Viologen-based flexible electrochromic devices

Electrochromic technology has gained significant attention in various fields such as displays,smart windows,biomedical monitoring,military camouflage,human-machine interaction,and electronic skin due to its ability to provide reversible and fast color changes under applied voltage.With the rapid development and increasing demand for flexible electronics,flexible electrochromic devices(FECDs)that offer smarter and more controllable light modulation hold great promise for practical applications.The electrochromic material(ECM)undergoing color changes during the electrochemical reactions is one of the key components in electrochromic devices.Among the ECMs,viologens,a family of organic small molecules with 1,1'-disubstituted-4,4'-dipyridinium salts,have garnered extensive research interest,due to their well-reversible redox reactions,excellent electron acceptance ability,and the ability to produce multiple colors.Notably,viologen-based FECDs demonstrate color changes in the liquid or semisolid electrolyte layer,eliminating the need for two solid electrodes and thus simplifying the device structure.Consequently,viologens offer significant potential for the development of FECDs with high optical contrast,fast response speed,and excellent stability.This review aims to provide a comprehensive overview of the progress and perspectives of viologen-based FECDs.It begins by summarizing the typical structure and recent exciting developments in viologen-based FECDs,along with their advantages and disadvantages.Furthermore,the review discusses recent advancements in FECDs with additional functionalities such as sensing,photochromism,and energy storage.Finally,the remaining challenges and potential research directions for the future of viologen-based FECDs are addressed.

Exploring innovative synthetic solutions for advanced polymer-based electrochromic energy storage devices:Phenoxazine as a promising chromophore

The current investigation offers an innovative synthetic solution regarding electrochromic(EC)and energy storage applications by exploring phenoxazine(POZ)moiety.Subsequently,three POZ-based polymers(polyimide,polyazomethine,and polyamide)were synthesized to ascertain the superior performer.The polyamide exhibited remarkable attributes,including high redox stability during 500 repetitive CVs,optical contrast of 61.98%,rapid response times of 1.02 and 1.38 s for coloring and bleaching,EC efficiency of 280 cm^(2)C^(-1).and decays of the optical density and EC efficiency of only 12.18%and 6.23%after 1000 cycles.Then,the energy storage performance of polyamide PA was tested,for which the following parameters were obtained:74.7 F g^(-1)(CV,scan rate of 10 mV s^(-1))and 118 F g^(-1)(GCD,charging current of 0.1 A g^(-1)).Then,the polyamide was tested in EES devices,which yielded the following EC parameters:an optical contrast of 62.15%,response times of 9.24 and 5.01 s for coloring and bleaching,EC efficiency of 178 cm^(2)C^(-1),and moderate decays of 20.25%and 23.24%for the optical density and EC efficiency after 500 cycles.The energy storage performance included a capacitance of 106 F g^(-1)(CV,scan rate of 0.1 mV s^(-1))and 9.23 F g^(-1)(GCD,charging current of 0.1 A g^(-1)),capacitance decay of 11.9%after500 cycles,and 1.7 V retention after 2 h.Also,two EES devices connected in series powered a 3 V LED for almost 30 s.

Self-powered electrochromic devices with tunable infrared intensity

Triboelectric nanogenerator(TENG) is an efficient way to convert ambient mechanical energy into electricity to power up portable electronics.In this work,a flexible infrared electrochromical device(IR-ECD)with stable performances was assembled with a TENG for building self-powered infrared detector with tunable intensity.As driven by TENG,the electrochromic device could be operated in the mid-IR region due to the reversible electrochromic reactions.An average infrared reflectance contrast of 46% was achieved in 8–14 lm regions and as well a clear thermal image change can be observed.This work indicates that the TENG-driven infrared electrochromical device has potential for use in self-powered camouflage and thermal control.

