Fabricating polypyrrole/tungsten oxide hybrid based electrochromic devices using different ionic liquids

A facile approach of polypyrrole (PPy)/tungsten oxide (WO₃) composites electrosynthesized in ionic liquids for fabrication of electrochromic devices is discussed. The electrochromic properties of PPy/tungsten oxide nanocomposite films (PPy/WO₃) prepared in the presence of four different ionic liquids, 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIMBF₄), 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆), 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIMTFSI), and 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMPTFSI) were investigated in detail. Cyclic voltammetry results revealed that PPy/WO₃ nanocomposite films have much more electrochemical activity than those of WO₃ and PPy film. The electrochromic contrast, coloration efficiency, and switching speed of the composite films were determined for electrochromic characteristics. The maximum contrast and the maximum coloration efficiency values were measured as 33.25% and 227.89 cm²/C for the PPy/WO₃/BMIMTFSI composite film. Copyright © 2015 John Wiley & Sons, Ltd.     

Solution thermolysed tungsten oxide-based electrochromic devices: thickness-dependent step potential analysis

The characterisation of electrochemical behaviour of electrochromic (EC) devices based on solution thermolysed (ST) tungsten oxide (WO₃) thin films was carried out using the step potential excitation method. The method, based on generating plots of current density (J) as a function of passed charge (ΔQ), has been applied for the characterisation of EC-WO₃ thin films in proton-containing aqueous electrolyte. EC devices have been fabricated by employing WO₃ thin films with variable thickness (T) ranging from 0.04 to 0.52 μm. The J vs time (t) responses (chronoamperometry) of these devices were recorded at a fixed applied potential (±0.7 V vs S.C.E.) and values of total passed H⁺ charges (ΔQ) into the WO₃ host lattice during the coloration process are calculated. The J-ΔQ curves corresponding to films of different thickness were plotted as a function of the passed charge volume density, ΔQ /T, and an intercalatable film thickness is calculated to be 0.13 μm. The modulation in optical transmittance after coloration and bleaching was studied in the wavelength range between 350 and 850 nm and an optical efficiency (ξ_λ) is calculated at λ=700 nm. It is found that the ξ_λ wanes with increasing intercalation. Electronic Publication     

Influence of PEG additive and annealing temperature on structural and electrochromic properties of sol–gel derived WO<Subscript>3</Subscript> films

Sol–gel derived tungsten oxide (WO₃) films have been deposited by spin coating route using acetylated peroxotungstic acid (APTA) or a mixture of APTA and polyethylene glycol (PEG) dissolved in ethanol as the precursor solution, followed by thermal treatment in air. The influence of PEG additive and annealing temperature on the structural and electrochromic (EC) behavior of the films have been investigated. For films annealed at 300 °C, a porous nanocrystalline/amorphous microstructure was obtained in the WO₃-PEG film, while monoclinic microstructure was formed in the pure WO₃ film. Moreover, for the WO₃-PEG films, the film microstructure was found to depend on the annealing temperature. Electrochemical studies indicate that the WO₃-PEG film annealed at 300 °C (WP-300) exhibits superior EC properties, which produces faster switching speed (t _c = 19 s, t _b = 3 s),better reversibility (K = 0.97) as well as higher optical modulation (ΔT = 32% at 550 nm) and coloration efficiency (η = 22 cm²/C at 550 nm). Our results suggest that PEG addition in combination with an appropriate annealing treatment can benefit the EC properties, arising from the ease of ion diffusion within the EC material, as evident from the nanocrystallines embedded into the amorphous matrix with a porous character.     

