3D-Printed Hydrogel-Based Flexible Electrochromic Device for Wearable Displays.

Flexible electrochromic devices (FECDs) are widely explored for diverse applications including wearable electronics, camouflage, and smart windows. However, the manufacturing process of patterned FECDs remains complex, costly, and non-customizable. To address this challenge, a strategy is proposed to prepare integrated FECDs via multi-material direct writing 3D printing. By designing novel viologen/polyvinyl alcohol (PVA) hydrogel inks and systematically evaluating the printability of various inks, seamless interface integration can be achieved, enabling streamlined manufacturing of patterned FECDs with continuous production capabilities. The resultant 3D-printed FECDs exhibit excellent electrochromic and mechanical properties, including high optical contrast (up to 54% at 360 nm), nice cycling stability (less than 5% electroactivity reduction after 10 000 s), and mechanical stability (less than 19% optimal contrast decrease after 5000 cycles of bending). The potential applications of these 3D-printed hydrogel-based FECDs are further demonstrated in wearable electronics, camouflage, and smart windows.

Spectrum Reconstruction Model Based on Multispectral Electrochromic Devices.

Reconstructing the visible spectra of real objects is critical to the spectral camouflage from emerging spectral imaging. Electrochromic materials exhibit unique superiority for this goal due to their subtractive color-mixing model and structural diversity. Herein, a simulation model is proposed and a method is developed to fabricate electrochromic devices for dynamically reproducing the visible spectrum of the natural leaf. Over 20 kinds of pH-dependent leuco dyes have been synthesized/prepared through molecular engineering and offered available spectra/bands to reconstruct the spectrum of the natural leaf. More importantly, the spectral variance between the device and leaf is optimized from an initial 98.9 to an ideal 10.3 through the simulation model, which means, the similarity increased nearly nine-fold. As a promising spectrum reconstruction approach, it will promote the development of smart photoelectric materials in adaptive camouflage, spectral display, high-end encryption, and anti-counterfeiting.

Exploiting Mixed Valence Charge Transfer for Electrochromic and Electrofluorochromic Use.

An asymmetric mixed valence fluorophore with two different electron rich termini was investigated as a dual-role active material for electrochromism and electrofluorochromism. The fluorescence quantum yield (Φfl) and emission wavelength of the fluorophore were dependent on solvent polarity. The quantum yield of the material in an electrolyte gel, on a glass substrate and in a device was 40 %, 20 % and 13 % respectively. The fluorophore further underwent two near-simultaneous electrochemical oxidations. The first oxidation resulted in a 1000 nm red shift in the absorption to broadly absorb in the NIR, corresponding to the intervalence charge transfer (IVCT). Whereas the second oxidation led to a perceived green color at 715 nm with the extinction of the NIR absorbing IVCT. Owing to the dissymmetry of the fluorophore along with its two unique oxidation sites, the IVCT gives rise to a mixed valence transfer charge (MVCT). The coloration efficiency of the fluorophore in both solution and a device was 1433 and 200 cm2 C-1, respectively. The fluorescence intensity could be reversibly modulated electrochemically. The photoemission intensity of the fluorophore was modulated with applied potential in an operating electrochromic/electrofluorochromic device. Both the dual electrochromic and the electrofluorochromic behavior of the fluorophore were demonstrated.

A Flexible Long-Wave Infrared Radiation Modulator Integrated with Electrochromic Behavior for Dual-Band Camouflage.

Electrochromic devices (ECDs), which are capable of modulating optical properties in the visible and long-wave infrared (LWIR) spectra under applied voltage, are of great significance for military camouflage. However, there are a few materials that can modulate dual frequency bands. In addition, the complex and specialized structural design of dual-band ECDs poses significant challenges. Here, we propose a novel approach for a bendable ECD capable of modulating LWIR radiation and displaying multiple colors. Notably, it eliminates the need for a porous electrode or a grid electrode, thereby improving both the response speed and fabrication feasibility. The device employs multiwalled carbon nanotubes (MWCNTs) as both the transparent electrode and the LWIR modulator, polyaniline (PANI) as the electrochromic layer, and ionic liquids (HMIM[TFSI]) as the electrolyte. The ECD is able to reduce its infrared emissivity (Δε = 0.23) in a short time (resulting in a drop in infrared temperature from 50 to 44 °C) within a mere duration of 0.78 ± 0.07 s while changing its color from green to yellow within 3 s when a positive voltage of 4 V is applied. In addition, it exhibits excellent flexibility, even under bending conditions. This simplified structure provides opportunities for applications such as wearable adaptive camouflage and multispectral displays.

