CN109704591B - Visible-near infrared double-frequency modulated single-phase electrochromic film and preparation method thereof - Google Patents
Visible-near infrared double-frequency modulated single-phase electrochromic film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a visible-near infrared double-frequency modulated single-phase electrochromic film, which takes soda-lime glass as a substrate, and a niobium and fluorine co-doped titanium dioxide nanocrystalline film covers the substrate. The film has good double-frequency modulation electrochromic characteristic, and can solve the problems of relatively complex structure and relatively high cost of the current complex-phase electrochromic material. The preparation method comprises the following steps: step 1, preparing a composite sol G containing Ti-Nb-F elements; step 2, preparing a gel film by lifting; and 3, placing the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate in a vacuum furnace, and annealing at 400-500 ℃ for 60 minutes to obtain the visible-near infrared double-frequency modulated single-phase electrochromic film. The method can be used for preparing the membrane in a large area and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of electrochromic film preparation, and particularly relates to a visible-near infrared double-frequency modulated single-phase electrochromic film; the invention also relates to a preparation method of the electrochromic film.
Background
Titanium dioxide is a typical cathode electrochromic material, and the material can be displayed under the action of an external driving voltage
The phenomenon of reversible change has important application value in the fields of electrochromic smart windows and electronic paper. At present, related patents exist in China, for example, a patent with application number 201210086783.0 published by 2012.07.18 proposes a micro-arc oxidation preparation method of a pure rutile phase titanium dioxide electrochromic film, the electrochromic film prepared by micro-arc oxidation is pure rutile phase titanium dioxide, electrochromism is realized in a solution containing hydrogen ions, and the preparation method has good wear resistance, can generate a high-wear-resistance and high-thickness electrochromic film, and has good application prospect. 2018.08.17, published under application No. 201810333908.2, proposes a WO3/TiO2Preparation method of porous electrochromic glass film, WO prepared by adopting dip-coating method3/TiO2The porous electrochromic glass film has good electrochromic performance and no pollution. However, these patents produce an electrical transformationThe color films do not have visible-near infrared dual-frequency modulation characteristics. However, by introducing the local surface plasma vibration effect into the electrochromic film, the visible-near infrared dual-frequency modulated electrochromic material can be obtained. For example, patent application No. 201280036901.5 published by 2012.07.24 proposes an electrochromic nanocomposite film, in which a plated film is formed by compounding a transition metal oxide with a wide bandgap semiconductor; 2018.08.24 patent application No. 201810111317.0 discloses a method for uniformly and orderly distributing nano ITO lattice/grating on amorphous WO3And preparing the high-performance double-frequency independent modulation color-changing film in the film. Although the films have visible-near infrared dual-frequency modulation characteristics, most of the films are complex phase materials, have complex structures and high preparation difficulty, so that the technical problem to be solved in the electrochromic field at present is to select a single-phase electrochromic film with dual-frequency modulation capability and research the preparation method of the single-phase electrochromic film, thereby achieving the purposes of simplifying the structure and reducing the cost.
Disclosure of Invention
The invention aims to provide a visible-near infrared double-frequency modulated single-phase electrochromic film which has a good double-frequency modulated electrochromic characteristic and can solve the problems of relatively complex structure and relatively high cost of the current complex-phase electrochromic material.
The invention also aims to provide a preparation method of the visible-near infrared double-frequency modulated single-phase electrochromic film, which can be used for preparing the film in a large area and is suitable for industrial mass production.
The technical scheme adopted by the invention is as follows: the visible-near infrared double-frequency modulated single-phase electrochromic film takes soda-lime glass as a substrate, and a niobium and fluorine co-doped titanium dioxide nanocrystalline film covers the substrate.
