CN108585539B - Long-life electrochromic film capable of selectively regulating light and heat and preparation method thereof - Google Patents

Long-life electrochromic film capable of selectively regulating light and heat and preparation method thereof Download PDF

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CN108585539B
CN108585539B CN201810344704.9A CN201810344704A CN108585539B CN 108585539 B CN108585539 B CN 108585539B CN 201810344704 A CN201810344704 A CN 201810344704A CN 108585539 B CN108585539 B CN 108585539B
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任洋
周晓歌
赵高扬
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Xian University of Technology
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Abstract

The invention discloses a long-life electrochromic film capable of selectively regulating and controlling light and heat, which takes transparent conductive coated glass as a substrate, and an FTO (fluorine-doped tin oxide) nano-pore array film and amorphous WO (tungsten oxide) are sequentially prepared on the substrate3Thin film to form amorphous WO with embedded FTO nanoarrays3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The film fills the circular holes of the FTO nano-pore array film and is higher than the depth of the circular holes of the FTO nano-pore array film. The preparation method comprises the following steps: preparing FTO (fluorine-doped tin oxide) nano pore array by combining laser interference with photosensitive sol-gel technology, and filling amorphous WO (tungsten oxide) on the pore array by using sol-gel technology3A substrate to form a composite membrane. Due to the ultrahigh chemical stability of FTO, the composite film can still keep a better light and heat selective modulation effect after 10 ten thousand electrochromic cycles, and the preparation method of the composite film has the characteristics of controllable process and easiness in large-area film forming, and is suitable for industrial mass production.

Description

Long-life electrochromic film capable of selectively regulating light and heat and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectric functional films, and particularly relates to a long-life electrochromic film capable of selectively regulating and controlling light and heat; the invention also relates to a preparation method of the long-life electrochromic film capable of selectively regulating and controlling light and heat.
Background
The electrochromic film is a novel intelligent material which can be reversibly changed between a colored state with low transmissivity and a faded state with high transmissivity under the action of alternating high and low or positive and negative external electric fields, and is a core part of an energy-saving intelligent window. At present, the commercial electrochromic film takes an amorphous tungsten oxide film as a main material, and the heat penetrating through the film can be controlled by regulating the transmissivity of the film in a near infrared band, so that the aim of saving energy is fulfilled. However, the film can obtain lower near infrared transmittance, and simultaneously, the visible light transmittance is also sharply reduced, which affects the lighting capability of the coated glass window, and moreover, due to the instability of the amorphous structure, the chemical property of the tungsten oxide film after repeated cycles is sharply changed, the electrochromic performance gradually disappears, and the cycle service life is not high.
In order to solve the above problems, a reported solution is to design and prepare a tungsten oxide electrochromic film with a conductive oxide nanoparticle embedded type (the name of the invention is: a nanocrystal-enhanced tungsten oxide electrochromic film and a preparation method thereof, the application number is 201510358853.7, the publication number is CN 105036564 a, the publication number is 2015.11.11), the conductive oxide nanoparticles are used for adjusting near-infrared transmission light, and the tungsten oxide is used for adjusting visible light, so as to achieve the purpose of selectively adjusting light (visible light) and heat (near-infrared light). Moreover, the better conductivity of the oxide nanoparticles can effectively promote the injection and extraction of electrons in the tungsten oxide, and the tungsten oxide still keeps better chemical stability after the composite film is subjected to multiple color change cycles. However, the service life of the composite material is not only influenced by tungsten oxide, but also restricted by the chemical stability of the conductive oxide nanoparticles, and the chemical state of the conductive oxide nanoparticles after multiple electrochemical discoloration cycles is changed, so that the light and heat selective modulation effect of the composite film disappears, and the requirement of the minimum service life of 25 years is also difficult to meet. Therefore, in order to realize the large-area popularization and application of the novel electrochromic film in the field of building energy conservation, the film layer structure must be redesigned, and the preparation technology of the corresponding film layer must be researched.
Disclosure of Invention
The invention aims to provide a long-life electrochromic film capable of selectively regulating and controlling light and heat, which can effectively solve the problems of short service life and lack of light and heat selective regulation and control of a commercial tungsten oxide film.
Another object of the present invention is to provide a method for preparing a long-life electrochromic film capable of selectively controlling light and heat, which is capable of forming a film in a large area and suitable for industrial mass production.
