Electrochromic WO3 thin films attain unprecedented durability by potentiostatic pretreatment.
ABSTRACT: Electrochromic windows and glass facades are able to impart energy efficiency jointly with indoor comfort and convenience. Long-term durability is essential for practical implementation of this technology and has recently attracted broad interest. Here we show that a simple potentiostatic pretreatment of sputter-deposited thin films of amorphous WO3-the most widely studied electrochromic material-can yield unprecedented durability for charge exchange and optical modulation under harsh electrochemical cycling in a Li-ion-conducting electrolyte and effectively evades harmful trapping of Li. The pretreatment consisted of applying a voltage of 6.0 V vs. Li/Li+ for several hours to a film backed by a transparent conducting In2O3:Sn layer. Associated compositional and structural modifications were probed by several techniques, and improved durability was associated with elemental intermixing at the WO3/ITO and ITO/glass boundaries as well as with carbonaceous solid-electrolyte interfacial layers on the WO3 films. Our work provides important new insights into long-term durability of ion-exchange-based devices.
Project description:Nanoporous structures have proven as an effective way for enhanced electrochromic performance by providing a large surface area can get fast ion/electron transfer path, leading to larger optical modulation and fast response time. Herein, for the first time, application of vacuum cathodic arc plasma (CAP) deposition technology to the synthesis of WO3/NiO electrode films on ITO glass for use in fabricating complementary electrochromic devices (ECDs) with a ITO/WO3/LiClO4-Perchlorate solution/NiO/ITO structure. Our objective was to optimize electrochromic performance through the creation of electrodes with a nanoporous structure. We also examined the influence of WO3 film thickness on the electrochemical and optical characteristics in terms of surface charge capacity and diffusion coefficients. The resulting 200-nm-thick WO3 films achieved ion diffusion coefficients of (7.35?×?10-10 (oxidation) and 4.92?×?10-10?cm2/s (reduction)). The complementary charge capacity ratio of WO3 (200?nm thickness)/NiO (60?nm thickness) has impressive reversibility of 98%. A demonstration ECD device (3?×?4?cm2) achieved optical modulation (?T) of 46% and switching times of 3.1?sec (coloration) and 4.6?sec (bleaching) at a wavelength of 633?nm. In terms of durability, the proposed ECD achieved ?T of 43% after 2500 cycles; i.e., 93% of the initial device.
Project description:Porous WO3 films with ultra-high transmittance modulation were successfully fabricated on different substrates by a novel, facile and economical pulsed electrochemical deposited method with 1.1 s interval time between each pulse. The near ideal optical modulation (97.7% at 633 nm), fast switching speed (6 and 2.7 s), high coloration efficiency (118.3 cm2 C-1), and excellent cycling stability are achieved by the porous WO3 on ITO-coated glass. The outstanding electrochromic performances of the porous WO3 film were mainly attributed to the porous structure, which facilitates the charge-transfer, promotes the electrolyte infiltration and alleviates the expansion of the WO3 during H+ insertion compared to that of the compact structure. In addition, the relationships between the structural and electrochemical activity of the electrochromic WO3 films were further explored by the scanning electrochemical microscopy. These results testify that the porous structure can promote the infiltration of electrolyte and reduce the diffusion path, which consequently enhance the electrochemical activity.
