Fast Switching ITO Free Electrochromic Devices

Indium‐doped tin oxide free electrochromic devices are prepared by coating electrochromic polymers onto polyethylene terephthalate substrates encompassing two different silver grids as electrodes. One design comprises a flexoprinted highly conductive silver grid electrode, yielding electrochromic devices with a response time of 2 s for an optical contrast of 27%. The other design utilizes an embedded silver grid electrode whereupon response times of 0.5 s for a 30% optical contrast are realized when oxidizing the device. A commercially available conductive poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate acid) formulation (PEDOT:PSS) is coated onto the silver grids as a charge balancing polymer, and is in this setting found to be superior to a polypyrrole previously employed in electrochromic devices. In addition, the PEDOT:PSS layer increases the conductivity in the hexagonal grid structure.     

Paper‐Based Electrochromic Devices Enabled by Nanocellulose‐Coated Substrates

As environmental considerations for both the processing and disposal of electronic devices become increasingly important, the ability to replace plastic and glass substrates with bioderived and biodegradable materials remains a major technological goal. Here, the use of cellulose nanofiber‐coated paper is explored as an environmentally benign substrate for preparing low‐resistance (460 Ω sq^?1), colorless (a* = ?2.3, b* = ?2.7) printed poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes. The PEDOT:PSS/paper electrodes support the reversible oxidation of three electrochromic polymers (ECPs) (cyan, magenta, and yellow), affording the possibility for fully printed, color displays on paper. Lateral electrochromic devices (ECDs) incorporating an ion gel electrolyte are demonstrated where a magenta‐to‐colorless device achieves a color contrast (ΔE*) of 56 owing to a highly color‐neutral bleached state of the ECP (a* = ?0.5, b* = 2.9). Black‐to‐colorless devices achieve ΔE* = 29 and are able to retain 86% of their color contrast after 9000 switches. The switching times of these lateral devices are quantified through colorimetric image analysis which shows comparable performance for devices constructed on paper as devices using ITO/glass electrodes (10 Ω sq^?1). The paper ECDs are then combusted in air leaving 3% of the initial mass at 600 °C, highlighting this approach as a promising route toward disposable displays.     

Multistage Coloring Electrochromic Device Based on TiO2 Nanotube Arrays Modified with WO3 Nanoparticles

WO₃ nanoparticles loaded in TiO₂ nanotube arrays, fabricated by a chemical bath deposition (CBD) technique in combination with a pyrolysis process, is uniform and the diameter can be easily adjusted by the deposition times. The resultant hybrid nanotubes array shows a multistage coloring electrochromic response at different potential bias. The formation of a 3‐dimensional WO₃/TiO₂ junction promotes unidirectional charge transport due to the one‐dimensional features of the tubes, which leads to the significant positive‐shift onset potential of the cathodic reaction (ion insertion) and the highly increased proton storage capacity. Compared to non‐decorated nanotube arrays, the enhanced electrochromic properties of longer lifetime, higher contrast ratio (bleaching time/coloration time), and improved tailored electrochromic behavior could be achieved using the composite films.     

电致变色写入与显示器件

描述了电致变色写入和显示器件的结构、工作原理与实验结果，提出了这种新型电致变色器件的应用前景。     

Electrochromic properties as a function of electrolyte on the performance of electrochromic devices consisting of a single-layer polymer

Herein, a study on varying salts and their composition used in the gel electrolyte for a one-step lamination assembly procedure for electrochromic devices was carried out to explore their effects on various electrochromic performance parameters, such as color uniformity, photopic contrast, switching speed, and optical memory. Electrochromic polymers formed in different gel electrolyte compositions are highly dependent on the type, amount, and composition of salt used. The following groups of salts were investigated: ionic liquids, ammonium salts, and lithium salts. The lithium salts yielded devices with the best color uniformity, photopic contrast as high as 48%, and switching response speeds as low as 1 s for 5.5 cm² devices using the electroactive monomer 2,2-dimethyl-3,4-propylenedioxythiophene (ProDOT-Me₂) to generate the electrochromic polymer. Hermetically sealed electrochromic devices exhibited optical memory of 27 h for a 2% photopic transmittance loss under normal laboratory conditions, and a 171 cm² electrochromic device was demonstrated.     