Potential Gradient-Driven Dual-Functional Electrochromic and Electrochemical Device Based on a Shared Electrode Design.

The integration of electrochromic devices and energy storage systems in wearable electronics is highly desirable yet challenging, because self-powered electrochromic devices often require an open system design for continuous replenishment of the strong oxidants to enable the coloring/bleaching processes. A self-powered electrochromic device has been developed with a close configuration by integrating a Zn/MnO2 ionic battery into the Prussian blue (PB)-based electrochromic system. Zn and MnO2 electrodes, as dual shared electrodes, the former one can reduce the PB electrode to the Prussian white (PW) electrode and serves as the anode in the battery; the latter electrode can oxidize the PW electrode to its initial state and acts as the cathode in the battery. The bleaching/coloring processes are driven by the gradient potential between Zn/PB and PW/MnO2 electrodes. The as-prepared Zn||PB||MnO2 system demonstrates superior electrochromic performance, including excellent optical contrast (80.6%), fast self-bleaching/coloring speed (2.0/3.2 s for bleaching/coloring), and long-term self-powered electrochromic cycles. An air-working Zn||PB||MnO2 device is also developed with a 70.3% optical contrast, fast switching speed (2.2/4.8 s for bleaching/coloring), and over 80 self-bleaching/coloring cycles. Furthermore, the closed nature enables the fabrication of various flexible electrochromic devices, exhibiting great potentials for the next-generation wearable electrochromic devices.

A Strong and Highly Transparent Ionogel Electrolyte Enabled by In Situ Polymerization-Induced Microphase Separation for High-Performance Electrochromic Devices.

Electrochromic devices built with ionogel electrolytes are seen as a pivotal step toward the future of quasi-solid electrochromic devices, due to their striking properties like exceptional safety and high ionic conductivity. Yet, the poor mechanical strength of electrolyte of these devices remains a constraint that hampers their advancement. As a resolution, this research explores the use of a robust, transparent ionogel electrolyte, which is designed using an in situ microphase separation strategy. The ionogels are highly transparent and robust and exhibit excellent physicochemical stability, including a wide electrochemical window and high temperature tolerance. Benefitting from these properties, a high-performance electrochromic device is fabricated through in situ polymerization with the ionogels, PPRODOT as the electrochromic layer, and PEDOT: PSS as the ion storage layer, achieving high transmittance contrast (43.1%), fast response (1/1.7 s), high coloring efficiency (1296.4 cm2 C-1), and excellent cycling endurance (>99.9% retention after 2000 cycles). In addition, using ITO-poly(ethylene terephthalate) as flexible substrates, a deformable electrochromic device displaying high stability is realized, highlighting the potential use in functional wearables.

Optical-Cavity-Incorporated Colorful All-Solid-State Electrochromic Devices for Dual Anti-Counterfeiting.

The fusion of electrochromic technology with optical resonant cavities presents an intriguing innovation in the electrochromic field. However, this fusion is mainly achieved in liquid electrolyte-based or sol-gel electrolyte-based electrochromic devices, but not in all-solid-state electrochromic devices, which have broader industrial applications. Here, a new all-solid-state electrochromic device is demonstrated with a metal-dielectric-metal (MDM) resonant cavity, which can achieve strong thin-film interference effects through resonance, enabling the device to achieve unique structural colors that have rarely appeared in reported all-solid-state electrochromic devices, such as yellow green, purple, and light red. The color gamut of the device can be further expanded due to the adjustable optical constants of the electrochromic layer. What is more, this device exhibits remarkable cycling stability (maintaining 84% modulation capability after 7200 cycles), rapid switching time (coloration in 2.6 s and bleaching in 2.8 s), and excellent optical memory effect (only increasing by 13.8% after almost 36 000 s). In addition, this exquisite structural design has dual-responsive anti-counterfeiting effects based on voltage and angle, further demonstrating the powerful color modulation capability of this device.