Project description:Different polyaniline (PANI)-based hybrid films were successfully prepared by electro-polymerizing aniline monomers onto pre-spin-coated indium tin oxide (ITO) glass slides with WO3, graphene, or WO3/graphene films. Comparing with pristine PANI, the shifts of the characteristic peaks of PANI-based nanocomposites in UV-visible absorption spectra (UV-vis) and Fourier transform infrared spectroscopy (FT-IR) indicate the chemical interaction between the PANI matrix and the nanofillers, which is also confirmed by the scanning electron microscope (SEM) images. Corresponding coloration efficiencies were obtained for the WO3/PANI (40.42 cm2 C-1), graphene/PANI (78.64 cm2 C-1), and WO3/graphene/PANI (67.47 cm2 C-1) films, higher than that of the pristine PANI film (29.4 cm2 C-1), suggesting positive effects of the introduced nanofillers on the electrochromic performance. The areal capacitances of the films were observed to increase following the order as bare WO3 < WO3/graphene < pristine PANI < WO3/PANI < graphene/PANI < WO3/graphene/PANI films from both the cyclic voltammogram (CV) and galvanostatic charge-discharge (GCD) results. The enhanced energy storage and electrochromic performances of the PANI-based nanocomposite films can be attributed to the capacitance contributions of the introduced nanofillers, increased PANI amount, and the rougher morphology due to the embedment of the nanofillers into the PANI matrix. This extraordinary energy storage and electrochromic performances of the WO3/graphene/PANI film make it a promising candidate for combined electrochromic and energy storage applications.
Project description:In this paper, a novel Ti-doped hierarchically mesoporous silica microspheres/tungsten oxide (THMS/WO3) hybrid film was prepared by simultaneous electrodeposition of Ti-doped hierarchically mesoporous silica microspheres (THMSs) and WO3 nanocrystallines onto the fluoride doped tin dioxide (FTO) coated glass substrate. It is demonstrated that the incorporation of THMSs resulted in the hybrid film with improved electrochromic property. Besides, the content of THMSs plays an important role on the electrochromic property of the hybrid film. An excellent electrochromic THMS/WO3 hybrid film with good optical modulation (52.00% at 700 nm), high coloration efficiency (88.84 cm2 C-1 at 700 nm), and superior cycling stability can be prepared by keeping the weight ratio of Na2WO4·2H2O (precursor of WO3):THMSs at 15:1. The outstanding electrochromic performances of the THMS/WO3 hybrid film were mainly attributed to the porous structure, which facilitates the charge-transfer, promotes the electrolyte infiltration and alleviates the expansion of the film during Li+ insertion. This kind of porous THMS/WO3 hybrid film is promising for a wide range of applications in smart homes, green buildings, airplanes, and automobiles.
Project description:There is keen interest in the use of amorphous WO3 thin films as cathodic electrodes in transmittance-modulating electrochromic devices. However, these films suffer from ion-trapping-induced degradation of optical modulation and reversibility on extended Li(+)-ion exchange. Here, we demonstrate that ion-trapping-induced degradation, which is commonly believed to be irreversible, can be successfully eliminated by constant-current-driven de-trapping; that is, WO3 films can be rejuvenated and regain their initial highly reversible electrochromic performance. Pronounced ion trapping occurs when x exceeds ?0.65 in LixWO3 during ion insertion. We find two main kinds of Li(+)-ion-trapping site (intermediate and deep) in WO3, where the intermediate ones are most prevalent. Li(+) ions can be completely removed from intermediate traps but are irreversibly bound in deep traps. Our results provide a general framework for developing and designing superior electrochromic materials and devices.
Project description:In common commercially available electrochromic glass panes, the active materials such as WO3 and NiOx films are typically deposited by either physical vapor or sputtering under vacuum. In the present studies, we report on the inkjet printing method to deposit both electrochromic and ion storage electrode layers under ambient conditions. An ion storage layer based on cerium modified TiO2 and electrochromic nanocrystalline WO3 were both prepared under the wet method and deposited as inks on conductive substrates. Both compounds possess porous morphology facilitating high ion diffusion during electrochemical processes. In particular, the ion storage layer was evaluated in terms of porosity, charge capacity and ion diffusion coefficient. A scaled up 90 cm2 electrochromic device with quasi-solid-state electrolyte was made with the aforementioned materials and evaluated in terms of optical modulation in the visible region, cyclic voltammetry and color efficiency. High contrast between 13.2% and 71.6% for tinted and bleached states measured at 550 nm was monitored under low bias at +2.5 volt and -0.3 volts respectively. Moreover, the calculated energy density equal to 1.95 × 10-3 mWh cm-2 and the high areal capacitance of 156.19 mF cm-2 of the device could combine the electrochromic behavior of the cell with energy storage capability so as to be a promising candidate for future applications into smart buildings.
