Electrochromic and auto-bleaching processes at the WO2 anodic film in 0. 5 mol/L H2SO4 solution were investigated by cyclic voltammetry, a. c. impedance technique and photocurrent spectrometry. The colouration mechani...Electrochromic and auto-bleaching processes at the WO2 anodic film in 0. 5 mol/L H2SO4 solution were investigated by cyclic voltammetry, a. c. impedance technique and photocurrent spectrometry. The colouration mechanism consists of hydrogen adsorption on the WO2 surface and the transport of H atoms in the WO, lattice. The bleaching process involves at least two steps: transport of interstitial H atoms and hydrogen desorption on the W surface, resulting in interstitial H+ ions; then extration of the H+ ions driven by the external electric field. The auto-bleaching arises from the hydroxylation due to both partial interstitial H atoms and a little of water contained in the film.展开更多
Building fresh air supply needs to meet certain regulations and fit people’s ever-growing indoor air quality de-mand.However,fresh air handling requires huge energy consumption that goes against the goal of net-zero ...Building fresh air supply needs to meet certain regulations and fit people’s ever-growing indoor air quality de-mand.However,fresh air handling requires huge energy consumption that goes against the goal of net-zero energy buildings.Thus,in this work,an adaptive fresh air pre-handling system is designed to reduce the cool-ing and heating loads of HVAC system.The sky-facing surface of the system uses electrochromic mechanism to manipulate the optical properties and thus make full use of solar energy(solar heating)and deep space cold source(radiative cooling)by switching between heating and cooling modes.In the cooling mode,the sky-facing surface shows a transmittance of down to zero,while the reflectance is high at 0.89 on average.In the heating mode,the electrochromic glass is highly transparent,allowing the sunlight to reach the solar heat absorber.To obtain the energy-saving potential under different climates,six cities were selected from various climate regions in China.Results show that the adaptive fresh air pre-handling system can be effective in up to 55.4%time of a year.The maximum energy-saving ratios for medium office,warehouse,and single-family house can reach up to 11.52%,26.62%,and 18.29%,respectively.In addition,the system shows multi-climate adaptability and broad application scenarios,making it a potential solution to building energy saving.展开更多
Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate sma...Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate smart sensors with high robustness,reliability,and visible readout.Herein,high-performance electrochromic(EC),electro-fluorochromic(EFC),and double-network ionogels with excellent transmissivity,high mechanical robustness,and ultrastable reversibility are prepared by combination of thienoviologen-containing ionic liquids with poly(ethyl acrylate)elastomer.The ionogels exhibit good mechanical properties(1000%stretchability and 3.2 kJ m^(−2) fracture energy).The ionogel-based EC devices have a significantly simplified device fabrication process as well as superior cycling stability in which 88%of the contract ratio is maintained at 88%at 500 cycles,even after being stored for 2 years under ambient atmosphere(relative humidity:30%∼40%,25°C).The conductivity of ionogels showed a fast and reproducible response to strain,and the conductivity decreased with increased strain.By virtue of the EC and EFC properties of the thienoviologen component,the EC and EFC efficiency decreased with the increased strain loaded on the ionogels,and almost no EC or EFC phenomena were observed when the strain was above 300%.This feasible strategy provides an opportunity for the development of visible strain sensors to monitor the body’s movements through color and fluorescence emission.展开更多
Prussian blue(PB)is an anodic coloring candidate in the wide area of electrochromic(EC)applications.However,the co-influence of weak adhesion and low electrical conductivity leads to the poor stability and slow switch...Prussian blue(PB)is an anodic coloring candidate in the wide area of electrochromic(EC)applications.However,the co-influence of weak adhesion and low electrical conductivity leads to the poor stability and slow switching speed.To tackle this bottleneck,a novel TiO_(2)/Au/PB nanorod array is designed through hydrothermal and electrodeposition approaches on fluorine-doped tin oxide(FTO)glass.Such a designed ternary array structure could not only increase reactive site and conductivity,but also improve ion storage capacity and promote charge transfer,attributed to the synergistic effect of TiO_(2)/Au/PB core–shell heterostructure and the localized surface plasmon resonance(LSPR)effect of Au nanoparticles.Besides,density functional theory(DFT)calculation confirms the strong interaction between rutile TiO_(2)and FTO substrate,which contributes to the improvement of EC cycle stability.Benefiting from these effects,the TiO_(2)/Au/PB film shows a fast coloration/bleaching response of 1.08/2.01 s(2.17/4.48 s,PB film)and ultra-stable EC performance of 86.8%after 20,000 cycles(50%after 600 cycles,PB film).Furthermore,the high-intensity light source can be shot clearly by the designed and assembled EC iris device(ECID)with TiO_(2)/Au/PB film as an EC layer,while the photograph without an ECID is blurry,confirming the feasibility of the material in portable digital products.展开更多