Preparation of an Inorganic All-Solid-State Electrochromic Device with Excellent Open-Circuit Memory.

Due to the spontaneous transport of small-sized cations and redox reactions under open circuit conditions, the currently reported coloring electrochromic devices (ECDs) may self-bleach easily. The resulting ECDs exhibit poor open-circuit memory, which limits their applications in static display advertisement. By constructing energy barriers to effectively control small-sized cation transport, the redox reaction could be suppressed, thereby inhibiting the self-bleaching of ECDs. In this study, phosphate glass is used as an electrolyte to construct high-energy barriers. Sodium ions in phosphate glass absorb external heat to cross energy barriers and become conductive charge carriers. In this case, the electrochromism of ECDs is allowed. On the contrary, after the absorbed heat energy is released, sodium ions are immediately trapped by oxygen ions in the PO4 unit, becoming frozen ions. At this point, the electrochromization of ECDs is prohibited. Based on the ionic conductive feature of phosphate glass, ECDs absorb heat and are colored by applying an electric field first. Then, ECDs release the thermal energy and the sodium ions transport in the electrolyte is blocked to cut off the self-bleaching pathway. The prepared inorganic all-solid-state ECDs maintained the colored state for several months using the method mentioned above, which solved the problem of the poor open-circuit memory of ECDs.

Color-Shifting Iontronic Skin for On-Site, Nonpixelated Pressure Mapping Visualization.

Mimicking the function of human skin is highly desired for electronic skins (e-skins) to perceive the tactile stimuli by both their intensity and spatial location. The common strategy using pixelated pressure sensor arrays and display panels greatly increases the device complexity and compromises the portability of e-skins. Herein, we tackled this challenge by developing a user-interactive iontronic skin that simultaneously achieves electrical pressure sensing and on-site, nonpixelated pressure mapping visualization. By merging the electrochromic and iontronic pressure sensing units into an integrated multilayer device, the interlayer charge transfer is regulated by applied pressure, which induces both color shifting and a capacitance change. The iontronic skin could visualize the trajectory of dynamic forces and reveal both the intensity and spatial information on various human activities. The integration of dual-mode pressure responsivity, together with the scalable fabrication and explicit signal output, makes the iontronic skin highly promising in biosignal monitoring and human-machine interaction.

One-step achieving high performance all-solid-state and all-in-one flexible electrochromic supercapacitor by polymer dispersed electrochromic device strategy.

Electrochromic devices (ECD) are widely used to regulate the transmittance of sunlight by applying a small voltage, but the drawbacks like complex layer-by-layer preparation procedures and inconvenient assembling process still exist. To address these problems, gel or solution-type all-in-one ECDs were recently developed for the simple structure, however, the leakage risk and absence of flexible large-area production have limited real applications. Herein, a novel all-solid-state and all-in-one flexible ECD was reported by originally developed polymer dispersed electrochromic device (PDECD) strategy. This all-solid-state flexible ECD could be efficiently prepared only by one step of phase separation without any extra treatment, and demonstrated outstanding stability (92.1 % of original ΔT remained after 10,000 cycles), high coloration efficiency (197 cm2/C), low power consumption (86.4 µW/cm2) and satisfied response time (≤12 s). Meanwhile, the stored power in ECD during coloring process could drive a LED with excellent cyclic stability (93 % of original capacity remained after 3000 cycles), implying that ECD could also serve as an idea electrochromic supercapacitor. What'more, a reported largest viologen-based all-solid-state flexible ECD (17.8 × 13.2 cm2) with robust bending resistance (up to 1000 bending cycles) was successfully fabricated with industrial roller coating technique, which indicated the huge potential in real world.