The technical scheme adopted by the invention is as follows: the long-life electrochromic film capable of selectively regulating and controlling light and heat uses transparent conductive coated glass as base plate, on the base plate the FTO nano hole array film and amorphous WO film are successively prepared3Thin film to form amorphous WO with embedded FTO nanoarrays3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The film fills the circular holes of the FTO nano-pore array film and is higher than the depth of the circular holes of the FTO nano-pore array film.
The present invention is also characterized in that,
the depth of the hole array is 30-60 nm, the period of the hole array is 200nm, and the diameter of a circular hole of the FTO nano hole array is 100 nm.
Amorphous WO3The thickness of the film is 200 to 300 nm.
The other technical scheme adopted by the invention is as follows: the preparation method of the long-life electrochromic film capable of selectively regulating and controlling light and heat comprises the following specific steps:
step 1: mixing benzoylacetone and absolute ethyl alcohol, and stirring at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved to obtain a solution A; mixing di-n-butyltin oxide with the solution A, and stirring for 2 hours at 60 ℃ in a dry nitrogen atmosphere to obtain light yellow sol B; mixing a certain amount of polyethylene glycol 400 and trifluoroacetic acid into the sol B, and stirring for 1 hour at the temperature of 45 ℃ in a dry nitrogen atmosphere to obtain light yellow FTO photosensitive sol C;
step 2: coating the sol C on a transparent conductive coated glass substrate by adopting a spin coating method, and drying for 10 minutes at 80 ℃ in a vacuum furnace to form an FTO photosensitive gel film;
and step 3: placing the FTO photosensitive gel film substrate in a four-beam laser interference system for exposure for 20min, wherein the exposure wavelength is 325nm, the laser power is 20mW, and the included angle between coherent beams is 108 degrees;
and 4, step 4: placing the exposed FTO photosensitive gel membrane substrate in a solvent for solvent washing, and removing the unexposed part by solvent washing to obtain the FTO gel membrane with a nano-pore array, wherein the period of the pore array is 200 nm;
and 5: annealing the FTO gel film substrate with the nanopore array for 1 hour at 500 ℃ in an oxygen atmosphere to obtain an FTO nanopore array film;
step 6: mixing WCl6Mixing with anhydrous ethanol under dry nitrogen atmosphere, stirring for 1 hr to obtain yellow WO3Sol D;
and 7: and filling the sol D in the FTO nanopore array by adopting a spin coating method, and carrying out annealing treatment at 300 ℃ for 0.5 hour to obtain the required electrochromic film.
The present invention is also characterized in that,
in the step 1, the molar ratio of di-n-butyltin oxide, benzoylacetone, trifluoroacetic acid, polyethylene glycol 400 and absolute ethyl alcohol is 1: 0.5: 0.167: 0.02: 20.
in the step 2, the adopted spin coating process is as follows: the rotating speed of the rotating disc is controlled to be 2500-3000 r/min, and the rotating time is controlled to be 30-50 seconds.
In the step 4, the solvent-washing agent is a mixed solution of methanol and n-butyl alcohol, wherein the volume ratio of the methanol to the n-butyl alcohol is 1:4, and the solvent-washing time is 20-50 seconds.
In step 7, the adopted spin coating process is as follows: the rotating speed of the rotating disc is 800-1500 rpm, and the rotating time is 60-80 seconds.
The electrochromic film prepared in the step 7 takes transparent conductive coated glass as a substrate, and an FTO (fluorine-doped tin oxide) nano-pore array film and amorphous WO (tungsten trioxide) are sequentially prepared on the substrate3Thin film to form amorphous WO with embedded FTO nanoarrays3The composite film comprises an array of regularly arranged holes, wherein the depth of the hole array is 30-60 nm, the period of the hole array is 200nm, the diameter of a circular hole of an FTO (fluorine-doped tin oxide) nano hole array is 100nm, and amorphous WO3The film fills the circular holes of the FTO nano-pore array film and is higher than the depth of the circular holes of the FTO nano-pore array film, and the thickness of the film is 200-300 nm.
