All Sol-Gel Electrochromic Devices with Li+ Ionic Conductor, WO3 Electrochromic Films and SnO2 Counter-Electrode Films

This paper reports on the development of all sol-gel EC devices, having the configuration WO₃/ormolyte/SnO₂:Mo, WO₃/ormolyte/SnO₂:Sb and WO₃/ormolyte/SnO₂:Sb:Mo, where all three internal layers, including the ionically conductive inorganic-organic hybrid (ormolyte), are prepared via the sol-gel route. The electrochemical and optical properties of EC devices are presented and their cycling stability and reversibility of their optical modulation assessed. The transmission modulation of the devices depends on the thickness of the active electrochromic, counter-electrode and ormolyte layer. The electrochemical and optical properties of individual films and the structural properties of the ormolyte are described and correlated with the stability of the all sol-gel EC devices.     

The Synthesis of l-Ethyl-1''''-(4-vinylbenzyl)-4, 4''''-bipyridinium Chloride and Iodide and its Electrochromic Property

A new compound 1-ethyl-1'-(4-vinylbenzyl)-4, 4'-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen's electrochromic (EC) film could be deposited on conductive ITO glass working electrode. With polyelectrolyte as ionic conduction layer, solid EC devices based on this compound have been assembled and their thickness was about 2.35 mm. When different voltages were added, they showed blue or violet red color. After optimization, its response time was less than 50 ms, the number of redox circulation was over 107 and the color of coloration states could be kept for 3 days. This kind of EC device can meet the demand of electronic ink.     

A complementary electrochromic system based on Prussian blue and indium hexacyanoferrate

A new complementary electrochromic device (ECD) based on Prussian blue (PB), indium hexacyanoferrate (InHCF), and KCl-saturated poly(2-acrylamido-2-methylpropanesulfonic acid) (K-PAMPS) was proposed and studied in this work. This novel PB-InHCF ECD (PIECD) exhibits blue-to-yellowish electrochromism with a high coloration efficiency of ca. 103 cm²/C at 690 nm. Although the operating voltages for the fully bleached and fully colored states were determined to be 1.2 V and 0 V (InHCF vs. PB), respectively, the major transmittance modulation occurs within a much narrower voltage window (0.9 V↔0.5 V). That is, the PIECD is energetically favorable. Furthermore, it is unnecessary to precolor either electrochromic (EC) electrode during the cell assembly so that the charge balance between two electrochromic films becomes much easier. In addition to the above performance, the compatibility between the K-PAMPS electrolyte and EC electrodes was also demonstrated. In short, this work proposes another promising PB-based ECD and provides a new choice in the EC field. Electronic Publication     

聚氧乙烯－高氯酸锂配合物电致变色光窗的研究

以ＷＯ３为电致变色层、ＮｉＯｘ为离子贮存层、具有较好透光性的氧亚甲基连接聚氧乙烯／ＬｉＣｌＯ４，配合物为电解质制备了全固态电致变色光窗。电色窗在７００～９００ｎｍ之间的调制深度超过５０％。电色窗的电色能力随温度的升高及ＬｉＣｌＯ４盐浓度的增大而加强，并且电色窗具有较好的信息贮存能力。     

Synthesis,electrochemistry, and electrochromic properties of branched thiophene polymers with different conjugation lengths

Here the authors designed and synthesized three branched thiophene polymers with different effective conjugation lengths of thiophene groups, pTPBT, pTPTT, and pTPQT, mainly based on bithiophene, trithiophene, and quadruple thiophene. The electrochemical curves and theoretical calculation results reflect that the oxidation potential of polymers decreased gradually as the conjugation lengths of thiophene groups increased, which is favorable for the appearance of electrochromism. Electrochromic properties demonstrate that pTBTT displays no electrochromism, pTPTT exhibits an unstable one, while pTPQT shows an obvious stable electrochromism between yellow‐orange and blue‐violet colors. These results indicate that thiophene polymers with effective electrochromism should be the smallest conjugation length of quadruple thiophene at least. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2340–2348     

Electrosynthesis and electrochromic properties of free‐standing copolymer based on oligo(oxyethylene) cross‐linked 2,2’‐bithiophene and 3,4‐ethylenedioxythiophene

Oligo(oxyethylene) chains cross‐linked 2,2’‐bithiophene (BT‐E5‐BT) has been synthesized successfully. A free‐standing copolymer film based on BT‐E5‐BT and 3,4‐ethylenedioxythiophene (P(BT‐E5‐BT‐co‐EDOT)) has been synthesized by electrochemical polymerization. The electrical conductivity of P(BT‐E5‐BT‐co‐EDOT) copolymer (16 S m^?1) has improved by four orders of magnitude compared to the homopolymer of BT‐E5‐BT (P(BT‐E5‐BT), 5 × 10^?3 S m^?1) at room temperature. Both homopolymer and copolymer films exhibit well‐defined redox and satisfied coloration efficiency. Spectroelectrochemistry studies indicate that the P(BT‐E5‐BT‐co‐EDOT) has a lower band gap in the range of 1.83–1.90 eV and shows more plentiful electrochromic colours (green, blue, purple and salmon pink) compared with the homopolymer P(BT‐E5‐BT). The Copolymer P(BT‐E5‐BT‐co‐EDOT) shows the moderate optical contrast (26% of 480 nm) and coloration efficiency (205.41 cm^?1 C^?2). The copolymer method provides a novel way to fabricate a free‐standing organic electrochromic device. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1583–1592     

Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1,2‐phenylenediamine moiety

A series of novel triphenylamine‐containing aromatic polyamides and polyimides having a crank and twisted noncoplanar structures were synthesized in inherent viscosities of 0.14–0.64 dL/g and 0.11–0.67 dL/g, respectively. These polymers had useful levels of thermal stability associated with relatively high glass‐transition temperatures (174–311 °C). They exhibited strong UV–Vis absorption bands at around 300 nm in NMP solutions. The PL spectra of these polymers in NMP solutions (1 × 10^?5 M) showed maximum peaks around 396–479 nm. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammetry (CV) of the polymer films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at potentials of 0.70–1.01 V and 1.10–1.46 V, respectively, vs. Ag/AgCl in acetonitrile solution. The polymer films revealed electrochromic characteristics, with a color change from neutral pale yellowish to green and then to a blue oxidized form at applied potentials ranging from 0.00 to 1.75 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2587–2603, 2006     

Benzooxadiazaole‐based D–A–D co‐oligomers: Synthesis and electropolymerization

Four D–A–D type co‐oligomers have been synthesized by Stille condensation between monostannyl derivatives of furan/thiophene/selenophene/3,4‐ethylenedioxythiophene (EDOT) and 4,7‐dibromo‐benzo[1,2,5]oxadiazole. All these co‐oligomers were successfully electrochemically polymerized in dichloromethane and characterized by spectroelectrochemistry. All four polymers possess narrow optical band gap. Spectroelectrochemical studies of polymer films on indium tin oxide revealed that the replacement of donor EDOT with furan/thiophene/selenophene has affected the low‐energy charge‐carrier (bipolaron) formation significantly. Kinetic studies based on chronoamperometry show that the polymer P5 (EDOT‐capped benzo[1,2,5]oxadiazole system) possess better electrochromic property with high transmittance (66%) in visible region than the other copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

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.