CN105060733A - Electrochromic film adopting amorphous/crystalline tungsten trioxide core-shell structure and preparation method of film - Google Patents
Electrochromic film adopting amorphous/crystalline tungsten trioxide core-shell structure and preparation method of film Download PDFInfo
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Abstract
The invention discloses an electrochromic film adopting an amorphous/crystalline tungsten trioxide core-shell structure and a preparation method of the film. The method comprises steps as follows: white tungstic acid is dissolved in a hydrogen peroxide solution, the mixture is applied to a conductive surface of a conductive substrate, and a conductive substrate covered with a crystal seed layer is obtained; a tungsten source is dissolved in water, the pH value is adjusted, ammonium sulfate is added, a precursor solution is formed, a reaction is conducted in the precursor solution at the temperature of 150-250 DEG C for 4-10 h, and a tungsten trioxide nanowire array film is obtained. The tungsten source is dissolved in the water, the hydrogen peroxide is dropwise added, the pH value is adjusted, an electrodeposition solution is formed, and the film can be obtained through electrodeposition of amorphous tungsten oxide with a constant voltage method. The film prepared with the preparation method has the nanowire core-shell coating morphology, is good in electric connectivity and has the advantages of large spectrum adjusting range, high coloration efficiency and long cycle life, meanwhile, the preparation technology is convenient to control, the production cost is lower, massive production can be realized, and industrialization is easy to realize.
Description
Technical field
The present invention relates to field of material preparation, be specifically related to a kind of non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films and preparation method thereof.
Background technology
Electrochromism (Electrochromics, EC) refers to that the optical property of material, under the effect of extra electric field, reversible change phenomenon occurs.Electrochromism only needs less voltage (about 2V) to get final product work, can keep original painted or bleached state is constant, therefore less energy intensive under open-circuit condition.Electrochromic device (Electrochromicdevices, ECD) is expected to the surface temperature control etc. being applied in building energy conservation window, automobile anti-dazzle light rear vision mirror, display equipment, change transmitance glasses, vehicle dormer window and spacecraft.Electrochromic material is mainly divided into three kinds, namely inorganic electrochromic material (being generally transition metal oxide), organic supramolecular off-color material are (as Prussian blue, purple sieve essence, metallo phthalocyanine etc.) and conducting polymer composite (as polyaniline, polypyrrole, Polythiophene etc.).As a kind of inorganic electrochromic material, tungstic oxide (WO
3) there is pure color, stable chemical nature, with the advantage such as substrate caking power is strong, but traditional tungstic oxide also also exists the shortcoming that color change is slow, coloration efficiency is low, colour-change is single and cycle life is short.Comparatively speaking, nano structure membrane have specific surface area large, conduct electricity very well make variable color rapidly, optical analogy performance is good, coloration efficiency is high and the advantage such as good cycle.
The most frequently used preparation method of WO 3 film is electrochemical deposition method, hydrothermal method, magnetron sputtering method and thermal evaporation deposition etc.All there are some defects in these methods, the film such as prepared is non-crystalline state, and colouring speeds is fast, but cycle performance is poor or the film of preparation is crystalline state, and cycle performance is good, but color change is slow, and coloration efficiency is low.
At present, the design of tungstic oxide and the nucleocapsid structure such as titanium dioxide, zinc oxide nano rod is mainly concerned with about tungstic oxide composite material of core-shell structure.Tungsten trioxide nanowires can play the crystalline state of tungstic oxide/amorphous advantage own as the homogeneous material nucleocapsid structure of skeleton, improves its cycle performance by constructional feature.
Therefore, the present invention proposes a kind of new preparation method to obtain the homogeneity non-crystalline state/crystalline state matrix material of excellent performance.
Summary of the invention
The invention provides a kind of non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films and preparation method thereof, this preparation method achieves tungstic oxide crystalline state, non-crystalline state in the compound of molecular level, avoid the defect that in existing preparation method, two-phase does not coexist, the film obtained has that spectrum regulation range is large, the advantage of good cycle, simultaneously, preparation method controls conveniently, and manufacturing cost is lower, is easy to realize industrialization.