The invention has the beneficial effects that:
(1) the strong chemical stability of FTO is utilized to improve the capacity of the film for maintaining the near-infrared electrochromic performance after multiple cycles of color change, the controllability of the nano array structure is utilized to optimize the electrochromic capacity of the composite film for near-infrared light (common conductive oxide nano particles are in a disordered structure, and the electrochromic performance for the near-infrared light is difficult to control), and further the electrochromic film with long service life, high performance and selective modulation of multiple frequency bands is obtained. The film can effectively solve the problems of short service life and lack of light and heat selective regulation of a commercial tungsten oxide film;
(2) selected FTO and tungsten oxide (WO)3) The combination of the two can combine the two electrochromic wave bands to realize the selective regulation and control of the composite film on light and heat. More importantly, the FTO has stronger chemical stability, the FTO is placed in an electrochemical system, the chemical property of the FTO is still stable after 10 ten thousand times of color change circulation, and the FTO is compounded with amorphous tungsten oxide, so that the cycle service life of the tungsten oxide is prolonged, and the problem that the commercial tungsten oxide electrochromic film is difficult to meet the requirement that the service life exceeds 25 years can be effectively solved;
(3) the preparation method combines the laser interference exposure technology with the ultraviolet photosensitive sol-gel technology, can prepare the FTO nano-pore array with higher resolution, and has more obvious local surface plasma resonance coupling effect compared with a corresponding lattice structure, thereby bringing stronger near-infrared electrochromic capability. In addition, the laser interference combined photosensitive sol-gel method for preparing the hole array or the sol-gel method for preparing the amorphous tungsten oxide can be used for preparing large-area films, the process is controllable, and the foundation is laid for realizing industrial mass production.
Drawings
FIG. 1 is a graph showing the variation of the negative and positive extreme currents with the number of color-changing cycles of an electrochromic film prepared by the method of the present invention;
FIG. 2 is a graph of transmittance curves of electrochromic films prepared by the method of the present invention at different voltages.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a long-life electrochromic film capable of selectively regulating and controlling light and heat, which takes transparent conductive coated glass as a substrate, and a fluorine-doped tin dioxide (FTO for short) nanopore array film and amorphous WO (tungsten oxide) are sequentially prepared on the substrate3Thin film to form amorphous WO with embedded FTO nanoarrays3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The film is filled in the round hole of the FTO nano-pore array film and is higher than the depth of the round hole of the FTO nano-pore array filmDegree;
wherein the depth of the FTO hole array is 30-60 nm, the period of the hole array is 200nm, and the diameter of the circular hole is 100 nm; amorphous WO3The thickness of the film is 200 to 300 nm.
The invention also provides a preparation method of the long-life electrochromic film capable of selectively regulating and controlling light and heat, which comprises the following specific steps:
step 1: mixing benzoylacetone and absolute ethyl alcohol, and stirring at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved to obtain a solution A; mixing di-n-butyltin oxide with the solution A, and stirring for 2 hours at 60 ℃ in a dry nitrogen atmosphere to obtain light yellow sol B; mixing a certain amount of polyethylene glycol 400 and trifluoroacetic acid into the sol B, and stirring for 1 hour at the temperature of 45 ℃ in a dry nitrogen atmosphere to obtain light yellow FTO photosensitive sol C;
in the step 1, the molar ratio of di-n-butyltin oxide, benzoylacetone, trifluoroacetic acid, polyethylene glycol 400 and absolute ethyl alcohol is 1: 0.5: 0.167: 0.02: 20;
step 2: coating the sol C on a transparent conductive coated glass substrate by adopting a spin coating method, and drying for 10 minutes at 80 ℃ in a vacuum furnace to form an FTO photosensitive gel film with uniform thickness;
in the step 2, the adopted spin coating process is as follows: the rotating speed of the rotating disc is controlled to be 2500-3000 r/min, and the rotating time is controlled to be 30-50 seconds;
and step 3: placing the FTO photosensitive gel film substrate in a four-beam laser interference system for exposure for 20 minutes, wherein the exposure wavelength is 325nm, the laser power is 20mW, and the included angle between coherent beams is 108 degrees;
and 4, step 4: placing the exposed FTO photosensitive gel membrane substrate in a dissolving agent for dissolving and washing, and removing the unexposed part by dissolving and washing due to the solubility difference to obtain the FTO gel membrane with a nano-pore array, wherein the pore array period is 200 nm;
in the step 4, the dissolving and washing agent is a mixed solution of methanol and n-butyl alcohol, wherein the volume ratio of the methanol to the n-butyl alcohol is 1:4, and the dissolving and washing time is 20-50 seconds;
and 5: annealing the FTO gel film substrate with the nanopore array for 1 hour at 500 ℃ in an oxygen atmosphere to obtain an FTO nanopore array film;
step 6: mixing WCl6Mixing with anhydrous ethanol under dry nitrogen atmosphere, stirring for 1 hr to obtain yellow WO3Sol D;
and 7: filling sol D in the FTO nanopore array by adopting a spin coating method, and carrying out annealing treatment at 300 ℃ for 0.5 hour to obtain the required electrochromic film;
in step 7, the adopted spin coating process is as follows: the rotating speed of the rotating disc is 800-1500 rpm, and the rotating time is 60-80 seconds;
the electrochromic film prepared in the step 7 is prepared by sequentially preparing an FTO (fluorine-doped tin oxide) nano-pore array film and amorphous WO (tungsten trioxide) on a transparent conductive coated glass substrate3Thin film to form amorphous WO with embedded FTO nanoarrays3The composite film comprises a regularly arranged hole array, a hole array depth of 30-60 nm, a hole array period of 200nm, a circular hole diameter of 100nm and amorphous WO3The film is filled with FTO nanopore array film round holes and is higher than the depth of the FTO nanopore array film round holes, and amorphous WO3The thickness of the film is 200 to 300 nm.