Bifunctional flexible electrochromic energy storage devices based on silver nanowire flexible transparent electrodes

Flexible electrochromic energy storage devices(FECESDs)for powering flexible electronics have attracted considerable attention.Silver nanowires(AgNWs)are one kind of the most promising flexible transparent electrodes(FTEs)materials for the emerging flexible devices.Currently,fabricating FECESD based on AgNWs FTEs is still hindered by their intrinsic poor electrochemical stability.To address this issue,a hybrid AgNWs/Co(OH)_(2)/PEDOT:PSS electrode is proposed.The PEDOT:PSS could not only improve the resistance against electrochemical corrosion of AgNWs,but also work as functional layer to realize the color-changing and energy storage properties.Moreover,the Co(OH)_(2)interlayer further improved the color-changing and energy storage performance.Based on the improvement,we assembled the symmetrical FECESDs.Under the same condition,the areal capacitance(0.8 mF cm^(−2))and coloration efficiency(269.80 cm^(2)C−1)of AgNWs/Co(OH)_(2)/PEDOT:PSS FECESDs were obviously higher than AgNWs/PEDOT:PSS FECESDs.Furthermore,the obtained FECESDs exhibited excellent stability against the mechanical deformation.The areal capacitance remained stable during 1000 times cyclic bending with a 25 mm curvature radius.These results demonstrated the broad application potential of the AgNWs/Co(OH)_(2)/PEDOT:PSS FECESD for the emerging portable and multifunctional electronics.

An overview of recent progress in the development of flexible electrochromic devices

Electrochromic materials are capable of reversibly switching their colors or optical properties through redox reactions under applied voltages,which have shown great potential applications including smart windows,nonemissive displays,optical filters,among others.Although the current rigid electrochromic devices have shown emerging interest and developed rapidly,many applications(e.g.,wearable/deformable optoelectronics)are blocked due to their inflexible features.Herein,the adaption of rigid electrochromic devices to flexible ones is of particular interest for the new era of smart optoelectronics.In this review,the current state-of-the-art achievements of flexible electrochromic devices(FECDs)are highlighted,along with their design strategies and the choice of electrochromic materials.The recent research progress of FECDs is reviewed in detail,and the challenges and corresponding solutions for real-world applications of FECDs are discussed.Furthermore,we summarize the basic fabrication strategies of FECDs and their potential applications.In addition,the development trend,the perspectives,and the outlook of FECDs are discussed at the end of this Review,which may provide recommendations and potential directions to advance the practical applications of FECDs.

Metal-Halide Perovskite Submicrometer-Thick Films for Ultra-Stable Self-Powered Direct X-Ray Detectors

Metal-halide perovskites are revolutionizing the world of X-ray detectors,due to the development of sensitive,fast,and cost-effective devices.Self-powered operation,ensuring portability and low power consumption,has also been recently demonstrated in both bulk materials and thin films.However,the signal stability and repeatability under continuous X-ray exposure has only been tested up to a few hours,often reporting degradation of the detection performance.Here it is shown that self-powered direct X-ray detectors,fabricated starting from a FAPbBr_(3)submicrometer-thick film deposition onto a mesoporous TiO_(2)scaffold,can withstand a 26-day uninterrupted X-ray exposure with negligible signal loss,demonstrating ultra-high operational stability and excellent repeatability.No structural modification is observed after irradiation with a total ionizing dose of almost 200 Gy,revealing an unexpectedly high radiation hardness for a metal-halide perovskite thin film.In addition,trap-assisted photoconductive gain enabled the device to achieve a record bulk sensitivity of 7.28 C Gy^(−1)cm^(−3)at 0 V,an unprecedented value in the field of thin-film-based photoconductors and photodiodes for“hard”X-rays.Finally,prototypal validation under the X-ray beam produced by a medical linear accelerator for cancer treatment is also introduced.