Functional materials may change color by heat and electricity separately or simultaneously in smart windows.These materials have not only demonstrated remarkable potential in the modulation of solar radiation but are ...Functional materials may change color by heat and electricity separately or simultaneously in smart windows.These materials have not only demonstrated remarkable potential in the modulation of solar radiation but are also leading to the development of indoor environments that are more comfortable and conducive to improving individuals'quality of life.Unfortunately,dual-responsive materials have not received ample research attention due to economic and technological challenges.As a consequence,the broader utilization of smart windows faces hindrances.To address this new generational multistimulus responsive chromic materials,our group has adopted a developmental strategy to create a poly(NIPAM)n-HV as a switchable material by anchoring active viologen(HV)onto a phase-changing poly(NIPAM)n-based smart material for better utility and activity.These constructed smart windows facilitate individualistic reversible switching,from a highly transparent state to an opaque state(thermochromic)and a red state(electrochromic),as well as facilitate a simultaneous dual-stimuli response reversible switching from a clear transparent state to a fully opaque(thermochromic)and orange(electrochromic)states.Absolute privacy can be attained in smart windows designed for exclusive settings by achieving zero transmittance.Each unique chromic mode operates independently and modulates visible and near-infrared(NIR)light in a distinct manner.Hence,these smart windows with thermal and electric dual-stimuli responsiveness demonstrate remarkable heat regulation capabilities,rendering them highly attractive for applications in building facades,energy harvesting,privacy protection,and color display.展开更多
This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine con...This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.展开更多
A cyclometalated diruthenium complex 2 bridged by 1,2,4,5-tetra(pyrid-2-yl)benzene with six carboxylic acid groups at two ends was synthesized.Monolayer and multilayer films FTO/TiO2/(2)n(Zr)(n=1,2)and FTO/SnO2:Sb/(2)...A cyclometalated diruthenium complex 2 bridged by 1,2,4,5-tetra(pyrid-2-yl)benzene with six carboxylic acid groups at two ends was synthesized.Monolayer and multilayer films FTO/TiO2/(2)n(Zr)(n=1,2)and FTO/SnO2:Sb/(2)n(Zr)(n=1-4)have been prepared via interfacial layer-by-layer coordination assembly of 2 with zirconium(IV)ions.All films show two consecutive redox couples in the potential range between 0 and+1.0 V vs.Ag/AgCl.These films exhibit reversible near-infrared electrochromism upon switching of redox potential.The response time of the films on SnO2:Sb is around a few seconds,while that on TiO2 is around a few tens of seconds.The film deposition cycles were found to have a great impact on the electrochromic performance.Among six films examined,the two-layered film on SnO2:Sb displays the best balanced performance with a contrast ratio of 56%at 1,150 nm and good cyclic stability(9%loss of contrast ratio after 1,000 continuous double-potential-switching cycles),which is superior to that of the previously reported electropolymerized films of a related diruthenium complex with the same bridging ligand.In addition,the X-ray photoelectron spectroscopy,scanning electron microscopy,and electron transfer mechanism of these films have been investigated.展开更多
Doping plays an essential role in the properties of conducting polymers.Film thickness not only has a direct influence on their photoelectric properties,but also affects the doping ability,which may lead to the declin...Doping plays an essential role in the properties of conducting polymers.Film thickness not only has a direct influence on their photoelectric properties,but also affects the doping ability,which may lead to the decline of capacitance and electrochromic properties caused by incomplete doping.Therefore,it is essential to study the quantitative relationship between doping level and film thickness in application.Herein,empirical formula between doping level and thickness was obtained by studying the spectroelectrochemistry behaviors of two different electrochromic materials,poly(N,N'-bis(3,5-(2-thienyl)-phenyl)-1,6,7,12-tetrachloroperylene-3,4,9,10-perylenetetracarboxylic diimide)(poly(Th-Cl-PBI))and poly(3,4-ethylenedioxythiophene)(PEDOT).The doping level is verified to be correlated to the reciprocal of the 3^(rd)power of film thickness.Experimental results fit these formulas very well,giving correlation coefficient R^(2)higher than 0.99.The optical contrast prediction of these two electrochromic materials is also used to verify this relationship formula.For the first time,we quantitatively connect these two important parameters of conducting polymers,doping level and thickness.展开更多
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,polyazo...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.展开更多
In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development o...In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development of electrochromic-energy storage systems designed to visualize electrochemical charging and discharging processes.The conventional electrochromic-energy storage devices primarily integrated supercapacitors,known for their high power density,to enable rapid color contrast.However,the low energy density of supercapacitors restricts overall energy storage capacity,acting as a significant barrier to expanding the application range of such systems.In this review,we introduce electrochromic zinc(Zn)-ion battery systems,which effectively overcome the limitation of low energy density,and provide illustrative examples of their applicability across diverse fields.Although many recent research works are present for electrochromic Zn-ion batteries,little review has so far taken place.Our objective is to discuss on the current progress and future directions for electrochromic Zn-ion batteries,which are applicable for wearable electronics applications and energy storage systems.This review provides an initial milestone for future researchers in electrochromic energy storage and zinc-ion batteries,which will lead to a stream of future works related to them.展开更多