High‐performance Flexible Complementary Electrochromic Device Based on Plasma Modified WO3 Nano Hybrids and V2O5 Nanofilm with Low Operation Voltages

Tungsten trioxide‐poly(3,4‐ethylenedioxythiophene) (WO₃‐PEDOT) and tungsten trioxide‐polyfuran (WO₃‐PFu) were prepared by rf rotating plasma polymerization. Electrochromic hybrid thin films were fabricated onto flexible polyethylene terephthalate (PET)/ indium tin oxide (ITO) film using electron beam evaporation method. In order to deeply characterize all films, scanning electron microscopy‐energy dispersive X‐ray spectroscopy (SEM‐EDS) and electrochemical impedance spectroscopy (EIS) techniques were used. The counter electrode effect on plasma modified WO₃ nano hybrids‐based electrochromic devices (ECDs) was evaluated. By incorporating flexible vanadium pentoxide (V₂O₅) film as counter electrode, complementary ECDs were constructed through combining the hybrid flexible films (WO₃‐PEDOT, WO₃‐PFu) as working electrodes, which exhibit highly efficient electrochromic performance with low voltage operation. Especially, WO₃‐PEDOT/V₂O₅‐based ECD owns a high optical modulation of 61.5 % at 750 nm driven by −1.0 V (coloration) and +1 V (bleaching) with fast response times (coloration time: 13.58 s, bleaching time: 8.07 s) and a high coloration efficiency of 527 cm² C⁻¹. This study can supply useful and efficient avenue for designing flexible complementary electrochromic device for energy‐saving flexible electronics.     

X-Ray Analysis of Multi-Films for Electrochromic Device Application

Multilayer films based on tungsten oxide (WO₃), ITO (indium tin oxide) and CdS were deposited mainly by reactive dc magnetron sputtering onto glass substrates for electrochromic application. The thin films were analyzed by means of XPS (X-ray photoelectron spectroscopy), GIXD (grazing incidence X-ray diffraction) and XRD (X-ray diffraction). XRD and XPS results confirmed that the films were WO₃, CdS and ITO, respectively. The surface and interface of the CdS/ITO bi-layered film was studied by GIXD in different incidence angles. Detailed results about the amorphous characterization of the films during room temperature growth and post annealing are given.     

Electrochromic properties of WO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>:P thin films

WO₃ and WO₃:P (5 mol% H₃PO₄) thin films were prepared using the sol-gel route and the electrochromic properties of the films were investigated using in situ spectroelectrochemical methods. The measurements were performed in propylene carbonate solution with 0.1 M LiClO₄ as electrolyte. During the cathodic polarization at –0.8 V a blue coloration is observed with a reversible variation between 14% and 84% of the transmittance at λ=633 nm. The kinetics for the bleaching process is faster for the WO₃:P film than for the undoped WO₃ film. Electronic Publication     

Oxygen addition effects on electrochromic properties of PECVD-synthesized WO x C y films for flexible electrochromic devices

An investigation was conducted into the electrochromic properties of organotungsten oxide WO _x C _y films synthesized onto 60 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates using low temperature, plasma-enhanced chemical vapor deposition (PECVD) at varying oxygen concentrations. The PECVD-synthesized WO _x C _y films were proven to offer remarkable electrochromic performance. Cyclic voltammetry switching measurements revealed that only low driving voltages from −1 to 1 V are needed to provide reversible Li⁺ ion intercalation and de-intercalation in a 0.1 M LiClO₄–PC electrolyte. Light modulation with transmittance variation of up to 72.9% and coloration efficiency of 62.5 cm²/C at a wavelength of 650 nm was obtained.     

Self-assembled films from WO3: Electrochromism and lithium ion diffusion

WO₃/chitosan and WO₃/chitosan/poly(ethylene oxide) (PEO) films were prepared by the layer-by-layer method. The presence of chitosan enabled PEO to be carried into the self-assembled structure, contributing to an increase in the Li⁺ diffusion rate. On the basis of the galvanostatic intermittent titration technique (GITT) and the quadratic logistic equation (QLE), a spectroelectrochemical method was used for determination of the “optical” diffusion coefficient (D_op), enabling analysis of the Li⁺ diffusion rate and, consequently, the coloration front rate in these host matrices. The D_op values within the WO₃/chitosan/PEO film were significantly higher than those within the WO₃/chitosan film, mainly for higher values of injected charge. The presence of PEO also ensured larger accessibility to the electroactive sites, in accordance with the method employed here. Hence, this spectroelectrochemical method allowed us to separate the contribution of the diffusion process from the number of accessible electroactive sites in the materials, thereby aiding a better understanding of the useful electrochemical and electrochromic properties of these films for use in electrochromic devices.     