Fig. 1 is a graph showing the variation of the cathode-anode extreme current of the electrochromic film prepared by the method of the present invention with the number of color-changing cycles, which is used to characterize the cycle life of the film, and it can be seen from fig. 1 that the cathode-anode extreme current of the film still maintains a high value after 10 ten thousand color-changing cycles.
FIG. 2 is a graph of transmittance curves of an electrochromic film prepared by applying the method of the present invention under different voltages, which is used to characterize the electrochromic properties of the film selectively modulated to light and heat, and it can be seen from FIG. 2 that when a voltage of 1.5V is applied, the composite film has higher transmittance in both visible (400-800 nm) and near infrared (800-2500 nm) regions; when a voltage of-0.3V is applied, the transmissivity of the composite film in a near infrared region is remarkably reduced, but the transmissivity in a visible region is still kept unchanged, so that the independent regulation and control of the transmissivity of near infrared light are realized; when a voltage of-1.5V is applied, the transmissivity of the composite film in visible and near infrared regions is reduced, so that the composite film can realize selective regulation and control on light and heat.
Example 1
A long-life electrochromic film with selectively controllable light and heat is an amorphous WO film with embedded FTO nano array3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The thin film fills the circular holes of the FTO nano hole array and is higher than the depth of the circular holes. The depth of FTO hole array is 60nm, the period is 200nm, the diameter of circular hole is 100nm, and the amorphous WO is3The film thickness was 300 nm.
The preparation method of the composite film with the structural parameters comprises the following specific steps:
0.81g of benzoylacetone and 9.22g of absolute ethyl alcohol are mixed, stirred at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved, then transferred into a three-neck flask provided with a dry nitrogen device, 2.49g of di-n-butyltin oxide is added into the flask, the flask is heated and stirred at 60 ℃ for 2 hours, the flask is naturally cooled to 45 ℃, 0.19g of trifluoroacetic acid and 0.08g of polyethylene glycol 400 are added into the flask, and stirring is continued for 1 hour, so that light yellow FTO photosensitive sol is obtained.
And coating the FTO photosensitive sol on a transparent conductive coated glass substrate by using a spin coating process, wherein the rotating speed of a turntable is 2500 rpm, and the rotating time is 50 seconds, so as to form the FTO gel film with uniform surface thickness. And then placing the gel film substrate coated with the FTO photosensitive sol in a drying oven, baking for 10 minutes at 80 ℃, taking out, cooling to room temperature, placing in a four-beam laser interference system for exposure, wherein the included angle between coherent beams is 108 degrees, the laser power is 20mW, the exposure wavelength is 325nm, after 20 minutes of exposure, placing the substrate in an organic solvent (a mixed solution of methanol and n-butyl alcohol with the volume ratio of 1:4) for dissolving and washing for 50 seconds, taking out and drying by using dry nitrogen, finally placing in a vacuum furnace filled with high-purity oxygen, and annealing for 1 hour at 500 ℃ to obtain the FTO nano pore array film, wherein the diameter of a circular hole is 100nm, the depth of the circular hole is 60nm, and the pore array period is 200 nm.
Then, 5g of WCl6Dissolving in 30ml of absolute ethanol, and stirring at room temperature for 1 hour to obtain yellow WO3And (3) sol. Coating the sol on the surface of an FTO (fluorine-doped tin oxide) nanopore array by a spin coating process, wherein the rotating speed of a rotating disc is 800 revolutions per minuteMinute, rotation time 80 seconds to form WO with uniform surface thickness3And (3) gel films. And finally, placing the gel film substrate in an oxygen atmosphere at 300 ℃ for heat treatment for 0.5 hour to obtain the amorphous tungsten oxide composite film with the FTO nano array embedded type and the film thickness of 300 nm.