Electrochromic Effect in Titanium Carbide MXene Thin Films Produced by Dip‐Coating

MXenes, a large family of 2D transition metal carbides and nitrides, have shown potential in energy storage and optoelectronic applications. Here, the optoelectronic and pseudocapacitive properties of titanium carbide (Ti₃C₂T_x) are combined to create a MXene electrochromic device, with a visible absorption peak shift from 770 to 670 nm and a 12% reversible change in transmittance with a switching rate of <1 s when cycled in an acidic electrolyte under applied potentials of less than 1 V. By probing the electrochromic effect in different electrolytes, it is shown that acidic electrolytes (H₃PO₄ and H₂SO₄) lead to larger absorption peak shifts and a higher change of transmittance than the neutral electrolyte (MgSO₄) (Δλ is 100 nm vs 35 nm and ΔT_{770 nm} is ≈12% vs ≈3%, respectively), hinting at the surface redox mechanism involved. Further investigation of the mechanism by in situ X‐ray diffraction and Raman spectroscopy reveals that the reversible shift of the absorption peak is attributed to protonation/deprotonation of oxide‐like surface functionalities. As a proof of concept, it is shown that Ti₃C₂T_x MXene, dip‐coated on a glass substrate, functions as both transparent conductive coating and active material in an electrochromic device, opening avenues for further research into optoelectronic and photonic applications of MXenes.     

Highly Stable Ag–Au Core–Shell Nanowire Network for ITO-Free Flexible Organic Electrochromic Device

Solid and flexible electrochromic (EC) devices require a delicate design of every component to meet the stringent requirements for transparency, flexibility, and deformation stability. However, the electrode technology in flexible EC devices stagnates, wherein brittle indium tin oxide (ITO) is the primary material. Meanwhile, the inflexibility of metal oxide usually used in an active layer and the leakage issue of liquid electrolyte further negatively affect EC device performance and lifetime. Herein, a novel and fully ITO-free flexible organic EC device is developed by using Ag–Au core–shell nanowire (Ag–Au NW) networks, EC polymer and LiBF₄/propylene carbonate/poly(methyl methacrylate) as electrodes, active layer, and solid electrolyte, respectively. The Ag–Au NW electrode integrated with a conjugated EC polymer together display excellent stability in harsh environments due to the tight encapsulation by the Au shell, and high area capacitance of 3.0 mF cm⁻² and specific capacitance of 23.2 F g⁻¹ at current density of 0.5 mA cm⁻². The device shows high EC performance with reversible transmittance modulation in the visible region (40.2% at 550 nm) and near-infrared region ( − 68.2% at 1600 nm). Moreover, the device presents excellent flexibility ( > 1000 bending cycles at the bending radius of 5 mm) and fast switching time (5.9 s).     

Highly contrasted and stable electrochromic device based on well-matched viologen and triphenylamine

An electrochromic device (ECD) can change color absorption when subjected to an appropriate voltage. Such a device includes three components: a working electrode, a counter electrode and an electrolyte. Compatibility of these three components is important for ECD’s stability. In this study, two novel compatible electrochromic materials, cathodic 1-(9-hexyl-9H-carbazole)-1′-(propylphosphonic acid)-4,4′-bipyridilium dichloride and anodic (4-(diphenylamino)phenyl)methylphosphonic acid were designed, synthesized and fabricated into electrochromic electrodes using a chemisorption method. We characterized the electrochromic performance of these two electrodes, including the degree of color change, color changing voltage and charge capacity; the results indicated that they matched each other very well. An electrochromic device fabricated using these two electrodes, as expected, exhibited rapid, vivid color changes and proved highly stable for up to 100,000 cycles.     