Electropolymerization of an EDOT-Quinoxaline Monomer for Green Electrochromic Thin Films and Devices.

In this study, we present a 5,8-bis(3,4-ethylenedioxythiophene)quinoxaline monomer with two 4-(octyloxy)phenyl side chains (EDOTPQ) that can be electropolymerized on ITO glass in standard electrolytes containing lithium salts and propylene carbonate as solvent. The electrochemically deposited PEDOTPQ layers show very good adhesion and homogeneity on ITO. The green-colored polymer thin films exhibit promising electrochromic (EC) properties and are interesting for applications such as adaptive camouflage, as well as smart displays, labels, and sensors. Novel organic-inorganic (hybrid) EC cell configurations were realized with Prussian blue (PB) or titanium-vanadium oxide (TiVOx) as ion storage electrodes, showing a highly reversible and fast color change from green to light yellow.

Electrochromic Devices Based on 2D MoO3-x/PEDOT:PSS Composite Film with Boosted Ion Transport.

Electrochromic materials allow for optical modulation and have attracted much attention due to their bright future in applications such as smart windows and energy-saving displays. Two-dimensional (2D) molybdenum oxide nanoflakes with combined advantages of high active specific surface area and natural layered structure should be highly potential candidates for electrochromic devices. However, the efficient top-down preparation of 2D MoO3 nanoflakes is still a huge challenge and the sluggish ionic kinetics hinder its electrochromic performance. Herein, we demonstrated a feasible thiourea-assisted exfoliation procedure, which can not only increase the yield but also reduce the thickness of 2D MoO3-x nanoflakes down to a few nanometers. Furthermore, electrophoretic-deposited MoO3-x nanoflakes were combined with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-conjugated polymer to simultaneously enhance the ionic kinetics and electronic conductivity, with a diffusion coefficient of 3.09 × 10-10 cm2 s-1 and a charge transport resistance of 33.7 Ω. The prepared 2D MoO3-x/PEDOT:PSS composite films exhibit improved electrochromic performance, including fast switching speed (7 s for bleaching, 5 s for coloring), enhanced coloration efficiency (87.1 cm2 C-1), and large transmittance modulation (ΔT = 65%). This study shows outstanding potential for 2D MoO3-x nanoflakes in electrochromic applications and opens new avenues for optimizing the ion transport in inorganic-organic composites, which will be possibly inspired for other electrochemical devices.

Flexible Composite Electrochromic Device with Long-Term Bistability Based on a Viologen Derivative and Prussian Blue.

Viologen and Prussian blue (PB) exhibit good electrochromic properties, but certain limitations still exist. To improve the electrochromic properties of viologen, a viologen derivative 1,1'-bis(4-(bromomethyl)benzyl)-[4,4'-bipyridine]-1,1'-diium hexafluorophosphate (BBDV) was synthesized, and its electrochromic properties were investigated. Additionally, a flexible composite electrochromic device (FC-ECD) was prepared by using BBDV and PB as active materials. The structure of the FC-ECD was PET-ITO/gel electrolyte-BBDV/PB/PET-ITO. The applied voltage required for the FC-ECD was found to be lower than that of the ECD based on BBDV(FBBDV-ECD). Compared to FBBDV-ECD, FC-ECD exhibited a higher optical contrast (71.42%) and cyclic stability (89.51%). The FC-ECD exhibited multicolor changes under different applied voltages (ranging from -2.0 to +1.6 V). Especially, the color of the FC-ECD remained stable for 14 h after the removal of the applied voltage.

Nonconventional Symmetric Double-Side Electrochromic Devices Employing a Nafion Conductive Layer to Unlock Superior Durability.