Exploring materials with high electrochemical activity is of keen interest for electrochemistry-controlled optical and energy storage devices.However,it remains a great challenge for transition metal oxides to meet th...Exploring materials with high electrochemical activity is of keen interest for electrochemistry-controlled optical and energy storage devices.However,it remains a great challenge for transition metal oxides to meet this feature due to their low electron conductivity and insufficient reaction sites.Here,we propose a type of transition metal phosphate(NiHPO_(4)·3H_(2)O,NHP)by a facile and scalable electrodeposition method,which can achieve the capability of efficient ion accommodation and injection/extraction for electrochromic energy storage applications.Specifically,the NHP film with an ultra-high transmittance(approach to 100%)achieves a large optical modulation(90.8%at 500 nm),high coloration efficiency(75.4 cm^(2)C^(-1)at 500 nm),and a high specific capacity of 47.8 mAh g^(-1)at 0.4 A g^(-1).Furthermore,the transformation mechanism of NHP upon electrochemical reaction is systematically elucidated using in situ and ex situ techniques.Ultimately,a large-area electrochromic smart window with 100 cm^(2)is constructed based on the NHP electrode,displaying superior electrochromic energy storage performance in regulating natural light and storing electrical charges.Our findings may open up new strategies for developing advanced electrochromic energy storage materials and smart windows.展开更多
Dual-band electrochromic smart windows(DESWs)with independent control of the transmittance of near-infrared and visible light show great potential in the application of smart and energy-saving buildings.The current st...Dual-band electrochromic smart windows(DESWs)with independent control of the transmittance of near-infrared and visible light show great potential in the application of smart and energy-saving buildings.The current strategy for building DESWs is to screen materials for composite or prepare plasmonic nanocrystal films.These rigorous preparation processes seriously limit the further development of DESWs.Herein,we report a facile and effective sol-gel strategy using a foaming agent to achieve porous Ti-doped tungsten oxide film for the high performance of DESWs.The introduction of foaming agent polyvinylpyrrolidone during the film preparation can increase the specific surface area and free carrier concentration of the films and enhance their independent regulation ability of near-infrared electrochromism.As a result,the optimal film shows excellent dual-band electrochromic properties,including high optical modulation(84.9%at 633 nm and 90.3%at 1200 nm),high coloration efficiency(114.9 cm^(2) C^(-1) at 633 nm and 420.3 cm^(2) C^(-1) at 1200 nm),quick switching time,excellent bistability,and good cycle stability(the transmittance modulation losses at 633 and 1200 nm were 11%and 3.5%respectively after 1000 cycles).A demonstrated DESW fabricated by the sol-gel film showed effective management of heat and light of sunlight.This study represents a significant advance in the preparation of dual-band electrochromic films,which will shed new light on advancing electrochromic technology for future energy-saving smart buildings.展开更多
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,none...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.展开更多
Multifunctional electrochromic-induced rechargeable aqueous batteries(MERABs) integrate electrochromism and aqueous ion batteries into one platform, which is able to deliver the conversion and storage of photo-thermal...Multifunctional electrochromic-induced rechargeable aqueous batteries(MERABs) integrate electrochromism and aqueous ion batteries into one platform, which is able to deliver the conversion and storage of photo-thermal-electrochemical sources.Aqueous ion batteries compensate for the drawbacks of slow kinetic reactions and unsatisfied storage capacities of electrochromic devices. On the other hand, electrochromic technology can enable dynamically regulation of solar light and heat radiation. However,MERABs still face several technical issues, including a trade-off between electrochromic and electrochemical performance, low conversion efficiency and poor service life. In this connection, novel device configuration and electrode materials, and an optimized compatibility need to be considered for multidisciplinary applications. In this review,the unique advantages, key challenges and advanced applications are elucidated in a timely and comprehensive manner. Firstly, the prerequisites for effective integration of the working mechanism and device configuration, as well as the choice of electrode materials are examined. Secondly, the latest advances in the applications of MERABs are discussed, including wearable, self-powered, integrated systems and multisystem conversion. Finally, perspectives on the current challenges and future development are outlined, highlighting the giant leap required from laboratory prototypes to large-scale production and eventual commercialization.展开更多
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(...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.展开更多
Inorganic metal oxide electrochromic materials have good application prospects for energy-saving windows in buildings and smart display applications.Therefore,the development of electrochromic films with good cycling ...Inorganic metal oxide electrochromic materials have good application prospects for energy-saving windows in buildings and smart display applications.Therefore,the development of electrochromic films with good cycling stabilities,fast color-change response times,and high coloring efficiencies has attracted considerable attention.In this study,nanoflake Li-doped NiO electrochromic films were prepared using a hydrothermal method,and the films exhibited superior electrochromic performances in the LiOH electrolyte.Li^(+)ions doping increased the ion transmission rates of the NiO films,and effectively promoted the transportation of ions from the electrolyte into NiO films.Meanwhile,the nanoflake microstructure caused the NiO films to have larger specific surface areas,providing more active sites for electrochemical reactions.It was determined that the NiO-Li20%film exhibited an ultra-fast response in the LiOH electrolyte(coloring and bleaching times reached 3 and 1.5 s,respectively).Additionally,the coloration efficiency was 62.1 cm^(2)C^(−1),and good cycling stability was maintained beyond 1500 cycles.Finally,the simulation calculation results showed that Li doping weakened the adsorption strengths of the NiO films to OH^(−),which reduced the generation and decomposition of NiOOH and helped to improve the cycling stabilities of the films.Therefore,the research presented in this article provides a strategy for designing electrochromic materials in the future.展开更多