The preparation method of described non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, comprises the following steps:
1) white tungstic acid is dissolved in aqueous hydrogen peroxide solution, adds water and be mixed with the tungstic add peroxide solution that tungstenic concentration is 1 ~ 5mol/L, tungstic add peroxide solution is coated on the conducting surface of conductive substrates, obtains the conductive substrates being coated with crystal seed layer;
2) by soluble in water for tungsten source, adjust ph to 1 ~ 3.5, add ammonium sulfate, form precursor solution, the conductive substrates being coated with crystal seed layer is fixed in reactor, precursor solution is added in reactor, at 150 DEG C ~ 250 DEG C reaction 4h ~ 10h, after taking-up, obtain tungsten trioxide nanowires array film;
3) by soluble in water for tungsten source, drip hydrogen peroxide, adjust ph to 0.5 ~ 3, form electric depositing solution, utilizing constant voltage method to step 2) the tungsten trioxide nanowires array film electrode prepared carries out Electrodeposited Amorphous Tungsten oxide 99.999, obtains non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films.
Step 1) in, as preferably, the preparation of described white tungstic acid comprises: by hydrochloric acid and sodium wolframate aqueous solution, produce precipitation after reaction, the precipitation obtained after filtration is white tungstic acid.The preparation of white tungstic acid obtains by following methods: by the sodium tungstate solution of excessive concentrated hydrochloric acid instillation 1mol/L, to producing without new precipitation.By deionized water wash precipitation, with 1mol/L silver nitrate solution instillation washing lotion chlorine detection ionic concn, in washing lotion, chlorine ion concentration does not produce silver nitride precipitation.After washing, gained oyster white to faint yellow gelatinous precipitate is white powdery tungstic acid.White powdery tungstic acid prepared by the method, be conducive to being dissolved in aqueous hydrogen peroxide solution on the one hand, and generate tungstic add peroxide solution, on the other hand, be conducive in reaction and heat treatment process, form the Tungsten trioxide nanometer array electrochromic film of nanocluster, nanotrees and nano-wire array pattern, electrical connectivity is good.
Further preferably, in order to white powdery tungstic acid can be made to precipitate completely, described salt excessive acid, by hydrochloric acid and sodium wolframate aqueous solution is: in the sodium wolframate aqueous solution, drip hydrochloric acid, till not producing precipitation.
Further preferably, precipitate to make white powdery tungstic acid and precipitate better, described hydrochloric acid can be preferably concentrated hydrochloric acid, and the concentration of namely described hydrochloric acid is 3 ~ 12mol/L.
Further preferably, in order to hydrochloric acid and the sodium wolframate aqueous solution can be made better to react, generate white powdery tungstic acid precipitation, also have certain requirement to the concentration of the sodium wolframate aqueous solution, in the described sodium wolframate aqueous solution, the concentration of sodium wolframate is 0.5 ~ 2mol/L.
In order to aqueous hydrogen peroxide solution can be dissolved in better by white tungstic acid, also certain requirement is had to the concentration of aqueous hydrogen peroxide solution, as preferably, in described aqueous hydrogen peroxide solution, the mass percent of hydrogen peroxide is 20% ~ 40%, the aqueous hydrogen peroxide solution of namely suitable mass percent is conducive to white tungstic acid and is dissolved in aqueous hydrogen peroxide solution, and reacts.
In order to make the hydroperoxidation in white tungstic acid and aqueous hydrogen peroxide solution, generate tungstic add peroxide, as preferably, in described white tungstic acid and aqueous hydrogen peroxide solution, the mol ratio of hydrogen peroxide is 1:2 ~ 5.
Tungstenic concentration is the tungstic add peroxide solution of 1 ~ 5mol/L, be conducive to being coated on the conducting surface of clean clean conductive substrates, concentration is too high or too low, make coating difficulty greatly strengthen for a moment, two is cannot form specific pattern in reaction and heat treatment process, affects very much the performance of Tungsten trioxide nanometer array electrochromic film.
Conveniently at conductive substrates coated Tungsten oxide 99.999 acid solution and prevent the pattern of other impurity to finally prepd tungsten trioxide nanowires array electrochomeric films from having an impact, before the coated Tungsten oxide 99.999 acid solution of conductive substrates, need to clean up it, as preferably, described conductive substrates need clean totally, comprise: first conductive substrates is cleaned with acetone, deionized water and EtOH Sonicate respectively, then blow clean with nitrogen.The method cleaning effect is better.