PREPARATION OF STAR NETWORK PEG-BASED GEL POLYMER ELECTROLYTES FOR ELECTROCHROMIC DEVICES

An amorphous,colorless,and highly transparent star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized from the poly(ethylene glycol)(PEG),pentaerythritol,and dichloromethane by Williamson reaction.FTIR and ~1H-NMR measurement demonstrated that the polymer repeating units were C[CH_2-OCH_2O-(CH_2CH_2O)_m-CH_2O-(CH_2CH_2O)_n-CH_2O]_4.The polymer host held well mechanical properties for pentaerythritol cross-linking.The gel polymer electrolytes based on Lithium pe...

Oxidative Molecular Layer Deposition Tailoring Eco-Mimetic Nanoarchitecture to Manipulate Electromagnetic Attenuation and Self-Powered Energy Conversion

Advanced electromagnetic devices,as the pillars of the intelligent age,are setting off a grand transformation,redefining the structure of society to present pluralism and diversity.However,the bombardment of electromagnetic radiation on society is also increasingly serious along with the growing popularity of"Big Data".Herein,drawing wisdom and inspiration from nature,an eco-mimetic nanoarchitecture is constructed for the first time,highly integrating the advantages of multiple components and structures to exhibit excellent electromagnetic response.Its electromagnetic properties and internal energy conversion can be flexibly regulated by tailoring microstructure with oxidative molecular layer deposition(oMLD),providing a new cognition to frequency-selective microwave absorption.The optimal reflection loss reaches≈−58 dB,and the absorption frequency can be shifted from high frequency to low frequency by increasing the number of oMLD cycles.Meanwhile,a novel electromagnetic absorption surface is designed to enable ultra-wideband absorption,covering almost the entire K and Ka bands.More importantly,an ingenious self-powered device is constructed using the eco-mimetic nanoarchitecture,which can convert electromagnetic radiation into electric energy for recycling.This work offers a new insight into electromagnetic protection and waste energy recycling,presenting a broad application prospect in radar stealth,information communication,aerospace engineering,etc.

Self-powered and self-sensing devices based on piezoelectric energy harvesting

Wearable devices,interactive human-machine interface equipment,wireless sensors,and small-scale cleaning devices play crucial roles in biomedical implantation,disease treatment,health monitoring,environmental purification,etc.These devices require a sustainable energy source to work effectively.With the consideration of the global energy crisis and environmental pollution,researchers are exploring new,stable,and environmentally friendly methods to power these low-powered devices.Mechanical energy is one of the most abundant natural energy sources.Converting mechanical energy from the ambient environment or host structures into electrical energy via the direct piezoelectric effect is an efficient energy harvesting technique.This paper reviews the application of advanced piezoelectric materials,and small-scale self-powered and self-sensing piezoelectric devices at the cubic centimeter scale in energy harvesting and health monitoring of human,animal,machinery,roads,bridges,as well as the pollutant degradation of the environment.Some of these devices have the capability to not only harvest mechanical energy but also enable real-time monitoring and analysis of the electrical signals generated by the direct piezoelectric effect,facilitating prompt decision-making and appropriate responses.In addition,potential challenges and future prospects of small-scale self-powered and self-sensing piezoelectric devices are discussed.

Complementary multicolor electrochromic devices with excellent stability based on porous tin oxide nanosheet scaffold

Electrochromic devices(ECDs)have been extensively investigated as promising candidates in broad cutting-edge applications,such as smart windows,electronic labels,adaptive camouflage,etc.However,they have suffered from either inadequate color variations or poor cycling stability for a long time.Herein,we developed a general strategy to boost the cyclic stability and enrich the color variations of ECDs by scrupulous design of the composition and nanostructure of electrodes,in which porous tin oxide(SnO_(2))nanosheets serve as the scaffold and typical metal oxides or conducting polymers as the active electrochromic materials.Various electrochromic composite materials,including polyaniline(PANI)@SnO_(2),V2O5@SnO_(2),and WO_(3)@SnO_(2) heterostructured nanoarrays were prepared by the facile wet-chemical method.These composite electrodes exhibit remarkable electrochromic performances,e.g.,superior cycling stability(more than 2000 cycles),rich color variations(more than 5 colors for PANI@SnO_(2)),and enlarged optical modulation.These excellent performances account for the heterogenous porous nanoarrays,which not only facilitate the intercalation/extraction of ions but also relieve the stress generated during the electrochemical process.In addition,diverse prototypes of complementary multicolor ECD with excellent cycling stability(over thousands of cycles)and rich color variations(8 colors)were realized for the first time.We believe that our work put forward a general strategy for developing high-quality multicolor complementary electrochromic devices.