After the film is subjected to color change circulation for 10 ten thousand times, the current of the extreme value of the negative and positive is only reduced by 10 percent (shown in figure 1), which shows that the film has good circulation stability and longer service life; in addition, the optical modulation value of the optical fiber is 40% in 632.5nm wave band and 45% in 2000nm wave band, and the optical fiber has better selective modulation capability to light and heat (figure 2).
Example 2
A long-life electrochromic film with selectively controllable light and heat is an amorphous WO film with embedded FTO nano array3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The thin film fills the circular holes of the FTO nano hole array and is higher than the depth of the circular holes. The depth of the FTO hole array is 30nm, the period is 200nm, the diameter of the round hole is 100nm, and the thickness of the amorphous film is 200 nm.
The preparation method of the composite film with the structural parameters comprises the following specific steps:
0.81g of benzoylacetone and 9.22g of absolute ethyl alcohol are mixed, stirred at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved, then transferred into a three-neck flask provided with a dry nitrogen device, 2.49g of di-n-butyltin oxide is added into the flask, the flask is heated and stirred at 60 ℃ for 2 hours, the flask is naturally cooled to 45 ℃, 0.19g of trifluoroacetic acid and 0.08g of polyethylene glycol 400 are added into the flask, and stirring is continued for 1 hour, so that light yellow FTO photosensitive sol is obtained.
And coating the FTO photosensitive sol on a transparent conductive coated glass substrate by using a spin coating process, wherein the rotating speed of a rotating disc is 3000 r/min, and the rotating time is 30 seconds, so as to form the FTO gel film with uniform surface thickness. And then placing the gel film substrate coated with the FTO photosensitive sol in a drying oven, baking for 10 minutes at 80 ℃, taking out, cooling to room temperature, placing in a four-beam laser interference system for exposure, wherein the included angle between coherent beams is 108 degrees, the laser power is 20mW, the exposure wavelength is 325nm, after 20 minutes of exposure, placing the substrate in an organic solvent (a mixed solution of methanol and n-butyl alcohol with the volume ratio of 1:4) for dissolving and washing for 20 seconds, taking out and drying by using dry nitrogen, finally placing in a vacuum furnace filled with high-purity oxygen, and annealing for 1 hour at 500 ℃ to obtain the FTO nano pore array film, wherein the diameter of a circular hole is 100nm, the depth of the circular hole is 30nm, and the pore array period is 200 nm.
Then, 5g of WCl6Dissolving in 30ml of absolute ethanol, and stirring at room temperature for 1 hour to obtain yellow WO3And (3) sol. Coating the sol on the surface of an FTO (fluorine-doped tin oxide) nanopore array by a spin coating process, wherein the rotating speed of a turntable is 1500 rpm, and the rotating time is 60 seconds, so as to form WO with uniform surface thickness3And (3) gel films. And finally, placing the gel film substrate in an oxygen atmosphere at 300 ℃ for heat treatment for 0.5 hour to obtain the amorphous tungsten oxide composite film with FTO nano array embedded type and the film thickness of 200 nm.
After the film is subjected to color change circulation for 10 ten thousand times, the current of the extreme value of the negative and positive is only reduced by 5 percent, which shows that the film has good circulation stability and longer service life; in addition, the optical modulation value of the optical fiber is 42% in 632.5nm wave band and 60% in 2000nm wave band, and the optical fiber has good selective modulation capability on light and heat.
Example 3
A long-life electrochromic film with selectively controllable light and heat is an amorphous WO film with embedded FTO nano array3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The thin film fills the circular holes of the FTO nano hole array and is higher than the depth of the circular holes. The depth of the FTO hole array is 45nm, the period is 200nm, the diameter of the round hole is 100nm, and the thickness of the amorphous film is 260 nm.
The preparation method of the composite film with the structural parameters comprises the following specific steps:
0.81g of benzoylacetone and 9.22g of absolute ethyl alcohol are mixed, stirred at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved, then transferred into a three-neck flask provided with a dry nitrogen device, 2.49g of di-n-butyltin oxide is added into the flask, the flask is heated and stirred at 60 ℃ for 2 hours, the flask is naturally cooled to 45 ℃, 0.19g of trifluoroacetic acid and 0.08g of polyethylene glycol 400 are added into the flask, and stirring is continued for 1 hour, so that light yellow FTO photosensitive sol is obtained.
