CN110967887B - Electrochromic film and preparation method thereof - Google Patents
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Abstract
The invention provides an electrochromic film which comprises a substrate and an electrochromic layer arranged on the substrate in a laminated mode, wherein the electrochromic layer comprises W which are mutually wound 18 O 49 A nanowire. The invention also provides a preparation method of the electrochromic film, which comprises the following steps: adding a tungsten salt, polyvinyl alcohol and polyvinylpyrrolidone into absolute ethyl alcohol to form a first solution; carrying out solvothermal reaction on the first solution to form intertwined W 18 O 49 A nanowire; winding the W around each other 18 O 49 Nanowires are disposed on the substrate, thereby forming an electrochromic layer on the substrate.
Description
Technical Field
The invention relates to an electrochromic film and a preparation method thereof, in particular to a film containing W 18 O 49 The electrochromic film and the preparation method thereof.
Background
Electrochromism (EC) refers to a phenomenon that the optical properties of a material generate stable and reversible color changes under the action of an applied electric field, and the optical properties of the material show reversible changes in color and transparency. When current flows, the electrochromic film generates color change, and the original color is kept unchanged after the current is cut off. When a reverse current is applied to the electrochromic film, the film discolors. Therefore, the electrochromic film has wide application prospect in the fields of display devices, automobiles, military camouflage, intelligent materials, energy-saving building materials and the like.
At present, electrochromic films are divided into inorganic and organic types, and the electrochromic material in the inorganic electrochromic film is mainly tungsten trioxide (WO) 3 ) It has the advantages of stable chemical property and obvious color change. However, tungsten trioxide has the disadvantages of a small optical modulation range, a slow color change speed, and the like, which hinders practical application thereof. On the other hand, W 18 O 49 The application of the material as a novel material in the field of inorganic electrochromism is receiving more and more attention.
Disclosure of Invention
Accordingly, it is necessary to provide an electrochromic film having a wide optical modulation range and a high color change speed.
The invention provides an electrochromic film, which comprises a substrate and a layerStacking an electrochromic layer comprising W intertwined with each other disposed on a substrate 18 O 49 A nanowire.
In one embodiment, the substrate is a flexible transparent conductive substrate, and comprises a flexible substrate and a transparent conductive layer arranged between the electrochromic layer and the flexible substrate.
In one embodiment, the optical modulation at a wavelength of 633nm ranges from 15% to 40%.
In one embodiment, the coloring time is 12s to 14s and the fading time is 10s to 12 s.
In one embodiment, W is 18 O 49 The nanowires have a diameter of 5nm to 10nm and a length of 10 μm to 20 μm.
The invention also provides a preparation method of the electrochromic film, which comprises the following steps:
adding a tungsten salt, polyvinyl alcohol and polyvinylpyrrolidone into absolute ethyl alcohol to form a first solution;
carrying out solvothermal reaction on the first solution to form intertwined W 18 O 49 A nanowire;
the W wound with each other 18 O 49 Nanowires are disposed on the substrate, thereby forming an electrochromic layer on the substrate.
In one embodiment, the temperature of the solvothermal reaction is 140 ℃ to 250 ℃ and the reaction time is 24h to 48 h.
In one embodiment, the molar concentration of the tungsten salt in the first solution is 3 × 10 -4 mol/L to 2X 10 -3 mol/L。
In one embodiment, the tungsten salt is WCl 6 。
In one embodiment, the volume ratio of the polyethylene glycol to the absolute ethyl alcohol in the first solution is 1:4 to 1: 8.
In one embodiment, the polyvinylpyrrolidone is added in the first solution in an amount of 0.01g to 0.1g per 100mL of anhydrous ethanol.
In one embodiment, the method further comprises adding at least one of polyvinyl alcohol and cyclohexanol to the first solution.
In one embodiment, the at least one of polyvinyl alcohol and cyclohexanol is added in an amount of 0.01g to 0.1g per 100mL of anhydrous ethanol in the first solution.
In one embodiment, the step of subjecting the first solution to a solvothermal reaction yields a solution containing the intertwined W 18 O 49 A second solution of the nanowires is then added,
the W to be intertwined 18 O 49 The step of disposing nanowires on the substrate includes disposing the second solution on the substrate, and drying the second solution on the substrate.
