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%.     

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.     

Step potential analysis of cobalt oxide-based electrochromic devices

The characterization of electrochemical behavior of electrochromic intercalation device based on cobalt oxide thin film was carried out using the step potential excitation method. A method based on generating plots of current density as a function of passed charge has been applied for characterization of electrochromic cobalt oxide thin films using an aqueous KOH electrolyte. The device resistance and the intercalation capacity of the material are calculated. Dynamic built-in potential estimated from step potential experiment and plots of the built-in potential as function of the passed charge, V_bi(ΔQ), are generated for intercalation process. The intercalation efficiency curve is obtained to confirm the nature of energy distribution of intercalation sites in electrochromic cobalt oxide.     

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.     

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).     

Photo-polymerized films of lithium ion conducting solid polymer electrolyte for electrochromic windows (ECWs)

Films of solid polymer electrolyte (spe) have been prepared by the photo-polymerization of the monomer: 2-hydroxyethylmethacrylate (HEMA) simultaneously accompanied by chemical crosslinking with neopentyl glycol which is dissolved in a liquid electrolyte, namely, 1 M LiClO₄ in EC:PC binary solvent mixed in two different volume ratios. The spe films exhibit ionic conductivities greater than 10⁻³ Scm⁻¹ at 25°C. Thermal and structural characteristics of the films have been determined by DSC and XRD, respectively. The electrochemical redox behavior of an electrochromic device (PWECD) fabricated with an electrodeposited tungsten oxide film as the primary electrode, a prussian blue film as the counter electrode and a poly(HEMA) based electrolyte film as well as that of the individual components of the device has been examined by cyclic voltammetry. Transmission modulation of 60% (λ=650 nm) shown by the PWECD renders it to be a promising candidate for electrochromic window applications.     

Binder free and high performance of sputtered tungsten nitride thin film electrode for supercapacitor device

Here, we demonstrates the fabrication of binder free and very efficient supercapacitor electrode based on tungsten nitride (W₂N) thin film on stainless steel (SS) substrate using reactive sputtering technique. W₂N thin film as a working electrode exhibits high specific capacitance (163 F g⁻¹ at 0.5 mA cm⁻² in 1 M H₂SO₄) along with excellent cycling stability. The binder free symmetric supercapacitor (W₂N||W₂N) device delivers a high specific capacitance (80 Fg^-1) and long life span (90.46% capacitance retention after 10,000 cycles) along with high energy (12.92 Whkg⁻¹) and power (∼674 kWkg⁻¹ at 9.36 Whkg⁻¹) densities. These observed excellent electrochemical performances of the present W₂N thin film based supercapacitor device, recommend it as a potential candidate for energy storage applications.     

Cycle test and degradation analysis of WO3/PC+LiClO4/CeO2·TiO2 electrochromic device

We fabricated an electrochromic full cell device adopting WO₃ as a working electrode, and 1 M LiClO₄ in PC with 3% water addition as an electrolyte and CeO₂·TiO₂ with various thicknesses as an ion storage layer. CeO₂·TiO₂ with less than 100 nm shows large charge density but the long-term cyclability is not good due to lithium ion diffusion into ITO thin film. Therefore, the thickness of CeO₂·TiO₂ ion storage layer should be coated at more than 200 mm/min. Long-term cycle test results show that CeO₂·TiO₂ ion storage layer with more than 150 nm thickness and two time coating enhance the long-term stability. SIMS analysis results show that the degradation is due to the remaining lithium ion in the working electrode, WO₃.     

Optical properties of electrochromic all-solid-state devices

We have investigated the optical properties of an all-thin-film electrochromic device, with a thin film of ZrO₂ acting as an ion conductor. The device also employed electrochromic layers of amorphous or crystalline WO₃ and NiV_xO_yH_z. Transmission (T) and reflection (R) spectra were recorded in the wavelength range 300–2500 nm at different intercalation levels, both for single films and complete devices. The results show that T decreases significantly upon intercalation in the WO₃ thin films as well as in the devices. The reflectance only shows minor changes.     

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.     

Electrochromic properties of tungsten oxide nanowires fabricated by electrospinning method

In this work, we report electrochromic properties of polycrystalline WO₃ nanowire electrodes fabricated on an indium tin oxide (ITO)-coated substrate by electrospinning method. The electrochromic and electrical properties of the electrospun WO₃ nanowire electrodes are investigated and compared with those of conventional WO₃ thin film electrodes. As a result, the one-dimensional WO₃ nanowires show faster charge transfer and optical responses with a bleaching time of 1.0 s and a coloring time of 4.2 s than the thin film electrodes. The coloration efficiency of the electrospun WO₃ nanowires is also greater (56 cm²/C) by 21% than the thin film along with an improved memory effect after coloring process.     

