CN108483939B - Electrochromic film capable of effectively modulating sunlight transmittance and preparation method thereof - Google Patents
Electrochromic film capable of effectively modulating sunlight transmittance and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000002834 transmittance Methods 0.000 title claims description 25
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 77
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 108010025899 gelatin film Proteins 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 41
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 22
- 238000004528 spin coating Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910003091 WCl6 Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims 1
- 238000003980 solgel method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses an electrochromic film for effectively modulating sunlight transmissivity, which contains CsxWO3The nano lattice embedded amorphous tungsten oxide composite film is characterized in that x is 0.06-0.2, and the lattice diameter is 80-300 nmThe distance between adjacent grid points is 200-600 nm, and the height of the grid points is 30-80 nm. The film solves the problems that the commercial electrochromic film has narrow adjustable and controllable waveband range of sunlight and can not realize independent adjustment and control of near-infrared radiant heat. The preparation method firstly adopts the laser interference combined photosensitive sol-gel method to prepare CsxWO3And (3) nano lattice, and filling an amorphous tungsten oxide matrix in the lattice gap by adopting a sol-gel method to form the composite film. The preparation method has the characteristics of controllable process and large-area membrane preparation, and is very suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of transparent semiconductor film preparation methods, and particularly relates to an electrochromic film for effectively modulating sunlight transmittance; the invention also relates to a preparation method of the electrochromic film for effectively modulating the solar light transmittance.
Background
The electrochromic film has great application potential in the field of building energy-saving coated glass due to the dynamic adjustability of the sunlight transmittance. The solar spectrum is a continuous spectrum composed of different wavelengths, and covers ultraviolet, visible and near-infrared regions from a wave band of 200-2500 nm. Wherein the radiation energy of the ultraviolet region, the visible region and the near infrared region accounts for 4 percent, 43 percent and 53 percent in sequence. The electrochromic film is fully absorbing to ultraviolet light, the electrochromic wave band is a visible light wave band and a near infrared light wave band, and the change of transmissivity of the two wave bands is reflected, wherein the aim of building energy saving can be achieved by adjusting the near infrared transmissivity. However, the adjustable waveband of the conventional electrochromic film does not completely cover visible and near-infrared light regions, for example, in the existing commercial tungsten oxide electrochromic film, the adjustable waveband is mainly concentrated in the range of 400-1500 nm, the near-infrared light adjusting capability in the waveband range of 1500-2500 nm is very limited, and the adjusting effect on solar heat radiation is influenced. In order to obtain an electrochromic film with a better energy-saving effect, the film is required to be capable of effectively regulating and controlling the transmission light within the wavelength range of 400-2500 nm, and along with the improvement of the requirement of people on living comfort, the electrochromic film is urgently required to have the capability of independently regulating and controlling the near-infrared transmittance, so that the solar heat radiation can be regulated while the lighting effect of the film is not reduced.
Disclosure of Invention
The invention aims to provide an electrochromic film for effectively modulating the solar light transmittance, and solves the problems that a commercial electrochromic film is narrow in adjustable waveband range and cannot independently regulate and control near-infrared radiant heat.
It is another object of the present invention to provide a method for preparing an electrochromic film that effectively modulates solar light transmittance.
The technical scheme adopted by the invention is as follows: an electrochromic film for effectively modulating the transmittance of sunlight contains CsxWO3The nano lattice embedded amorphous tungsten oxide composite film is characterized in that x is 0.06-0.2, the diameter of each lattice point is 80-300 nm, the distance between every two adjacent lattice points is 200-600 nm, and the height of each lattice point is 30-80 nm.