In this work, we present a methodology to create an effective novel double-sided symmetric architecture of solid-state electrochromic devices. This principally new nonconventional configuration provides access to novel electrochromic systems that could be applicable for the creation of smart double-side signage, smart boards, nonemissive displays, and other smart interactive devices that change their color upon application of a voltage. The proposed configuration is based on the assembly of two identical electrochromic materials facing each other through an opaque optical separator. As a proof of concept, we use an electrochromic material based on bis(4'-(pyridin-4-yl)-2,2':6',2″-terpyridine) iron complex, covalently immobilized on screen-printed surface-extended ITO support. The symmetric configuration allows for a drastic enhancement of the overall stability of the device due to both attenuation of the counter electrode polarization and minimization of electrolyte decomposition. A nontransparent ion-permeable separator, in turn, allows observing the color change of only one of the electrodes by cutting off the optical contribution of the electrode located behind it. Further functionalization of the electrochromic material with a thin layer of Nafion is a beneficial strategy to significantly boost up long-term durability of the devices. Applying a layer of Nafion to the electrochromic material results in an increase in ionic conductivity within the device and ensures better retention of electrochromic molecules on the surface, thus minimizing device decomposition during long-term electrochemical cycling. An electrochromic device that bears Nafion-functionalized electrodes can operate (i) in the dual-side mode, where both sides demonstrate effective electrochromic performance; or (ii) in a one-side manner, where only one side of the device changes color. Notably, when operating in the one-side mode, the device withstands 70,000 cycles, after which the performance of the device can be resumed by simply turning the device to the other side (via switching the polarity of the electrodes).

C-Rich Carbon Nitride Conjugated Polymer Enabling Ion-Migration-Induced Precise Electrochromic Display.

The development of electrochromic (EC) displays has been in the challenge of displaying precise patterns, such as characters or high-resolution images of small size. High-performance EC materials as well as efficient, precise-display strategies are still urgent. To enable a microfactor-guided strategy for highly precise display, I3-/I- ion-migration-induced localized electrochromism is developed in an EC device based on the C-rich polymeric carbon nitride (CPCN). The CPCN material with an extended conjugated backbone of individual aromatic nuclei and heptazine rings has been reported possessing remarkable photorechargeable performance. Owing to the self-charging behavior, the CPCN exhibits color switching by the interfacial charge recombination with I3- ions in electrolyte and serves as the EC material with a coloration efficiency of 210.2 cm2 C-1 and an optical contrast of 48.6%. Material synthesis, electrode preparation, device design and fabrication, mechanism analysis, and performance evaluation of the CPCN-based EC display device are described.

High-Voltage Pulse-Assisted Operation of Single-Layer Electrochromic Systems for High Performance and Reliability.

A single-layer electrochromic device (SL-ECD) based on ionic conductors containing EC chromophores provides a very simple platform that can be readily fabricated by sandwiching the EC layer between two electrodes. The operation of SL-ECDs is governed by the diffusion of redox species due to their SL structure, which causes a relatively slow dynamic response. In this study, we propose an effective high-voltage pulse injection strategy to improve the performance of SL-ECDs. Applying a programmed voltage wave composed of DC and high-voltage pulses promotes coloration/bleaching switching without degrading device stability, which is more advantageous than applying high DC voltages. We modified the input voltage profile by considering fundamental parameters, such as the amplitude and duty ratio of additional voltage pulses. The coloration and bleaching dynamic responses with the optimized voltage wave are ∼62 and ∼20% faster, respectively, compared with those with the simple DC input. Furthermore, the additionally injected pulse aids in increasing the coloration efficiency from ∼95.3 to ∼168.6 cm2 C-1. Another notable feature of this system is that the device operates stably when a programmed voltage wave is used. These results indicate that the concept of high-voltage pulse-assisted operation of SL-ECDs is a straightforward but effective method for improving device performance without changing the EC chromophore or device structure.

Temperature Sensors Integrated with an Electrochromic Readout toward Visual Detection.