In-situ characterization of electrochromism based on ITO/PEDOT:PSS towards preparation of high performance device

Poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate）（PEDOT：PSS） is usually sandwiched between indium tin oxide（ITO） and a functional polymer in order to improve the performance of the device. However, because of the strong acidic nature of PEDOT：PSS, the instability of the ITO/PEDOT：PSS interface is also observed. The mechanism of degradation of the device remains is unclear and needs to be further studied. In this article, we investigate the in-situ electrochromism of PEDOT：PSS to disclose the cause of the degradation. X-ray photoelectron spectroscopy（XPS） was used to characterize the PEDOT：PSS films, as well as the PEDOT：PSS plus polyethylene glycol（PEG） films with and without indium ions. The electrochromic devices（ECD） based on PEDOT：PSS and PEG with and without indium ions are carried out by in-situ micro-Raman and laser reflective measurement（LRM）. For comparison, ECD based on PEDOT：PSS and PEG films with LiCl, KCl, NaCl or InCl_3 are also investigated by LRM. The results show that PEDOT：PSS is further reduced when negatively biased, and oxidized when positively biased. This could identify that PEDOT：PSS with indium ions from PEDOT：PSS etching ITO will lose dopants when negatively biased. The LRM shows that the device with indium ions has a stronger effect on the reduction property of PEDOT：PSS-PEG film than the device without indium ions. The contrast of the former device is 44%, that of the latter device is about 3%. The LRM also shows that the contrasts of the device based on PEDOT：PSS＋PEG with LiCl, KCl, NaCl, InCl_3 are 30%, 27%, 15%, and 18%, respectively.

A high-performance electrochromic device assembled with WO_(3)/Ag and TiO_(2)/NiO composite electrodes towards smart window

The choice of cathode and anode materials for electrochromic devices plays a key role in the performance of electrochromic smart windows.In this research,WO_(3)/Ag and TiO_(2)/NiO composite thin films were separately prepared by the hydrothermal method combined with electrodeposition.The electrochromic properties of the single WO_(3) thin film were optimized,and TiO_(2)/NiO composite films showed better electrochromic performance than that of the single NiO film.WO_(3)/Ag and TiO_(2)/NiO composite films with excellent electrochromic properties were respectively chosen as the cathode and the anode to construct a WO_(3)/Ag‒TiO_(2)/NiO electrochromic device.The response time(tc=4.08 s,tb=1.08 s),optical modulation range(35.91%),and coloration efficiency(30.37 cm^(2)·C^(-1))of this electrochromic device are better than those of WO_(3)-NiO and WO_(3)/Ag-NiO electrochromic devices.This work provides a novel research idea for the performance enhancement of electrochromic smart windows.

The Synthesis of 1-Ethyl-1'-(4-vinylbenzyl)-4,4'-bipyridinium Chloride and Iodide and its Electrochromic Property

Abstract： A new compound 1-ethyl-1＇-（4-vinylbenzyl）-4, 4＇-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen＇s electrochromic （EC） film could be deposited on conductive ITO glass working electrode With polyelectrolyte as ionic conduction layer, solid EC devices based on this compound have been assembled and their thickness was about 2.35 mm. When different voltages were added, they showed blue or violet red color. After optimization, its response time was less than 50 ms, the number of redox circulation was over 107 and the color of coloration states could be kept for 3 days. This kind of EC device can meet the demand of electronic ink.

