Cycling and at-rest stabilities of a complementary electrochromic device containing poly(3,4-ethylenedioxythiophene) and Prussian blue

PEDOT-based electrochromic devices (ECDs) have been investigated intensively in recent years. In order to obtain an ECD having long cycle life, the counter electrode and electrolyte used should be compatible in the electrochemical environment. Prussian blue (PB) is proven to be electrochemically stable when cycling in non-aqueous solutions. Thus a new organic-inorganic complementary ECD was assembled in combination with a PMMA-based gel polymer electrolyte. This ECD exhibited deep blue-violet when applying −2.1 V and became light blue when applying 0.6 V. Under these conditions, the transmittance of the ECD at 590 nm changed from 13.8% (−2.1 V) to 60.5% (+0.6 V) with a coloration efficiency of 338 cm²/C. The cell retained 55% of its maximum transmittance window (ΔT_max) after 50,640 repeated cycles. Moreover, the at-rest stability test revealed a transmittance window (ΔT) decay of 9.6% over a period of 107 days. Therefore, the proposed PEDOT-PB ECD may have potential for practical applications.     

An all-thiophene electrochromic device fabricated with poly(3-methylthiophene) and poly(3,4-ethylenedioxythiophene)

A novel all-organic electrochromic device (ECD) is presented. By electrodepositing poly(3-methylthiophene) (PMeT) in boron fluoride ethyl ether (BFEE), a strong Lewis acid, a good-quality PMeT film was obtained. On the basis of studies of PMeT, it can be regarded as a pseudo-anodic coloring material for ECDs. On the other hand, poly(3,4-ethylenedioxythiophene) (PEDOT) is an ideal cathodic coloring electrochromic material known for its high optical contrast, long-term stability, and high coloration efficiency. By combining these two thiophene derivatives, the application potential of this device was determined. The color of the ECD switches between deep blue at −1.4 V (PEDOT vs. PMeT) and light red at 0.6 V. The device exhibits stable electrochromic performance, with a maximum optical attenuation (ΔT_max) at 655 nm reaching 46% (from 9% to 55%), and achieves a high coloration efficiency of 336 cm²/C. After 100 repeated cycles, the cell still retained at 91.3% of its ΔT_max at 655 nm.     

Incorporation of a stable radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) in an electrochromic device

A stable organic radical, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), was studied. We employed TEMPO as a cathodic radical provider in propylene carbonate (PC) and poly(3,4-propylenedioxythiophene) derivatives (PProDOT-Et₂) as an anodic electrochromic (EC) thin film, which was obtained through electropolymerization. On assembling them together in a device, the electrochemical and optical performances of this hybrid electrochromic device (ECD) showed reversible cycling stability and high absorbance attenuation in the visible range. By selecting proper electrolytes (LiClO₄/PC) and controlling the deposited charge of the PProDOT-Et₂ thin film, it was possible to obtain a transmittance change (ΔT) of up to 59% at 590 nm with no noticeable degradation after operating between 0 and 0.9 V for 1000 cycles. Furthermore, an electrochemical quartz crystal microbalance (EQCM) was used to investigate ion migrations in the PProDOT-Et₂ thin film, which influenced its long-term stability.     

Electrochromic device of PEDOT–PANI hybrid system for fast response and high optical contrast

An organic–organic hybrid system composed of the polyaniline (PANI) and poly-(3,4-ethylenedioxythiophene) (PEDOT) with controlled thickness was developed successfully in order to realize synergetic effects in electrochromic (EC) properties such as optical contrast and color-switching rate. From the UV transmittance spectra, we found that the optical contrast (Δ%T) was enhanced up to 6–72% at the wavelength of 580 nm compared with the previous PANI–PEDOT ECDs. Furthermore, the optimized ECD showed an extremely fast response time of less than 160 ms. It is therefore concluded that such a complementary full .cell system of PEDOT–PANI ECD is applicable as an optical device.     