Described conductive substrates can adopt prior art, can adopt commercially available prod, as the FTO conductive glass (SnO of doped with fluorine
2transparent conducting glass), the conductive glass etc. that formed of ITO (tin indium oxide) conductive glass, ITO/PET (poly terephthalic acid class plastics) flexible conducting substrate and glass and metal.
Owing to containing a certain amount of water in tungstic add peroxide solution, therefore, as preferably, step 1) in, tungstic add peroxide solution divides and is coated on the conducting surface of conductive substrates 3 ~ 6 times, each with spin coating instrument with the speed spin coating 20 ~ 50s of 2000 ~ 4000r/min, all need 200 ~ 400 DEG C of insulations 5 ~ 20 minutes after each spin coating completes, tungstic add peroxide firmly can be attached on the conducting surface of clean clean conductive substrates, and be conducive to the formation of tungsten trioxide nanowires array film.
Step 2) in, tungsten trioxide nano array of the present invention is formed together by the acting in conjunction under the condition at 150 ~ 250 DEG C of reaction 4 ~ 10h of tungsten source in the tungstic add peroxide be coated in conductive substrates and precursor solution, wherein, tungstic add peroxide in conductive substrates helps out, in precursor solution, tungsten salt plays a major role, and finally obtains tungsten trioxide nanowires array film.
Described tungsten source is one or more in sodium wolframate, tungstic add peroxide, wolframic acid;
Described water is deionized water;
In described precursor solution, the concentration in tungsten source is 0.001 ~ 0.10mol/L.
In described precursor solution, the concentration in tungsten source is 0.001 ~ 0.20mol/L, and in precursor solution, tungsten source is formed tungsten trioxide nanowires array and helps out, and the precursor solution of above-mentioned concentration is more conducive to tungsten trioxide nanowires array and is formed.
Step 3) in, described hydrogen peroxide is the aqueous hydrogen peroxide solution of the mass percent 20% ~ 40% of hydrogen peroxide.
In order to Tungsten oxide 99.999 can under certain voltage better with tungsten trioxide nanowires coating function, utilize perchloric acid regulator solution pH value to 0.5 ~ 3; In described electric depositing solution, tungsten source concentration is 5 ~ 5mmol/L; Described hydrogen peroxide and the volume ratio of water are 1:200 ~ 1250.
In order to make Tungsten oxide 99.999 play coating function on tungsten trioxide nanowires surface well, the voltage that we select is generally-0.5 ~-1V, and depositing time is 100 ~ 1200s.Length by changing depositing time controls the coated effect of the oxidized tungsten of tungsten trioxide nanowires array.As preferably, the voltage of described constant voltage method is-0.5 ~-1V, and depositing time is 100 ~ 1200s.
With step 2) the tungsten trioxide nanowires array film prepared is working electrode, Ag/AgCl electrode is reference electrode, and platinum plate electrode is to electrode, and electric depositing solution is the electrolytic solution of electro deposition oxidation tungsten.
Step 2) and step 3) in, as preferably, described tungsten source is one or more in sodium wolframate, tungstic add peroxide, wolframic acid, and above-mentioned tungsten source all can form the tungsten trioxide nanowires array electrochomeric films of special appearance with the tungstic add peroxide in conductive substrates under specific reaction conditions.
Described water is deionized water, and deionized water low price is widely applicable.
Described non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, be the laminated film of tungstic oxide amorphous layer and crystalline state nano wire, the thickness of film is 0.2 ~ 2 μm, and surface has nano-wire array pattern, is line clad structure.Laminated film casing ply is tungstic oxide, and it has pure color, stable chemical nature, with the advantage such as substrate caking power is strong.Coating layer is Tungsten oxide 99.999, Tungsten oxide 99.999 pure color, stable chemical nature, and non-crystalline state is conducive to improving its electrochemistry and electrochromic property further.This film has the core-shell nano linear array pattern of vertically arrangement, good conductivity, and film has the advantage that spectrum regulation range is large, response speed very fast and have extended cycle life.