Trilayer Nanomesh Films with Tunable Wettability as Highly Transparent,Flexible, and Recyclable Electrodes

Metallic mesh materials are promising candidates to replace traditional transparent conductive oxides such as indium tin oxide (ITO) that is restricted by the limited indium resource and its brittle nature. The challenge of metal based transparent conductive networks is to achieve high transmittance, low sheet resistance, and small perforation size simultaneously, all of which significantly relate to device performances in optoelectronics. In this work, trilayer dielectric/metal/dielectric (D/M/D) nanomesh electrodes are reported with precisely controlled perforation size, wire width, and uniform hole distribution employing the nanosphere lithography technique. TiO₂/Au/TiO₂ nanomesh films with small hole diameter (≤700 nm) and low thickness (≤50 nm) are shown to yield high transmittance (>90%), low sheet resistance (≤70 Ω sq^?1), as well as outstanding flexural endurance and feasibility for large area patterning. Further, by tuning the surface wettability, these films are applied as easily recyclable flexible electrodes for electrochromic devices. The simple and cost‐effective fabrication of diverse D/M/D nanomesh transparent conductive films with tunable optoelectronic properties paves a way for the design and realization of specialized transparent electrodes in optoelectronics.     

New Roll‐to‐Roll Processable PEDOT‐Based Polymer with Colorless Bleached State for Flexible Electrochromic Devices

Conjugated electrochromic (EC) polymers for flexible EC devices (ECDs) generally lack a fully colorless bleached state. A strategy to overcome this drawback is the implementation of a new sidechain‐modified poly(3,4‐ethylene dioxythiophene) derivative that can be deposited in thin‐film form in a customized high‐throughput and large‐area roll‐to‐roll polymerization process. The sidechain modification provides enhanced EC properties in terms of visible light transmittance change, Δτ_v = 59% (ΔL* = 54.1), contrast ratio (CR = 15.8), coloration efficiency (η = 530 cm² C^?1), and color neutrality (L* = 83.8, a* = ?4.3, b* = ?4.1) in the bleached state. The intense blue‐colored polymer thin films exhibit high cycle stability (10 000 cycles) and fast response times. The design, synthesis, and polymerization of the modified 3,4‐ethylene dioxythiophene derivative are discussed along with a detailed optical, electrochemical, and spectroelectrochemical characterization of the resulting EC thin films. Finally, a flexible see‐through ECD with a visible light transmittance change of Δτ_v = 47% (ΔL* = 51.9) and a neutral‐colored bleached state is developed.     

Energy Saving Electrochromic Polymer Windows with a Highly Transparent Charge‐Balancing Layer

Highly transparent TiO₂ nanoparticles are explored as a non‐electrochromic (non‐EC) charge‐balancing layer for a high color contrast, bistable electrochromic window (ECW). The TiO₂ nanoparticle (TNP) layer increases the potential at the EC polymer electrode, thereby lowering the working voltage of the ECW. This leads to lower the power consumption of ECWs without loss in the high color contrast (ΔT > 72%) and to remarkably improve the cyclability (ΔT change <1% over 3000 cycles), mainly due to the low overvoltage (<0.1 V) on the electrochromic polymer layer. Furthermore, the ECWs including the non‐EC TNP layer show long‐term bistability (>2.7 h, 40% increase) and UV stability (ΔT change <1%) to provide a low‐power automatic ECW. This finding shows that the charge balanced ECP window has the potential to be used for an energy saving ECW with low‐power consumption and will be widely applied in various ECWs as well as electrochemical devices with multiple functions.     

Bioinspired Dynamically Switchable PANI/PS-b-P2VP Thin Films for Multicolored Electrochromic Displays with Long-Term Durability

Electrochromism has attracted wide attention as futuristic adaptive camouflage technologies due to its reversible and sustainable optical modulation with low energy consumption. However, limited color control of the electrochromic materials has hampered its applications. Inspired by the remarkable dynamic camouflage capabilities of cephalopods, polyaniline (PANI) and polystyrene-block-poly (2-vinyl pyridine) (PS-b-P2VP) thin films are integrated to simulate chromatophores and iridophores in the skin of cephalopods, respectively. Herein, it is demonstrated that the adaptive lamellar PANI/PS-b-P2VP thin film exhibits a wide range of color control, switchable vivid coloration, and excellent durability. It serves as an ideal multicolored electrochromic platform due to the combined effect of electrochromism from PANI and structural coloration from PS-b-P2VP. Unambiguous evidence shows that optical properties of the PANI/PS-b-P2VP thin film are related to the thickness of each layer and nanostructure of PANI, pronounced color changes mainly depend on electronic states of PANI and transition of hydrated SO₄²⁻ ions between PANI and P2VP. The coloration mechanism is discussed using quantitative analysis via RGB color specification and optical transmittance and reflectance simulations. The new insights will advance the design of reflection-contributed superior multicolored electrochromic materials, and have great potential in the fields of displays and camouflage.     

