电致变色氧化钨薄膜锂离子阈值注入量的研究

探讨了ＷＯ３薄膜与１ＭＬｉＣｌＯ４－ＰＣ溶液之间的界面电位差的变化规律及测量方法，制备了三种具有不同电致变色性能的ＷＯ３薄膜，并对它们进行了界面电位差随Ｌｉ＾＋注入量大小变化的测量，通过实验发现，界面电位差的变化趋势能够反映出氧化钨薄膜的Ｌｉ＾＋离子阈值注入量的大小。进而找到了用电阻热蒸发方法制备了电致变色氧化钨薄膜的最佳工艺条件。     

Optical Properties of Sol-Gel Derived Vanadium Oxide Films

Vanadium oxide gels can be made from vanadate aqueous solutions or from vanadium alkoxides. The condensation of vanadic acid gives long ribbon-like oxide particles which macroscopically orient in the same direction in aqueous sols when their concentration is larger than 0.12 mol·l⁻¹. These anisotropic sols and gels should be considered as lyotropic nematic liquid crystals. Thick films in which ribbons align along the same direction can be deposited. These oriented coatings exhibit improved electrochemical properties as reversible cathodes for lithium batteries. Amorphous oxo-polymers are formed via the controlled hydrolysis of vanadium alkoxides. They allow the deposition of optically transparent thin films that exhibit interesting electrochromic properties and turn reversibly from yellow to green upon electrochemical reduction. Moreover these alkoxide derived films can be easily reduced into vanadium dioxide. These VO₂ thin films exhibit thermochromic properties and could be used as optical switches in the infrared. The transition temperature of these VO₂ films can be modified by doping the vanadium oxide with other cations.     

Unconventional Aluminum Ion Intercalation/Deintercalation for Fast Switching and Highly Stable Electrochromism

Electrochromic devices have many important commercial applications ranging from electronic paper like displays, antiglare rear‐view mirrors in cars, to energy‐saving smart windows in buildings. Monovalent ions such as H⁺, Li⁺, and Na⁺ are widely used as insertion ions in electrochromic devices but have serious limitations such as instability, high‐cost, and hard handling. The utilization of trivalent ions as insertion ions has been largely overlooked probably because of the strong electrostatic interactions between ions and intercalation framework and the resulted difficulties of intercalation. It is demonstrated that the trivalent ion, Al³⁺, can be used as efficient insertion ion by using metal oxide hosts in nanostructured form, which brings the desired fast‐switch, high‐contrast, and high‐stability as well to electrochromic devices. Differing from the usual structure degradation by repeated guest intercalation/deintercalation, the Al³⁺ insertion introduces strong electrostatic forces, which on some degree stabilize the crystal structure and consequently yield much enhanced performances.     

Electrochemical and Solvent-Mediated Visible-to-Near-Infrared Spectroscopic Switching of Benzoselenadiazole Fluorophores

A series of electronic push–pull, pull–pull, and push fluorophores has been prepared from a benzoselenadiazole core so that their spectroscopic, electrochemical, spectro-electrochemical, and spectro-electrofluorescence properties could be examined. The emission wavelengths and fluorescence quantum yields (Φ_fl) of the N,N-dimethyl fluorophores were contingent on the solvent polarity and they ranged from 615 to 850 nm in aprotic solvents. The positive solvatochromism and the quenched Φ_fl in polar solvents were consistent with an intramolecular charge-transfer state (ICT). Meanwhile, a locally excited state (LE) was assigned in nonpolar solvents from the blue-shifted emission and high Φ_fl. The N,N-dimethylamine fluorophores examined could be both electrochemically oxidized and reduced, whereas the symmetric dinitro pull–pull derivative could be only reversibly reduced. Courtesy of their electrochemical reversibility, the fluorophores could reversibly change color from yellow to blue with an applied potential in addition to switching off their emission. The absorption of the electrochemically generated intermediates of the N,N-dimethyl derivatives spanned 500 nm over the visible and the NIR regions. The colors could be switched for upwards of two hours with applied potential, illustrating their potential use as electroactive materials in electrochromic devices.     