Compared with prior art, tool of the present invention has the following advantages:
Non-crystalline state of the present invention/crystalline state tungstic oxide nucleocapsid structure electrochomeric films and preparation method thereof, take the preparation method in conjunction with hydro-thermal and galvanic deposit, in various substrate (as ITO conductive glass, ITO/PET flexible conducting substrate and glass and metal etc.), first preparation has the tungstic oxide electrochromism optically variable films of nano-wire array pattern, and then adopt the method for galvanic deposit to form the unbodied Tungsten oxide 99.999 of one deck on the surface at tungsten oxide nano, form self non-crystalline state coated.Further, this preparation technology is simple, and the nano array structure pattern of composition film can conveniently control, and manufacturing cost is lower, is easy to realize large area deposition.
The non-crystalline state that the present invention obtains/crystalline state tungstic oxide core-shell nano line electrochomeric films, there is core-shell nano linear array pattern, the advantages such as spectrum regulation range is large, coloration efficiency is high, response speed is very fast, have extended cycle life, not only can be used for electrochromism field, susceptible device susceptor, photochemical catalysis, protection against corrosion and photovoltaic art can also be used for, there is wide application background.
Accompanying drawing explanation
Fig. 1 is the SEM photo in embodiment 2 gained non-crystalline state/crystalline state tungstic oxide core-shell nano line electrochomeric films plane and cross section;
Fig. 2 is enforcement 2 gained non-crystalline state/crystalline state tungstic oxide core-shell nano line electrochomeric films transmission photo;
Fig. 3 is the visible and near infrared spectrum of embodiment 1 ~ 3 gained non-crystalline state/crystalline state tungstic oxide core-shell nano line electrochomeric films;
Fig. 4 is the Infrared Reflective Spectra of embodiment 1 ~ 3 gained non-crystalline state/crystalline state tungstic oxide core-shell nano line electrochomeric films;
Fig. 5 is the cycle performance of embodiment 2 gained non-crystalline state/crystalline state tungstic oxide core-shell nano line electrochomeric films.
Embodiment
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1
(1) FTO conductive glass (Shenzhen Di Sipurui photoelectric material company limited, Rs≤10ohmTr>85%) is cleaned 10 minutes with acetone, deionized water and EtOH Sonicate respectively, blow clean with nitrogen, obtain clean clean FTO conductive glass;
(2) excessive concentrated hydrochloric acid (10mol/L) is instilled in the sodium wolframate aqueous solution of 1mol/L, to producing without new precipitation, precipitate with deionized water wash, after washing, gained oyster white to faint yellow gelatinous precipitate is white tungstic acid, the mass percent white tungstic acid of acquisition being dissolved in hydrogen peroxide is the aqueous hydrogen peroxide solution of 30%, in white tungstic acid and aqueous hydrogen peroxide solution, the mol ratio of hydrogen peroxide is 1:3, add deionized water and be mixed with the tungstic add peroxide solution that tungstenic concentration is 3mol/L, stand-by 4 DEG C of refrigerations;
(3) the tungstic add peroxide solution spin coating instrument in step (2) with the speed of 3000r/min spin coating 30s on the conducting surface of clean clean FTO conductive glass, insulation 10 minutes in the box-type furnace putting into 300 DEG C again, repeat spin coating four times, obtain the FTO conductive glass being coated with crystal seed layer;
(4) 3.29g Disodium tungstate (Na2WO4) dihydrate is joined in 76mL deionized water solution stir, utilize 3M (mol/L) salt acid for adjusting pH to 2.0, add 3.30g ammonium sulfate and stir 1 hour, obtain precursor solution, in precursor solution, the concentration of sodium wolframate is 0.14mol/L;
(5) with the FTO conductive glass being coated with crystal seed layer in step (3) for substrate, and substrate is stood vertically and is fixed in reactor polytetrafluoroethylliner liner, then precursor solution prepared by step (4) is poured in reactor, by reactor isothermal reaction 4h in 190 DEG C of loft drier, after having reacted, take out reactor, cool with tap water, then with 60 DEG C of vacuum-dryings after deionized water rinsing, tungsten trioxide nanowires array film is obtained.