And coating the FTO photosensitive sol on a transparent conductive coated glass substrate by using a spin coating process, wherein the rotating speed of a rotating disc is 2800 r/min, and the rotating time is 40 seconds, so as to form the FTO gel film with uniform surface thickness. And then placing the gel film substrate coated with the FTO photosensitive sol in a drying oven, baking for 10 minutes at 80 ℃, taking out, cooling to room temperature, placing in a four-beam laser interference system for exposure, wherein the included angle between coherent beams is 108 degrees, the laser power is 20mW, the exposure wavelength is 325nm, after 20 minutes of exposure, placing the substrate in an organic solvent (a mixed solution of methanol and n-butyl alcohol with the volume ratio of 1:4) for dissolving and washing for 30 seconds, taking out and drying by using dry nitrogen, finally placing in a vacuum furnace filled with high-purity oxygen, and annealing for 1 hour at 500 ℃ to obtain the FTO nano pore array film, wherein the diameter of a circular hole is 100nm, the depth of the circular hole is 45nm, and the pore array period is 200 nm.
Then, 5g of WCl6Dissolving in 30ml of absolute ethanol, and stirring at room temperature for 1 hour to obtain yellow WO3And (3) sol. The sol is coated on the surface of an FTO (fluorine-doped tin oxide) nanopore array by a spin coating process, the rotating speed of a turntable is 1200 r/min, the rotating time is 70 seconds, and WO with uniform surface thickness is formed3And (3) gel films. And finally, placing the gel film substrate in an oxygen atmosphere at 300 ℃ for heat treatment for 0.5 hour to obtain the amorphous tungsten oxide composite film with FTO nano array embedded type and the film thickness of 260 nm.
After the film is subjected to color change circulation for 10 ten thousand times, the current of the extreme value of the negative and positive is only reduced by 8 percent, which shows that the film has good circulation stability and longer service life; in addition, the optical modulation value of the optical fiber is 41% in 632.5nm wave band and 55% in 2000nm wave band, and the optical fiber has good selective modulation capability on light and heat.
Example 4
A long-life electrochromic film with selectively controllable light and heat is an amorphous WO film with embedded FTO nano array3Composite film in which the array is a regularly arranged array of holesAmorphous WO3The thin film fills the circular holes of the FTO nano hole array and is higher than the depth of the circular holes. The depth of the FTO hole array is 50nm, the period is 200nm, the diameter of the round hole is 100nm, and the thickness of the amorphous film is 280 nm.
The preparation method of the composite film with the structural parameters comprises the following specific steps:
0.81g of benzoylacetone and 9.22g of absolute ethyl alcohol are mixed, stirred at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved, then transferred into a three-neck flask provided with a dry nitrogen device, 2.49g of di-n-butyltin oxide is added into the flask, the flask is heated and stirred at 60 ℃ for 2 hours, the flask is naturally cooled to 45 ℃, 0.19g of trifluoroacetic acid and 0.08g of polyethylene glycol 400 are added into the flask, and stirring is continued for 1 hour, so that light yellow FTO photosensitive sol is obtained.
And coating the FTO photosensitive sol on a transparent conductive coated glass substrate by using a spin coating process, wherein the rotating speed of a rotating disc is 2600 r/min, and the rotating time is 45 seconds, so as to form the FTO gel film with uniform surface thickness. And then placing the gel film substrate coated with the FTO photosensitive sol in a drying oven, baking for 10 minutes at 80 ℃, taking out, cooling to room temperature, placing in a four-beam laser interference system for exposure, wherein the included angle between coherent beams is 108 degrees, the laser power is 20mW, the exposure wavelength is 325nm, after 20 minutes of exposure, placing the substrate in an organic solvent (a mixed solution of methanol and n-butyl alcohol with the volume ratio of 1:4) for dissolving and washing for 40 seconds, taking out and drying by using dry nitrogen, finally placing in a vacuum furnace filled with high-purity oxygen, and annealing for 1 hour at 500 ℃ to obtain the FTO nano pore array film, wherein the diameter of a circular hole is 100nm, the depth of the circular hole is 50nm, and the pore array period is 200 nm.