The present invention is characterized in that it comprises,
niobium and fluorine co-doped titanium dioxide nanocrystalline film: fluorine: the titanium atomic ratio is 0.03-0.06: 0.02: 1, the nano-crystalline size of the titanium dioxide is 5-15 nm, the average grain gap in the nano-crystalline film is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022A cm3。
The other technical scheme adopted by the invention is as follows: the preparation method of the visible-near infrared double-frequency modulated single-phase electrochromic film comprises the following specific steps:
step 1, preparing a composite sol G containing Ti-Nb-F elements;
step 1.1, preparing a sol C containing Nb: mixing niobium chloride and methanol, stirring for 1 hour at room temperature to obtain sol A, mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain solution B, mixing the sol A and the solution B, adding acrylic acid, and obtaining clear sol C after 2 to 3 hours;
step 1.2, preparing a sol E containing Ti: the preparation process comprises the steps of mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain a solution D, adding butyl titanate into the solution D, and stirring for 1 hour at room temperature to obtain sol E;
step 1.3, mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements;
step 1.4, adding a trifluoroacetic acid solution into the composite sol F containing the Nb-Ti element, and mixing and stirring at room temperature to obtain a composite sol G containing the Ti-Nb-F element;
step 2, preparing a gel film by lifting;
preparing a gel film on the soda-lime glass by the obtained Ti-Nb-F element-containing composite sol G through a dip-coating method, drying the gel film substrate prepared through coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front;
and 3, placing the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate in a vacuum furnace, and annealing at 400-500 ℃ for 60 minutes to obtain the visible-near infrared double-frequency modulated single-phase electrochromic film.
The present invention is characterized in that it comprises,
the molar ratio of niobium pentachloride, butyl titanate, acetylacetone, acrylic acid, methanol and trifluoroacetic acid used in the step 1 is 0.03-0.06: 1: 1: 2: 60: 0.167.
in the step 1.1, the molar ratio of niobium pentachloride to methanol is 0.03-0.06: 20; the molar ratio of acetylacetone to methanol in step 1.1 and step 1.2 is 0.5: 20.
in step 3, the niobium content in the visible-near infrared double-frequency modulated single-phase electrochromic film is as follows: fluorine: the titanium atomic ratio is 0.03-0.06: 0.02: 1, in the single-phase electrochromic film, the titanium dioxide nanocrystal size is 5-15 nm, the average crystal grain gap is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022Per cm3。
The beneficial effect of the invention is that,
(1) the single-phase electrochromic film with visible-near infrared dual-frequency modulation has a simple structure and low preparation cost;
(2) the electrochromic film can be subjected to visible-near infrared dual-frequency modulation;
(3) the preparation method adopted by the invention is a sol-gel method, and the method can be used for large-area film preparation and is suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides a visible-near infrared double-frequency modulated single-phase electrochromic film, which takes common soda-lime glass as a substrate, and a niobium and fluorine co-doped titanium dioxide nanocrystalline film covers the substrate.
Niobium and fluorine co-doped titanium dioxide nanocrystalline film: fluorine: the titanium atomic ratio is (0.03-0.06): 0.02: 1, the nano-crystalline size of the titanium dioxide is 5-15 nm, the average grain gap in the nano-crystalline film is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022Per cm3。
The invention also provides a preparation method of the visible-near infrared double-frequency modulated single-phase electrochromic film, which comprises the following specific steps:
step 1, preparing a composite sol G containing Ti-Nb-F elements;
step 1.1, preparing a sol C containing Nb: mixing niobium chloride and methanol, stirring for 1 hour at room temperature to obtain sol A, mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain solution B, mixing the sol A and the solution B, adding acrylic acid, and obtaining clear sol C after 2 to 3 hours;
step 1.2, preparing a sol E containing Ti: the preparation process comprises the steps of mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain a solution D, adding butyl titanate into the solution D, and stirring for 1 hour at room temperature to obtain sol E;
step 1.3, mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements;
step 1.4, adding a trifluoroacetic acid solution into the composite sol F containing the Nb-Ti element, and mixing and stirring at room temperature to obtain a composite sol G containing the Ti-Nb-F element;
step 2, preparing a gel film by lifting;
preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front;
and 3, placing the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate in a vacuum furnace, and annealing at 400-500 ℃ for 60 minutes to obtain the visible-near infrared double-frequency modulated single-phase electrochromic film.