(6) 2.06g Disodium tungstate (Na2WO4) dihydrate is joined 500mL deionized water for stirring, add wherein with 1.25mL30wt% aqueous hydrogen peroxide solution, drip perchloric acid and regulate pH to 1.2, obtain the electrolytic solution of galvanic deposit, in the electrolytic solution of galvanic deposit, the concentration of sodium wolframate is 12.5mM (mmol/L);
(7) with the tungsten oxide nanometer linear array obtained in step (5) for working electrode, Ag/AgCl electrode is reference electrode, platinum plate electrode is to electrode, the electrolytic solution of the galvanic deposit in step (6) is the electrolytic solution of electro deposition oxidation tungsten, electrochemical workstation CHI660E deposits 200s by the method for constant voltage deposition under-0.7V voltage, obtains non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films.
Carry out composition analysis and structure and performance characterization to the above-mentioned non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films that obtains, measuring it is the coated array electrochomeric films of tungsten trioxide nano with nano-wire array pattern, and concrete outcome is as follows:
By X-ray diffraction analysis, tungsten trioxide nanowires array electrochomeric films skeleton tungsten trioxide nanowires prepared by the present embodiment belongs to hexagonal system structure tungstic oxide (JCPDSNo.85-2459; P63/mcm (193)), contrast (100) peak with other peak values and significantly strengthen with (200) peak value.Coated tungsten oxide film is noncrystalline membrane.
Scanning electronic microscope (SEM) is utilized to observe this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films surface, compared with not coated tungsten oxide nano, embodiment 1 film surface keeps nano-wire array pattern, the diameter of nano wire is about 110nm, and single nano-wire surface is evenly coated by small-particle.
This non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films grows in substrate, and thickness is 1 ± 0.1 μm.
Spectrum change and the electrochromism response speed of above-mentioned non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films is tested with electrochemical workstation and spectrophotometer.The square-wave voltage of-0.7V to 1.0V is applied respectively in the aqueous sulfuric acid of 0.5mol/L, measure this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films at the transmitance changing value of 400 ~ 2100nm wavelength region with at 2.5 ~ 25 mum wavelength scope internal reflection rate changing values, and with the transmitance time of response at 750nm place for electrochromism speed.Result, as shown in table 1 and Fig. 3,4, is respectively 53.8% and 63.9% at 750nm and 2000nm transmitance changing value after visible embodiment 1 applies the square-wave voltage of-0.7V and 1.0V; 10 μm place reflectivity be changed to 36.1%, fade and painted response speed be respectively 2.6/4.2s.As can be seen here, above-mentioned obtained non-crystalline state/crystalline state tungstic oxide core-shell nano array electrochomeric films has in optical analogy regulation range that is visible and infrared band larger, the advantage of fast response time.
Embodiment 2
(1) FTO conductive glass (Shenzhen Di Sipurui photoelectric material company limited, Rs≤10ohmTr>85%) is cleaned 10 minutes with acetone, deionized water and EtOH Sonicate respectively, blow clean with nitrogen, obtain clean clean FTO conductive glass;
(2) excessive concentrated hydrochloric acid (10mol/L) is instilled in the sodium wolframate aqueous solution of 1mol/L, to producing without new precipitation, precipitate with deionized water wash, after washing, gained oyster white to faint yellow gelatinous precipitate is white tungstic acid, the mass percent white tungstic acid of acquisition being dissolved in hydrogen peroxide is the aqueous hydrogen peroxide solution of 30%, in white tungstic acid and aqueous hydrogen peroxide solution, the mol ratio of hydrogen peroxide is 1:3, add deionized water and be mixed with the tungstic add peroxide solution that tungstenic concentration is 3mol/L, stand-by 4 DEG C of refrigerations;
(3) the tungstic add peroxide solution spin coating instrument in step (2) with the speed of 3000r/min spin coating 30s on the conducting surface of clean clean FTO conductive glass, insulation 10 minutes in the box-type furnace putting into 300 DEG C again, repeat spin coating four times, obtain the FTO conductive glass being coated with crystal seed layer;
(4) joined in 76mL deionized water solution by 3.29g Disodium tungstate (Na2WO4) dihydrate and stir, utilize 3M salt acid for adjusting pH to 2.0, add 3.30g ammonium sulfate and stir 1 hour, obtain precursor solution, in precursor solution, the concentration of sodium wolframate is 0.14mol/L;
(5) with the FTO conductive glass being coated with crystal seed layer in step (3) for substrate, and substrate is stood vertically and is fixed in reactor polytetrafluoroethylliner liner, then precursor solution prepared by step (4) is poured in reactor, by reactor isothermal reaction 4h in 190 DEG C of loft drier, after having reacted, take out reactor, cool with tap water, then with 60 DEG C of vacuum-dryings after deionized water rinsing, tungsten trioxide nanowires array film is obtained.