Flexible energy storage devices for wearable bioelectronics

With the growing market of wearable devices for smart sensing and personalized healthcare applications,energy storage devices that ensure stable power supply and can be constructed in flexible platforms have attracted tremendous research interests.A variety of active materials and fabrication strategies of flexible energy storage devices have been intensively studied in recent years,especially for integrated self-powered systems and biosensing.A series of materials and applications for flexible energy storage devices have been studied in recent years.In this review,the commonly adopted fabrication methods of flexible energy storage devices are introduced.Besides,recent advances in integrating these energy devices into flexible self-powered systems are presented.Furthermore,the applications of flexible energy storage devices for biosensing are summarized.Finally,the prospects and challenges of the self-powered sensing system for wearable electronics are discussed.

Deep eutectic solvent-based gel electrolytes for flexible electrochromic devices with excellent high/low temperature durability

With the increasing interest in the application of electrochromism to flexible and wearable electronics in recent years,flexible electrochromic devices(ECDs)that can function at extreme temperatures are required.However,the functionalities of flexible ECDs are severely hampered by the inadequate choice of electrolytes,which might ultimately result in performance fading during low-and high-temperature operations.Here,we develop a deep eutectic solvent(DES)-based gel electrolyte that can maintain its optical,electrical,and mechanical properties over a wide range of temperatures(-40 to 150℃),exhibiting an extremely high visible-range transmittance over 90%,ion conductivity of 0.63 mS cm^(-1),and fracture strain exceeding 2000%.Owing to the excellent processability of the DES-based electrolytes,provided by dynamic interactions such as the lithium and hydrogen bonding between the DES and polymer matrix,a directly written patterning in ECDs is realized for the first time.The fabricated ECDs exhibit an excellent electrochromic behavior superior to the behavior of the ECDs fabricated with traditional gel electrolytes.The introduction of such DES-based electrolytes is expected to pave the way for a widespread application of electrochromic products.

Tungsten oxide nanowires and polyaniline hybrid film-based electrochromic device with multicolor display and enhanced capacitance

Electrochromic devices(ECDs)have exhibited promising applications in the fields of energy-saving intelligent buildings and next-generation displays because of their simple structure,low power consumption,and multicolor displays.W_(18)O_(49)/polyaniline(PANI)hybrid films are prepared and assembled to ECDs.Compared with pure PANI and W_(18)O_(49) films,the hybrid film exhibits superior electrochemical and electrochromic performance,including high optical modulation(70.2%),large areal capacity(79.6 mF/cm^(2)),and good capacitance retention.The excellent electrochemical and electrochromic performance is ascribed to the formation of the donor(PANI)-acceptor(W_(18)O_(49))pair,the porous structure in the nanowires,and the large surface area,which enhance electron delocalization of the W_(18)O_(49)/PANI,improve the ion diffusion rate,and increase the charge storage sites.Furthermore,benefitting from the outstanding optical,electrical,and multifunctional properties,the W_(18)O_(49)/PANI hybrid film-based ECD platform is expected to play an important role in electrochromism and energy storage.

聚苯胺红外电致变色器件研究进展

电致变色是材料反射、吸收等光学性质在外加电场驱动下发生稳定、可逆变化的现象,在不同波段可表现为颜色、红外发射率等变化。红外电致变色器件(IR-ECDs)能够动态调节物体的红外光学特性,在自适应伪装、热管理等应用中受到广泛关注。作为最有代表性的有机电致变色材料,聚苯胺(PANI)制备方法简单,电化学性能优异,在多波段电致变色领域有着巨大的潜在应用价值。本文从电致变色器件结构出发,介绍了从可见电致变色到红外电致变色的原理和器件结构的演变,对近年来增强聚苯胺红外电致变色器件性能的策略和最新进展进行了归纳和分析,讨论了其多功能化应用的拓展方向,最后对所面临的挑战与未来的发展方向进行了总结与展望,为今后发展优异性能的IR-ECDs提供了参考,希望能够对本领域研究者有所启发,促进电致变色领域的发展。