Electrochromic and photoelectrochromic properties of sol–gel derived tungsten trioxide/titania composite thin films

Tungsten trixoide/titania (WO₃-titania) composite thin films with W/Ti molar ratios of 100/0, 98/2, 96/4, 94/6 92/8 and 90/10 were prepared on fluorine-doped tin oxide conducting glass, and their electrochromic (EC) and photoelectrochromic (PEC) performances were investigated in this study. The composite thin films were synthesized by sol–gel process using peroxotungstic acid and titanium (IV) n-butoxide as the precursors. The surface morphology and composition of the composite thin films were characterized using scanning electron microscope with energy dispersive spectrometer. Electrochemical experiments with in situ spectroscopic measurement were employed to study the EC properties of the composite thin films. It was found that the presence of titania in the WO₃ matrix might slightly decreases its EC performance. PEC cells using the composite thin films as the working electrode and a sputtered semitransparent platinum thin film on ITO as the counter electrode were fabricated and their PEC performances were investigated. The device using composite thin film prepared from sol solution with a W/Ti molar ratio of 96/4 exhibited the best PEC performance.     

Synthesis of nanoporous activated iridium oxide films by anodized aluminum oxide templated atomic layer deposition

Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices, pH sensing, and neural stimulation. Previous work has demonstrated that both Ir and IrOx films with porous morphologies prepared by sputtering exhibit significantly enhanced charge storage capacities. However, sputtering provides only limited control over film porosity. In this work, we demonstrate an alternative scheme for synthesizing nanoporous Ir and activated IrOx films (AIROFs). This scheme utilizes atomic layer deposition to deposit a thin conformal Ir film within a nanoporous anodized aluminum oxide template. The Ir film is then activated by potential cycling in 0.1 M H₂SO₄ to form a nanoporous AIROF. The morphologies and electrochemical properties of the films are characterized by scanning electron microscopy and cyclic voltammetry, respectively. The resulting nanoporous AIROFs exhibit a nanoporous morphology and enhanced cathodal charge storage capacities as large as 311 mC/cm².     

Electrochromic properties of MoO<Subscript>3</Subscript> thin films derived by a sol–gel process

Molybdenum trioxide (MoO₃) films were deposited on ITO/Glass substrates by the sol–gel method using a spin-coating technique and heat treated at various temperatures under different ambient atmosphere. Effects of the process parameters on the electrochromic properties of MoO₃ films were studied using cyclic voltammetry (CV) in a propylene carbonate (PC) non-aqueous solution containing 1 M lithium perchlorate (LiClO₄). Electrochromic MoO₃ film on lithium intercalation was investigated by in-situ transmittance measurement during the CV process. The MoO₃ films showed reversible recharge ability on Li⁺/e⁻ intercalation/deintercalation. Experimental results revealed that the heat-treatment temperature, the ambient atmosphere, and the thickness will have the string influence on the electrochromic properties of MoO₃ thin films. X-ray diffraction (XRD) results show that the amorphous MoO₃ films can be obtained with the heat-treatment temperature below 300 °C in O₂ ambient atmosphere. The optimum electrochromic MoO₃ film, with a thickness of 130 nm, exhibits a maximum transmittance variation (ΔT%) of 30.9%, an optical density change (ΔOD) of 0.213, an intercalation charge (Q) of 8.47 mC/cm², an insertion coefficient x in Li _x MoO₃ was 0.21 and a coloration efficiency (η) of 25.1 cm²/C between the colored and bleached states at a wavelength (λ) of 550 nm.     