A complementary electrochromic device based on Prussian blue and poly(ProDOT-Et2) with high contrast and high coloration efficiency

A complementary electrochromic device (ECD) based on Prussian blue (PB) and poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepine) (PProDOT-Et₂) has been systematically investigated. PB is regarded as an anodic coloring material with high electrochemical stability, while PProDOT-Et₂ is a cathodic coloring polymer with high contrast and high coloration efficiency (η). The electro-optical properties of the two electrochromic (EC) materials are characterized separately in a 0.1 M LiClO₄ in propylene carbonate (PC). A complementary ECD is assembled based on the two EC materials. The maximum transmittance of the ECD at 590 nm can be changed reversibly from 11.3% to 70.6% at the applied voltages of 1.2 and −1.3 V, and achieved a high coloration efficiency of 1214 cm²/C. Moreover, this ECD still remains at 98% of its maximum transmittance window (ΔT_max) even after 1,200 cycles, namely, the ΔT value decreases from 59% to 58%.     

Characteristics of laminated electrochromic devices using polyorganodisulfide electrodes

The application of polyorganodisulfides as optically passive counter-electrodes in a variety of electrochromic smart glazing devices are discussed. Characteristic data is presented for electrochromic devices using proton, and lithium coloration ions with modified polyethylene oxide electrolyte and polydimercaptothiadiazole positive electrodes. Solid state devices consisting of molybdenum doped WO₃, amorphous polyethylene oxide electrolyte (a-PEO), and a polyorganodisulfide counter-electrode colored rapidly from a pale yellow to a deep blue-green, upon application of −1.2 V DC. The photopic transmittance (T_p) changes from 61 to 9%, and the solar transmittance (T_s) changes from 45 to 5% during the coloration process. Also, our experiments with polyimidazole are detailed. This family of compounds due to its unique electrical and ion conduction properties allow a single composite ion storage and ion conductor electrode to be made, simplifying the device construction. Devices made from this family of compounds color to deep blue-gray upon application of −1.2–1.5 V DC. Bleaching occurs at −0.4 to −0.5 V DC. The photopic transmittance changed from 55 to 9%, and the solar transmittance from 34 to 4% during coloration. Both coloration and bleaching are quite rapid.     

All-plastic electrochromic devices based on PEDOT as switchable optical attenuator in the near IR

Advanced materials for IR applications such as thermal control in spacecraft applications or variable optical attenuators which could replace the present systems have been sought. The use of electrochromic devices based on conducting polymers will add lightness and flexibility to the final device in order to overcome the limitations of the present materials used in IR applications. In this work, we present a new all-plastic electrochromic device with optical contrast (%ΔT) of 44% at 1971 nm in the IR region based on PEDOT formulations and ionic liquid blends as electrolytes. The switching time of the device is in the order of a few seconds, with a t_c 2.7 s and t_b 3.8 s.     

A complementary electrochromic device based on polyaniline and poly(3,4-ethylenedioxythiophene)

In this study, two conducting polymers, polyaniline (PANI) and poly(3,4-ethylenedioxythiophene) (PEDOT), were used to construct an electrochromic device (ECD). PANI was employed as the anodic coloring polymer while PEDOT was used as the cathodic coloring polymer. The electrochemical and optical properties of PANI, which has a coloration efficiency of 25 cm²/C at 570 nm, were coupled with the complementary coloring material, PEDOT, which has a coloration efficiency of 206 cm²/C at 570 nm. A suitable operating potential window was switched between −0.6 and 1.0 V to explore the cycle life of the ECD. We tested the PANI–PEDOT ECD, which consisted of PANI, PEDOT, and an organic electrolyte containing 0.1 M LiClO₄ in propylene carbonate and 1 mM HClO₄. The transmittance of the ECD at 570 nm changed from 58% (−0.6 V) to 14% (1.0 V) with a coloration efficiency of 285 cm²/C. Within the selected operating voltage range, the PANI–PEDOT ECD could be cycled for up to 2×10⁴ cycles.     

