CN109240014A - A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide - Google Patents
A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide Download PDFInfo
- Publication number
- CN109240014A CN109240014A CN201811236230.2A CN201811236230A CN109240014A CN 109240014 A CN109240014 A CN 109240014A CN 201811236230 A CN201811236230 A CN 201811236230A CN 109240014 A CN109240014 A CN 109240014A
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- flexible
- tungsten
- electrochromic film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a kind of flexible electrochromic film and its preparation method and application based on tungsten oxide, is made of unformed tungsten oxide, has loose porous nanotopography, with a thickness of 200~400nm, average pore size is about 100~300nm.The flexibility electrochomeric films shorten the path of electric charge transfer, therefore the electrochromic property of the flexibility electrochomeric films is good due to being not only conducive to the infiltration and contact of electrolyte with loose and porous structure, and optical modulation range is big.Flexible electrochromic film based on tungsten oxide of the invention has the characteristics that flexible bendable, and bending still has electrochromic property more than 90 °.Preparation method preparation process of the invention is simple, reaction temperature is mild, low in cost, provides a kind of possible preparation method for industrialized production tungsten oxide base flexibility electrochomeric films.
Description
Technical field
The invention belongs to flexible electrochromism film applications, in particular to a kind of flexible electrochromic film based on tungsten oxide
And its preparation method and application.
Background technique
Electrochromism (Eletrochromism) refers under the action of extra electric field, passes through charge (ion or electronics)
Injection or extraction, the optical properties (reflectivity, transmitance, absorptivity etc.) of material stablize, reversible color change shows
As showing as the reversible change of color and transparency in appearance.Electrochromic device can be adjusted under different voltages effect and be arrived
The light transmittance of different stage, and there is bistable performance, the state after color and transparency change does not need additional
Voltage can also be maintained persistently, therefore have bright prospects in terms of the green energy conservations such as smart window, Electronic Paper, anti-dazzle glasses.
The method that the electrochomeric films of existing business pass through magnetron sputtering, vacuum evaporation mostly, with brittle glass
For substrate, but since brittleness substrate limits, it is not able to satisfy the demand flexible such as bending, wearing, therefore exploitation flexible electrical mutagens
Color film is increasingly becoming the hot spot of research.Flexible electrochromism needs with flexible transparent conducting film to be basic material, realizes its light
Learn attribute (reflectivity, transmitance, absorptivity etc.) stablize under the action of extra electric field, reversible color change.But
Traditional preparation method and device package technique largely constrains the production and application of flexible electro-chromic device.
Tungsten oxide is a kind of indirect bandgap material, has electrochromic effect from Deb discovery tungsten oxide in 1969
Since, it is always to grind in electrochromism field since its electrochromic property is stable, optical modulation range is big, the response time is fast
The hot spot studied carefully.As traditional inorganic electrochromic material, the electrochromic effect of tungsten oxide shows as applying negative voltage to it
Its color can be from colourless transformation au bleu, and application its color of positive voltage can be changed into colourless from blue again.The electroluminescent change of tungsten oxide
Color performance depends primarily on its crystallinity and microstructure coloured silk looks.Fine and close tungsten oxide electrochomeric films are expanded by its low electronics
The defects of dissipating coefficient and long ion diffusion length restricts and cannot give full play to performance.Tungsten oxide electrochomeric films are prepared at present
Method mainly have magnetron sputtering, electron beam evaporation, sol-gel, hydro-thermal method, electro-deposition etc., but magnetron sputtering and electronics
Experiment condition needed for the methods of beam evaporation is harsh, and equipment is expensive, the oxidation of the traditional chemical routes such as sol-gel, hydro-thermal preparation
The adhesion of W film and substrate is poor, is easy to fall off from substrate, to influence electrochromic property.
105366954 A of Chinese patent CN discloses a kind of preparation method of nanometer tungsten oxide electrochomeric films, uses
Method of the liquid laser ablation in conjunction with electrophoretic deposition prepares tungsten oxide film, but required equipment is expensive, and step is complicated.China
104932169 A of patent CN discloses a kind of flexible electrochomeric films, prepares H using magnetron sputtering and czochralski method2WO4·
H2O film, but tungsten oxide film obtained is fine and close, and porosity is low.