The molar ratio of niobium pentachloride, butyl titanate, acetylacetone, acrylic acid, methanol and trifluoroacetic acid used in the step 1 is (0.03-0.06): 1: 1: 2: 60: 0.167.
in the step 1.1, the molar ratio of niobium pentachloride to methanol is (0.03-0.06): 20; the molar ratio of acetylacetone to methanol in step 1.1 and step 1.2 is 0.5: 20.
in step 3, the niobium content in the visible-near infrared double-frequency modulated single-phase electrochromic film is as follows: fluorine: titanium atom ratio of (0.03 to 0.06): 0.02: 1, in the single-phase electrochromic film, the titanium dioxide nanocrystal size is 5-15 nm, the average crystal grain gap is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022Per cm3。
Example 1
Visible-near infrared double-frequency modulated single-phase electrochromic film and niobium and fluorine co-doped titanium dioxide nanocrystalline film, wherein the ratio of niobium: fluorine: titanium atomic ratio of 0.03: 0.02: 1, the nano-crystalline size of the titanium dioxide is 15nm, the average grain gap is 2nm, the film thickness is 400nm, and the carrier concentration is 1021Per cm3. The preparation method of the composite film with the structural parameters comprises the following specific steps:
mixing 0.16g of niobium pentachloride and 12.81g of anhydrous methanol, and stirring at room temperature for 1 hour to obtain sol A; mixing 1g of acetylacetone and 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution B, mixing the sol A with the solution B, adding 2.88g of acrylic acid, and obtaining a clear sol C after 2 hours; mixing 1g of acetylacetone with 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution D, adding 6.80g of butyl titanate into the solution D, and stirring at room temperature for 1 hour to obtain a sol E; mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements; and adding 0.38G of trifluoroacetic acid solution into the Nb-Ti element-containing composite sol F, and mixing and stirring at room temperature to obtain the Ti-Nb-F element-containing composite sol G.
Preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front; the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate is placed in a vacuum furnace to be annealed at 500 ℃ for 60 minutes, so that the niobium and fluorine co-doped titanium dioxide nanocrystalline film, namely the single-phase electrochromic film with visible-near infrared dual-frequency modulation, is obtained, wherein the optical modulation amplitude of the single-phase electrochromic film on the near infrared band can reach 45%, and the optical modulation amplitude on the visible light band can reach 50%.
Example 2
Visible-near infrared double-frequency modulated single-phase electrochromic film and niobium and fluorine co-doped titanium dioxide nanocrystalline film, wherein the ratio of niobium: fluorine: titanium atomic ratio of 0.04: 0.02: 1, the nano-crystalline size of the titanium dioxide is 13nm, the average grain gap is 4nm, the film thickness is 360nm, and the carrier concentration is 7 multiplied by 1021Pieces/cm 3. The preparation method of the composite film with the structural parameters comprises the following specific steps:
mixing 0.22g of niobium pentachloride and 12.81g of anhydrous methanol, and stirring at room temperature for 1 hour to obtain sol A; mixing 1g of acetylacetone and 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution B, mixing the sol A with the solution B, adding 2.88g of acrylic acid, and obtaining a clear sol C after 3 hours; mixing 1g of acetylacetone with 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution D, adding 6.80g of butyl titanate into the solution D, and stirring at room temperature for 1 hour to obtain a sol E; mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements; and adding 0.38G of trifluoroacetic acid solution into the Nb-Ti element-containing composite sol F, and mixing and stirring at room temperature to obtain the Ti-Nb-F element-containing composite sol G.
Preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front; the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate is placed in a vacuum furnace to be annealed at 460 ℃ for 60 minutes, so that the niobium and fluorine co-doped titanium dioxide nanocrystalline film, namely the single-phase electrochromic film with visible-near infrared dual-frequency modulation, is obtained, the optical modulation amplitude of the single-phase electrochromic film on the near infrared band can reach 46%, and the optical modulation amplitude on the visible light band can reach 51%.