The other technical scheme adopted by the invention is as follows: a preparation method of an electrochromic film for effectively modulating sunlight transmissivity comprises the following specific steps:
step 1, preparing photosensitive tungsten oxide sol A and photosensitive tungsten oxide sol B containing Cs doping;
step 1.1, WCl6Mixing the sol with absolute ethyl alcohol at room temperature, stirring for 2 hours to obtain yellow tungsten oxide sol, then adding a certain amount of 2, 2-pyridine into the sol, and refluxing for 2 hours at 45-60 ℃ to obtain photosensitive tungsten oxide sol A;
step 1.2, adding a certain amount of CsCl into the photosensitive tungsten oxide sol A prepared in the step 1.1, and stirring for 10 hours at 60 ℃ to obtain a Cs-doped tungsten oxide photosensitive sol B;
step 2, coating the sol B on a transparent conductive coated glass substrate by adopting a spin coating technology to form a gel film;
step 3, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise by 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate;
and 4, putting the exposed gel film substrate into a prepared organic solvent for dissolving and washing for 10-80 seconds, then taking out, putting the gel film substrate into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain the CsxWO3Nano lattice;
step 5, uniformly coating the sol A on the Cs by a spin coating technologyxWO3And forming a tungsten oxide gel film on the nano lattice, then placing the tungsten oxide gel film in a muffle furnace, annealing for 1 hour at the temperature of 300 ℃, and air cooling to obtain the electrochromic film.
The present invention is also characterized in that,
in step 1, WCl6The molar ratio of the absolute ethyl alcohol to the 2, 2-pyridine to the CsCl is 1: 30: 1: 0.06 to 0.2.
In the step 2, the rotating speed of the rotating disc is 2500-3000 r/min, and the rotating time is 20-40 seconds.
In step 3, the parameters selected by the laser interference exposure system are as follows: the laser wavelength is 325nm, the power is 50mW, and the included angle between the two beams is set to be 30-108 degrees.
In the step 4, the organic solvent is a mixed solution of acetone and n-butanol, wherein the volume ratio of the acetone to the n-butanol is 1: 2.
in the step 4, during dissolving and washing, the organic solution is rotated in a certain direction by adopting a magnetic stirring method, the rotating speed is 800-1000 r/min, and the surface of the gel film is placed along the flowing direction of the organic solution.
Step 5, the prepared electrochromic film contains CsxWO3The nano lattice embedded amorphous tungsten oxide composite film is characterized in that x is 0.06-0.2, the diameter of each lattice point is 80-300 nm, the distance between every two adjacent lattice points is 200-600 nm, and the height of each lattice point is 30-80 nm.
The invention has the beneficial effects that: selecting proper lattice material (Cs)xWO3X is 0.06-0.2) and structural parameters (lattice point diameter 80-300 n)m, the spacing between the lattice points is 200-600 nm, and the height of the lattice points is 30-80 nm), so that Cs isxWO3The absorption of the plasma on the local surface of the nano lattice is in the wave band range of 800-2500 nm, and the absorption wave band can be adjusted in the near infrared (800-2500 nm) to short wave middle infrared region (2500-5000 nm) along with the change of an external electrochemical electric field, so that the nano lattice has CsxWO3The nano lattice embedded amorphous tungsten oxide composite film has the capability of independently regulating and controlling near-infrared transmission light, and can be made to have broadband electrochromic performance by combining the electrochromic characteristic of the amorphous tungsten oxide. The method adopted for preparing the composite film, namely the laser interference combined photosensitive sol-gel method and the sol-gel technology, can realize large-area film preparation, is expected to be applied to industrial mass production, and has great practical significance.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides an electrochromic film for effectively modulating the solar light transmittance, which contains CsxWO3The nano lattice embedded amorphous tungsten oxide composite film is characterized in that x is 0.06-0.2, the diameter of each lattice point is 80-300 nm, the distance between every two adjacent lattice points is 200-600 nm, and the height of each lattice point is 30-80 nm.
The invention also provides a preparation method of the electrochromic film for effectively modulating the solar light transmittance, which comprises the following specific steps:
step 1, preparing photosensitive tungsten oxide sol A and photosensitive tungsten oxide sol B containing Cs doping;
step 1.1, WCl6Mixing the sol with absolute ethyl alcohol at room temperature, stirring for 2 hours to obtain yellow tungsten oxide sol, then adding a certain amount of 2, 2-pyridine into the sol, and refluxing for 2 hours at 45-60 ℃ to obtain photosensitive tungsten oxide sol A;
step 1.2, adding a certain amount of CsCl into the photosensitive tungsten oxide sol A prepared in the step 1.1, and stirring for 10 hours at 60 ℃ to obtain a Cs-doped tungsten oxide photosensitive sol B;
step 1Middle and middle WCl6The molar ratio of the absolute ethyl alcohol to the 2, 2-pyridine to the CsCl is 1: 30: 1: (0.06-0.2);
step 2, coating the sol B on a transparent conductive coated glass substrate by adopting a spin coating technology to form a gel film; controlling the thickness of the gel film by adjusting the rotating speed and the rotating time of the rotating disc;
in the step 2, the rotating speed of the rotating disc is 2500-3000 r/min, and the rotating time is 20-40 seconds.