Temperature sensors have attracted great attention for personal health care and disease diagnosis in recent years. However, it is still a great challenge to fabricate reliable and highly sensitive temperature sensors that can convert physiological signals into easily readable signals in a convenient way. Herein, an integrated smart temperature sensor system based on a traditional temperature sensor and electrochromic display is proposed for real-time visual detection of temperature. Significantly, a voltage-regulated electrochromic device (ECD) based on tungsten oxide (WO3) and polyaniline (PANI) as the real-time visualization window was integrated into the platform to provide feedback on the temperature change. The ECD would change its color from green to blue based on the electrical signal of the temperature sensor, resulting in a visualized readout that can be monitored through our naked eye. Additionally, the smart temperature sensor system possesses an extremely durable property and cycle stability, remaining around 90% of the initial value even after 15,000 s continuous cycle. Thus, the novel design and low power consumption advantages make it a good candidate to pave the way for developing interactive wearable electronics and intelligent robots as real-time temperature feedback systems.

New Anodic Discoloration Materials Applying Energy-Storage Electrochromic Device.

We have assessed new anodic coloring materials that can be used as ion storage layers in complementary energy storage electrochromic devices (ESECDs) to enhance their electrochromic storage performance. In our study, we fabricated counter electrodes (ion storage layers) using an IrO2-doping NiO (Ir:NiO) film through cathodic arc plasma (CAP) with varying surface charge capacities. We have also investigated the influence of a MoO3-doped WO3 (Mo:WO3) film using various Ar/O2 gas flow ratios (1/4, 1/5, and 1/6, respectively). The ESECDs used in the demonstration were 10 × 10 cm2 in size and achieved an optical transmittance modulation of the Ir:NiO ESECDs (glass/ITO/ Mo:WO3/gel polymer electrolytes/ Ir:NiO/ITO/glass), with ΔT = 53.3% (from Tbleaching (66.6%) to Tcoloration (13.1%)). The ESECDs had a quick coloration time of 3.58 s, a rapid bleaching time of 1.24 s, and a high cycling durability. Furthermore, it remained at a 45% transmittance modulation level even after 3000 cycles. New anodic materials can thereby provide an alternative to traditional active materials for bi-functional electrochromic batteries.

The Influence of Thermal and Mechanical Stress on the Electrical Conductivity of ITO-Coated Polycarbonate Films.

The influence of thermomechanical stress on the conductivity of indium tin oxide (ITO)-coated polycarbonate (PC) films was investigated. PC is the industry's standard material for window panes. ITO coatings on polyethylene terephthalate (PET) films are the main commercially available option; as such, most investigations refer to this combination. The investigations in this study aim to investigate the critical crack initiation strain at different temperatures and crack initiation temperatures for two different coating thicknesses and for a commercially available PET/ITO film for validation purposes. Additionally, the cyclic load was investigated. The results show the comparatively sensitive behavior of the PC/ITO films, with a crack initiation strain at room temperature of 0.3-0.4% and critical temperatures of 58 °C and 83 °C, with high variation depending on the film's thickness. Under thermomechanical loading, the crack initiation strain decreases with increasing temperatures.

Proton and Redox Couple Synergized Strategy for Aqueous Low Voltage-Driven WO3 Electrochromic Devices.

Aqueous electrolytes possess non-combustible and eco-friendly features compared to organic electrolytes, leading them to be more suitable for application in smart windows for daily use. However, limited by the narrow electrochemical window of water (1.23 V), its use in conventional electrochromic devices (ECDs) would result in irreversible performance loss, which arises from decomposition caused by high voltage. Here, we propose a synergistic scheme combining a redox couple-catalytic counter electrode (RC-CCE) strategy with protons as guest ions. With the help of the intelligent matching of the reaction potentials of the RC and amorphous WO3 electrochromic electrodes and the highly active and fast kinetic features of protons, it successfully reduces the working voltage range of the device to 1.1 V. The assembled HClO4-ECD can possess an overall modulation rate (350-1200 nm) of 0.43 and 0.94 at -0.1 and -0.7 V, respectively, and a modulation of 66.8% at 600 nm at -0.7 V. Moreover, compared with other guest ions, the proton-based ECD exhibits higher coloration efficiency, a broader color modulation capability, and better stability. In addition, the house model equipped with the proton-based ECD effectively blocks solar radiation, which provides a potential solution for the design of aqueous smart windows.