Influence of coloring voltage on the optical performance and cycling stability of a polyaniline–indium hexacyanoferrate electrochromic system

An electrochromic system based on the multielectrochromic polyaniline (PANI) and pseudo-transparent indium hexacyanoferrate (InHCF) thin-film electrodes was studied in this work. In combination with a hybrid H⁺/K⁺-conducting solid polymer electrolyte—KCl-doped poly(2-acrylamido-2-methylpropanesulfonic acid) (K-PAMPS), a precoloring-free PANI–InHCF electrochromic device (ECD) with an active area of 3×3 cm² was fabricated and exhibited yellowish-green-blue multicolor electrochromism. From in situ spectroelectrochemical experiments, we found that the performance of a PANI/K-PAMPS/InHCF ECD was significantly affected by the operating voltages, especially by the coloring voltage. Both the bleached and yellowish state of the ECD could be attained reversibly by applying a voltage ranging from +1.5 to +1.7 V (InHCF vs. PANI). Different coloring voltages resulted in different optical properties and cycling stabilities, however. For instance, the device biased at −1.6 V (InHCF vs. PANI) showed a deep blue color, but the optical activity decayed quickly (less than 50 cycles) when the device was switched between +1.6 and −1.6 V. Nevertheless, the device could be reversibly operated between +1.6 and 0 V for several hundred cycles, although a narrower electrochromic extent (yellowish-to-green) was observed correspondingly. The optimization of the coloring voltage is therefore of paramount importance to the PANI/K-PAMPS/InHCF ECD.     

Characterization and electrochromic properties of CuxNi1−xO films prepared by sol–gel dip-coating

Cu_xNi_1−xO electrochromic thin films were prepared by sol–gel dip coating and characterized by XRD, UV–vis absorption and electrochromic test. XRD results show that the structure of the Cu_x Ni_1−xO thin films is still in cubic NiO structure. UV–vis absorption spectra show that the absorption edges of the Cu_xNi_1−xO films can be tuned from 335 nm (x = 0) to 550 nm (x = 0.3), and the transmittance of the colored films decrease as the content of Cu increases. Cu_xNi_1−xO films show good electrochromic behavior, both the coloring and bleaching time for a Cu_0.2Ni_0.8O film were less than 1 s, with a variation of transmittance up to 75% at the wavelength of 632.8 nm.     

First a-SiC : H photovoltaic-powered monolithic tandem electrochromic smart window device

We report on the first monolithic, amorphous-silicon-based, photovoltaic-powered electrochromic window coating. The coating employs a wide band gap a-Si_1−xC_x : H n–i–p photovoltaic (PV) cell as a semitransparent power supply, and an Li_yWO₃/LiAlF₄/V₂O₅ electrochromic (EC) device as an optical-transmittance modulator. The EC device is deposited directly on top of a PV device that coats a glass substrate. The a-Si_1−xC_x : H PV cell has a Tauc gap of 2.2 eV and a transmittance of 80% over a large portion of the visible light spectrum. We reduced the thickness of the device to about 600 Å while maintaining a 1-sun open-circuit voltage of 0.9 V and short-circuit current of 2 mA/cm². By employing the LiAlF₄ as the Li⁺ ion electrolyte, the parasitic electronic current through the device has been significantly reduced (<10 μA/cm² under 1 V bleaching voltage). By properly controlling y and the thickness of each layer, the coloration and bleaching voltage of the EC device could be adjusted within the range of −0.6 to −1.3 V (coloring) and 0.1–0.6 V (bleaching) for compatibility with the underlying PV cell. Our prototype 16 cm² PV/EC device modulates the transmittance by more than 60% over a large portion of the visible spectrum. Its color is pale yellow at bleached state and dark blue at colored state. The coloring and bleaching times of the electrochromic device are approximately 2 min under normal operating conditions (±1 V). The device is hermetically sealed for a long lifetime.     

Solid hybrid polyelectrolyte with high performance in electrochromic devices: Electrochemical stability and optical study

This paper presents a high-stability, single-phase hybrid polyelectrolyte (SPHP) applied in a large EC device (5×10 cm²) using WO₃ (electrochromic) and CeO₂–TiO₂ (counter-electrode–ion storage) electrodes, both produced by Leibniz—Institut of New Materials (Leibniz—INM, Germany). The electrochromic device exhibited excellent color and bleach reversibility, high coloration efficiency (>35 cm²/C) from the first cycle up to more than 60,000 CA cycles, and a maximum constant rate of deintercalation/intercalation (O_out/Q_in=1). Its remarkable behavior and high stability render this material an excellent candidate for application in electrochromic devices.     