Example 3
Visible-near infrared double-frequency modulated single-phase electrochromic film, niobium and fluorine co-doped dioxideA nanocrystalline film of titanium, wherein the ratio of niobium: fluorine: titanium atomic ratio of 0.04: 0.02: 1, the titanium dioxide nanocrystal size is 11nm, the average grain gap is 5nm, the film thickness is 370nm, and the carrier concentration is 4 multiplied by 1021Pieces/cm 3. The preparation method of the composite film with the structural parameters comprises the following specific steps:
mixing 0.22g of niobium pentachloride and 12.81g of anhydrous methanol, and stirring at room temperature for 1 hour to obtain sol A; mixing 1g of acetylacetone and 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution B, mixing the sol A with the solution B, adding 2.88g of acrylic acid, and obtaining a clear sol C after 2.5 hours; mixing 1g of acetylacetone with 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution D, adding 6.80g of butyl titanate into the solution D, and stirring at room temperature for 1 hour to obtain a sol E; mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements; and adding 0.38G of trifluoroacetic acid solution into the Nb-Ti element-containing composite sol F, and mixing and stirring at room temperature to obtain the Ti-Nb-F element-containing composite sol G.
Preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front; the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate is placed in a vacuum furnace to be annealed at 450 ℃ for 60 minutes, so that the niobium and fluorine co-doped titanium dioxide nanocrystalline film, namely the single-phase electrochromic film with visible-near infrared dual-frequency modulation, is obtained, the optical modulation amplitude of the single-phase electrochromic film on the near infrared band can reach 48%, and the optical modulation amplitude on the visible light band can reach 52%.
Example 4
Visible-near infrared double-frequency modulated single-phase electrochromic film and niobium and fluorine co-doped titanium dioxide nanocrystalline film, wherein the ratio of niobium: fluorine: titanium atomic ratio of 0.05: 0.02: 1, the titanium dioxide nanocrystal size is 8nm, the average grain gap is 7nm, the film thickness is 330nm, and the carrier concentration is 6 multiplied by 1021Per cm3. The preparation method of the composite film with the structural parameters comprises the following specific steps:
mixing 0.27g of niobium pentachloride and 12.81g of anhydrous methanol, and stirring at room temperature for 1 hour to obtain sol A; mixing 1g of acetylacetone and 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution B, mixing the sol A with the solution B, adding 2.88g of acrylic acid, and obtaining a clear sol C after 3 hours; mixing 1g of acetylacetone with 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution D, adding 6.80g of butyl titanate into the solution D, and stirring at room temperature for 1 hour to obtain a sol E; mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements; and adding 0.38G of trifluoroacetic acid solution into the Nb-Ti element-containing composite sol F, and mixing and stirring at room temperature to obtain the Ti-Nb-F element-containing composite sol G.
Preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front; the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate is placed in a vacuum furnace to be annealed at 450 ℃ for 60 minutes, so that the niobium and fluorine co-doped titanium dioxide nanocrystalline film, namely the single-phase electrochromic film with visible-near infrared dual-frequency modulation, is obtained, the optical modulation amplitude of the single-phase electrochromic film on the near infrared band can reach 53%, and the optical modulation amplitude on the visible light band can reach 58%.
Example 5
Visible-near infrared double-frequency modulated single-phase electrochromic film and niobium and fluorine co-doped titanium dioxide nanocrystalline film, wherein the ratio of niobium: fluorine: titanium atomic ratio of 0.06: 0.02: 1, the titanium dioxide has a nanocrystalline size of 5nm, an average grain gap of 10nm, a film thickness of 300nm, and a carrier concentration of 9.7 × 1021Per cm3. The preparation method of the composite film with the structural parameters comprises the following specific steps:
mixing 0.32g of niobium pentachloride and 12.81g of anhydrous methanol, and stirring at room temperature for 1 hour to obtain sol A; mixing 1g of acetylacetone and 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution B, mixing the sol A with the solution B, adding 2.88g of acrylic acid, and obtaining a clear sol C after 2 hours; mixing 1g of acetylacetone with 12.81g of methanol, stirring at room temperature for 30 minutes to obtain a solution D, adding 6.80g of butyl titanate into the solution D, and stirring at room temperature for 1 hour to obtain a sol E; mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements; and adding 0.38G of trifluoroacetic acid solution into the Nb-Ti element-containing composite sol F, and mixing and stirring at room temperature to obtain the Ti-Nb-F element-containing composite sol G.