An EQCM study for a novel aromatic poly(amine-imide) electrochromic thin film

A new aromatic poly(amine-imide) electrochromic thin film synthesized with N,N-bis(4-aminophenyl)-N′,N′-diphenyl-1,4-phenylenediamine and 3,3′,4,4′-benzo-phenonetetra carboxylic dianhydride, abbreviated as poly(PD-BCD), was studied. The poly(PD-BCD) thin-film electrode has been characterized by cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM). As the polymer chain acquires positive charge during the oxidation of poly(PD-BCD) to its radical cation state or dication state, the anions would insert into the polymer matrix in order to neutralize the charge. However, when the electrodes were cycled in electrolytes containing different cations, including 0.1 M LiClO₄/acetonitrile (ACN), 0.1 M NaClO₄/ACN and 0.1 M TBAClO₄/ACN, the experimental results revealed two mechanisms for the redox reaction. A plot of mass change (Δm) vs. accumulated charge (Q) gave a slope, from which the electrochromic mechanism can be extracted. The slopes of Δm–Q obtained from the CV–EQCM measurements in three electrolytes were different for the first redox stage, but the slopes were almost the same for the second redox stage. This means that, in addition to the involvement of anions, cations also play an important role in the first redox stage, however, the role of the cations is less in the second stage. Moreover, two reaction mechanisms for the two reaction stages of poly(PD-BCD) are proposed in this study.     

A high-performance counter electrode based on poly(3,4-alkylenedioxythiophene) for dye-sensitized solar cells

A poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepine) (PProDOT-Et₂) counter electrode prepared by electrochemical polymerization on a fluorine-doped tin oxide (FTO) glass substrate was incorporated in a platinum-free dye-sensitized solar cell (DSSC). The surface roughness and I⁻/I₃⁻ redox reaction behaviors based on PProDOT-Et₂, poly(3,4-propylenedioxythiophene) (PProDOT), poly(3,4-ethylenedioxythiophene) (PEDOT), and sputtered-Pt electrodes were characterized, and their performances as counter electrodes in DSSCs were compared. Cells fabricated with a PProDOT-Et₂ counter electrode showed a higher conversion efficiency of 7.88% compared to cells fabricated with PEDOT (3.93%), PProDOT (7.08%), and sputtered-Pt (7.77%) electrodes. This enhancement was attributed to increases in the effective surface area and good catalytic properties for I₃⁻ reduction. In terms of the film thickness effect, the fill factor was strongly dependent on the deposition charge capacity of the PProDOT-Et₂ layer, but the aggregation of PProDOT-Et₂ in thicker layers (>80 mC cm⁻²) resulted in decreases in J_SC and the cell conversion efficiency. The charge transfer resistances (R_ct1) of the PProDOT-Et₂ counter electrodes had the lowest value of ∼18 Ω at a deposition charge capacity of 40 mC cm⁻². These results indicate that films with high conductivity, high active surface area, and good catalytic properties for I₃⁻ reduction can potentially be used as the counter electrode in a high-performance DSSC.     

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.     

Electrochromic properties of porous NiO thin films prepared by a chemical bath deposition

Highly porous nickel oxide thin films were prepared on ITO glass by a simple chemical bath deposition (CBD) method in combination with a following heat-treatment process. XRD analysis revealed that the as-deposited precursor film contained β-Ni(OH)₂ and γ-NiOOH, and they changed to cubic polycrystalline NiO after annealing. The FTIR results showed presence of free hydroxyl ion and water in the NiO thin films. The electrochromic properties of NiO thin films were investigated in an aqueous alkaline electrolyte (1 M KOH) by means of transmittance, cyclic voltammetry (CV) and chronoamperometry (CA) measurements. The NiO thin film annealed at 300 °C exhibited a noticeable electrochromism and good memory effect. The coloration efficiency was calculated to be 42 cm² C⁻¹ at 550 nm, with a variation of transmittance up to 82%. The porous NiO thin films also showed good reaction kinetics with fast switching speed, and the coloration and bleaching time were 8 and 10 s, respectively.     

Electrochromic windows based on viologen-modified nanostructured TiO2 films

The construction of an electrochromic window based on a modified transparent nanostructured metal oxide film (TiO₂ anatase, 4.0 μm thick) supported on conducting glass (F-doped tin oxide, 10 Ω/square, 0.5 μm thick) is described. The nanostructured TiO₂film is modified by adsorption of a monolayer of the redox chromophore bis-(2-phosphonoethyl)-4,4′-bipyridinium dichloride, the electrolyte is 0.05 M LiClO₄ and 0.05 M ferrocene in γ-butyrolactone and the counter electrode is conducting glass. The performance of the above device (colouration efficiency of 170 cm² C⁻¹ at 608 nm, switching time of 1 s and stability over 10 000 standard test cycles) suggests an electrochromic technology with commercial potential.     