Multifunctional Self-Charging Electrochromic Supercapacitors Driven by Direct-Current Triboelectric Nanogenerators

Electrochromic supercapacitor devices (ESCDs) are highly promising for energy-saving applications or smart windows, whereas they still require electrical energy inputs. In this study, a self-charging ESCD (SC-ESCD) based on the ESCD and a sliding-mode direct-current triboelectric nanogenerators is successfully proposed. The SC-ESCD cannot merely convert mechanical sliding kinetic energy into electrical energy and store the electricity in electrochromic supercapacitors but can also show optical responses to the mechanical sliding motions. The prominent electrochemical performances of the SC-ESCD are confirmed by the high areal capacitance (15.2 mF cm⁻² at 0.1 mA cm⁻²) and stable cycling performance (99% for 5000 cycles). Besides, it can be prepared into arbitrary characters or patterns to adapt to various applications. The study demonstrates a potential approach to develop multifunctional self-charging power sources which combine energy harvesting, energy storage, and electrochromic functions.     

一种新型互补溶液型电致变色器件的研究

用TiCl4作为钛离子源，发现Ti^4＋离子和紫罗精之间具有互补效应。利用这种互补溶液，设计了一种结构简单的电致变色器件。施加不同的外加电压，可以调节电致变色器件的光强透过率以及器件的颜色。去掉外加电压，电致变色器件迅速变为透明态，具有自擦除效果。紫外-可见分光光度计表征表明，器件透过率在600nm附近可以由80％下降到20％；用自己设计的光电响应测试系统，测得电致变色器件退色时间小于2S，在智能窗、纸张型电子书等方面具有使用价值。这种互补溶液体系是将现有的纯有机溶液互补体系扩展到无机体系中，并且得到了一种新的廉价的电子D-A（Donor-Accept）对，为新型溶液型电致变色器件的实用化提供了新的技术途径。     

High-Performance Aqueous Zn2+/Al3+ Electrochromic Batteries based on Niobium Tungsten Oxides

Electrochromic energy storage devices (EESDs) are incorporating electrochromic and energy storage functions, which can visually display energy storage levels in real-time to promote the next generation of transparent battery development. However, their performances are still limited for practical applications. Herein, a self-powered EESD based on complex niobium tungsten oxide is designed using aqueous Zn²⁺ and hybrid Zn²⁺/Mⁿ⁺ (Mⁿ⁺ = Al³⁺, Mg²⁺, and K⁺) electrolytes. The results reveal that the use of Zn²⁺/Al³⁺ hybrid electrolyte achieves superior electrochromic performances including a short self-coloring time, high optical contrast, and excellent cyclic stability. Furthermore, it is also found that the self-coloring process is accompanied by a high discharged capacity of niobium tungsten oxide, with high optical modulation in the Zn²⁺/Al³⁺ hybrid electrolyte. The detailed mechanism on the performances of EESD using various electrolytes is systematically studied. This work provides a simple and effective strategy for an aqueous and self-powered EESD with high optical contrast and good cycle stability.     

Li4Ti5O12: A Visible‐to‐Infrared Broadband Electrochromic Material for Optical and Thermal Management

Broadband electrochromism from visible to infrared wavelengths is attractive for applications like smart windows, thermal camouflage, and temperature control. In this work, the broadband electrochromic properties of Li₄Ti₅O₁₂ (LTO) and its suitability for infrared camouflage and thermoregulation are investigated. Upon Li⁺ intercalation, LTO changes from a wide bandgap semiconductor to a metal, causing LTO nanoparticles on metal to transition from a super‐broadband optical reflector to a solar absorber and thermal emitter. Large tunabilities of 0.74, 0.68, and 0.30 are observed for the solar reflectance, mid‐wave infrared (MWIR) emittance, and long‐wave infrared (LWIR) emittance, respectively, with a tunability of 0.43 observed for a wavelength of 10 µm. The values exceed, or are comparable to notable performances in the literature. A promising cycling stability is also observed. MWIR and LWIR thermography reveal that the emittance of LTO‐based electrodes can be electrochemically tuned to conceal them amidst their environment. Moreover, under different sky conditions, LTO shows promising solar heating and subambient radiative cooling capabilities depending on the degree of lithiation and device design. The demonstrated capabilities of LTO make electrochromic devices based on LTO highly promising for infrared‐camouflage applications in the defense sector, and for thermoregulation in space and terrestrial environments.     