In one embodiment, the step of disposing the second solution on the substrate is disposing the second solution on the substrate by atomized deposition.
In one embodiment, the step of subjecting the first solution to a solvothermal reaction yields a solution containing the intertwined W 18 O 49 A second solution of the nanowires is then added,
the W to be intertwined 18 O 49 The step of disposing the nanowires on the substrate includes adding a dispersant and an active agent to the second solution to mix them to obtain a dispersion, disposing the dispersion on the substrate, and drying the dispersion on the substrate.
In one embodiment, the substrate is a flexible transparent conductive substrate.
The invention is realized by winding W mutually 18 O 49 The nano-wires are arranged on the substrate to be used as an electrochromic layer, so that the electrochromic film with a large optical modulation range and a high color-changing speed is obtained. The preparation method of the electrochromic film can directly form W which is mutually wound 18 O 49 Nanowires, and W intertwined with each other 18 O 49 Nanowire and method of manufacturing the sameHas a large number of oxygen vacancies, thereby increasing the ion and electron insertion/extraction sites and further improving the optical modulation range and the color change speed of the electrochromic film. In addition, in the preparation method of the electrochromic film of the present invention, W is obtained by solvothermal reaction 18 O 49 The solution of the nano wire can be directly dried on the substrate to form a film without purification, the process is simple, the process is controllable, the cost is low, and the purification process of W can be avoided 18 O 49 The electrochromic properties of the nanowires are adversely affected.
Drawings
FIG. 1 shows W in an electrochromic film provided in example 1 of the present invention 18 O 49 Scanning Electron Microscope (SEM) photographs of the nanowires;
FIG. 2 shows W in an electrochromic film provided in example 1 of the present invention 18 O 49 An X-ray diffraction (XRD) spectrum of the nanowire;
FIG. 3 shows W in an electrochromic film provided in example 2 of the present invention 18 O 49 SEM photograph of the nanowires;
FIG. 4 shows W in an electrochromic film provided in example 3 of the present invention 18 O 49 SEM photograph of the nanowires;
FIG. 5 is a graph showing the transmittance of an electrochromic film provided in example 5 of the present invention in a colored state and a non-colored state;
fig. 6 is a graph showing the transmittance of the electrochromic film according to example 5 of the present invention as a function of time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides an electrochromic film which comprises a substrate and an electrochromic layer arranged on the substrate in a laminated mode, wherein the electrochromic layer comprises W which are mutually wound 18 O 49 A nanowire.
The electrochromic film is formed by winding W around each other 18 O 49 The nano-wires are arranged on the substrate to be used as an electrochromic layer, so that the electrochromic film with a large optical modulation range and a high color-changing speed is obtained.
W intertwined with each other in the electrochromic film 18 O 49 The nano-wire has a large number of oxygen vacancies, thereby increasing the insertion/extraction sites of ions and electrons and further improving the optical modulation range and the color-changing speed of the electrochromic film.
The electrochromic film can be applied to electrochromic devices, such as electrochromic intelligent windows, can effectively reduce the radiation of sunlight and has the functions of energy conservation and temperature regulation.
In some embodiments, the electrochromic film has an optical modulation at a wavelength of 633nm in the range of 15% to 40%. Preferably, the optical modulation range of the electrochromic film at the wavelength of 633nm is 23% to 37.33%.
In some embodiments, the electrochromic film has a tinting time of 12s to 14s and a fade time of 10s to 12 s. Preferably, the coloring time of the electrochromic film is 12.8s to 13.6 s, and the fading time is 10.6s to 11.6 s.
The electrochromic film may further include an electron transport layer. Preferably, the substrate is a flexible transparent conductive substrate, and comprises a flexible substrate and a transparent conductive layer arranged between the electrochromic layer and the flexible substrate. The material of the transparent conductive layer can be selected to be Indium Tin Oxide (ITO), and the material of the flexible substrate can be selected to be polyethylene terephthalate (PET).
In the electrochromic film, W 18 O 49 The nanowires are preferably 5nm to 10nm in diameter and 10 μm to 20 μm in length. The electrochromic layer is formed by winding W 18 O 49 A porous network structure formed by the nanowires. In one embodiment, the electrochromic layer consists of only the intertwined W 18 O 49 And (4) forming the nano wire.
