Pseudocapacitive contributions to electrochemical kinetics in NiOx electrochromic anodes

Because of its ability to change optical absorption dynamically by applied electric field, nickel oxide (NiO) is a promising anodic material in smart windows, which can improve energy conversion efficiency in construction buildings. Although many works have achieved high electrochromic performance with different method. The underlying mechanism is still not fully investigated. In this article, we prepared the NiO films with large specific surface area and high stability by electron beam evaporation. X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to figure out the surface morphology and composition of as-deposited films. Afterwards, the electrochemical properties and optical performance of the prepared NiO films were investigated. On this basis, the origin of surface charge was fully analyzed by cyclic voltammetry and diffusion coefficient test. These experimental and theoretical results firmly confirm that both the surface reaction and capacitive effect bring about the excellent EC performance in NiO films. These results not only provide clear evidence about electrochemical kinetics in NiO films, but also offer some useful guidelines for the design of EC materials with higher performance and longer stability.     

Dynamic behaviour of viologen-activated nanostructured TiO2: correlation between kinetics of charging and coloration

The dynamic response of viologen-activated nanostructured titanium dioxide has been studied by means of electrical and electro-optical measurements. We show that the state of charge of the semiconductor network is the key factor mediating between the electrode potential and colouration of viologen. Theoretically, we relate the electrode potential to the statistics of occupancy of both TiO₂ nanoparticles and oxidized viologen molecules attached to the surface, on the assumption of quasi-equilibrium of Fermi levels in these contacting phases. Experimentally, we determine the statistical function from steady-state measurements (electrochemical impedance spectroscopy) of the capacitance of the semiconductor film. From this understanding we explain the main features that correlate the simultaneous voltammetry and transmittance responses. Finally, the redox process of viologen is resolved separately from the TiO₂ response by means of transmittance data.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.     

Thionine immobilized in crosslinked chitosan films

Redox and acid–base properties of thionine immobilized in crosslinked chitosan films are analyzed. The experimental conditions for the preparation of the films are described. Results obtained with cyclic voltammetry, spectroelectrochemistry and spectrophotometry indicate that the immobilized dye retains the redox and acid–base activity of free thionine. An acid dissociation constant (K_a) for the immobilized dye of K_a = 2.7 × 10⁻¹¹ was obtained.

Due to the stable and reversible pH dependent optical signal of the studied film, this membrane can be used as a building component of an optical pH sensor.     

Thieno[3,2-b]thiophene as π-bridge at different acceptor systems for electrochromic applications

Benzoselenadiazole, quinoxaline and thieno[3,2-b]thiophene are the units preferred in conducting polymers due to their electrochemical properties. There are no reports in the literature on polymers containing both moieties. In this study, novel benzoselenadiazole, quinoxaline and thieno[3,2-b]thiophene based monomers; 4-(3a,6a-dihydrothieno[3,2-b]thiophen-2-yl)-7-(thieno[3,2-b]thiophenyl)benzo[c][1,2,5]selenadiazole (BSeTT) and 2,3-bis(3,4-bis(decyloxy)phenyl)-5,8-dibromo-2,3-dihydroquinoxaline (QTT) were synthesized via Stille Coupling and polymerized electrochemically. These polymers were characterized in terms of their spectroelectrochemical and electrochemical properties by cyclic voltammetry and UV–Vis–NIR spectroscopy. Spectroelectrochemistry analysis of PBSeTT revealed an electronic transition at 525 nm corresponding to π–π* transition with a band gap of 0.93 eV whereas PQTT revealed electronic transitions at 440 and 600 nm corresponding to π–π* transitions with a band gap of 1.30 eV. Electrochromic investigations showed that PBSeTT has gray color PQTT switching between green and gray. Switching time of the polymers was evaluated by a kinetic study upon measuring the percent transmittance (%T) at the maximum contrast point.     