Summary of the invention
The purpose of the present invention is above-mentioned tungsten oxide base flexibility electrochomeric films there are aiming at the problem that, propose a kind of letter
Single, easy-operating flexible electrochromic film based on tungsten oxide and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of flexible electrochromic film based on tungsten oxide, is made of unformed tungsten oxide, has loose porous receive
Rice pattern.The flexibility electrochromic film contracts due to loose and porous structure, being not only conducive to the infiltration and contact of electrolyte
The short path of electric charge transfer, therefore the electrochromic property of the flexibility electrochromic film is good, optical modulation range is big.
The flexibility electrochromic film has the characteristics that flexible bendable, and bending still has electrochromism more than 90 °
Energy.
The flexibility electrochromic film with a thickness of 200~400nm, loose porous aperture is 100~300nm.
A kind of preparation method of the flexible electrochromic film based on tungsten oxide, comprising the following steps:
(1) flexible cleaning substrate: flexible substrates are successively surpassed in acetone, isopropanol, dehydrated alcohol, deionized water respectively
Sound cleaning, naturally dry after cleaning, for use；
(2) spin coating tungsten oxide precursor liquid: taking tungsten oxide predecessor to be dissolved in dehydrated alcohol, is configured to tungsten oxide precursor liquid,
Then it is spun on step (1) treated in flexible substrates；
(3) it is heavy that flexible substrates obtained in step (2) ultraviolet light deposition: are transferred to progress ultraviolet light in ultraviolet lamp box
Product, and it is alternately repeated spin coating tungsten oxide precursor liquid and ultraviolet light deposition for several times；
(4) it is heat-treated: the surface that step (3) obtains is heated under air atmosphere with the flexible substrates of tungsten oxide
It handles, the flexible electrochromic film based on tungsten oxide is prepared after natural cooling.
In the step (1), flexible substrates are polyethylene terephthalate (PET), PI conductive film, silver-based is transparent leads
One kind of electrolemma, graphene-based transparent conductive film；The ultrasonic cleaning time is no less than 20min.
In the step (2), tungsten oxide predecessor is tungsten hexachloride, tungsten pentachloride, tungsten tetrachloride, tungsten dichloride, hexabromo
Change one or more mixtures of tungsten, tungsten tetraiodide, the concentration of tungsten oxide precursor liquid is 0.2~0.3M.
In the step (2), the condition of spin coating are as follows: 3000~4000rpm of revolving speed, time are 30~60s.
In the step (3), the condition of ultraviolet light deposition are as follows: ultraviolet lamp wavelength is 185~254nm, time of ultraviolet irradiation
For 3~5min.
In the step (4), the condition of heat treatment are as follows: 50~100 DEG C of temperature, 1~2h of time.
Flexible electrochromic film based on tungsten oxide of the invention can be applied in flexible electro-chromic device.
The utility model has the advantages that the present invention uses flexible material as conductive substrates, flexible degree is high, overcomes the electroluminescent change of tradition
Color film using substrate of glass in the case where bending is more than 90 ° due to, without the brittleness disadvantage such as bent, still being had certain
Electrochromic property, provide possibility to prepare flexible wearable electrochromic device.Flexibility tungsten oxide prepared by the present invention
Electrochomeric films are made of unformed tungsten oxide, have loose porous nanostructured morphologies, and thickness is about 200~400nm,
Average pore size is about 100~300nm.The electrochromic property of the film is stablized, and color change interval is big, the light near wavelength 700nm
It learns modulation range and is greater than 40%.The method system that flexible electrochromic film of the invention is combined using ultraviolet light deposition and heat treatment
, using flexible transparent conducting films such as PET, PI conductive films as substrate, overcome the limitation of the brittleness substrate such as traditional ITO, FTO.
The present invention prepares a kind of flexible electrochomeric films using the method that spin coating and ultraviolet light deposition combine, and splashes compared to traditional magnetic control
Penetrate, equipment cost needed for the methods of plasma enhanced chemical vapor deposition it is cheap, easy to operate, economical and practical.The preparation side
Method preparation simple process, reaction temperature are mild, low in cost, provide for industrialized production tungsten oxide base flexibility electrochomeric films
A kind of possible preparation method.