The embodiment of the invention also provides a preparation method of the electrochromic film, which is used for preparing the electrochromic film and comprises the following steps:
adding a tungsten salt, polyvinyl alcohol and polyvinylpyrrolidone into absolute ethyl alcohol to form a first solution;
carrying out solvothermal reaction on the first solution to form intertwined W 18 O 49 A nanowire;
winding the W around each other 18 O 49 Nanowires are disposed on the substrate, thereby forming an electrochromic layer on the substrate.
In the preparation method of the electrochromic film, the combined reaction system of tungsten salt, polyvinyl alcohol, polyvinylpyrrolidone and absolute ethyl alcohol is adopted in a solvothermal method, so that the W which is intertwined with each other can be directly formed 18 O 49 Nanowires, and W intertwined with each other 18 O 49 The nano-wire has a large number of oxygen vacancies, thereby increasing the ion and electron embedding/extracting sites and improving the optical modulation range and the color changing speed of the electrochromic film. And W contained by solvothermal reaction 18 O 49 The second solution of the nanowire can be directly dried on the substrate to form a thin film without purification, the process is simple, the process is controllable, the cost is low, and the purification process of W can be avoided 18 O 49 The electrochromic properties of the nanowires are adversely affected.
Preferably, the tungsten salt is WCl 6 . Preferably, the molar concentration of the tungsten salt in the first solution is 3 × 10 -4 mol/L to 2X 10 -3 mol/L。
The absolute ethyl alcohol is simultaneously used as a solvent and a reducing agent in a reaction system and used for reducing the tungsten salt to obtain W 18 O 49 。
The molecular weight of the polyethylene glycol is preferably 190 to 220, more preferably 200. In the first solution, the volume ratio of the polyethylene glycol to the anhydrous ethanol is preferably 1:4 to 1:8, more preferably 1: 6.
The molecular weight of the polyvinylpyrrolidone is preferably 8000 to 700000, more preferably 10000 to 150000. In the first solution, the polyvinylpyrrolidone is added in an amount of 0.01 to 0.1g, more preferably 0.025 to 0.05g, per 100mL of anhydrous ethanol.
Preferably, the step of forming the first solution includes mixing polyethylene glycol, ethanol and tungsten salt to fully dissolve the tungsten salt, adding polyvinylpyrrolidone, and continuously stirring until the mixture is uniformly mixed to form the first solution.
Preferably, the preparation method further comprises the step of adding polyvinyl alcohol to the first solution, wherein the polyvinyl alcohol can be used as a stabilizer and can enable the W to be generated 18 O 49 The shape of the nano-wire is more uniform. Preferably, the polyvinyl alcohol is added in an amount of 0.01 to 0.1g, more preferably 0.025 to 0.05g, per 100mL of anhydrous ethanol. Preferably, the polyvinyl alcohol has a molecular weight of 10000 to 150000.
Preferably, the preparation method further comprises the step of adding cyclohexanol, which can be used as a surfactant, to the first solution so that W is generated 18 O 49 The nanowires have a larger aspect ratio. Preferably, the cyclohexanol is added in an amount of 0.01g to 0.1g, more preferably 0.025g to 0.05g, per 100mL of anhydrous ethanol.
The reaction system is preferably an anhydrous system, i.e. the first solution of the solvent thermal reaction contains no water. In one embodiment, the reaction system, i.e., the first solution, consists only of tungsten salt, absolute ethanol, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, and cyclohexanol.
Optionally, the reaction vessel for the solvothermal reaction is a sealable polytetrafluoroethylene reaction kettle.
The temperature of the solvothermal reaction is 140 ℃ to 250 ℃. Preferably, the temperature of the solvothermal reaction is 140 ℃ to 200 ℃. The relatively low temperature is more favorable for the W produced 18 O 49 The nano-wire contains more oxygen vacancies, and ion and electron insertion/extraction sites are increased. Preferably, the solvothermal reaction process is carried out for a period of 24h to 48 h.
The W containing intertwining can be obtained by solvothermal reaction 18 O 49 A second solution of nanowires, the W in the second solution 18 O 49 The concentration of the nanowires is 0.0001 to 0.1g/mL, preferably 0.0001 to 0.08g/mL, more preferably 0.0001 to 0.05 g/mL.