(6) 2.06g Disodium tungstate (Na2WO4) dihydrate is joined 500mL deionized water for stirring, add wherein with 1.25mL30wt% superoxol, drip perchloric acid and regulate pH to 1.2, obtain the electrolytic solution of galvanic deposit, in the electrolytic solution of galvanic deposit, the concentration of sodium wolframate is 12.5mM (mmol/L);
(7) with the tungsten oxide nanometer linear array obtained in step (5) for working electrode, Ag/AgCl electrode is reference electrode, platinum plate electrode is to electrode, electrolytic solution in step (6) is the electrolytic solution of electro deposition oxidation tungsten, electrochemical workstation CHI660E deposits 400s by the method for constant voltage deposition under-0.7V voltage, obtains non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films.
Carry out composition analysis and structure and performance characterization to the above-mentioned non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films that obtains, measuring it is the coated array electrochomeric films of tungsten trioxide nano with nano-wire array pattern, and concrete outcome is as follows:
By X-ray diffraction analysis, tungsten trioxide nanowires array electrochomeric films skeleton tungsten trioxide nanowires prepared by the present embodiment belongs to hexagonal system structure tungstic oxide (JCPDSNo.85-2459; P63/mcm (193)), contrast (100) peak with other peak values and significantly strengthen with (200) peak value.Coated tungsten oxide film is noncrystalline membrane.
As shown in Figure 1, scanning electronic microscope (SEM) is utilized to observe this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films surface, visible film surface has nano-wire array pattern, the diameter of nano wire is about 120nm, and single nano-wire surface is evenly coated by small-particle.This non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films grows in substrate, and thickness is 1 ± 0.1 μm.
By transmission electron microscope (TEM) as Fig. 2, non-crystalline state/crystalline state tungstic oxide core-shell nano the line of typical case in observation, find that the tungsten oxide nano of crystallization is well coated with by amorphous Tungsten oxide 99.999 shell as core, the thickness of non-crystalline state Tungsten oxide 99.999 is about 18nm.
Spectrum change and the electrochromism response speed of above-mentioned non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films is tested with electrochemical workstation and spectrophotometer.The square-wave voltage of-0.7V to 1.0V is applied respectively in the aqueous sulfuric acid of 0.5mol/L, measure this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films at the transmitance changing value of 400 ~ 2100nm wavelength region with at 2.5 ~ 25 mum wavelength scope internal reflection rate changing values, and with the transmitance time of response at 750nm place for electrochromism speed.Result, as shown in table 1 and Fig. 3,4 and 5, is respectively 70.3% and 42.1% at 750nm and 2000nm transmitance changing value after visible embodiment 2 applies the square-wave voltage of-0.7V and 1.0V; Be changed to 51.4% at the reflectivity at 10 μm of places, fade and painted response speed 3.5/4.8s respectively.Still maintain through 3000 circulations and have 68.5% of initial optical analogy scope.As can be seen here, the non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films of above-mentioned preparation has in optical analogy regulation range that is visible and infrared band large, the advantage of fast response time and good cycle.