Step 3, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system for double-beam exposure for 10 minutes, then rotating the gel film clockwise by 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate;
in step 3, the parameters selected by the laser interference exposure system are as follows: the laser wavelength is 325nm, the power is 50mW, and the included angle between two beams is set to be 30-108 degrees;
and 4, putting the exposed gel film substrate into a prepared organic solvent for dissolving and washing for 10-80 seconds, then taking out, putting the gel film substrate into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain the CsxWO3Nano lattice;
in the step 4, the organic solvent is a mixed solution of acetone and n-butanol, wherein the volume ratio of the acetone to the n-butanol is 1: 2;
in the step 4, the organic solution is rotated in a certain direction by adopting a magnetic stirring method during solution washing, the rotating speed is 800-1000 r/min, and the surface of the gel film is placed along the flowing direction of the organic solution;
step 5, uniformly coating the sol A on the Cs by a spin coating technologyxWO3Forming a tungsten oxide gel film on the nano lattice, then placing the tungsten oxide gel film in a muffle furnace to anneal for 1 hour at 300 ℃, and air-cooling to obtain an electrochromic film;
step 5, the prepared electrochromic film contains CsxWO3The nano lattice embedded amorphous tungsten oxide composite film is characterized in that x is 0.06-0.2, the diameter of lattice points is 80-300 nm, the distance between adjacent lattice points is 200-600 nm, and the lattice points areThe height is 30-80 nm.
Example 1
An electrochromic film with Cs for effectively modulating the transmittance of sunlightxWO3The nano lattice embedded amorphous tungsten oxide composite film has x of 0.06, nano lattice point diameter of 80nm, lattice point interval of 200nm and lattice point height of 30 nm.
The preparation method with the structural parameters comprises the following specific steps:
firstly, non-doped tungsten oxide sol A and Cs-doped tungsten oxide sol B are respectively prepared. The process comprises the following steps:
4g of WCl6And 13.83g of absolute ethyl alcohol were mixed at room temperature, and stirred for 2 hours, then 1.56g of 2, 2-pyridine was added to the sol, and the mixture was refluxed at 45 ℃ for 2 hours, to obtain a photosensitive tungsten oxide sol a.
And adding 0.1g of CsCl into the photosensitive tungsten oxide sol A, and stirring for 10 hours at 60 ℃ to obtain the Cs-doped tungsten oxide photosensitive sol B.
Secondly, the sol B is coated on the transparent conductive coated glass substrate by adopting a spin coating technology to ensure the annealed CsxWO3The lattice height of the nano lattice film is 30nm, the rotating speed of a rotating disc adopted in the spin coating process is 3000 r/min, and the rotating time is 20 seconds.
And then, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system, carrying out double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise for 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate. Wherein, the selected laser wavelength is 325nm, the power is 50mW, and in order to ensure the lattice point spacing to be 200nm, the included angle between the two beams is set to be 108 degrees in the stage.
Then, the exposed gel film substrate is put into a prepared organic solvent for dissolving and washing for 80 seconds, then taken out and put into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain CsxWO3And (4) nano lattice. Wherein the organic solvent is a mixed solution of acetone and n-butanol, and the volume ratio of the acetone to the n-butanol is 1: 2, when dissolving and washing, the solution needs to be washedThe organic solution is rotated in a certain direction by adopting a magnetic stirring method, the rotating speed is controlled at 800 r/min, the surface of the gel film is placed along the flowing direction of the organic solution, and Cs with lattice point diameter of 80nm can be obtained after solution washing and annealingxWO3And (3) a nano lattice film.
Finally, the sol A is uniformly coated on the Cs by a spin coating technologyxWO3Forming tungsten oxide gel film on the nano lattice, then placing the film in a muffle furnace to anneal for 1 hour at 300 ℃, and air cooling to obtain the material containing CsxWO3A nano lattice embedded amorphous tungsten oxide composite film.