The second solution can be used directly for the preparation of the electrochromic layer. In one embodiment, the second solution may be directly disposed on the substrate, and the second solution layer on the substrate may be dried, so as to obtain the electrochromic layer. The drying temperature is preferably 60 ℃ to 120 ℃, more preferably, the drying temperature is 80 ℃ to 100 ℃.
Preferably, the second solution is deposited on the substrate by spin coating, spray coating or aerosol deposition. More preferably, the second solution is deposited on the substrate by aerosol deposition. Compared with the common spraying method, the atomization deposition can form fine and uniform mist through the secondary atomization step, and the mist deposition can form a more uniform film of the second solution on the substrate. Experiments prove that the optical modulation range of the electrochromic film can be larger by forming the film through atomization deposition.
Alternatively, an electrochromic layer of a desired thickness may be obtained by forming the second solution on the substrate a plurality of times and drying. Preferably, the electrochromic layer has a thickness of 2 to 3 μm.
In another embodiment, a dispersant and an active agent may be further added to the second solution, mixed and ultrasonically dispersed to obtain a dispersion, and then the dispersion is disposed on the substrate, and the layer of the dispersion on the substrate is dried to obtain the electrochromic layer. The dispersant is preferably N, N-dimethylformamide and the activator is preferably an FC-4430 activator.
Example 1
And cleaning the PET-ITO flexible transparent conductive substrate with ethanol and deionized water in sequence, and drying for later use. 0.02g WCl was weighed 6 Adding 10mL of polyethylene glycol with molecular weight of 200 into 60mL of anhydrous ethanol, adding 0.02g of polyvinylpyrrolidone into the anhydrous ethanol, and continuously stirring for 4-6 h to form a uniform transparent first layerA solution. And putting the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at 140-200 ℃ for 24h to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then placing the PET-ITO flexible transparent conductive substrate in an oven at 80 ℃ for drying to obtain W 18 O 49 A PET-ITO flexible electrochromic film. Referring to fig. 1, the formed W can be seen by observing the morphology of the electrochromic layer formed on the flexible transparent conductive substrate through a scanning electron microscope 18 O 49 The nanowires are uniformly distributed and intertwined with each other to form a porous network structure. Referring to FIG. 2, it can be seen that W 18 O 49 Existence of characteristic peak proves component W of the obtained nanowire 18 O 49 。
Example 2
This example was substantially the same as the production method of example 1 except that polyvinyl alcohol was further added to the reaction system.
Specifically, the PET-ITO flexible transparent conductive substrate is sequentially cleaned by ethanol and deionized water and dried for later use. 0.02g WCl was weighed 6 Adding 10mL of polyethylene glycol with molecular weight of 200 into 60mL of absolute ethyl alcohol, adding 0.02g of polyvinyl alcohol and 0.02g of polyvinylpyrrolidone into the absolute ethyl alcohol, and continuously stirring for 4-6 h to form a uniform and transparent first solution. And putting the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at the temperature of 140-200 ℃ for 24 hours to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then placing the PET-ITO flexible transparent conductive substrate in an oven at 80 ℃ for drying to obtain W 18 O 49 A PET-ITO flexible electrochromic film. Referring to fig. 3, the formed W can be seen by observing the morphology of the electrochromic layer formed on the flexible transparent conductive substrate through a scanning electron microscope 18 O 49 The nanowires are uniformly distributed and intertwined with each other to form a porous network structure.
Example 3
This example was substantially the same as the production method of example 1 except that polyvinyl alcohol and cyclohexanol were further added to the reaction system.
Specifically, the PET-ITO flexible transparent conductive substrate is sequentially cleaned by ethanol and deionized water and dried for later use. 0.02g WCl was weighed 6 Adding 10mL of polyethylene glycol with molecular weight of 200 into 60mL of absolute ethanol, adding 0.02g of polyvinyl alcohol, 0.02g of polyvinylpyrrolidone and 0.02g of cyclohexanol into the absolute ethanol, and continuously stirring for 4-6 h to form a uniform and transparent first solution. And putting the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at 140-200 ℃ for 24h to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then drying in an oven at 80 ℃ to obtain W 18 O 49 A PET-ITO flexible electrochromic film. Referring to fig. 4, the formed W can be seen by observing the morphology of the electrochromic layer formed on the flexible transparent conductive substrate through a scanning electron microscope 18 O 49 The nanowires are uniformly distributed and intertwined with each other to form a porous network structure.