Detailed description of the invention
Fig. 1 is flexible electrochromism film scanning Electronic Speculum (SEM) figure of tungsten oxide prepared by embodiment 1；
Fig. 2 is flexible electrochromism film spectrum (EDS) figure of tungsten oxide prepared by embodiment 2；
Fig. 3 is flexible electrochomeric films X-ray diffraction (XRD) map of tungsten oxide prepared by embodiment 2；
Fig. 4 is the flexible electrochromism film transmission rate spectrogram of tungsten oxide prepared by embodiment 3；
Fig. 5 is flexible electrochomeric films cyclic voltammetric (CV) curve graph of tungsten oxide prepared by embodiment 3；
Fig. 6 is that the flexible electrochomeric films of tungsten oxide prepared by embodiment 4 colour (left side) and bleached state (right side) is curved
Bent photo.
Specific embodiment
A kind of flexible electrochromic film based on tungsten oxide of the invention, is made of unformed tungsten oxide, has loose
Porous nanotopography., with a thickness of 200~400nm, loose porous aperture is 100~300nm for it.The flexibility electrochromic film
Due to being not only conducive to the infiltration and contact of electrolyte with loose and porous structure, and the path of electric charge transfer is shortened, therefore
The electrochromic property of the flexibility electrochomeric films is good, and optical modulation range is big.In addition, flexible electrochromic film is with soft
Property bent feature, bending is more than 90 ° still with electrochromic property.
The preparation method of the above-mentioned flexible electrochromic film based on tungsten oxide, comprising the following steps:
(1) flexible cleaning substrate: flexible substrates are successively surpassed in acetone, isopropanol, dehydrated alcohol, deionized water respectively
Sound cleaning, naturally dry after cleaning, for use；
Wherein, flexible substrates are polyethylene terephthalate (PET), PI conductive film, silver-based transparent conductive film, graphite
One kind of alkenyl transparent conductive film；The ultrasonic cleaning time is no less than 20min；
(2) spin coating tungsten oxide precursor liquid: taking tungsten oxide predecessor to be dissolved in dehydrated alcohol, is configured to tungsten oxide precursor liquid,
Then it is spun on step (1) treated in flexible substrates；
Wherein, tungsten oxide predecessor is tungsten hexachloride, tungsten pentachloride, tungsten tetrachloride, tungsten dichloride, six tungsten bromides, the tetraiodo
Change one or more mixtures of tungsten, the concentration of tungsten oxide precursor liquid is 0.2~0.3M；The condition of spin coating are as follows: revolving speed 3000
~4000rpm, time are 30~60s；
(3) it is heavy that flexible substrates obtained in step (2) ultraviolet light deposition: are transferred to progress ultraviolet light in ultraviolet lamp box
Product, and it is alternately repeated spin coating tungsten oxide precursor liquid and ultraviolet light deposition for several times；
Wherein, the condition of ultraviolet light deposition are as follows: ultraviolet lamp wavelength is 185~254nm, and time of ultraviolet irradiation is 3~5min；
(4) it is heat-treated: the surface that step (3) obtains is heated under air atmosphere with the flexible substrates of tungsten oxide
It handles, the flexible electrochromic film based on tungsten oxide is prepared after natural cooling；
Wherein, the condition of heat treatment are as follows: 50~100 DEG C of temperature, 1~2h of time.
Flexible electrochromic film based on tungsten oxide of the invention can be applied in flexible electro-chromic device.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
The present embodiment is implemented premised on technical solution of the present invention, gives detailed embodiment and specific behaviour
Make process, but protection scope of the present invention is not limited to following embodiments, and only protection is specifically addressed.For example, in embodiment
Tungsten hexachloride not only can be used as precursor liquid, can also select tungsten pentachloride, tungsten tetrachloride, tungsten dichloride, six tungsten bromides,
Tungsten tetraiodide replacement.Flexible substrates can select PET, PI conductive film, silver-based transparent conductive film, graphene-based transparent conductive film.