Magnesium–titanium alloy thin-film switchable mirrors

In this paper, we show gasochromic and electrochromic switching properties of Pd top capped magnesium–titanium (Mg–Ti) thin films prepared by DC magnetron sputtering. These films show excellent switchable mirror properties. By exposing to 4% H₂ in Ar, Pd (4 nm)/Mg_0.82Ti_0.18 (40 nm) film changed from the metallic state to the transparent state drastically within 5 s. By exposing to air, it goes back to the metallic state within 60 s. The transmittance spectrum in the hydride state is quite flat in the wavelength range from 400 to 2500 nm. It looks complete color neutral and its chromaticity coordinates are x=0.326 and y=0.340. Simple electrochromic device of Mg–Ti thin film using a liquid electrolyte works very well. It can be switched between the mirror state and the color-neutral transparent state.     

Electrochromic characterization of Co(OH)2 thin film prepared by sol–gel process

Electrochemical, spectroscopic and structural measurements were used to characterize the electrochromic behavior and stability of sol–gel deposited Co(OH)₂ thin films. These films were prepared from polymeric solutions containing cobalt methoxyethoxide precursor by spin coating technique. The as-deposited films are amorphous and show crystalline structure after heat treatment at 450°C. Sol–gel-deposited cobalt hydroxide films show reversible electrochromic response in 1 M LiClO₄/ propylene carbonate solution beyond 500 cycles. The structural and chemical properties of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Spectral transmittance change was T_p=29.9–60.2% for cobalt hydroxide films. It is argued that reversible lithium insertion capacity, good cyclic reversibility of Co(OH)₂ films make them suitable as counterelectrode layers in the electrochromic devices.     

An all-solid-state electrochromic device based on NiO/WO3 complementary structure and solid hybrid polyelectrolyte

An all-solid-state electrochromic (EC) device based on NiO/WO₃ complementary structure and solid polyelectrolyte was manufactured for modulating the optical transmittance. The device consists of WO₃ film as the main electrochromic layer, single-phase hybrid polyelectrolyte as the Li⁺ ion conductor layer, and NiO film as the counter electrochromic layer. Indium tin oxide- (ITO) coated glass was used as substrate and ITO films act as the transparent conductive electrodes. The effective area of the device is 5×5 cm². The device showed an optical modulation of 55% at 550 nm and achieved a coloration efficiency of 87 cm² C⁻¹. The response time of the device is found to be about 10 s for coloring step and 20 s for bleaching step. The electrochromic mechanism in the NiO/WO₃ complementary structure with Li⁺ ion insertion and extraction was investigated by means of cyclic voltammograms (CV) and X-ray photoelectron spectroscopy (XPS).     

Effect of modified ITO substrate on electrochromic properties of polyaniline films

In this work, we report the morphological and electrochromic properties of electrochemically synthesized polyaniline (PANI) thin films on bare and modified indium–tin oxide (ITO) glass substrates. In the last case, the surface of ITO glass was covered by a self-assembled monolayer of N-phenyl-γ-aminopropyl-trimethoxysilane (PAPTS). Atomic force microscopy images and perfilometry show that smoother and thinner PANI films were grown on PAPTS-modified ITO substrates. PANI-based electrochromic devices (ECDs) were assembled by using a viscous polymeric electrolyte (PE) of LiClO₄ and polymethyl methacrylate (PMMA) co-dissolved in a mixture of propylene and ethylene carbonate. The architectural design of the devices was glass/ITO/PANI/PE/ITO/glass. A dual ECD was also prepared by collocating a poly(3-methylthiophene) (P3MT) thin film as a complementary electrochromic element. The effect of the PAPTS-modified ITO substrate is reflected in a higher optical transmittance at bleach state and a little less color change at 550 nm of PANI-based ECDs.     