Embodiment 3
(1) FTO conductive glass (Shenzhen Di Sipurui photoelectric material company limited, Rs≤10ohmTr>85%) is cleaned 10 minutes with acetone, deionized water and EtOH Sonicate respectively, blow clean with nitrogen, obtain clean clean FTO conductive glass;
(2) excessive concentrated hydrochloric acid (10mol/L) is instilled in the sodium wolframate aqueous solution of 1mol/L, to producing without new precipitation, precipitate with deionized water wash, after washing, gained oyster white to faint yellow gelatinous precipitate is white tungstic acid, the mass percent white tungstic acid of acquisition being dissolved in hydrogen peroxide is the aqueous hydrogen peroxide solution of 30%, in white tungstic acid and aqueous hydrogen peroxide solution, the mol ratio of hydrogen peroxide is 1:3, add deionized water and be mixed with the tungstic add peroxide solution that tungstenic concentration is 3mol/L, stand-by 4 DEG C of refrigerations;
(3) the tungstic add peroxide solution spin coating instrument in step (2) with the speed of 3000r/min spin coating 30s on the conducting surface of clean clean FTO conductive glass, insulation 10 minutes in the box-type furnace putting into 300 DEG C again, repeat spin coating four times, obtain the FTO conductive glass being coated with crystal seed layer;
(4) joined in 76mL deionized water solution by 3.29g Disodium tungstate (Na2WO4) dihydrate and stir, utilize 3M salt acid for adjusting pH to 2.0, add 3.30g ammonium sulfate and stir 1 hour, obtain precursor solution, in precursor solution, the concentration of sodium wolframate is 0.14mol/L;
(5) with the FTO conductive glass being coated with crystal seed layer in step (3) for substrate, and substrate is stood vertically and is fixed in reactor polytetrafluoroethylliner liner, then precursor solution prepared by step (4) is poured in reactor, by reactor isothermal reaction 4h in 190 DEG C of loft drier, after having reacted, take out reactor, cool with tap water, then with 60 DEG C of vacuum-dryings after deionized water rinsing, tungsten trioxide nanowires array film is obtained.
(6) 2.06g Disodium tungstate (Na2WO4) dihydrate is joined 500mL deionized water for stirring, add wherein with 1.25mL30wt% superoxol, drip perchloric acid and regulate pH to 1.2, obtain the electrolytic solution of galvanic deposit, in the electrolytic solution of galvanic deposit, the concentration of sodium wolframate is 12.5mM (mmol/L);
(7) with the tungsten oxide nanometer linear array obtained in step (5) for working electrode, Ag/AgCl electrode is reference electrode, platinum plate electrode is to electrode, electrolytic solution in step (6) is the electrolytic solution of electro deposition oxidation tungsten, electrochemical workstation CHI660E deposits 600s by the method for constant voltage deposition under-0.7V voltage, obtains non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films.
Carry out composition analysis and structure and performance characterization to the above-mentioned non-crystalline state/crystalline state Tungsten oxide 99.999 core-shell nano linear array electrochomeric films that obtains, measuring it is the coated array electrochomeric films of tungsten trioxide nano with nano-wire array pattern, and concrete outcome is as follows:
From X-ray diffraction analysis, tungsten trioxide nanowires array electrochomeric films skeleton tungsten trioxide nanowires prepared by the present embodiment belongs to hexagonal system structure tungstic oxide (JCPDSNo.85-2459; P63/mcm (193)), contrast (100) peak with other peak values and significantly strengthen with (200) peak value.Coated tungsten oxide film is noncrystalline membrane.
Scanning electronic microscope (SEM) is utilized to observe this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films surface, visible film surface has nano-wire array pattern, the diameter of nano wire is about 130nm, and single nano-wire surface is evenly coated by small-particle.
This non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films grows in substrate, and thickness is 1 ± 0.1 μm.
Spectrum change and the electrochromism response speed of above-mentioned non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films is tested with electrochemical workstation and spectrophotometer.The square-wave voltage of-0.7V to 1.0V is applied respectively in the aqueous sulfuric acid of 0.5mol/L, measure this non-crystalline state/crystalline state tungstic oxide core-shell nano linear array electrochomeric films at the transmitance changing value of 400 ~ 2100nm wavelength region with at 2.5 ~ 25 mum wavelength scope internal reflection rate changing values, and with the transmitance time of response at 750nm place for electrochromism speed.Result, as shown in table 1 and Fig. 3,4, is respectively 51.0% and 45.2% at 750nm and 2000nm transmitance changing value after visible embodiment 3 applies the square-wave voltage of-0.7V and 1.0V; 10 μm place reflectivity be changed to 40.6%, fade and painted response speed be respectively 4.4/6.4s.As can be seen here, above-mentioned obtained non-crystalline state/crystalline state tungstic oxide core-shell nano array electrochomeric films has in optical analogy regulation range that is visible and infrared band larger, the advantage of fast response time.