Example 4
This example was substantially the same as the production method of example 1 except that cyclohexanol was further added to the reaction system.
Specifically, the PET-ITO flexible transparent conductive substrate is sequentially cleaned by ethanol and deionized water and dried for later use. 0.02g WCl was weighed 6 Dissolving 10mL of polyethylene glycol with molecular weight of 200 in 60mL of absolute ethanol, adding 0.02g of polyvinylpyrrolidone and 0.02g of cyclohexanol into the absolute ethanol, and continuously stirring for 4-6 h to form a uniform and transparent first solution. And putting the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at 140-200 ℃ for 24h to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then placing the PET-ITO flexible transparent conductive substrate in an oven at 80 ℃ for drying to obtain W 18 O 49 A PET-ITO flexible electrochromic film.
Example 5
This example is prepared in essentially the same manner as example 3, except that the second solution is atomized by atomization deposition to be finer than spray coatingThe uniform mist is deposited on a PET-ITO flexible transparent conductive substrate to form a more uniform film of a second solution, and then the film is placed in a drying oven at 80 ℃ to be dried to obtain W 18 O 49 PET-ITO flexible electrochromic film.
Comparative example 1
Comparative example 1 the preparation method was substantially the same as that of example 1 except that WCl was used only in the reaction system 6 And ethanol.
Specifically, the PET-ITO flexible transparent conductive substrate is sequentially washed by ethanol and deionized water and dried for later use. 0.02g WCl was weighed 6 Added to 60mL of absolute ethanol and stirred continuously for 4 to 6 hours to form a uniform and transparent first solution. And adding the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at 140-200 ℃ for 24h to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then drying in an oven at 80 ℃ to obtain W 18 O 49 A PET-ITO flexible electrochromic film.
Comparative example 2
Comparative example 2 was prepared in substantially the same manner as in example 1, except that WCl alone was used in the reaction system 6 A combination of polyvinylpyrrolidone and ethanol.
Specifically, the PET-ITO flexible transparent conductive substrate is sequentially cleaned by ethanol and deionized water and dried for later use. 0.02g WCl was weighed 6 Adding into 60mL of absolute ethyl alcohol, adding 0.02g of polyvinylpyrrolidone into the absolute ethyl alcohol, and continuously stirring for 4-6 h to form a uniform and transparent first solution. And adding the first solution into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, and reacting the first solution at 140-200 ℃ for 24h to obtain a second solution. Directly spraying the second solution on the PET-ITO flexible transparent conductive substrate, and then placing the PET-ITO flexible transparent conductive substrate in an oven at 80 ℃ for drying to obtain W 18 O 49 PET-ITO flexible electrochromic film.
The electrochromic film obtained in each example or comparative example is subjected to electrochromic performance and optical performance tests by combining an electrochemical workstation and an ultraviolet-visible spectrophotometer.
The electrochemical system used in the electrochemical workstation adopts a three-electrode system and adopts 1M LiClO 4 The preparation method comprises the following steps of taking/PC (propylene carbonate) as an electrolyte, taking an electrochromic film sample as a working electrode, taking a Pt sheet as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, and taking Li as a counter electrode + And e - The insertion and extraction of (2) was studied.
Testing the ultraviolet-visible light transmission spectrum of the colored state and the faded state of the electrochromic film in the electrochemical system under different voltages by an ultraviolet-visible spectrophotometer under the following test conditions: reacting for a certain time under-2V voltage to obtain a colored film, and reacting for a certain time under +2V voltage to obtain a faded film. And respectively carrying out spectrum scanning on the film in the colored state and the faded state, wherein the wavelength scanning range is 300nm to 900nm, and obtaining the ultraviolet-visible light transmission spectrum of the electrochromic film. The optical modulation range at 633nm was obtained by calculating the difference in transmittance of the film at 633nm between the colored state and the discolored state.
The test conditions of the response time of the electrochromic film are as follows: and (3) adopting +/-2V voltage circulation, keeping each section of voltage for a certain time, and obtaining the response time of the electrochromic film and the change curve of the transmittance of the film along with the time, wherein the wavelength of in-situ spectral dynamic scanning is 633 nm.