Vanadates are a class of the most promising electrochromic materials for displays as their multicolor characteristics.However,the slow switching times and vanadate dissolution issues of recently reported vanadates sig...Vanadates are a class of the most promising electrochromic materials for displays as their multicolor characteristics.However,the slow switching times and vanadate dissolution issues of recently reported vanadates significantly hinder their diverse practical applications.Herein,novel strategies are developed to design electrochemically stable vanadates having rapid switching times.We show that the interlayer spacing is greatly broadened by introducing sodium and lanthanum ions into V_(3)O_(8)interlayers,which facilitates the transportation of cations and enhances the electrochemical kinetics.In addition,a hybrid Zn^(2+)/Na^(+)electrolyte is designed to inhibit vanadate dissolution while significantly accelerating electrochemical kinetics.As a result,our electrochromic displays yield the most rapid switching times in comparison with any reported Zn-vanadate electrochromic displays.It is envisioned that stable vanadate-based electrochromic displays having video speed switching are appearing on the near horizon.展开更多
Zinc-anode-based electrochromic devices(ZECDs) are emerging as the next-generation energy-e cient transparent electronics. We report anatase W-doped TiO_(2) nanocrystals(NCs) as a Zn^(2+) active electrochromic materia...Zinc-anode-based electrochromic devices(ZECDs) are emerging as the next-generation energy-e cient transparent electronics. We report anatase W-doped TiO_(2) nanocrystals(NCs) as a Zn^(2+) active electrochromic material. It demonstrates that the W doping in TiO_(2) highly reduces the Zn^(2+) intercalation energy,thus triggering the electrochromism. The prototype ZECDs based on W-doped TiO_(2) NCs deliver a high optical modulation(66% at 550 nm),fast spectral response times(9/2.7 s at 550 nm for coloration/bleaching),and good electrochemical stability(8.2% optical modulation loss after 1000 cycles).展开更多
Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g....Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g.,chlorine evolution reaction,detoxification,and oxygen evolution reaction).Such versatility is attributed to the distinct features of iridium oxides,such as their activity,biocompatibility,conductivity,and durability.The features and properties of iridium oxides are strongly dependent on the fabrication method.In this review,methodologies relating to the synthesis and fabrication of solid-state iridium oxides have been thoroughly collected and discussed.Structuring and crystallization techniques for iridium oxides are also noted.At the end of the review,the effects of utilizing a certain fabrication method on the characteristics of the iridium oxide product are recapitulated,together with the recommended application of the product in various fields.展开更多
In this paper, the poling properties of (PS)O-DCV, a derivative of poly (p-hydroxystyrene ), was reported. The investigations showed that the thermochromism correction, which was neglected in the literatures, shou...In this paper, the poling properties of (PS)O-DCV, a derivative of poly (p-hydroxystyrene ), was reported. The investigations showed that the thermochromism correction, which was neglected in the literatures, should be considered in the measurements of order parameter of poled films with electrochromism technique Here, another linear optical method, IR and polarized IR spectra for characterizing of poled films was suggested first time. The bulk second nonlinear optical coefficient d<sub>33</sub> of poled films could be estimated by measured order parameter semi-qualitatively.展开更多
基金The project Supported by National Natural Science Foundation of China.
文摘Electrochromic and auto-bleaching processes at the WO2 anodic film in 0. 5 mol/L H2SO4 solution were investigated by cyclic voltammetry, a. c. impedance technique and photocurrent spectrometry. The colouration mechanism consists of hydrogen adsorption on the WO2 surface and the transport of H atoms in the WO, lattice. The bleaching process involves at least two steps: transport of interstitial H atoms and hydrogen desorption on the W surface, resulting in interstitial H+ ions; then extration of the H+ ions driven by the external electric field. The auto-bleaching arises from the hydroxylation due to both partial interstitial H atoms and a little of water contained in the film.
基金the support from National Natural Sci-ence Foundation of China(52276178)Natural Science Foundation of Jiangsu Province,China(BK20200373).
文摘Building fresh air supply needs to meet certain regulations and fit people’s ever-growing indoor air quality de-mand.However,fresh air handling requires huge energy consumption that goes against the goal of net-zero energy buildings.Thus,in this work,an adaptive fresh air pre-handling system is designed to reduce the cool-ing and heating loads of HVAC system.The sky-facing surface of the system uses electrochromic mechanism to manipulate the optical properties and thus make full use of solar energy(solar heating)and deep space cold source(radiative cooling)by switching between heating and cooling modes.In the cooling mode,the sky-facing surface shows a transmittance of down to zero,while the reflectance is high at 0.89 on average.In the heating mode,the electrochromic glass is highly transparent,allowing the sunlight to reach the solar heat absorber.To obtain the energy-saving potential under different climates,six cities were selected from various climate regions in China.Results show that the adaptive fresh air pre-handling system can be effective in up to 55.4%time of a year.The maximum energy-saving ratios for medium office,warehouse,and single-family house can reach up to 11.52%,26.62%,and 18.29%,respectively.In addition,the system shows multi-climate adaptability and broad application scenarios,making it a potential solution to building energy saving.