The optical modulation scope of table 1 embodiment 1 ~ 3 at different wave length place and response speed
Claims (10)
1. a preparation method for non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, is characterized in that, comprise the following steps:
1) white tungstic acid is dissolved in aqueous hydrogen peroxide solution, adds water and be mixed with the tungstic add peroxide solution that tungstenic concentration is 1 ~ 5mol/L, tungstic add peroxide solution is coated on the conducting surface of conductive substrates, obtains the conductive substrates being coated with crystal seed layer;
2) by soluble in water for tungsten source, adjust ph to 1 ~ 3.5, add ammonium sulfate, form precursor solution, the conductive substrates being coated with crystal seed layer is fixed in reactor, precursor solution is added in reactor, at 150 DEG C ~ 250 DEG C reaction 4h ~ 10h, after taking-up, obtain tungsten trioxide nanowires array film;
3) by soluble in water for tungsten source, drip hydrogen peroxide, adjust ph to 0.5 ~ 3, form electric depositing solution, utilizing constant voltage method to step 2) the tungsten trioxide nanowires array film electrode prepared carries out Electrodeposited Amorphous Tungsten oxide 99.999, obtains non-crystalline state/crystalline state tungstic oxide nucleocapsid structure electrochomeric films.
2. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, it is characterized in that, in step 1), the preparation of described white tungstic acid comprises: by hydrochloric acid and sodium wolframate aqueous solution, produce precipitation after reaction, the precipitation obtained after filtration is white tungstic acid.
3. the preparation method of non-crystalline state according to claim 2/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, it is characterized in that, in step 1), by hydrochloric acid and sodium wolframate aqueous solution be: in the sodium wolframate aqueous solution, drip hydrochloric acid, till not producing precipitation;
The concentration of described hydrochloric acid is 3 ~ 12mol/L;
In the described sodium wolframate aqueous solution, the concentration of sodium wolframate is 0.5 ~ 2mol/L.
4. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, it is characterized in that, in step 1), described conductive substrates need clean totally, comprise: first conductive substrates is cleaned with acetone, deionized water and EtOH Sonicate respectively, then blow clean with nitrogen.
5. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide core-shell nano linear array electrochomeric films, it is characterized in that, in step 1), tungstic add peroxide solution divide be coated in clean clean conductive substrates for 3 ~ 6 times conducting surface on, each spin coating instrument, all need 200 ~ 400 DEG C of insulations 5 ~ 20 minutes after each spin coating completes with the speed spin coating 20 ~ 50s of 2000 ~ 4000r/min.
6. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, is characterized in that, step 2) in, in described precursor solution, the concentration in tungsten source is 0.001 ~ 0.20mol/L;
Step 2) and 3) in, described tungsten source is one or more in sodium wolframate, tungstic add peroxide, wolframic acid;
Described water is deionized water.
7. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, is characterized in that, in step 3), utilizes perchloric acid regulator solution pH value to 0.5 ~ 3;
In described electric depositing solution, tungsten source concentration is 5 ~ 15mmol/L;
Described hydrogen peroxide and the volume ratio of water are 1:200 ~ 1250.
8. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, is characterized in that, in step 3), the voltage of described constant voltage method is-0.5 ~-1V, and depositing time is 100 ~ 1200s.
9. the preparation method of non-crystalline state according to claim 1/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, it is characterized in that, in step 3), with step 2) the tungsten trioxide nanowires array film prepared is working electrode, Ag/AgCl electrode is reference electrode, platinum plate electrode is to electrode, and electric depositing solution is the electrolytic solution of electro deposition oxidation tungsten.
10. non-crystalline state prepared by the preparation method according to any one of claim 1 ~ 9/crystalline state tungstic oxide nucleocapsid structure electrochomeric films, it is characterized in that, for the laminated film of tungstic oxide amorphous layer and crystalline state nano wire, the thickness of film is 0.2 ~ 2 μm, surface has nano-wire array pattern, is line clad structure.
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