The results of the tests on the electrochromic films of the respective examples and comparative examples are shown in table 1.
Table 1 results of performance test of electrochromic films of examples and comparative examples
As can be seen from the data in table 1, the electrochromic film provided by the embodiment of the present invention has a wider optical modulation range and shorter coloring and fading times, and the optical modulation range of the electrochromic film formed by coating the second solution on the substrate by using the atomization deposition method in example 5 can reach 37%.
Referring to fig. 5, it can be seen that the optical tuning range of the electrochromic film of example 5 at 633nm can reach 37.33%.
Referring to fig. 6, it can be seen that the time required for coloring and discoloring the electrochromic film of example 5 is 12.8s and 10.8s, respectively, having a fast electrochromic response rate.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (16)
1. The preparation method of the electrochromic film is characterized by comprising the following steps of:
adding tungsten salt, polyethylene glycol, cyclohexanol, polyvinyl alcohol and polyvinylpyrrolidone into absolute ethyl alcohol to form a first solution;
carrying out solvothermal reaction on the first solution to form intertwined W 18 O 49 A nanowire;
winding the W around each other 18 O 49 The nanowires are disposed on a substrate, thereby forming an electrochromic layer on the substrate.
2. The method for preparing an electrochromic film according to claim 1, wherein the temperature of the solvothermal reaction is 140 ℃ to 250 ℃ and the reaction time is 24h to 48 h.
3. The method of claim 1, wherein the molar concentration of the tungsten salt in the first solution is 3 x 10 -4 mol/L to 2X 10 -3 mol/L。
4. The method of claim 1, wherein the tungsten salt is WCl 6 。
5. The method for preparing an electrochromic film according to claim 1, wherein the volume ratio of the polyethylene glycol to the absolute ethyl alcohol in the first solution is 1:4 to 1: 8.
6. The method of claim 1, wherein the polyvinylpyrrolidone is added in an amount of 0.01g to 0.1g per 100mL of the anhydrous ethanol in the first solution.
7. The method of claim 1, wherein the total amount of the polyvinyl alcohol and the cyclohexanol added to the first solution is 0.01g to 0.1g per 100mL of the anhydrous ethanol.
8. The method of claim 1, wherein the step of solvothermally reacting the first solution yields a solution containing the intertwined Ws 18 O 49 A second solution of the nanowires is then added,
the W to be intertwined 18 O 49 The step of disposing nanowires on the substrate includes disposing the second solution on the substrate, and drying the second solution on the substrate.
9. The method of claim 8, wherein the step of disposing the second solution on the substrate is disposing the second solution on the substrate by atomized deposition.
10. The method of claim 1, wherein the step of solvothermally reacting the first solution yields a solution containing the intertwined Ws 18 O 49 A second solution of the nanowires is then formed,
the W to be intertwined 18 O 49 The step of disposing the nanowires on the substrate includes adding a dispersant and an active agent to the second solution to mix them to obtain a dispersion, disposing the dispersion on the substrate, and drying the dispersion on the substrate.
11. The method of claim 1, wherein the substrate is a flexible transparent conductive substrate.
12. The method of claim 11, wherein the substrate comprises a flexible substrate and a transparent conductive layer disposed between the electrochromic layer and the flexible substrate.
13. The method for preparing an electrochromic film according to any one of claims 1 to 12, wherein the thickness of the electrochromic layer is 2 to 3 μm.
14. The method for preparing an electrochromic film according to any one of claims 1 to 12, wherein W is selected from the group consisting of 18 O 49 The diameter of the nanowire is 5nm to 10nm, and the length of the nanowire is 10 mu m to 20 mu m.
15. The method for preparing an electrochromic film according to any one of claims 1 to 12, wherein the optical modulation range of the prepared electrochromic film at a wavelength of 633nm is 15% to 40%.
16. The method for preparing an electrochromic film according to any one of claims 1 to 12, wherein the prepared electrochromic film has a coloring time of 12s to 14s and a fading time of 10s to 12 s.
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| KR100406689B1 (en) * | 2001-03-05 | 2003-11-21 | 주식회사 엘지화학 | Multicomponent composite film for electrochemical device and method for preparing the same |
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