Embodiment 1
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate is cleaned: by PET flexible substrates difference successively in acetone, isopropanol, dehydrated alcohol, deionized water
It is cleaned by ultrasonic 20min, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: weighing 1.2g tungsten hexachloride powder and be dissolved in 15mL dehydrated alcohol, and 20
Magnetic agitation 20min obtains tungsten oxide precursor liquid at DEG C, and setting revolving speed is 3000rpm, time 30s, by tungsten oxide precursor liquid
It is spin-coated in PET flexible substrates；
Step 3, PET flexible substrates obtained in step 2 ultraviolet light deposition: are transferred to the ultraviolet lamp that wavelength is 185nm
In case, 3min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 3 times, 3 layers of oxidation tungsten film are obtained；
Step 4, by obtained oxidation tungsten film under air atmosphere, it is that 5 DEG C/min is warming up to 50 DEG C with heating rate, carries out
Heat 1h, obtains tungsten oxide flexibility electrochromic film.
The tungsten oxide flexibility electrochromism film surface appearance prepared to embodiment 1 is analyzed, scanning electron microscopy
Mirror (SEM) figure is as shown in Figure 1, it can be seen that the tungsten oxide film obtained by ultraviolet light deposition is loose porous shape pattern, tool
There is biggish specific surface area, is conducive to the transmission infiltration of electrolyte.
Embodiment 2
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate is cleaned: by PET flexible substrates difference successively in acetone, isopropanol, dehydrated alcohol, deionized water
It is cleaned by ultrasonic 30min, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: the tungsten hexachloride powder for weighing 2g is dissolved in 20mL dehydrated alcohol, and 30
Magnetic agitation 30min obtains tungsten oxide precursor liquid at DEG C, and setting revolving speed is 3500rpm, time 45s, by tungsten oxide precursor liquid
It is spin-coated in PET flexible substrates；
Step 3, PET flexible substrates obtained in step 2 ultraviolet light deposition: are transferred to the ultraviolet lamp that wavelength is 254nm
In case, 3min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 7 times, 7 layers of oxidation tungsten film are obtained；
It step 4, is that 10 DEG C/min is warming up to 80 DEG C with heating rate by obtained tungsten oxide film under air atmosphere,
Heat treatment 2h is carried out, tungsten oxide flexibility electrochomeric films are obtained.
Energy spectrum analysis is carried out to tungsten oxide flexibility electrochomeric films prepared by embodiment 2, it is such as Fig. 2 this it appears that thin
The peak that wolfram element and oxygen element are only existed in film illustrates in the tungsten oxide film of preparation almost without residual chlorine element.To implementation
Tungsten oxide flexibility electrochomeric films prepared by example 2 carry out X-ray diffraction analysis, and as shown in Figure 3, prepared tungsten oxide is brilliant
Type is amorphous.
Embodiment 3
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate is cleaned: by PET flexible substrates difference successively in acetone, isopropanol, dehydrated alcohol, deionized water
It is cleaned by ultrasonic 30min, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: the tungsten hexachloride powder for weighing 3.85g is dissolved in 40mL dehydrated alcohol,
Magnetic agitation 30min obtains tungsten oxide precursor liquid at 30 DEG C, and setting revolving speed is 3000rpm, time 60s, by tungsten oxide forerunner
Liquid is spin-coated in PET flexible substrates；
Step 3, PET flexible substrates obtained in step 2 ultraviolet light deposition: are transferred to the ultraviolet lamp that wavelength is 185nm
In case, 5min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 10 times, obtains 10 layers of tungsten oxide
Film；
It step 4, is that 10 DEG C/min is warming up to 100 DEG C with heating rate by obtained oxidation tungsten film in air atmosphere, into
Row heat treatment 2h, obtains tungsten oxide flexibility electrochomeric films.
Ultraviolet-visible spectrum characterization is carried out to embodiment 3, wave-length coverage chooses 400~900nm, coloration voltage and colour fading
Voltage is respectively -1.0V and 0.6V, and the light transmittance curve for obtaining corresponding coloured state and colour fading state is as shown in Figure 4.As seen from the figure,
Film Optics modulation range (Δ T%) is greater than 40% near 700nm wavelength.