基金research was made possible as a result of generous grants from the National Key Research and Development Program of China(grant no.2021YFB3200700)the Natural Science Foundation of China(grant nos.22175138,21875180,and 52203240)+4 种基金the Independent Innovation Capability Improvement Project of Xi’an Jiaotong University(grant no.PY3A066)the China National Postdoctoral Program for Innovative Talents(grant no.BX2021231)the Fundamental Research Funds for the Central Universities(grant no.sxjh032021099)the China Postdoctoral Science Foundation(grant no.2021M692545)the Natural Science Foundation of Shaanxi Province(grant no.2021JQ-043).
文摘Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate smart sensors with high robustness,reliability,and visible readout.Herein,high-performance electrochromic(EC),electro-fluorochromic(EFC),and double-network ionogels with excellent transmissivity,high mechanical robustness,and ultrastable reversibility are prepared by combination of thienoviologen-containing ionic liquids with poly(ethyl acrylate)elastomer.The ionogels exhibit good mechanical properties(1000%stretchability and 3.2 kJ m^(−2) fracture energy).The ionogel-based EC devices have a significantly simplified device fabrication process as well as superior cycling stability in which 88%of the contract ratio is maintained at 88%at 500 cycles,even after being stored for 2 years under ambient atmosphere(relative humidity:30%∼40%,25°C).The conductivity of ionogels showed a fast and reproducible response to strain,and the conductivity decreased with increased strain.By virtue of the EC and EFC properties of the thienoviologen component,the EC and EFC efficiency decreased with the increased strain loaded on the ionogels,and almost no EC or EFC phenomena were observed when the strain was above 300%.This feasible strategy provides an opportunity for the development of visible strain sensors to monitor the body’s movements through color and fluorescence emission.
基金Funds for the Central Universities(Nos.HIT.OCEF.2021004 and FRFCU5710090220).
文摘Prussian blue(PB)is an anodic coloring candidate in the wide area of electrochromic(EC)applications.However,the co-influence of weak adhesion and low electrical conductivity leads to the poor stability and slow switching speed.To tackle this bottleneck,a novel TiO_(2)/Au/PB nanorod array is designed through hydrothermal and electrodeposition approaches on fluorine-doped tin oxide(FTO)glass.Such a designed ternary array structure could not only increase reactive site and conductivity,but also improve ion storage capacity and promote charge transfer,attributed to the synergistic effect of TiO_(2)/Au/PB core–shell heterostructure and the localized surface plasmon resonance(LSPR)effect of Au nanoparticles.Besides,density functional theory(DFT)calculation confirms the strong interaction between rutile TiO_(2)and FTO substrate,which contributes to the improvement of EC cycle stability.Benefiting from these effects,the TiO_(2)/Au/PB film shows a fast coloration/bleaching response of 1.08/2.01 s(2.17/4.48 s,PB film)and ultra-stable EC performance of 86.8%after 20,000 cycles(50%after 600 cycles,PB film).Furthermore,the high-intensity light source can be shot clearly by the designed and assembled EC iris device(ECID)with TiO_(2)/Au/PB film as an EC layer,while the photograph without an ECID is blurry,confirming the feasibility of the material in portable digital products.
基金supported by the National Research Foundation (NRF)grants funded by the Ministry of Education (2020R1A6A1A03038817),Republic of Korea。
文摘Functional materials may change color by heat and electricity separately or simultaneously in smart windows.These materials have not only demonstrated remarkable potential in the modulation of solar radiation but are also leading to the development of indoor environments that are more comfortable and conducive to improving individuals'quality of life.Unfortunately,dual-responsive materials have not received ample research attention due to economic and technological challenges.As a consequence,the broader utilization of smart windows faces hindrances.To address this new generational multistimulus responsive chromic materials,our group has adopted a developmental strategy to create a poly(NIPAM)n-HV as a switchable material by anchoring active viologen(HV)onto a phase-changing poly(NIPAM)n-based smart material for better utility and activity.These constructed smart windows facilitate individualistic reversible switching,from a highly transparent state to an opaque state(thermochromic)and a red state(electrochromic),as well as facilitate a simultaneous dual-stimuli response reversible switching from a clear transparent state to a fully opaque(thermochromic)and orange(electrochromic)states.Absolute privacy can be attained in smart windows designed for exclusive settings by achieving zero transmittance.Each unique chromic mode operates independently and modulates visible and near-infrared(NIR)light in a distinct manner.Hence,these smart windows with thermal and electric dual-stimuli responsiveness demonstrate remarkable heat regulation capabilities,rendering them highly attractive for applications in building facades,energy harvesting,privacy protection,and color display.