Intercalation studies on electron beam evaporated MoO3 films for electrochemical devices

Now-a-days a large number of extensive research has been focused on electrochromic oxide thin films, owing to their potential applications in smart windows, low cost materials in filters, low cost electrochemical devices and also in solar cell windows. Among the varieties of electrochromic transition metal oxides, the molybdenum oxide (MoO₃) and tungsten oxide (WO₃), form a group of predominant ionic solids that exhibit electrochromic effect. The electrochromic response of these materials are aesthetically superior to many other electrochromic materials, because WO₃ and MoO₃ absorb light more intensely and uniformly. In the present case, we have discussed about the electrochromic behaviour of electron beam evaporated MoO₃ films. Moreover, the MoO₃ film can also be used as a potential electro-active material for high energy density secondary lithium ion batteries; because it exhibits two-dimensional van der Waals bonded layered structure in orthorhombic phase. The films were prepared by evaporating the palletized MoO₃ powder under the vacuum of the order of 1 × 10⁻⁵ mbar. The electrochemical behaviour of the films was studied by intercalating/deintercalating the K⁺ ions from KCl electrolyte solutions using three electrode electrochemical cell by the cyclic-voltammetry technique. The studies were carried out for different scanning rates. The films have changed their colour as dark blue in the colouration process and returns to the original colour while the bleaching process. The diffusion coefficient values (D) of the intercalated/deintercalated films were calculated by Randle's Servcik equation. The optical transparency of the coloured and bleached films was studied by the UV–Vis–NIR spectrophotometer. The change in bonding assignment of the intercalated MoO₃ films was studied by FTIR spectroscopic analysis. A feasible study on the effect of substrate temperatures and annealing temperatures on optical density (OD) and colouration efficiency of the films were discussed and explored their performance for the low cost electrochemical devices.     

Chicken nuggets-like core/shell nanosheet arrays as high performance flexible all-solid-state supercapacitor cathode and buckwheat shell as anode

The energy density of a flexible all-solid-state supercapacitor (ASC) requires new electrode material with special structure and morphology as a prerequisite for its secured improvement. In this paper, a new morphological exploration of chicken nuggets-like core/shell NiCo₂O₄/MnO₂ (NCM) nanosheet arrays on Ni foam was employed. The application of this special morphology aims to greatly improve the electrochemical performance of the cathode electrode. Additionally, Buckwheat Biochar (BBC) is utilized as the anode while the PVA/KOH thin film is prepared as the separator. The chicken nuggets-like core/shell NCM nanosheet arrays were obtained by a two-step hydrothermal method. A series of characterization methods were carried out to further support the core/shell's well-designed structure and precise composition. The tests exhibited excellent specific capacitance of 593.3 F g^?1 at 5 mA cm^?2 and outstanding cycling stability with a retention of 90% after 10000 cycles. Furthermore, the assembled NCM//BBC ASC device indicated a high specific capacitance (239 F g^?1 at the current density of 5 mA cm^?2), this is in due part of the unique architecture of NCM nanosheet arrays and interconnected special porous structure of the BBC and the thin film PVA/KOH. Hence, the assembled ASC device exhibited high energy density (an energy density of 58 Wh·kg^?1 at 3263 W kg^?1) and remarkable cycling stability.     

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.     

Electrochromic devices employing methacrylate-based polymer electrolytes

Poly(ethyl methacrylate) (PEMA)- and poly(2-ethoxyethyl methacrylate) (PEOEMA)-based polymer gel electrolytes with entrapped solutions of lithium perchlorate in propylene carbonate (PC) were prepared by direct, UV-initiated polymerization. The electrolytes were studied using electrochemical methods and they exhibit good ionic conductivity (up to 0.7 mS cm⁻¹ at 20 °C) as well as electrochemical stability up to 2.5 V vs. Cd/Cd²⁺ (5.1 V vs. Li/Li⁺) on gold electrode. The electrolytes have thermal stability up to 125 °C. The electrolytes were successfully tested as ionic conductors in the electrochromic device FTO/WO₃/Li⁺-electrolyte/V₂O₅/FTO using coupled optoelectrochemical methods to discuss the relationship between the electrolyte composition and parameters such as change of transmittance, response time and stability. The transmittance change Δτ was found to be 30-45% at 634 nm.