Fig. 5 is a kind of cyclic voltammetric (CV) the curve characterization of flexible electrochomeric films prepared by the embodiment of the present invention 3, is adopted
It is tested with Shanghai Chen Hua CHI660E electrochemical workstation three-electrode system.Wherein surface is covered with ultraviolet light to be deposited with tungsten oxide thin
The PET flexible substrates of film are working electrode, and Pt piece is to electrode, and Ag/AgCl is reference electrode, and electrolyte is the H of 0.5M2SO4It is molten
Liquid.It is -1.2~1V, sweep speed 50Mv/ that the cyclic voltammetry curve of tungsten oxide flexibility electrochomeric films, which is in voltage range,
s.As seen from the figure, prepared stable circulation performance is good.
Embodiment 4
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate is cleaned: by PET flexible substrates difference successively in acetone, isopropanol, dehydrated alcohol, deionized water
It is cleaned by ultrasonic 30min, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: the tungsten hexachloride powder for weighing 1.47g is dissolved in 15mL dehydrated alcohol,
Magnetic agitation 30min obtains tungsten oxide precursor liquid at 25 DEG C, and setting revolving speed is 3500rpm, time 45s, by tungsten oxide forerunner
Liquid is spin-coated in PET flexible substrates；
Step 3, PET flexible substrates obtained in step 2 ultraviolet light deposition: are transferred to the ultraviolet lamp that wavelength is 200nm
In case, 5min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 5 times, 5 layers of oxidation tungsten film are obtained；
Step 4, by obtained oxidation tungsten film in air atmosphere, 100 DEG C of progress are warming up to 10 DEG C/min of heating rate
It is heat-treated 1h, obtains tungsten oxide flexibility electrochomeric films.
Fig. 6 is a kind of number of flexible electrochomeric films for preparing in the embodiment of the present invention 4 under coloured state and colour fading state
Code photo figure, it can be seen that obtained thin film flexible is good.
Embodiment 5
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate clean: by silver-based transparent conductive film substrate respectively successively in acetone, isopropanol, dehydrated alcohol, go
It is cleaned by ultrasonic 20min in ionized water, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: the tungsten hexachloride powder for weighing 4.7g is dissolved in 30mL dehydrated alcohol,
Magnetic agitation 25min obtains tungsten oxide precursor liquid at 28 DEG C, and setting revolving speed is 4000rpm, time 30s, by tungsten oxide forerunner
Liquid is spin-coated in silver-based transparent conductive film substrate；
Step 3, ultraviolet light deposition, it is 185nm's that silver-based transparent conductive film substrate obtained in step 2, which is transferred to wavelength,
In ultraviolet lamp box, 5min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 8 times, 8 layers of oxidation are obtained
Tungsten film；
Step 4, by obtained oxidation tungsten film in air atmosphere, 60 DEG C is warming up to 5 DEG C/min of heating rate, carries out heat
2h is handled, tungsten oxide flexibility electrochomeric films are obtained.
Embodiment 6
It is a kind of flexible electrochomeric films based on tungsten oxide in the present embodiment, preparation method includes the following steps:
Step 1, substrate is cleaned: by PI flexible conducting substrate respectively successively in acetone, isopropanol, dehydrated alcohol, deionization
It is cleaned by ultrasonic 30min in water, removes the spots such as dust, the organic matter on surface, naturally dry after cleaning, for use；
Step 2, spin coating tungsten hexachloride precursor liquid: the tungsten hexachloride powder for weighing 1.42g is dissolved in 18mL dehydrated alcohol,
Magnetic agitation 30min obtains tungsten oxide precursor liquid at 27 DEG C, and setting revolving speed is 3200rpm, time 50s, by tungsten oxide forerunner
Liquid is spin-coated on PI flexible conducting substrate；
Step 3, ultraviolet light deposition: it is the ultraviolet of 200nm that PI flexible conducting substrate obtained in step 2, which is transferred to wavelength,
In lamp box, 3min is irradiated by the way of ultraviolet light deposition, is alternately repeated step 2 and step 3 totally 6 times, obtains 6 layers of tungsten oxide
Film；
Step 4, by obtained oxidation tungsten film in air atmosphere, 90 DEG C of progress heat are warming up to 10 DEG C/min of heating rate
1h is handled, tungsten oxide flexibility electrochomeric films are obtained.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flexible electrochromic film based on tungsten oxide, it is characterised in that: it is made of unformed tungsten oxide, has loose
Porous nanotopography.