The composite film has excellent subarea (visible area and near infrared area) regulation and control capability on solar transmission light, and has an optical modulation value of 60% at 632.5nm, 65% at 900nm and 55% at 2000 nm.
Example 2
An electrochromic film with Cs for effectively modulating the transmittance of sunlightxWO3The nano lattice embedded amorphous tungsten oxide composite film has x of 0.2, the diameter of nano lattice points of 300nm, the spacing between lattice points of 600nm and the height of lattice points of 80 nm.
The preparation method with the structural parameters comprises the following specific steps:
firstly, non-doped tungsten oxide sol A and Cs-doped tungsten oxide sol B are respectively prepared. The process comprises the following steps:
4g of WCl6And 13.83g of absolute ethyl alcohol were mixed at room temperature, and stirred for 2 hours, then 1.56g of 2, 2-pyridine was added to the sol, and the mixture was refluxed at 60 ℃ for 2 hours, to obtain a photosensitive tungsten oxide sol a.
And adding 0.34g of CsCl into the photosensitive tungsten oxide sol A, and stirring for 10 hours at 60 ℃ to obtain the Cs-doped tungsten oxide photosensitive sol B.
Secondly, the sol B is coated on the transparent conductive coated glass substrate by adopting a spin coating technology to ensure the annealed CsxWO3The lattice height of the nano lattice film is 80nm, and the rotating speed of a turntable adopted in the spin coating process is 2500 revolutionsPer minute, spin time 40 seconds.
And then, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system, carrying out double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise for 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate. Wherein, the selected laser wavelength is 325nm, the power is 50mW, and in order to ensure the lattice point spacing to be 600nm, the included angle between the two beams is set to be 30 degrees in the stage.
Then, the exposed gel film substrate is put into a prepared organic solvent for dissolving and washing for 10 seconds, then taken out and put into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain CsxWO3And (4) nano lattice. Wherein the organic solvent is a mixed solution of acetone and n-butanol, and the volume ratio of the acetone to the n-butanol is 1: 2, in the dissolving and washing process, the organic solution is rotated according to a certain direction by adopting a magnetic stirring method, the rotating speed is controlled to be 1000 r/min, the surface of the gel film is placed along the flowing direction of the organic solution, and Cs with the lattice point diameter of 300nm can be obtained after dissolving and washing and annealingxWO3And (3) a nano lattice film.
Finally, the sol A is uniformly coated on the Cs by a spin coating technologyxWO3Forming tungsten oxide gel film on the nano lattice, then placing the film in a muffle furnace to anneal for 1 hour at 300 ℃, and air cooling to obtain the material containing CsxWO3A nano lattice embedded amorphous tungsten oxide composite film.
The composite film has excellent subarea (visible area and near infrared area) regulation and control capability on solar transmission light, and has an optical modulation value of 60% at 632.5nm, 62% at 900nm and 60% at 2000 nm.
Example 3
An electrochromic film with Cs for effectively modulating the transmittance of sunlightxWO3The nano lattice embedded amorphous tungsten oxide composite film has x of 0.1, the diameter of nano lattice points of 200nm, the spacing between lattice points of 400nm and the height of lattice points of 50 nm.
The preparation method with the structural parameters comprises the following specific steps:
firstly, non-doped tungsten oxide sol A and Cs-doped tungsten oxide sol B are respectively prepared. The process comprises the following steps:
4g of WCl6And 13.83g of absolute ethyl alcohol were mixed at room temperature, and stirred for 2 hours, then 1.56g of 2, 2-pyridine was added to the sol, and the mixture was refluxed at 55 ℃ for 2 hours, to obtain a photosensitive tungsten oxide sol a.
And adding 0.17g of CsCl into the photosensitive tungsten oxide sol A, and stirring for 10 hours at 60 ℃ to obtain the Cs-doped tungsten oxide photosensitive sol B.
Secondly, the sol B is coated on the transparent conductive coated glass substrate by adopting a spin coating technology to ensure the annealed CsxWO3The lattice height of the nano lattice film is 50nm, the rotating speed of a rotating disc adopted in the spin coating process is 2900 rpm, and the rotating time is 30 seconds.