基金the National Natural Science Foundation of China(Nos.21271176,21472196,21521062,and 21501183)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB 12010400)for funding support
文摘This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.
基金supported by the National Natural Science Foundation of China (21872154), Beijing National Science Foundation (2191003)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB12010400)
文摘A cyclometalated diruthenium complex 2 bridged by 1,2,4,5-tetra(pyrid-2-yl)benzene with six carboxylic acid groups at two ends was synthesized.Monolayer and multilayer films FTO/TiO2/(2)n(Zr)(n=1,2)and FTO/SnO2:Sb/(2)n(Zr)(n=1-4)have been prepared via interfacial layer-by-layer coordination assembly of 2 with zirconium(IV)ions.All films show two consecutive redox couples in the potential range between 0 and+1.0 V vs.Ag/AgCl.These films exhibit reversible near-infrared electrochromism upon switching of redox potential.The response time of the films on SnO2:Sb is around a few seconds,while that on TiO2 is around a few tens of seconds.The film deposition cycles were found to have a great impact on the electrochromic performance.Among six films examined,the two-layered film on SnO2:Sb displays the best balanced performance with a contrast ratio of 56%at 1,150 nm and good cyclic stability(9%loss of contrast ratio after 1,000 continuous double-potential-switching cycles),which is superior to that of the previously reported electropolymerized films of a related diruthenium complex with the same bridging ligand.In addition,the X-ray photoelectron spectroscopy,scanning electron microscopy,and electron transfer mechanism of these films have been investigated.
基金This research was suported by the National Natural Science Foundation of China(Grant Nos.51521002,21905098)Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials(Grant No.20198121205002).
文摘Doping plays an essential role in the properties of conducting polymers.Film thickness not only has a direct influence on their photoelectric properties,but also affects the doping ability,which may lead to the decline of capacitance and electrochromic properties caused by incomplete doping.Therefore,it is essential to study the quantitative relationship between doping level and film thickness in application.Herein,empirical formula between doping level and thickness was obtained by studying the spectroelectrochemistry behaviors of two different electrochromic materials,poly(N,N'-bis(3,5-(2-thienyl)-phenyl)-1,6,7,12-tetrachloroperylene-3,4,9,10-perylenetetracarboxylic diimide)(poly(Th-Cl-PBI))and poly(3,4-ethylenedioxythiophene)(PEDOT).The doping level is verified to be correlated to the reciprocal of the 3^(rd)power of film thickness.Experimental results fit these formulas very well,giving correlation coefficient R^(2)higher than 0.99.The optical contrast prediction of these two electrochromic materials is also used to verify this relationship formula.For the first time,we quantitatively connect these two important parameters of conducting polymers,doping level and thickness.
基金supported by a grant of the Ministry of Research,Innovation and Digitization,CNCS–UEFISCDI,project number PNIII-P1-1.1-TE-2021-1110PNCDI III,contract number TE 83/2022,and project number PN-III-P2-2.1-PED-2019-3520PNCDI III,contract number 438PED/2020。
文摘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.
基金supported by funding from Bavarian Center for Battery Technology(Bay Batt),Bayerisch-Tschechische Hochschulagentur(BTHA)(BTHA-AP-2022-45,BTHA-AP-2023-5,BTHA-AP2023-12,and BTHA-AP-2023-38)the University of BayreuthDeakin University Joint Ph.D.Program,Bayerische Forschungallianz(Bay FOR)(Bay Int An_UBT_2023_84)+2 种基金BK21 program from National Research Foundation of Korea,Erasmus+program from the European Union,Ministry of Education,Science and Technology as part of the Higher Education for Economic Transformation(HEET)Project(World Bank)Verband der Chemischen Industrie(Fonds der Chemischen Industrie,No.661740)collaboration project funding from Kangwon National University and LINC 3.0 Research Center,and the Deutsche Forschungsgemeinschaft(DFG,project number:533115776)。
文摘In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development of electrochromic-energy storage systems designed to visualize electrochemical charging and discharging processes.The conventional electrochromic-energy storage devices primarily integrated supercapacitors,known for their high power density,to enable rapid color contrast.However,the low energy density of supercapacitors restricts overall energy storage capacity,acting as a significant barrier to expanding the application range of such systems.In this review,we introduce electrochromic zinc(Zn)-ion battery systems,which effectively overcome the limitation of low energy density,and provide illustrative examples of their applicability across diverse fields.Although many recent research works are present for electrochromic Zn-ion batteries,little review has so far taken place.Our objective is to discuss on the current progress and future directions for electrochromic Zn-ion batteries,which are applicable for wearable electronics applications and energy storage systems.This review provides an initial milestone for future researchers in electrochromic energy storage and zinc-ion batteries,which will lead to a stream of future works related to them.