2. the flexible electrochromic film according to claim 1 based on tungsten oxide, it is characterised in that: the flexible electrical mutagens
Color film has the characteristics that flexible bendable, and bending still has electrochromic property more than 90 °.
3. the flexible electrochromic film according to claim 1 based on tungsten oxide, it is characterised in that: the flexible electrical mutagens
Color film with a thickness of 200~400nm, loose porous aperture is 100~300nm.
4. a kind of preparation method of the flexible electrochromic film based on tungsten oxide, it is characterised in that: the following steps are included:
(1) flexible cleaning substrate: by flexible substrates, successively ultrasound is clear in acetone, isopropanol, dehydrated alcohol, deionized water respectively
It washes, naturally dry after cleaning, for use；
(2) spin coating tungsten oxide precursor liquid: taking tungsten oxide predecessor to be dissolved in dehydrated alcohol, is configured to tungsten oxide precursor liquid, then
It is spun on step (1) treated in flexible substrates；
(3) ultraviolet light deposition: flexible substrates obtained in step (2) being transferred in ultraviolet lamp box and carry out ultraviolet light deposition, and
It is alternately repeated spin coating tungsten oxide precursor liquid and ultraviolet light deposition for several times；
(4) it is heat-treated: the surface that step (3) obtains is carried out at heating under air atmosphere with the flexible substrates of tungsten oxide
It manages, the flexible electrochromic film based on tungsten oxide is prepared after natural cooling.
5. according to right want 4 described in the flexible electrochromic film based on tungsten oxide preparation method, it is characterised in that: the step
Suddenly in (1), flexible substrates are polyethylene terephthalate, PI conductive film, silver-based transparent conductive film, graphene-based transparent lead
One kind of electrolemma；The ultrasonic cleaning time is no less than 20min.
6. according to right want 4 described in the flexible electrochromic film based on tungsten oxide preparation method, it is characterised in that: the step
Suddenly in (2), tungsten oxide predecessor is tungsten hexachloride, tungsten pentachloride, tungsten tetrachloride, tungsten dichloride, six tungsten bromides, tungsten tetraiodide
One or more mixtures, the concentration of tungsten oxide precursor liquid are 0.2~0.3M.
7. according to right want 4 described in the flexible electrochromic film based on tungsten oxide preparation method, it is characterised in that: the step
Suddenly in (2), the condition of spin coating are as follows: 3000~4000rpm of revolving speed, time are 30~60s.
8. according to right want 4 described in the flexible electrochromic film based on tungsten oxide preparation method, it is characterised in that: the step
Suddenly in (3), the condition of ultraviolet light deposition are as follows: ultraviolet lamp wavelength is 185~254nm, and time of ultraviolet irradiation is 3~5min.
9. according to right want 4 described in the flexible electrochromic film based on tungsten oxide preparation method, it is characterised in that: the step
Suddenly in (4), the condition of heat treatment are as follows: 50~100 DEG C of temperature, 1~2h of time.