Then, 5g of WCl6Dissolving in 30ml of absolute ethanol, and stirring at room temperature for 1 hour to obtain yellow WO3And (3) sol. Coating the sol on the surface of an FTO (fluorine-doped tin oxide) nanopore array by a spin coating process, wherein the rotating speed of a turntable is 1000 revolutions per minute, and the rotating time is 75 seconds, so as to form WO with uniform surface thickness3And (3) gel films. Finally, the gel film substrate is placed in an oxygen atmosphere at 300 ℃ for heat treatment for 0.5 hour to obtain the amorphous tungsten oxide composite film with FTO nano array embedded type and the film thickness of 280nm。
After the film is subjected to color change circulation for 10 ten thousand times, the current of the extreme value of the negative and positive is only reduced by 6 percent, which shows that the film has good circulation stability and longer service life; in addition, the optical modulation value of the optical fiber is 40% in 632.5nm wave band and 50% in 2000nm wave band, and the optical fiber has better selective modulation capability to light and heat.
Example 5
A long-life electrochromic film with selectively controllable light and heat is an amorphous WO film with embedded FTO nano array3Composite film in which the array is a regularly arranged array of holes, amorphous WO3The thin film fills the circular holes of the FTO nano hole array and is higher than the depth of the circular holes. The depth of the FTO hole array is 40nm, the period is 200nm, the diameter of the round hole is 100nm, and the thickness of the amorphous film is 230 nm.
The preparation method of the composite film with the structural parameters comprises the following specific steps:
0.81g of benzoylacetone and 9.22g of absolute ethyl alcohol are mixed, stirred at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved, then transferred into a three-neck flask provided with a dry nitrogen device, 2.49g of di-n-butyltin oxide is added into the flask, the flask is heated and stirred at 60 ℃ for 2 hours, the flask is naturally cooled to 45 ℃, 0.19g of trifluoroacetic acid and 0.08g of polyethylene glycol 400 are added into the flask, and stirring is continued for 1 hour, so that light yellow FTO photosensitive sol is obtained.
And coating the FTO photosensitive sol on the transparent conductive coated glass substrate by using a spin coating process, wherein the rotating speed of a rotating disc is 2900 r/min, and the rotating time is 35 seconds, so as to form the FTO gel film with uniform surface thickness. And then placing the gel film substrate coated with the FTO photosensitive sol in a drying oven, baking for 10 minutes at 80 ℃, taking out, cooling to room temperature, placing the gel film substrate in a four-beam laser interference system for exposure, wherein the included angle between coherent beams is 108 degrees, the laser power is 20mW, the exposure wavelength is 325nm, after 20 minutes of exposure, placing the substrate in an organic solvent (a mixed solution of methanol and n-butyl alcohol with the volume ratio of 1:4) for dissolving and washing for 25 seconds, taking out and drying the substrate by using dry nitrogen, finally placing the substrate in a vacuum furnace filled with high-purity oxygen, and annealing for 1 hour at 500 ℃ to obtain the FTO nano pore array film, wherein the diameter of a circular hole is 100nm, the depth of the circular hole is 40nm, and the pore array period is 200 nm.
Then, 5g of WCl6Dissolving in 30ml of absolute ethanol, and stirring at room temperature for 1 hour to obtain yellow WO3And (3) sol. The sol is coated on the surface of an FTO (fluorine-doped tin oxide) nanopore array by a spin coating process, the rotating speed of a turntable is 1300 rpm, the rotating time is 65 seconds, and WO with uniform surface thickness is formed3And (3) gel films. And finally, placing the gel film substrate in an oxygen atmosphere at 300 ℃ for heat treatment for 0.5 hour to obtain the amorphous tungsten oxide composite film with FTO nano array embedded type and the film thickness of 230 nm.
After the film is subjected to color change circulation for 10 ten thousand times, the current of the extreme value of the negative and positive is only reduced by 5 percent, which shows that the film has good circulation stability and longer service life; in addition, the optical modulation value of the optical fiber is 42% in 632.5nm wave band and 58% in 2000nm wave band, and the optical fiber has good selective modulation capability on light and heat.
The invention has the advantages of controllable process, easy realization of large-area industrialized film preparation, less impurities in the obtained film, and less impurities in the amorphous WO3FTO nano arrays are uniformly distributed in the matrix, a large amount of structural reorganization exists around the arrays, originally compact nano crystal boundaries become loose and porous through nano modification, and the nano gaps form Li in the electrolyte+The electrochromic capacity of the composite film is stronger due to the ion transmission channel. Can meet the requirement of industrial application.