Preparing a gel film on common soda-lime glass by the obtained composite sol G containing the Ti-Nb-F element through a dip-coating method, drying the gel film substrate prepared by coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front; the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate is placed in a vacuum furnace to be annealed at 400 ℃ for 60 minutes, so that the niobium and fluorine co-doped titanium dioxide nanocrystalline film, namely the visible-near infrared double-frequency modulated single-phase electrochromic film, is obtained, the optical modulation amplitude of the niobium and fluorine co-doped titanium dioxide nanocrystalline film on the near infrared wave band can reach 60%, and the optical modulation amplitude of the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film on the visible light wave band can reach 61%.
Claims (2)
1. The visible-near infrared double-frequency modulated single-phase electrochromic film is characterized in that soda-lime glass is used as a substrate, and a niobium and fluorine co-doped titanium dioxide nanocrystalline film covers the substrate;
niobium and fluorine co-doped titanium dioxide nanocrystalline film contains niobium: fluorine: the titanium atomic ratio is 0.03-0.06: 0.02: 1, the nano-crystalline size of the titanium dioxide is 5-15 nm, the average grain gap in the nano-crystalline film is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022Per cm3。
2. The preparation method of the visible-near infrared double-frequency modulated single-phase electrochromic film is characterized by comprising the following specific steps of:
step 1, preparing a composite sol G containing Ti-Nb-F elements;
step 1.1, preparing a sol C containing Nb: mixing niobium chloride and methanol, stirring for 1 hour at room temperature to obtain sol A, mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain solution B, mixing the sol A and the solution B, adding acrylic acid, and obtaining clear sol C after 2 to 3 hours;
step 1.2, preparing a sol E containing Ti: the preparation process comprises the steps of mixing acetylacetone and methanol, stirring for 30 minutes at room temperature to obtain a solution D, adding butyl titanate into the solution D, and stirring for 1 hour at room temperature to obtain sol E;
step 1.3, mixing the sol C and the sol E at room temperature, and stirring for 1 hour to obtain a composite sol F containing Nb-Ti elements;
step 1.4, adding a trifluoroacetic acid solution into the composite sol F containing the Nb-Ti element, and mixing and stirring at room temperature to obtain a composite sol G containing the Ti-Nb-F element;
step 2, preparing a gel film by lifting;
preparing a gel film on the soda-lime glass by the obtained Ti-Nb-F element-containing composite sol G through a dip-coating method, drying the gel film substrate prepared through coating at 300 ℃ for 10 minutes, taking out, air-cooling to room temperature, wiping off the gel film on the back of the soda-lime glass by absolute ethyl alcohol, and only keeping the gel film on the front;
step 3, placing the niobium and fluorine co-doped titanium dioxide nanocrystalline gel film substrate in a vacuum furnace, and annealing for 60 minutes at 400-500 ℃ to obtain a visible-near infrared double-frequency modulated single-phase electrochromic film;
the molar ratio of niobium pentachloride, butyl titanate, acetylacetone, acrylic acid, methanol and trifluoroacetic acid used in the step 1 is 0.03-0.06: 1: 1: 2: 60: 0.167;
in the step 1.1, the molar ratio of niobium pentachloride to methanol is 0.03-0.06: 20; the molar ratio of acetylacetone to methanol in step 1.1 and step 1.2 is 0.5: 20;
in step 3, the niobium content in the visible-near infrared double-frequency modulated single-phase electrochromic film is as follows: fluorine: the titanium atomic ratio is 0.03-0.06: 0.02: 1, in the single-phase electrochromic film, the titanium dioxide nanocrystal size is 5-15 nm, the average crystal grain gap is 2-10 nm, the film thickness is 300-400 nm, and the carrier concentration is 1021～1022Per cm3。
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