10. the application of flexible electrochromic film in flexible electro-chromic device described in claim 1 based on tungsten oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811236230.2A CN109240014A (en) | 2018-10-23 | 2018-10-23 | A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811236230.2A CN109240014A (en) | 2018-10-23 | 2018-10-23 | A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109240014A true CN109240014A (en) | 2019-01-18 |
Family
ID=65081438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811236230.2A Pending CN109240014A (en) | 2018-10-23 | 2018-10-23 | A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109240014A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942023A (en) * | 2019-04-17 | 2019-06-28 | 同济大学 | A kind of metal ion mixing WO3Gas chromism film and its preparation method and application |
| CN110095912A (en) * | 2019-03-21 | 2019-08-06 | 天津城建大学 | A kind of WO3/MoO3The preparation method of composite electrochromic film |
| CN110467357A (en) * | 2019-08-01 | 2019-11-19 | 西安理工大学 | A kind of tungsten oxide film and preparation method thereof with horn-like pore structure |
| CN110488549A (en) * | 2019-09-10 | 2019-11-22 | 南京邮电大学 | A kind of large area pattern solid-state electrochromic film and its preparation method and application |
| CN110488551A (en) * | 2019-08-23 | 2019-11-22 | 南京邮电大学 | A kind of flexibility electrochromism sull, device and preparation method thereof |
| CN112441750A (en) * | 2019-08-28 | 2021-03-05 | 山西利虎玻璃（集团）有限公司 | Method for preparing tungsten oxide electrochromic film by electrochemical deposition method |
| CN114214595A (en) * | 2021-11-04 | 2022-03-22 | 万津实业(赤壁)有限公司 | Method for plating oxide optical film on flexible substrate and optical composite component |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969904A (en) * | 2014-05-26 | 2014-08-06 | 电子科技大学 | Preparation method for flexible electrochromic layer and device |
| CN104375350A (en) * | 2014-10-31 | 2015-02-25 | 合肥博一环保科技有限公司 | Multifunctional controllable electrochromic device and manufacturing method thereof |
| CN104492675A (en) * | 2014-11-17 | 2015-04-08 | 中山大学 | Low-temperature electrochromic NiO film preparation method |
| CN107216045A (en) * | 2017-05-22 | 2017-09-29 | 浙江大学 | A kind of preparation method of tungsten trioxide nanowires electrochomeric films |
| CN108227332A (en) * | 2018-01-16 | 2018-06-29 | 南京邮电大学 | A kind of electrochromic device based on organic/inorganic composite material and preparation method thereof |
| CN108298832A (en) * | 2017-12-29 | 2018-07-20 | 浙江大学 | Tungsten oxide electrochomeric films and preparation method thereof with EO-1 hyperion adjustable range |
| CN108663868A (en) * | 2018-07-05 | 2018-10-16 | 东华大学 | A kind of preparation method of tungsten oxide electrochromic electrode |
-
2018
- 2018-10-23 CN CN201811236230.2A patent/CN109240014A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969904A (en) * | 2014-05-26 | 2014-08-06 | 电子科技大学 | Preparation method for flexible electrochromic layer and device |
| CN104375350A (en) * | 2014-10-31 | 2015-02-25 | 合肥博一环保科技有限公司 | Multifunctional controllable electrochromic device and manufacturing method thereof |
| CN104492675A (en) * | 2014-11-17 | 2015-04-08 | 中山大学 | Low-temperature electrochromic NiO film preparation method |
| CN107216045A (en) * | 2017-05-22 | 2017-09-29 | 浙江大学 | A kind of preparation method of tungsten trioxide nanowires electrochomeric films |
| CN108298832A (en) * | 2017-12-29 | 2018-07-20 | 浙江大学 | Tungsten oxide electrochomeric films and preparation method thereof with EO-1 hyperion adjustable range |
| CN108227332A (en) * | 2018-01-16 | 2018-06-29 | 南京邮电大学 | A kind of electrochromic device based on organic/inorganic composite material and preparation method thereof |
| CN108663868A (en) * | 2018-07-05 | 2018-10-16 | 东华大学 | A kind of preparation method of tungsten oxide electrochromic electrode |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095912A (en) * | 2019-03-21 | 2019-08-06 | 天津城建大学 | A kind of WO3/MoO3The preparation method of composite electrochromic film |
| CN109942023A (en) * | 2019-04-17 | 2019-06-28 | 同济大学 | A kind of metal ion mixing WO3Gas chromism film and its preparation method and application |
| CN109942023B (en) * | 2019-04-17 | 2022-04-05 | 同济大学 | Metal ion doped WO3Gasochromic film and preparation method and application thereof |