And then, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system, carrying out double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise for 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate. Wherein, the laser wavelength is 325nm, the power is 50mW, and in order to ensure the lattice point spacing to be 400nm, the included angle between the two beams is set to be 48 degrees in the stage.
Then, the exposed gel film substrate is put into a prepared organic solvent for dissolving and washing for 30 seconds, then taken out and put into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain CsxWO3And (4) nano lattice. Wherein the organic solvent is a mixed solution of acetone and n-butanol, and the volume ratio of the acetone to the n-butanol is 1: 2, when dissolving and washing, the organic solution is rotated according to a certain direction by adopting a magnetic stirring method, the rotating speed is controlled at 925 rpm, the surface of the gel film is placed along the flowing direction of the organic solution, and Cs with the lattice point diameter of 200nm can be obtained after dissolving and washing and annealingxWO3And (3) a nano lattice film.
Finally, the sol A is uniformly coated on the Cs by a spin coating technologyxWO3Nano latticeForming tungsten oxide gel film, annealing in muffle furnace at 300 deg.C for 1 hr, and air cooling to obtain the product containing CsxWO3A nano lattice embedded amorphous tungsten oxide composite film.
The composite film has excellent subarea (visible area and near infrared area) regulation and control capability on solar transmission light, and has an optical modulation value of 62% at the wavelength of 632.5nm, an optical modulation value of 65% at the wavelength of 900nm and an optical modulation value of 58% at the wavelength of 2000 nm.
Example 4
An electrochromic film with Cs for effectively modulating the transmittance of sunlightxWO3The nano lattice embedded amorphous tungsten oxide composite film has x of 0.15, the diameter of nano lattice points of 100nm, the spacing between lattice points of 400nm and the height of lattice points of 70 nm.
The preparation method with the structural parameters comprises the following specific steps:
firstly, non-doped tungsten oxide sol A and Cs-doped tungsten oxide sol B are respectively prepared. The process comprises the following steps:
4g of WCl6And 13.83g of absolute ethyl alcohol were mixed at room temperature, and stirred for 2 hours, then 1.56g of 2, 2-pyridine was added to the sol, and the mixture was refluxed at 50 ℃ for 2 hours, to obtain a photosensitive tungsten oxide sol a.
And adding 0.25g of CsCl into the photosensitive tungsten oxide sol A, and stirring for 10 hours at 60 ℃ to obtain the Cs-doped tungsten oxide photosensitive sol B.
Secondly, the sol B is coated on the transparent conductive coated glass substrate by adopting a spin coating technology to ensure the annealed CsxWO3The lattice point height of the nano lattice film is 70nm, the rotating speed of a rotating disc adopted in the spin coating process is 2600 r/min, and the rotating time is 35 seconds.
And then, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system, carrying out double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise for 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate. Wherein, the laser wavelength is 325nm, the power is 50mW, and in order to ensure the lattice point spacing to be 400nm, the included angle between the two beams is set to be 48 degrees in the stage.
Then, the exposed gel film substrate is put into a prepared organic solvent for dissolution and washing for 70 seconds, then taken out and put into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain CsxWO3And (4) nano lattice. Wherein the organic solvent is a mixed solution of acetone and n-butanol, and the volume ratio of the acetone to the n-butanol is 1: 2, in the dissolving and washing process, the organic solution is rotated according to a certain direction by adopting a magnetic stirring method, the rotating speed is controlled at 950 rpm, the surface of the gel film is placed along the flowing direction of the organic solution, and Cs with the lattice point diameter of 100nm can be obtained after dissolving and washing and annealingxWO3And (3) a nano lattice film.
Finally, the sol A is uniformly coated on the Cs by a spin coating technologyxWO3Forming tungsten oxide gel film on the nano lattice, then placing the film in a muffle furnace to anneal for 1 hour at 300 ℃, and air cooling to obtain the material containing CsxWO3A nano lattice embedded amorphous tungsten oxide composite film.
The composite film has excellent subarea (visible area and near infrared area) regulation and control capability on solar transmitted light, and has an optical modulation value of 61% at 632.5nm, 64% at 900nm and 61% at 2000 nm.
