酸乙基联吡啶共聚物P(BrEMA-M_2-EV),其中M_2=AM,MMA,ST。循环伏安曲线和紫外-可见光谱的测定结果表明:活性中心的含量及不同第二共聚单体对联吡啶共聚物的电化学活性和稳定性有比较显著的影响,但不影响其光谱性质。三种联吡啶共聚物均能可逆地显示黄棕色浅紫色兰紫色的三色互变。     

Electrochromic properties of sputtered TiO2 thin films

TiO₂ thin films were deposited on ITO/Glass substrates by the rf magnetron sputtering in this study. The electrochromic properties of TiO₂ films were investigated using cyclic voltammograms (CV), which were carried out on TiO₂ films immersed in an electrolyte of 1 M LiClO₄ in propylene carbonate (PC). As- deposited TiO₂ thin film was amorphous, while the films post-annealed at 300~600°C contained crystallized anatase and rutile. With the increase of the annealing temperature, the surface roughness of film increased from 1.232 nm to 1.950 nm. Experimental results reveal that the processing parameters of TiO₂ thin films will influence the electrochromic properties such as transmittance, ion-storage capacity, inserted charge, optical density change, coloration efficiency and insertion coefficient.     

Synthesis and electropolymerization of 5,12-dihydrothieno[3′,4′:2,3][1,4]dioxocino[6,7-b]quinoxaline and its electrochromic properties

Synthesis of a new thiophene-based monomer; 5,12-dihydrothieno[3′,4′:2,3][1,4]dioxocino[6,7-b]quinoxaline (DDQ), was realized. The chemical structure of the monomer was characterized by ¹H NMR, FTIR and mass spectroscopy techniques. Electrochemical polymerization of DDQ and characterization of the resulting polymer [P(DDQ)] was performed. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. P(DDQ) has a low oxidation potential (0.9 V) and low band gap (1.73 eV) compared to polythiophene. In addition, dual-type polymer electrochromic device (ECD) based on P(DDQ) with poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed. Spectroelectrochemistry, electrochromic switching, stability and open-circuit stability of the device were studied. It was observed that polymer have good switching time, reasonable contrast and optical memory.     

Near-infrared and multicolor electrochromic device based on polyaniline derivative

Electroactive conducting copolymers of aniline(ANI) and diphenylamine(DPA) are prepared on indium tin oxide(ITO) surface from 1 mol/L H2SO4 aqueous solution with different feed ratios of ANI to DPA by using a potentiostatic method. FTIR spectra and SEM measurements are used to confirm the formation of copolymers. Due to the combination of the N,N′-diphenyl benzidine and aniline units in the molecular chain, the copolymer films exhibit improved electrochemical and electrochromic properties, compared to PANI and PDPA. The copolymer [marked as P(ANI9-co-DPA1)] film prepared at a ratio of 9:1(ANI/DPA) exhibits novel transmittance modulation both in visible and near-infrared(NIR) region between -0.8 V and 0.8 V(52% and 67% respectively) and fast response time(3.6 s for coloration and 2.3 s for bleaching at 600 nm). An electrochromic device(ECD) based on P(ANI9-co-DPA1) and PEDOT:PSS is also fabricated and shows a multicolor electrochromic performance, with a good optical contrast(29% in visible region and 40% in NIR region), acceptable response time(8.3 s for coloration and 7.5 s for bleaching at 600 nm) and long-term stability. Clear color changes from transparent(-0.8 V), bright green(0 V), seagreen(0.4 V) to dark slate gray(0.8 V) are demonstrated.     

Optical and electrochemical properties of Cu-doped NiO films prepared by electrochemical deposition

Cu-doped nickel oxide (NiO) thin films were prepared by electrochemial deposition (cathodic deposition) technique onto the fluorine doped tin oxide (F: SnO₂; FTO) coated glass substrates from organic solutions. Effects of Cu content on the morphology, structure, optical and electrochromic properties of NiO films were investigated by means of scanning electron microscope (SEM), X-ray diffraction (XRD), ultraviolet-visible spectrophotometer (UV-vis) and cyclic voltammetry (CV), respectively. SEM images indicated the formation of nanorods after Cu was added. The films were formed with amorphous or short-range ordered NiO grains and a trace of face-centered cubic Ni_xCu_1−xO confirmed by XRD. The transmittances of both bleached state and colored state were significantly lowered when Cu was added. The NiO films doped with Cu (the molar ratio was 1/8) exhibited the optimum electrochromic behavior with a variation of transmittance (ΔT) up to ∼80% at the wavelength range of 350-600 nm. Cu doping reduces the response time for both the coloring and bleaching states, and the reversibility of the redox reaction was increased as well.