| CN110467357A (en) * | 2019-08-01 | 2019-11-19 | 西安理工大学 | A kind of tungsten oxide film and preparation method thereof with horn-like pore structure |
| CN110467357B (en) * | 2019-08-01 | 2021-10-22 | 西安理工大学 | Tungsten oxide film with horn-shaped pore structure and preparation method thereof |
| CN110488551A (en) * | 2019-08-23 | 2019-11-22 | 南京邮电大学 | A kind of flexibility electrochromism sull, device and preparation method thereof |
| CN112441750A (en) * | 2019-08-28 | 2021-03-05 | 山西利虎玻璃（集团）有限公司 | Method for preparing tungsten oxide electrochromic film by electrochemical deposition method |
| CN110488549A (en) * | 2019-09-10 | 2019-11-22 | 南京邮电大学 | A kind of large area pattern solid-state electrochromic film and its preparation method and application |
| CN110488549B (en) * | 2019-09-10 | 2021-10-26 | 南京邮电大学 | Large-area patterned solid electrochromic film and preparation method and application thereof |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN114994997B (en) * | 2021-03-01 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN114214595A (en) * | 2021-11-04 | 2022-03-22 | 万津实业(赤壁)有限公司 | Method for plating oxide optical film on flexible substrate and optical composite component |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109240014A (en) | A kind of flexible electrochromic film and its preparation method and application based on tungsten oxide | |
| Yin et al. | Reactive sputter deposition of WO3/Ag/WO3 film for indium tin oxide (ITO)-free electrochromic devices | |
| Cai et al. | Hierarchical structure Ti-doped WO 3 film with improved electrochromism in visible-infrared region | |
| CN103903862B (en) | A kind of transparent flexible electrochemical device based on plane comb-like electrode structure and preparation method thereof | |
| Wang et al. | Pulsed electrochemical deposition of porous WO 3 on silver networks for highly flexible electrochromic devices | |
| CN107163928B (en) | A kind of tungstic acid/vanadic anhydride core-shell nano linear array electrochromic material and preparation method thereof | |
| CN107033892B (en) | A kind of polythiophene/tungsten trioxide nano-rod electrochromic material and preparation method thereof | |
| CN106782769A (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| CN106159040B (en) | A kind of method that Whote-wet method prepares flexible metal network transparency electrode | |
| CN105859151B (en) | A kind of method that spray coating method prepares the porous electrochomeric films of large area | |
| Wang et al. | High performance visible and near-infrared region electrochromic smart windows based on the different structures of polyoxometalates | |
| CN101576695A (en) | WO3 electrochromic thin film preparation method | |
| Kumara et al. | Preparation of fluoride-doped tin oxide films on soda–lime glass substrates by atomized spray pyrolysis technique and their subsequent use in dye-sensitized solar cells | |
| CN102220637A (en) | Micron/nanometer hierarchical structure of BiOCl, BiOBr and Bi2S3 | |
| Lv et al. | Transferable TiO2 nanotubes membranes formed via anodization and their application in transparent electrochromism | |
| CN102849963A (en) | Method for preparing WO3 film | |
| CN108996918A (en) | A kind of nano NiOxElectrochomeric films and its preparation method and application | |
| CN107512854B (en) | ITO/WO with nano mosaic structure3Composite electrochromic film and preparation method thereof | |
| CN107561811A (en) | A kind of flexible electrochromic electrode based on tungstic acid/zinc oxide and its preparation method and application | |
| Hua et al. | Enhanced electrochromic tungsten oxide by bio-inspired brochosomes | |
| CN109881198B (en) | Preparation method of multi-color electrochromic film with tin dioxide/vanadium pentoxide core-shell structure | |
| CN109119540A (en) | SnO is adulterated in F2SnO is prepared in situ on transparent conductive film matrix2The method of electron transfer layer | |
| CN107188236B (en) | A kind of preparation method of tungsten oxide nanometer band structure electrochomeric films | |
| CN110400703A (en) | A kind of preparation method of flexible and transparent supercapacitor | |
| CN112062170B (en) | Hydrothermal preparation method of nickel oxide electrochromic film with graded porous morphology and structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |
|
| RJ01 | Rejection of invention patent application after publication |