基金financially the National Natural Science Foundation of China(U2004175,51902086 and 62222402)China Postdoctoral Science Foundation(2022M711036)the Key Scientific Research Project plan of the University in Henan Province(22A430002)。
文摘Exploring materials with high electrochemical activity is of keen interest for electrochemistry-controlled optical and energy storage devices.However,it remains a great challenge for transition metal oxides to meet this feature due to their low electron conductivity and insufficient reaction sites.Here,we propose a type of transition metal phosphate(NiHPO_(4)·3H_(2)O,NHP)by a facile and scalable electrodeposition method,which can achieve the capability of efficient ion accommodation and injection/extraction for electrochromic energy storage applications.Specifically,the NHP film with an ultra-high transmittance(approach to 100%)achieves a large optical modulation(90.8%at 500 nm),high coloration efficiency(75.4 cm^(2)C^(-1)at 500 nm),and a high specific capacity of 47.8 mAh g^(-1)at 0.4 A g^(-1).Furthermore,the transformation mechanism of NHP upon electrochemical reaction is systematically elucidated using in situ and ex situ techniques.Ultimately,a large-area electrochromic smart window with 100 cm^(2)is constructed based on the NHP electrode,displaying superior electrochromic energy storage performance in regulating natural light and storing electrical charges.Our findings may open up new strategies for developing advanced electrochromic energy storage materials and smart windows.
基金supported by the National Natural Science Foundation of China(51902064)the Natural Science Foundation of Guangxi(2022GXNSFFA0350325)+2 种基金the Scientific and Technological Bases and Talents of Guangxi(Guike AD20159073)the special fund for“Guangxi Bagui Scholars”the“Guangxi HundredTalent Program”。
文摘Dual-band electrochromic smart windows(DESWs)with independent control of the transmittance of near-infrared and visible light show great potential in the application of smart and energy-saving buildings.The current strategy for building DESWs is to screen materials for composite or prepare plasmonic nanocrystal films.These rigorous preparation processes seriously limit the further development of DESWs.Herein,we report a facile and effective sol-gel strategy using a foaming agent to achieve porous Ti-doped tungsten oxide film for the high performance of DESWs.The introduction of foaming agent polyvinylpyrrolidone during the film preparation can increase the specific surface area and free carrier concentration of the films and enhance their independent regulation ability of near-infrared electrochromism.As a result,the optimal film shows excellent dual-band electrochromic properties,including high optical modulation(84.9%at 633 nm and 90.3%at 1200 nm),high coloration efficiency(114.9 cm^(2) C^(-1) at 633 nm and 420.3 cm^(2) C^(-1) at 1200 nm),quick switching time,excellent bistability,and good cycle stability(the transmittance modulation losses at 633 and 1200 nm were 11%and 3.5%respectively after 1000 cycles).A demonstrated DESW fabricated by the sol-gel film showed effective management of heat and light of sunlight.This study represents a significant advance in the preparation of dual-band electrochromic films,which will shed new light on advancing electrochromic technology for future energy-saving smart buildings.
基金the support from the “Qilu Young Scholar” program (62460082163097) of Shandong Universitythe National Natural Science Foundation of China (62105185)+1 种基金Shandong Excellent Young Scientists Fund Program (Overseas) (2022HWYQ-021)Guangdong Basic and Applied Basic Research Foundation (2022A1515011516)
文摘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.
基金support by Shanghai Municipal Education Commission (No. 2019-01-07-00-09E00020), for research conducted at the Shanghai Universitysupport by Independent depolyment project of Qinghai Institute of Salt Lakes, Chinese Academy of Sciences (E260GC0401)support by the Singapore National Research Foundation (NRF-CRP26-2021-0003, NRF), for research conducted at the National University of Singapore。
文摘Multifunctional electrochromic-induced rechargeable aqueous batteries(MERABs) integrate electrochromism and aqueous ion batteries into one platform, which is able to deliver the conversion and storage of photo-thermal-electrochemical sources.Aqueous ion batteries compensate for the drawbacks of slow kinetic reactions and unsatisfied storage capacities of electrochromic devices. On the other hand, electrochromic technology can enable dynamically regulation of solar light and heat radiation. However,MERABs still face several technical issues, including a trade-off between electrochromic and electrochemical performance, low conversion efficiency and poor service life. In this connection, novel device configuration and electrode materials, and an optimized compatibility need to be considered for multidisciplinary applications. In this review,the unique advantages, key challenges and advanced applications are elucidated in a timely and comprehensive manner. Firstly, the prerequisites for effective integration of the working mechanism and device configuration, as well as the choice of electrode materials are examined. Secondly, the latest advances in the applications of MERABs are discussed, including wearable, self-powered, integrated systems and multisystem conversion. Finally, perspectives on the current challenges and future development are outlined, highlighting the giant leap required from laboratory prototypes to large-scale production and eventual commercialization.
基金supports from the National Natural Science Foundation of China (Grant No. 52175300)Fundamental Research Funds for the Central Universities (2022FRFK060008)+2 种基金Heilongjiang Touyan Innovation Team Program (HITTY-20190013)Shenzhen Fundamental Research Programs (JCYJ20200925160843002)Start-up fund of SUSTech (Y01256114)
文摘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.
