High performance electrochromic devices based on anodized nanoporous Nb2O5

Despite the predictions, the true potential of Nb2O5 for electrochromic applications has yet to be fully realized. In this work, three-dimensional (3D) compact and well-ordered nanoporous Nb2O5 films are synthesized by the electrochemical anodization of niobium thin films. These films are formed using RF sputtering and then anodized in an electrolyte containing ethylene glycol, ammonium fluoride, and small water content (4%) at 50 °C which resulted in low embedded impurities within the structure. Characterization of the anodized films shows that a highly crystalline orthorhombic phase of Nb2O5 is obtained after annealing at 450 °C. The 3D structure provides a template consisting of a large concentration of active sites for ion intercalation, while also ensuring low scattering directional paths for electrons. These features enhance the coloration efficiency to 47.0 cm2 C?1 (at 550 nm) for a 500 nm thick film upon Li+ ion intercalation. Additionally, the Nb2O5 electrochromic device shows a high bleached state transparency and large optical modulation.

Enhanced coloration efficiency for electrochromic devices based on anodized N2O5 / Electrodeposited MoO3 Binary Systems

There is a continuous quest for developing electrochromic (EC)transition metal oxides (TMOs) with increased coloration efficiency. As emerging TMOs, Nb2O5 films, even those of ordered anodized nanochannels, have failed to produce the required EC performance for practical applications. This is attributed to limitations presented by its relatively wide bandgap and low capacity for accommodating ions. To overcome such issues, MoO3 was electrodeposited onto Nb2O5 nanochannelled films as homogeneously conformal and stratified α-MoO3 coatings of different thickness. The EC performance of the resultant MoO3 coated Nb2O5 binary system was evaluated. The system exhibited a coloration efficiency of 149.0 cm2 C−1, exceeding that of any previous reports on MoO3 and Nb2O5 individually or their compounds. The enhancement was ascribed to a combination of the reduced effective bandgap of the binary system, the increased intercalation probability from the layered α-MoO3 coating, and a high surface-tovolume ratio, while the Nb2O5 nanochannelled templates provided stability and low impurity pathways for charge transfer to occur.

All solid-state electrochromic devices with gelatin-based electrolyte

6 x 8cm(2) electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrotype/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 x 10(-5) S/CM for a lithium concentration of 0.3g/15ml. 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 (Delta OD = 0. 15) with a coloration efficiency increasing from 10cm(2)/C (initial cycle) to 23cm(2)/C (25,000th cycle). (c) 2007 Elsevier B.V. All rights reserved.

Development of Electrochromic Devices

Electrochromic devices (ECD) are systems of considerable commercial interest due to their controllable transmission, absorption and/or reflectance. For instance, these devices are mainly applied to glare attenuation in automobile rearview mirrors and also in some smart windows that can regulate the solar gains of buildings. Other possible applications of ECDs include solar cells, small-and large-area flat panel displays, frozen food monitoring and document authentication also are of great interest. Over the past 20 years almost 1000 patents and 1500 papers in journals and proceedings have been published with the keyword ""electrochromic windows"". Most of these documents report on materials for electrochromic devices and only some of them about complete systems. This paper describes the first patents and some of the recent ones on ECDs, whose development is possible due to the advances in nanotechnology.

Electrical characterization of new electrochromic devices

Electrochromic devices change their color and optical properties with applied voltage. A new symmetrical electrochromic configuration was constructed in previous works, where PEDOT acted as electrochromic layer or as counter electrode layer, depending on the polarity of the applied voltage. Devices of around 500mm2 and switching voltages from 0,5V to 2V are used in this work. Measured electrochemical impedance is fitted to an equivalent circuit based on a Randles cell, with Warburg impedance simulating ionic diffusion at low frequencies. Voltage dependence is analyzed for the first time in this kind of devices. Results show homogeneity problems in the contact layers, not seen in normal operation, and the voltage dependence on some construction parameters. This will be used to improve the devices construction, but improvements in the equivalent circuit should also be made. The proposed equivalent circuit is not valid after the redox reaction, from 1.5 to 2V.

Solid electrolytes for electrochromic devices based on reversible metal electrodeposition

Air conditioning and lighting costs can be reduced substantially by changing the optical properties of "intelligent windows." The electrochromic devices studied to date have used copper as an additive. Copper, used here as an electrochromic material, was dissolved in an aqueous animal protein-derived gel electrolyte. This combination constitutes the electrochromic system for reversible electrodeposition. Cyclic voltammetry, chronoamperometric and chromogenic analyses indicated that were obtained good conditions of transparency (initial transmittance of 70%), optical reversibility, small potential window (2.1 V), variation of transmittance in visible light (63.6%) and near infrared (20%) spectral regions. Permanence in the darkened state was achieved by maintaining a lower pulse potential (-0.16 V) than the deposition potential (-1.0 V). Increasing the number of deposition and dissolution cycles favored the transmittance and photoelectrochemical reversibility of the device. The conductivity of the electrolyte (10(-3) S/cm) at several concentrations of CuCl2 was determined by electrochemical impedance spectroscopy. A thermogravimetric analysis confirmed the good thermal stability of the electrolyte, since the mass loss detected up to 100 degrees C corresponded to water evaporation and decomposition of the gel started only at 200 degrees C. Micrographic and small angle X-ray scattering analyses indicated the formation of a persistent deposit of copper particles on the ITO. (C) 2012 Elsevier B.V. All rights reserved.

Ion-Conducting Membranes Based on Gelatin and Containing LiI/I-2 for Electrochromic Devices

Ionic conducting membranes of gelatin plasticized with glycerol and containing LiI/I-2 have been obtained and characterized by X-ray diffraction measurements, UV-Vis-NIR spectroscopy, thermal analysis and impedance spectroscopy. The transparent (80-90% in the visible range) membranes showed ionic conductivity value of 5 x 10(-5) S/cm at room temperature, which increased to 3 x 10(-3) S/cm at 80 degrees C. All the ionic conductivity measurements as a function of temperature showed VTF dependence and activation energy of 8 kJ/mol. These samples also showed low glass transition temperature of -76 degrees C. Moreover the samples were predominantly amorphous. The membranes applied to small electrochromic devices showed 20% of color change from colored to bleached states during more than 70 cronoamperometric cycles.

The anodized crystalline WO3 nanoporous network with enhanced electrochromic properties

We demonstrate that a three dimensional (3D) crystalline tungsten trioxide (WO3) nanoporous network, directly grown on a transparent conductive oxide (TCO) substrate, is a suitable working electrode material for high performance electrochromic devices. This nanostructure, with achievable thicknesses of up to 2 μm, is prepared at room temperature by the electrochemical anodization of a RF-sputtered tungsten film deposited on a fluoride doped tin oxide (FTO) conductive glass, under low applied anodic voltages and mild chemical dissolution conditions. For the crystalline nanoporous network with thicknesses ranging from 0.6 to 1 μm, impressive coloration efficiencies of up to 141.5 cm2 C−1 are achieved by applying a low coloration voltage of −0.25 V. It is also observed that there is no significant degradation of the electrochromic properties of the porous film after 2000 continuous coloration–bleaching cycles. The remarkable electrochromic characteristics of this crystalline and nanoporous WO3 are mainly ascribed to the combination of a large surface area, facilitating increased intercalation of protons, as well as excellent continuous and directional paths for charge transfer and proton migration in the highly crystalline material.