Project description:Electrochromic devices (ECDs) are emerging as a novel technology for various applications like commercialized smart window glasses, and auto-dimming rear-view mirrors. Recently, the development of low-power, lightweight, flexible, and stretchable devices has been accelerated to meet the growing demand in the new wearable devices market. Silver nanowires (AgNWs) can become new primary transparent conducting electrode (TCE) materials to replace indium tin oxide (ITO) for ECDs. However, issues such as substrate adhesion, delamination, and higher resistance still exist with AgNWs. Herein, we report a high-performance stretchable flash-induced AgNW-network-based TCE on surface-treated polydimethylsiloxane (PDMS) substrates. A Xe flash light method was used to create nanowelded networks of AgNWs. Surface silane treatments increased the adhesion and durability of the films as well. Finally, ECDs were fabricated under the optimal conditions and examined under strained conditions to demonstrate the resistance and mechanical behaviours of the devices. Results showed a flexible and durable film maintaining a high level of conductivity and reversible resistance behaviour, beyond those currently achievable with standard ITO/PET flexible TCEs.
Project description:Ultrathin nanosheets are considered as one kind of the most promising candidates for the fabrication of flexible electrochromic devices (ECDs) due to their permeable channels, high specific surface areas, and good contact with the substrate. Herein, we first report the synthesis of large-area nanosheets of tungsten oxide dihydrate (WO3·2H2O) with a thickness of only about 1.4 nm, showing much higher Li(+) diffusion coefficients than those of the bulk counterpart. The WO3·2H2O ultrathin nanosheets are successfully assembled into the electrode of flexible electrochromic device, which exhibits wide optical modulation, fast color-switching speed, high coloration efficiency, good cyclic stability and excellent flexibility. Moreover, the electrochromic mechanism of WO3·2H2O is further investigated by first-principle density functional theory (DFT) calculations, in which the relationship between structural features of ultrathin nanosheets and coloration/bleaching response speed is revealed.
Project description:Solar-driven electrochromic smart windows with energy-storage ability are promising for energy-saving buildings. In this work, a flexible photoelectrochromic device (PECD) was designed for this purpose. The PECD is composed of two flexible transparent conductive layers, a photocatalytic layer, an electrochromic material layer, and a transparent electrolyte layer. The photocatalytic layer is a dye-sensitized TiO2 thick film and the electrochromic layer is a WO3 thin film, which also possesses a supercapacitive property. Under illumination, dye-sensitized TiO2 thick film realizes photo-drive electrochromism that the WO3 changes from colorless to blue with large optical modulation. Meanwhile, the PECD has an electrochemical supercapacitance showing an energy storage property of 21 mF·cm-2 (114.9 F·g-1 vs the mass of WO3), stable mechanical performance and long cycle performance. The PECD can effectively adjust the transmittance of visible and near-infrared light without any external power supply, realizing zero energy consumption, and can convert solar energy into electrical energy for storage.
Project description:Nanomaterials have tremendous potential to increase electrochromic smart window efficiency, speed, and durability. However, nanoparticles vary in size, shape, and surface defects, and it is unknown how nanoparticle heterogeneity contributes to particle-dependent electrochromic properties. Here, we use single-nanoparticle-level electro-optical imaging to measure structure-function relationships in electrochromic tungsten oxide nanorods. Single nanorods exhibit a particle-dependent waiting time for tinting (from 100 ms to 10 s) due to Li-ion insertion at optically inactive surface sites. Longer nanorods tint darker than shorter nanorods and exhibit a Li-ion gradient that increases from the nanorod ends to the middle. The particle-dependent ion-insertion kinetics contribute to variable tinting rates and magnitudes across large-area smart windows. Next, we quantified how particle-particle interactions impact tinting dynamics and reversibility as the nanorod building blocks are assembled into a thin film. Interestingly, single particles tint 4 times faster and cycle 20 times more reversibly than thin films made of the same particles. These findings allow us to propose a nanostructured electrode architecture that optimizes optical modulation rates and reversibility across large-area smart windows.