无模板电化学沉积法制备多孔WO3·2H2O薄膜及其电致变色性能

二水合氧化钨(WO₃·2H₂O)因其独特的层状结构且富含层间结构水,与无水WO₃相比显示出更加优异的电致变色性能。我们采用简单、无模板的阴极电化学沉积方法,成功在氧化铟锡(ITO)导电玻璃基底上制备了WO₃·2H₂O薄膜。通过改变电沉积液中过氧化氢(H₂O₂)的加入量优化沉积液的成分,获得了具有纳米多孔结构的薄膜。由此制备的WO₃·2H₂O薄膜显示出大的光学对比度(633 nm处的光学对比度大于90%)、快速的响应速度(着色、褪色时间均小于10 s),以及良好的循环稳定性(经10 000次循环后,光学对比度仍保持在90%左右)。     

WO<Subscript>3</Subscript> thin film coating from H<Subscript>2</Subscript>O-controlled peroxotungstic acid and its electrochromic properties

We prepared PTA coating solution by hot plate evaporation, N₂ bubbling evaporation, and rotary evaporation. N₂ bubbling and rotary evaporation are very efficient way to synthesize PTA which reduces the synthesis process time to 1/5, compared to hot plate evaporation method. Another strong point is that N₂ bubbling and rotary evaporation make it possible to control excess hydrogen peroxide and water contents in PTA. The PTA formula were WO₃·0.13H₂O₂·10.0H₂O for hot plate method, WO₃·0.16H₂O₂·7.1H₂O for N₂ bubbling method, and WO₃·0.15H₂O₂·3.00H₂O for rotary evaporation method. Thermal analysis and mass spectroscopy analysis show that water is evaporated at around 100 °C and hydrogen peroxide is dissociated at the range of 150 and 250 °C. Amorphous phase of WO₃ thin film prepared from rotary evaporated PTA solution has the best electrochromic property, light transmission difference from 91% at its bleached state and 5.5% colored state, and charge density of 22 mC/cm². It is thought that the control of excess hydrogen peroxide and water contents in PTA is very important to enhance the electrochromic properties of WO₃ thin film.     

Understand the Degradation Mechanism of Electrochromic WO3 Films by Double‐step Chronoamperometry and Chronocoulometry Techniques Combined with in situ Spectroelectrochemical Study

In this paper, we demonstrate that the double‐step chronoamperometry and chronocoulometry techniques are efficient tools for characterizing the basic electrochromic performance of WO₃ films (i. e., coloration/bleaching conversion, charge capacity and coloration efficiency). In combination with in situ spectroelectrochemical study, the variations in the optical modulation and charge capacity of the WO₃ film under different potential windows were attributed to different ion diffusion depths and the quantity of WO₃ sites participating in the redox reaction. Moreover, the double‐step techniques have distinctive advantages for analyzing the cyclic mechanism of the WO₃ film. When the inserted Li⁺ ions in the coloration process cannot be completely extracted from the film in the next bleaching process, these ions accumulate in the film upon cycling, leading to the degradation of the electrochromic performance. Here the accumulated ions are referred to as “unrecoverable ions”. The abundant formation of unrecoverable ions may be due to incomplete reduction of a portion of Li_x WO₃, which is caused by collapse of the Li⁺ ion diffusion channels in the deep of film after repeated cycles. All these results support that the double‐step chronoamperometry and chronocoulometry techniques have significant advantages to analyze the cyclic stability and explore the degradation mechanism of electrochromic WO₃ films.     