All solid-state electrochromic devices with gelatin-based electrolyte

6×8 cm² electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrolyte/ion-storage (IS) layer/K-glass, have been assembled using Nb₂O₅:Mo EC layers, a (CeO₂)_0.81–TiO₂ IS-layer and a new gelatin electrolyte containing Li⁺ ions. The structure of the electrolyte is X-ray amorphous. Its ionic conductivity passed by a maximum of 1.5×10⁻⁵ S/cm for a lithium concentration of 0.3 g/15 ml. The value increases with temperature and follows an Arrhenius law with an activation energy of 49.5 kJ/mol. All solid-state devices show a reversible gray coloration, a long-term stability of more than 25,000 switching cycles (±2.0 V/90 s), a transmission change at 550 nm between 60% (bleached state) and 40% (colored state) corresponding to a change of the optical density (ΔOD=0.15) with a coloration efficiency increasing from 10 cm²/C (initial cycle) to 23 cm²/C (25,000th cycle).     

Formation of ultrafast-switching viologen-anchored TiO2 electrochromic device by introducing Sb-doped SnO2 nanoparticles

Ultrafast-switching viologen-anchored TiO₂ electrochromic device (ECD) was developed by introducing Sb-doped SnO₂ (Sb_xSn_1−xO₂, ATO) as counter electrode (CE), and the switching behavior of the fabricated ECD was investigated as a function of Sb-doping concentration. About 9-nm-sized Sb_xSn_1−xO₂ (x=0–0.3) nanoparticles were synthesized by a solvothermal reaction of tin (IV) chloride and antimony (III) chloride at 240 °C, and employed to fabricate 2.4-μm-thick transparent CE. Working electrode (WE) was formed from the 7-nm-sized TiO₂ nanoparticle by a doctor blade method, and the thickness of the nanoporous TiO₂ electrode was 4.5 μm. The phosphonated viologen, bis(2-phosphonylethyl)-4,4′-bipyridinium dibromide, was then adsorbed on the prepared films for the construction of the ECD. The response time was strongly dependent on the doping concentration of Sb in ATO, and the fastest switching response was observed at 3 mol%. At this composition, the coloration time was 5.7 ms, and the bleaching time was 14.4 ms, which is regarded as one of the best results so far reported.     

The electrochromic properties of sputtered nickel oxide films

Electrochromic nickel oxide films were prepared by reactive RF sputtering from a nickel target in an oxygen atmosphere. The films were deposited as a compact 40 nm layer of trivalent nickel oxide, Ni₂O₃. Reduction and oxidation of the films in 1 M KOH resulted in bleaching and coloration, respectively. Voltammetry indicated that the eventual electrochromic reaction involved the β-Ni(OH)₂/β-NiOOH couple. In situ visible spectra showed electrochromic modulation of the transmittance throughout the visible range with a peak change in transmittance of about 60% at a wavelength of 500 nm. In situ spectra in the near-infrared region indicated improved electrochromic switching in this region; the sputtered nickel oxide film exhibited about a 30% change in transmittance in comparison to less than 10% for a similar electroprecipitated nickel hydroxide film. The sputtered nickel oxide films exhibited durable electrochromic switching for over 2500 coloration/bleaching cycles, a significant improvement over the less than 500 switching cycles exhibited by electroprecipitated nickel hydroxide films.     

A note on fast protonic solid state electrochromic device: NiOx/Ta2O5/WO3−x

In the present investigation, the electrochromic properties of a fast protonic solid state device: NiO_x/Ta₂O₅/WO_3−x prepared at room temperature (300 K) is reported. The non-stoichiometric tungsten oxide thin film is prepared by reactive DC magnetron sputtering technique on ITO coated glass; the oxides of tantalum (300 nm) and nickel (100 nm) are prepared by electron beam evaporation. This proton device has a coloration efficiency of 82.4 cm²/C and coloration and bleaching time of 6 and 5 s, respectively, and a transmittance variation of 60%. The work function of WO_3−x thin films by Kelvin probe in uncolored and colored states are 4.73 and 4.30 eV, respectively.