Synthesis and electrochromic properties of aromatic polyimides bearing pendent triphenylamine units

A series of aromatic polyimides with pendent triphenylamine group were synthesized from equimolar mixtures of 4,4′-oxydianiline (ODA) and 4-(3,5-diaminobenzamido)triphenylamine (4), 4-(3,5-diaminobenzamido)-4′,4″-di-tert-butyltriphenylamine (t-Bu-4) or 4-(3,5-diaminobenzamido)-4′,4″-dimethoxytriphenylamine (MeO-4) with two aromatic tetracarboxylic dianhydrides (DSDA or 6FDA) via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical imidization. These polyimides exhibited good solubility in polar organic solvents and could be solution-cast into flexible and strong films. They showed excellent thermal stability, with T_g values in the range of 284–309 °C. The polyimides derived from diamines t-Bu-4 and MeO-4 exhibited reversible electrochemical oxidation, accompanied by strong color changes with high contrast ratio and electrochromic stability. For the polyimides derived from diamine 4, the coupling reaction between the triphenylamine radical cations occurred during the oxidative process forming a tetraphenylbenzidine structure, which resulted in an additional oxidation state and color change together with enhanced near-IR absorption at fully oxidized state.     

Synthesis and characterization of rough electrochromic phosphotungstic acid films obtained by spray-gel process

Rough electrochromic phosphotungstic acid (PWA) films were fabricated by spraying a gel of phosphotungstate anions with a molar ratio of P:W=1:12 onto glass substrates. The substrates were coated with transparent and electrically conducting SnO₂:F at 300°C. Analysis by X-ray photoelectron spectroscopy determined that the P:W molar ratio in the films was approximately 1:14. Infrared spectroscopy and X-ray diffraction showed that the film is a form of polycrystalline phosphotungstic acid. SEM micrographs showed that the films have a rough morphology based on fiber-shape bridges. Optoelectrochemical measurements demonstrated pronounced electrochromism in the PWA films upon H⁺ intercalation/deintercalation with a high diffuse reflectance (R_d) and transmittance (T_d). We found for as-deposited films that R_d/total reflectance (R_t) and T_d/total transmittance (T_t) at 550 nm was around 0.83 and 0.68, respectively. This ratio decreases at bleached state to 0.74 and 0.41 for R_d/R_t and T_d/T_t, respectively.     

Stress in photochromic and electrochromic effects on tungsten oxide film

Optical absorbance at 632.8 nm and the stress generated in tungsten oxide film due to photochromic and electrochromic effects were measured. WO₃ thin films were deposited by reactive sputtering and the absorbance was obtained by measuring the optical transmittance of a laser beam through the film. The stress was calculated by measuring the substrate curvature and using the Stoney equation for multilayered films, since two layers are deposited onto a substrate for the electrochromism studies. The optical absorbance and the stress in the tungsten oxide film, as a function of UV irradiation time in photochromism and of inserted charge in electrochromism, are showed and discussed. In both effects the stresses generated were rendered as due to cation insertions into the film: H⁺ protons in photochromism and Li⁺ ions in electrochromism. The accuracy of the Stoney equation used for the stress calculation was also discussed.     

Sol–gel derived nanocrystalline TiO2 thin films: A promising candidate for self-cleaning smart window applications

In the present work, anatase TiO₂ films are prepared by sol–gel spin coating method. The structural and optical properties of the films have been studied at different post-annealing temperatures. The photocatalytic activity and electrochromic performance of the films are investigated. The films annealed at 400 °C exhibit the highest photocatalytic activity with a rate constant of 4.56×10⁻³ min⁻¹. The electrochromic performance for the films annealed at 400 °C expressed in terms of difference in optical density (ΔOD) at 550 nm between coloured and bleached state is 0.5493. This combination of photocatalysis and electrochromism makes the sol–gel derived titania thin films as promising candidates for self-cleaning smart window applications.     

Electrochromism in nickel oxide and tungsten oxide thin films: Ion intercalation from different electrolytes

Electrochromic (EC) NiO_z and WO_y thin films were prepared by sputtering and were used in a feasibility study aimed at investigating mixtures of these two oxides. The object was to identify a suitable electrolyte, compatible with both NiO_z and WO_y. To that end we carried out cyclic voltammetry (CV) in potassium hydroxide (KOH), propionic acid, and lithium perchlorate in propylene carbonate (Li-PC). WO_y could be coloured in propionic acid and Li-PC, while NiO_z could be coloured only in KOH. Both films showed best stability in Li-PC, which hence is well suited for further studies of mixed NiO_z and WO_y.