无模板电化学沉积法制备多孔WO3·2H2O薄膜及其电致变色性能

二水合氧化钨(WO₃·2H₂O)因其独特的层状结构且富含层间结构水,与无水WO₃相比显示出更加优异的电致变色性能。我们采用简单、无模板的阴极电化学沉积方法,成功在氧化铟锡(ITO)导电玻璃基底上制备了WO₃·2H₂O薄膜。通过改变电沉积液中过氧化氢(H₂O₂)的加入量优化沉积液的成分,获得了具有纳米多孔结构的薄膜。由此制备的WO₃·2H₂O薄膜显示出大的光学对比度(633nm处的光学对比度大于90%)、快速的响应速度(着色、褪色时间均小于10s),以及良好的循环稳定性(经10000次循环后,光学对比度仍保持在90%左右)。     

Microstructure and infrared reflectance modulation properties in DC-sputtered tungsten oxide films

Tungsten oxide (WO₃) films were deposited on indium tin oxide glass by reactive DC magnetron sputtering of a tungsten target in an oxygen and argon atmosphere at different substrate temperatures. Infrared reflectance modulation properties of the films were investigated in the wavelength range of 2.5–25 μm. The morphology and structure of the films are strongly dependent on the substrate temperature, and therefore have a great influence on infrared reflectance modulation properties. The charge capacity and diffusion coefficient of H⁺ ions in WO₃ films decrease, and the infrared reflectance modulation and color efficiency first increase and then decrease with increasing the deposition temperature. The values achieve a maximum of 40% and 18.5 cm² C⁻¹, respectively, at 9 μm and 250 °C.     

Electrochromic and structural characteristics of mesoporous WO<Subscript>3</Subscript> films prepared by a sol-gel method

The preparation of electrochromic films of mesoporous tungsten trioxide from tungstic acid and tungstic hexaethoxide precursors with the addition of an organic stabiliser via a sol-gel method is reported. These films have been structurally characterised and both the film morphology and crystalline composition of the films were found to be significantly dependent on the temperature at which the films were annealed and upon the choice of precursor. Films annealed at lower temperatures consisted of amorphous and hexagonal tungsten trioxide, whereas films annealed above 500 °C comprised solely of monoclinic WO₃. The electrochromic activity of the films was found to be equally dependent on method of preparation, and both the composition and the structure of the WO₃ films were shown to clearly influence the colouration efficiency of the films.Dedicated to Zbigniew Galus on the occasion of his 70^th birthday.     

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.     

Influence of Pt and Au nanophases on electrochromism of WO3 in nanostructure thin-film electrodes

We report electrochromic properties of WO₃ in Au–WO₃ and Pt–WO₃ nanostructure thin-film electrodes prepared by co-sputtering deposition method. The nanostructure electrodes consisted of Au or Pt metallic nanophase and a tungsten oxidative phase, indicating the formation of crystalline metallic nanophases in the amorphous oxide matrix. In particular, due to metallic nanophases, the modified electrochromic properties of WO₃ were observed in the Au–WO₃ and Pt–WO₃. The nanostructure electrodes showed a reverse optical modulation with respect to applied potentials in H₂SO₄ solution compared to that of pure WO₃ electrode. However, due to an excellent electrocatalytic activity of platinum for methanol electrooxidation at 25 °C, the electrochromism of the Pt–WO₃ in contrast with that of the Au–WO₃ was affected by the potentials for methanol electrooxidation in 2 M CH₃OH and 0.5 M H₂SO₄.     

Electrochemical and Electrochromic Properties of Ni Oxide Thin Films Prepared by a Sol–Gel Method

Nickel oxide thin films, which are well known anodic coloration materials that are used in electrochromic devices, were prepared by a sol–gel method, and their electrochemical and electrochromic properties were investigated. The sol was prepared from Ni(OH)₂ powder with an average size of 7 nm, in a mixture of ethylene glycol and absolute ethanol. The films were coated on an ITO substrate using the powder, dispersed in the solution. When additive materials, acetyl acetone and glycerol, were added to the sol its hardness and adhesion properties were improved. The optimized thin film formed an amorphous, porous structure, and showed a large current density during continuous potential and pulse potential cycling. The film also was transparent and had a high coloration efficiency (33.5 cm²/C) and a rapid response time (1.0–2.5 s) during the coloring/bleaching process.