聚苯胺电致变发射率器件的制备及性能研究

本文采用电化学聚合方法制备了基于聚苯胺的电致变发射率器件,对器件的电致变色性能,电致变发射率性能及器件响应时间和循环使用寿命进行了研究.研究结果表明:器件在可见光波段具有良好的电致变色性能,不同电压下器件颜色在黄绿、深绿及蓝黑之间可逆变化;器件呈柔性,在工作状态下可弯折,具有一定的颜色记忆效应.发射率测试表明,不同电压下器件在8～12 μm波段平均发射率的变化幅度为0.23.器件在室温条件下的响应时间为秒级,具有一定的循环使用寿命.     

基于高分子电解质的全固态电致变色光窗

报道了氧亚甲基连接（氧乙烯－２－乙烯基吡啶）嵌段并聚物络合锂离子的高分于电解质与二氧化钨和氧化镍两种电致变色膜构成的电致变色光窗的制备。测量了电解质导电率与温度的关系，３３０～９００ｎｍ范围的透过光谱，并对电流响应、光响应以及器件的温度依赖关系进行了讨论。     

Electrochromic Switch Devices Mixing Small‐ and Large‐Sized Upconverting Nanocrystals

The hasty progress in smart, portable, flexible, and transparent integrated electronics and optoelectronics is currently one of the driving forces in nanoscience and nanotechnology. A promising approach is the combination of transparent conducting electrode materials (e.g., silver nanowires, AgNWs) and upconverting nanoparticles (UCNPs). Here, electrochromic devices based on transparent nanocomposite films of poly(methyl methacrylate) and AgNWs covered by UCNPs of different sizes and compositions are developed. By combining the electrical control of the heat dissipation in AgNW networks with size‐dependent thermal properties of UCNPs, tunable electrochromic transparent devices covering a broad range of the chromatic diagrams are fabricated. As illustrative examples, devices mixing large‐sized (>70 nm) β‐NaYF₄:Yb,Ln and small‐sized (<15 nm) NaGdF₄:Yb,Ln@NaYF₄ core@shell UCNPs (Ln = Tm, Er, Ce/Ho) are presented, permitting to monitor the temperature‐dependent emission of the particles by the intensity ratio of the Er^{3+ 2}H_11/2 and ⁴S_3/2 → ⁴I_15/2 emission lines, while externally controlling the current flow in the AgNW network. Moreover, by defining a new thermometric parameter involving the intensity ratio of transitions of large‐ and small‐sized UCNPs, a relative thermal sensitivity of 5.88% K^?1 (at 339 K) is obtained, a sixfold improvement over the values reported so far.     

A Ca-Ion Electrochromic Battery via a Water-in-Salt Electrolyte

Multivalent-ion batteries with electrochromic functionality are an emerging green technology for development of low-carbon society. Compared to Mg²⁺, Zn²⁺ and Al³⁺, Ca²⁺ has a low polarization strength similar to that of Li⁺, therefore Ca²⁺ for electrochromism and battery can avoid kinetic issues caused by other multivalent-ions with high polarization strength. Here, by exploiting Ca-ion carriers for electrochromism and a water-in-salt (WIS) Ca(OTF)₂ electrolyte for the first time, a new and safe aqueous Ca-ion electrochromic battery (CIEB) has been demonstrated. The WIS Ca(OTF)₂ electrolyte demonstrates enhanced anion-cation interactions and decreased water activity. Vanadium oxide (VO_x) and indium hexacyanoferrate (InHCF) films are respectively developed as anode and cathode because of their stable and high-rate Ca²⁺ insertion/extraction, as well as matched electrochromism. The CIEB demonstrates a stable and high-rate capability, a high energy density of 51.4 mWh m⁻² at a power density of 1737.3 mW m⁻², and a greenish yellow-to-black electrochromism. The presented results are beneficial for understanding redox kinetics in WIS electrolytes, and inspire researches on batteries and electrochromism with multivalent-ions.