Innocent or guilty? Redox activity in and magnetic and optical behaviour of dinuclear molydenum complexes

The phenomenon of ‘non-innocence’, first articulated by J?rgensen in 1966, is briefly reviewed. Spectroelectrochemical studies of a range of dinuclear complexes of the type [Mo(NO)Tp*Cl₂(bridge)] (bridge = dipyridyls) and [Mo(O)Tp*Cl₂(bridge)] (bridge = diphenolates) which are redox active, show that oxidised or reduced forms of these species exhibit ‘non-innocence’. The spectral behaviour is associated with metal-to-ligand or ligand-to-metal charge transfer phenomena, probably the first time that monodentate bridging ligands have been implicated in ‘non-innocent’ behaviour. These bridging ligands also determine the nature and extent of magnetic interaction between the unpaired spins in [Mo(NO)Tp*Cl₂(bridge)] and [Mo(O)Tp*Cl₂(bridge)], the dominant mechanism of spin-exchange relying on the extent of {ie291-01}-delocalisation within the bridging ligands. The unusual optical behaviour of these dinuclear complexes when oxidised (oxomolybdenum diphenolates) or reduced (nitrosyl molybdenum dipyridyls) has led to the exploration of electrochromism as a means to develop variable optical attenuators operating in the near-infrared region.     

Cyclic Acetal-Photosensitized Polymerization. XI. Photoirradiations onto Polycyclic Acetals

Photoirradiations onto polycyclic acetals, i. e., polymers containing cyclic acetal groups in the molecule, were carried out at 30 or 40°C. The terpolymer of vinyl formal/vinyl acetate/vinyl alcohol (PVFAcA) was decomposed by means of irradiation, while poly-2-vinyl-1,3-dioxolane (PVDO) and poly-2-vinyl-4-hydroxy-methyl-1,3-dioxolane (PVHDO) were crosslinked. These results indicate the possibility of control of the decomposition or the crosslinking of polymer.     

A platform to synthesize a soluble poly(3,4‐ethylenedioxythiophene) analogue

Alkyl‐substituted polyhedral oligomeric silsesquioxane (POSS) cage is combined with 3,4‐ethylenedioxythiophene under the same roof. The corresponding monomer called EDOT‐POSS is used to get soluble poly(3,4‐ethylenedioxythiophene) (PEDOT‐POSS) analogue. Both chemically and electrochemically obtained polymers are soluble in common organic solvents like dichloromethane, chloroform, tetrahydrofuran, and so forth. The PEDOT‐POSS has somewhat higher band gap (1.71 eV at 618 nm) than its parent PEDOT (1.60 eV at 627 nm) and as expected the PEDOT‐POSS exhibits higher optical contrast (74% at 618 nm) and coloration efficiency (582 cm²/C for 100% switching), lower switching time (0.9 s), higher electrochemical stability (93% of its electroactivity retains after 5000 cycles under ambient conditions) when compared to the PEDOT. A number of advantages of the PEDOT‐POSS over the PEDOT can make it a promising material in the areas of electro‐optical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3935–3941     

A new black to highly transmissive switching bilayer polymer composite films with electroactive pEA as a color buffer layer for improving electrochromic stability

Two reported D-A-D monomers based on 3,4-ethylenedioxythiophene (EDOT) were selected for electrochemical copolymerization to obtain copolymer film, named pRG. Then, a soluble polymer poly[3,4-ethylenedioxythiophene-alt-3,4-bis([2-ethylhexyl]oxy)thiophene] (pEA) based on the EDOT derivative was screened out, which is complementary to the absorption trough of the pRG film in visible region and matched with its working potential. The bilayer composite film pRG/pEA was obtained by spinning pEA basement membrane on fluorine doped tin oxide (FTO) coated glass surface, and then in situ electrochemical polymerization of pRG film. Compared to the pRG monolayer film, the bilayer composite film shows a more saturated black color in the neutral state and significant improvement on cyclic stability (only decreased by 1.7% after 250 cycles, while pRG film decreased by 17.1%). The introduction of pEA buffer layer not only achieves the full spectral absorption of the composite film in the visible region, but also significantly improves the cyclic stability of the bilayer composite film. The assembled EC prototype device based on the pRG/pEA composite film exhibits a “black to high transmission” reversible switch. Finally, this method combining electrochemical copolymerization, spin-coating, lamination and other methods provides a new research idea for designing and preparing black to transmissive electrochromic materials.