Example 5
An electrochromic film with Cs for effectively modulating the transmittance of sunlightxWO3The nano lattice embedded amorphous tungsten oxide composite film has x of 0.08, the diameter of nano lattice points of 150nm, the spacing between lattice points of 400nm and the height of lattice points of 40 nm.
The preparation method with the structural parameters comprises the following specific steps:
firstly, non-doped tungsten oxide sol A and Cs-doped tungsten oxide sol B are respectively prepared. The process comprises the following steps:
4g of WCl6Mixing with 13.83g anhydrous ethanol at room temperature, stirring for 2 hr, adding 1.56g 2, 2-pyridine into the sol, and refluxing at 53 deg.C for 2 hr to obtain photosensitive solutionTungsten oxide sol a.
And adding 0.13g of CsCl into the photosensitive tungsten oxide sol A, and stirring for 10 hours at 60 ℃ to obtain the Cs-doped tungsten oxide photosensitive sol B.
Secondly, the sol B is coated on the transparent conductive coated glass substrate by adopting a spin coating technology to ensure the annealed CsxWO3The lattice height of the nano lattice film is 40nm, the rotating speed of a rotating disc adopted in the spin coating process is 2950 rpm, and the rotating time is 25 seconds.
And then, placing the gel film substrate coated with the sol B in a drying oven, drying for 5 minutes at 70 ℃, taking out, placing in a laser interference exposure system, carrying out double-beam exposure for 10 minutes, then rotating the gel film substrate clockwise for 90 degrees, continuing to expose for 10 minutes, and taking out the gel film substrate. Wherein, the laser wavelength is 325nm, the power is 50mW, and in order to ensure the lattice point spacing to be 400nm, the included angle between the two beams is set to be 48 degrees in the stage.
Then, the exposed gel film substrate is put into a prepared organic solvent for dissolving and washing for 50 seconds, then taken out and put into a muffle furnace with the preset temperature of 550 ℃ for annealing treatment for 30 minutes to obtain CsxWO3And (4) nano lattice. Wherein the organic solvent is a mixed solution of acetone and n-butanol, and the volume ratio of the acetone to the n-butanol is 1: 2, in the dissolving and washing process, the organic solution is rotated according to a certain direction by adopting a magnetic stirring method, the rotating speed is controlled at 900 r/min, the surface of the gel film is placed along the flowing direction of the organic solution, and Cs with the lattice point diameter of 150nm can be obtained after dissolving and washing and annealingxWO3And (3) a nano lattice film.
Finally, the sol A is uniformly coated on the Cs by a spin coating technologyxWO3Forming tungsten oxide gel film on the nano lattice, then placing the film in a muffle furnace to anneal for 1 hour at 300 ℃, and air cooling to obtain the material containing CsxWO3A nano lattice embedded amorphous tungsten oxide composite film.
The composite film has excellent subarea (visible area and near infrared area) regulation and control capability on solar transmission light, and has an optical modulation value of 59% at 632.5nm, 60% at 900nm and 59% at 2000 nm.
The invention has the advantages that:
(1) selecting proper material components and structural parameters to obtain the Cs with the local surface plasma resonance absorption covering the near-infrared full-wave bandxWO3A nano-lattice embedded amorphous tungsten oxide composite film; the independent modulation of the composite film on the near-infrared transmittance is realized by utilizing the local surface plasma resonance electrochromic characteristic of the film, and the modulation of the composite film on the visible light transmittance is realized by utilizing the redox reaction electrochromic characteristic of amorphous tungsten oxide in the film; because the electrochemical driving voltage required by the modulation of near-infrared light and the modulation of visible light is different, the zonal regulation and control of the composite film on the visible-near infrared region can be realized by controlling the driving voltage; compared with a commercial tungsten oxide electrochromic film, the composite film designed by the invention not only has wider color-changing wave band, but also can independently select the modulatable wave band of the film, so that the film has stronger electrochromic function and is more energy-saving;
(2) preparation of CsxWO3The laser interference combined with the photosensitive sol-gel method adopted by the nano lattice and the sol-gel technology adopted by the amorphous tungsten oxide can prepare large-area films, the process is controllable, and the method is very suitable for industrialized mass film preparation and has wide application prospect.
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