基金supported by the Key Science and Technology Innovation Team of Shaanxi Province(No.2014KCT-03)Special Support Program for High-level Talents of Shaanxi Province(No.2020-44)China Postdoctoral Science Foundation(No.2019M663990).
文摘Inorganic metal oxide electrochromic materials have good application prospects for energy-saving windows in buildings and smart display applications.Therefore,the development of electrochromic films with good cycling stabilities,fast color-change response times,and high coloring efficiencies has attracted considerable attention.In this study,nanoflake Li-doped NiO electrochromic films were prepared using a hydrothermal method,and the films exhibited superior electrochromic performances in the LiOH electrolyte.Li^(+)ions doping increased the ion transmission rates of the NiO films,and effectively promoted the transportation of ions from the electrolyte into NiO films.Meanwhile,the nanoflake microstructure caused the NiO films to have larger specific surface areas,providing more active sites for electrochemical reactions.It was determined that the NiO-Li20%film exhibited an ultra-fast response in the LiOH electrolyte(coloring and bleaching times reached 3 and 1.5 s,respectively).Additionally,the coloration efficiency was 62.1 cm^(2)C^(−1),and good cycling stability was maintained beyond 1500 cycles.Finally,the simulation calculation results showed that Li doping weakened the adsorption strengths of the NiO films to OH^(−),which reduced the generation and decomposition of NiOOH and helped to improve the cycling stabilities of the films.Therefore,the research presented in this article provides a strategy for designing electrochromic materials in the future.
基金The authors acknowledge the support from the National Natural Science Foundation of China(62105185,62375157,52002196)Natural Science Foundation of Guangdong Province(2022A1515011516)+2 种基金Natural Science Foundation of Shandong Province(ZR2020QF084)Shandong Excellent Young Scientists Fund Program(Overseas,2022HWYQ-021)the Open Foundation of the State Key Laboratory of Featured Metal Materials and Life-Cycle Safety for Composite Structures,Guangxi University(2022GXYSOF06).
文摘Vanadates are a class of the most promising electrochromic materials for displays as their multicolor characteristics.However,the slow switching times and vanadate dissolution issues of recently reported vanadates significantly hinder their diverse practical applications.Herein,novel strategies are developed to design electrochemically stable vanadates having rapid switching times.We show that the interlayer spacing is greatly broadened by introducing sodium and lanthanum ions into V_(3)O_(8)interlayers,which facilitates the transportation of cations and enhances the electrochemical kinetics.In addition,a hybrid Zn^(2+)/Na^(+)electrolyte is designed to inhibit vanadate dissolution while significantly accelerating electrochemical kinetics.As a result,our electrochromic displays yield the most rapid switching times in comparison with any reported Zn-vanadate electrochromic displays.It is envisioned that stable vanadate-based electrochromic displays having video speed switching are appearing on the near horizon.
基金supported by the National Natural Science Foundation of China (51902064)the Scientific and Technological Bases and Talents of Guangxi (2019AC20198)+2 种基金Guangxi Natural Science Foundation (2017GXNSFGA198005)the special fund for “Guangxi Bagui Scholars”the “Guangxi Hundred-Talent Program”。
文摘Zinc-anode-based electrochromic devices(ZECDs) are emerging as the next-generation energy-e cient transparent electronics. We report anatase W-doped TiO_(2) nanocrystals(NCs) as a Zn^(2+) active electrochromic material. It demonstrates that the W doping in TiO_(2) highly reduces the Zn^(2+) intercalation energy,thus triggering the electrochromism. The prototype ZECDs based on W-doped TiO_(2) NCs deliver a high optical modulation(66% at 550 nm),fast spectral response times(9/2.7 s at 550 nm for coloration/bleaching),and good electrochemical stability(8.2% optical modulation loss after 1000 cycles).
基金supported by the Technology Development Program to Solve Climate Change through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT(2018M1A2A2063861)supported by the GIST Research Institute(GRI)grant funded by the GIST in 2019。
文摘Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g.,chlorine evolution reaction,detoxification,and oxygen evolution reaction).Such versatility is attributed to the distinct features of iridium oxides,such as their activity,biocompatibility,conductivity,and durability.The features and properties of iridium oxides are strongly dependent on the fabrication method.In this review,methodologies relating to the synthesis and fabrication of solid-state iridium oxides have been thoroughly collected and discussed.Structuring and crystallization techniques for iridium oxides are also noted.At the end of the review,the effects of utilizing a certain fabrication method on the characteristics of the iridium oxide product are recapitulated,together with the recommended application of the product in various fields.
文摘In this paper, the poling properties of (PS)O-DCV, a derivative of poly (p-hydroxystyrene ), was reported. The investigations showed that the thermochromism correction, which was neglected in the literatures, should be considered in the measurements of order parameter of poled films with electrochromism technique Here, another linear optical method, IR and polarized IR spectra for characterizing of poled films was suggested first time. The bulk second nonlinear optical coefficient d<sub>33</sub> of poled films could be estimated by measured order parameter semi-qualitatively.