Claims (7)

1. The long-life electrochromic film capable of selectively regulating and controlling light and heat is characterized by that it uses transparent conductive coated glass as base plate, on the base plate the FTO nano hole array film and amorphous WO film are successively prepared3Thin film to form amorphous WO with embedded FTO nanoarrays3Composite film in which the array is a regularly arranged array of holes, amorphous WO3Filling the circular holes of the FTO nano-pore array film by the film and enabling the film to be higher than the depth of the circular holes of the FTO nano-pore array film;
the depth of the hole array is 30-60 nm, the period of the hole array is 200nm, and the diameter of a round hole of the FTO nano hole array is 100 nm;
amorphous WO3The thickness of the film is 200 to 300 nm.
2. The preparation method of the long-life electrochromic film capable of selectively regulating and controlling light and heat is characterized by comprising the following specific steps of:
step 1: mixing benzoylacetone and absolute ethyl alcohol, and stirring at room temperature until the benzoylacetone and the absolute ethyl alcohol are dissolved to obtain a solution A; mixing di-n-butyltin oxide with the solution A, and stirring for 2 hours at 60 ℃ in a dry nitrogen atmosphere to obtain light yellow sol B; mixing a certain amount of polyethylene glycol 400 and trifluoroacetic acid into the sol B, and stirring for 1 hour at the temperature of 45 ℃ in a dry nitrogen atmosphere to obtain light yellow FTO photosensitive sol C;
step 2: coating the sol C on a transparent conductive coated glass substrate by adopting a spin coating method, and drying for 10 minutes at 80 ℃ in a vacuum furnace to form an FTO photosensitive gel film;
and step 3: placing the FTO photosensitive gel film substrate in a four-beam laser interference system for exposure for 20min, wherein the exposure wavelength is 325nm, the laser power is 20mW, and the included angle between coherent beams is 108 degrees;
and 4, step 4: placing the exposed FTO photosensitive gel membrane substrate in a solvent for solvent washing, and removing the unexposed part by solvent washing to obtain the FTO gel membrane with a nano-pore array, wherein the period of the pore array is 200 nm;
and 5: annealing the FTO gel film substrate with the nanopore array for 1 hour at 500 ℃ in an oxygen atmosphere to obtain an FTO nanopore array film;
step 6: mixing WCl6Mixing with anhydrous ethanol under dry nitrogen atmosphere, stirring for 1 hr to obtain yellow WO3Sol D;
and 7: and filling the sol D in the FTO nanopore array by adopting a spin coating method, and carrying out annealing treatment at 300 ℃ for 0.5 hour to obtain the required electrochromic film.
3. The method for preparing a long-life electrochromic film capable of selectively regulating light and heat as claimed in claim 2, wherein in the step 1, the molar ratio of di-n-butyltin oxide, benzoylacetone, trifluoroacetic acid, polyethylene glycol 400 and absolute ethyl alcohol is 1: 0.5: 0.167: 0.02: 20.
4. the method for preparing the long-life electrochromic film capable of selectively regulating light and heat as claimed in claim 2, wherein in the step 2, the adopted spin coating process is as follows: the rotating speed of the rotating disc is controlled to be 2500-3000 r/min, and the rotating time is controlled to be 30-50 seconds.
5. The method for preparing a long-life electrochromic film capable of selectively regulating light and heat according to claim 2, wherein in the step 4, the solvent-washing agent is a mixed solution of methanol and n-butanol, wherein the volume ratio of the methanol to the n-butanol is 1:4, and the solvent-washing time is 20-50 seconds.
6. The method for preparing a long-life electrochromic film capable of selectively regulating light and heat according to claim 2, wherein in the step 7, the adopted spin coating process is as follows: the rotating speed of the rotating disc is 800-1500 rpm, and the rotating time is 60-80 seconds.
7. The method for preparing a long-life electrochromic film capable of selectively regulating light and heat according to claim 2, wherein the electrochromic film prepared in step 7 is prepared by using transparent conductive coated glass as a substrate, and an FTO (fluorine-doped tin oxide) nanopore array film and amorphous WO (tungsten oxide) are sequentially prepared on the substrate3Thin film to form amorphous WO with embedded FTO nanoarrays3The composite film comprises an array of regularly arranged holes, wherein the depth of the hole array is 30-60 nm, the period of the hole array is 200nm, the diameter of a circular hole of an FTO (fluorine-doped tin oxide) nano hole array is 100nm, and amorphous WO3The film fills the circular holes of the FTO nano-pore array film and is higher than the depth of the circular holes of the FTO nano-pore array film, and the thickness of the film is 200-300 nm.
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