电致变色型智能可视化湿度系统

近年来,湿度传感器在食品安全、土壤监测等领域的应用引起了广泛关注。传统湿度传感器具有稳定性好、灵敏度高等优点,但大部分湿度传感系统通常采用有线连接和外接庞大设备来将湿度信号转换为可识别的波形,无法对湿度信息的变化进行实时的可视化监测。将湿度信息直接转换为肉眼可观测的颜色信号为上述问题提供了一种理想解决方案。本研究将湿度传感器与电致变色器件集成一体来制备智能可视化湿度指示系统,通过将湿度信号转换为电压信号来驱动电致变色器件(Electrochromic devices,ECDs),从而实现系统稳定可逆的颜色变化。采用三氧化钨(WO3)作为负极、锌箔(Zn)作为正极制备的ECDs会根据湿度传感器的输出电压的变化来转变不同的工作状态,从而产生肉眼可观测的颜色信号。采用紫外-可见分光光度计与电化学工作站对ECDs的电化学性能以及电致变色性能进行研究和表征。随后,通过示波器和湿度发生平台对调理电路性能进行分析。结果表明:智能电致变色型湿度指示器具有良好的稳定性和快速的响应性能,其中,着色时间与褪色时间仅为7.5和4.5 s,并且在300个循环后,光学调制幅度(ΔT)与初始值相比基本保持不变(保持率可达95%以上)。因此,这种设计新颖、结构简单的可视化湿度系统在人工智能、智能农业等领域具有广阔的应用前景。

Flexible bidirectional self-powered photodetector with significantly reduced volume and accelerated response speed based on hydrogel and lift-off GaN-based nanowires

Due to the wide range of potential applications for next-generation multi-functional devices,the flexible selfpowered photodetector(PD)with polarity-switchable behavior is essential but very challenging to be realized.Herein,a wearable bidirectional self-powered PD based on detached(Al,Ga)N and(In,Ga)N nanowires has been proposed and demonstrated successfully.Arising from the photovoltage-competing dynamics across(Al,Ga)N and(In,Ga)N nanowire photoelectrodes,such PD can generate the positive(33.3 mA W−1)and negative(-0.019 mA W−1)photo-responsivity under ultraviolet(UV)and visible illumination,respectively,leading to the bidirectional photocurrent behavior.Thanks to the introduction of quasi solid-state hydrogel,the PD can work without the liquid-electrolyte,thus remarkably reducing the volume from about 482 cm3 to only 0.18 cm3.Furthermore,the use of hydrogel is found to enhance response speed in the UV range by reducing the response time for more than 95%,which is mainly attributed to the increased open circuit potential and reduced ion transport distance.As the GaN connecting segment is pretty thin,the piezoelectric charges generated by stress are proposed to have only a limited effect on the photocurrent density.Therefore,both the stable on-off switching characteristics and photocurrent densities can still be achieved after being bent 400 times.With an excellent flexibility,this work creates opportunities for technological applications of bidirectional photocurrent PDs in flexible optoelectronic devices,e.g.,wearable intelligent sensors.

Polymer ionogels and their application in flexible ionic devices

Polymer ionogel(PIG)is a new type of flexible,stretchable,and ion-conductive material,which generally consists of two components(polymer matrix materials and ionic liquids/deep eutectic solvents).More and more attention has been received owing to its excellent properties,such as nonvolatility,good ionic conductivity,excellent thermal stability,high electrochemical stability,and transparency.In this review,the latest research and developments of PIGs are comprehensively reviewed according to different polymer matrices.Particularly,the development of novel structural designs,preparation methods,basic properties,and their advantages are respectively summarized.Furthermore,the typical applications of PIGs in flexible ionic skin,flexible electrochromic devices,flexible actuators,and flexible power supplies are reviewed.The novel working mechanism,device structure design strategies,and the unique functions of the PIG-based flexible ionic devices are briefly introduced.Finally,the perspectives on the current challenges and future directions of PIGs and their application are discussed.