CN105870330B - A kind of preparation method of perovskite solar cell nanometer TiO 2 sol and framework film - Google Patents

A kind of preparation method of perovskite solar cell nanometer TiO 2 sol and framework film Download PDF

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CN105870330B
CN105870330B CN201610228505.2A CN201610228505A CN105870330B CN 105870330 B CN105870330 B CN 105870330B CN 201610228505 A CN201610228505 A CN 201610228505A CN 105870330 B CN105870330 B CN 105870330B
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tio
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李建生
刘炳光
卢俊锋
胡兴兰
白净伊
董崇文
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Hefei Jiuzhou Longteng Scientific And Technological Achievement Transformation Co ltd
Jiangsu Hongxunhe New Energy Co ltd
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Abstract

The present invention relates to a kind of preparation methods of perovskite solar cell nanometer TiO 2 sol and framework film, in the nano-TiO of small particle2Large-sized Nano-meter SiO_2 is added in colloidal sol2The organic silicon nano resin sol of colloidal sol and a small amount of small particle, the nano-TiO of small particle2With large-sized Nano-meter SiO_22It is copolymerized, and is wrapped in big grain diameter nano SiO2Particle surface forms nuclear shell structure nano TiO2Particle, the organic silicon nano resin of a small amount of small particle further portion envelops nuclear shell structure nano TiO2Particle makes it be bonded in securely in substrate material surface and is bound to each other to form nuclear shell structure nano TiO2Framework film.The present invention uses nuclear shell structure nano TiO2Particle solves nano-TiO2Contradiction between framework film adhesive force and hole content, and flexible molecule group is introduced in framework film, it is strong to further enhance film adhesion, to eliminate nano-TiO2The high-temperature sintering process of framework film.

Description

A kind of preparation method of perovskite solar cell nanometer TiO 2 sol and framework film
Technical field
The present invention relates to a kind of preparation methods of perovskite solar cell nanometer TiO 2 sol and framework film, especially A kind of preparation method of non-sintered nuclear shell structure nano titanium dioxide framework film, belongs to new energy and field of new materials.
Technical background
The solar cell prepared based on organic metal halide perovskite structure light absorbing material is referred to as perovskite too Positive electricity pond, more than 20%, future is expected to reach 50% its photoelectric conversion efficiency at present.Perovskite solar cell only need to be by calcium titanium Mine light absorbing material, which is supported on nanometer framework material, can be made perovskite light absorbing layer and realize opto-electronic conversion, not only be easy Large-scale production, and expected manufacturing cost is very low, it is expected that technological break-through can bring new hope to solar energy industry, is made in the future Colorful film battery decoration is mounted on building surface and promotes integrated photovoltaic architectural development.
Perovskite solar cell be typically by transparent conducting glass, compacted zone, perovskite light absorbing layer, hole transmission layer, Five part of metal back electrode forms, wherein perovskite light absorbing layer is its most critical part, by perovskite light absorbing material and work It is constituted for the porous nanometer material film of skeleton.Common skeleton nano material includes nano-TiO2、Al2O3、ZrO2、SiO2、ZnO、 SnO2、WO3、ReO、BaSnO3、SrTiO3Deng, wherein the most commonly used is nano-TiOs2.Composition, the pattern knot of skeleton nano material Structure and preparation process influence perovskite light absorbing layer performance very big.Skeleton nano material is removed as perovskite light absorbing material It supports outside skeleton, electronics can also be transmitted, improve light absorbing material crystalline texture and increase perovskite light absorbing material surface area, To promote the photoelectric conversion efficiency of perovskite light absorbing layer.
Nano-TiO2Particle has three kinds of anatase titanium dioxide, plate titanium-type and rutile-type crystal forms, has spherical, needle-shaped and sheet etc. a variety of Particle shape, the wide particle size ranges of 2-100nm select commercially available or homemade nano-TiO according to purposes2Dispersion is added in particle Agent, stabilizer and other additives are dispersed in solvent, and the high dispersive of the various models of the easy coating of 3%-40% is made Nano-TiO2Slurry or colloid.Has a small amount of commercialization high-dispersion nano TiO at present2Slurry is supplied, wherein Australia The high-dispersion nano TiO of Dyesol companies2Size Technology is horizontal high, is now in evaluation phase on probation.
Nano-TiO2Method of spin coating, scraper plate method, rolling method or spray coating method may be used after slurry or colloid adjustment viscosity It is coated on basis material, forms perforated membrane in matrix surface after solvent volatile dry, film layer hole content is mainly by slurry or glue The composition of body determines that thicknesses of layers can pass through nano-TiO2The viscosity and coating speed of slurry or colloid adjust, it is desirable that nanometer Framework film can be securely attached on matrix surface.
Nano-TiO2Skeleton membrane preparation method mainly has high-temperature sintering process and sol-gel method.High-temperature sintering process is first will Nano-TiO2Slurry or colloid are coated on matrix, work as nano-TiO2It is normal during drying and forming-film when grain size is larger or film layer is thicker There is peeling and film layer obscission, needs the processing under 500 DEG C of high temperature that it is made to be sintered to fix on matrix.High-temperature sintering process adds Work is of high cost, can not use, limit its scope of application on flexible high molecular material substrate.Sol-gel method is will to receive Rice TiO2Colloid is coated on matrix, nano-TiO2It is securely attached on matrix surface by molecular separating force or adhesive, it can be Film-forming under lower temperature, advantage are to select more flexible, industrialization easy to implement to basis material.
The Institute of Technology of Lausanne, SUI federation patent of invention US2015200377（ 2015-07-16）A kind of prepare is disclosed to receive Rice TiO2The method of framework film, first by four butanol titaniums and hydrofluoric acid, hybrid reaction is for 24 hours, white by gained after cooling at 180 DEG C Precipitation and centrifugal separation, then it is 30nm to be washed with ethyl alcohol and deionized water, the length of side is made after drying, thickness is the flake nano of 7nm TiO2Particle is spin-coated on after being disperseed on the compacted zone of electro-conductive glass, thickness about 500nm, and 0.5 h is made annealing treatment at 500 DEG C, TiCl is used at 70 DEG C4Aqueous solution handles 0.5 h, after being washed with ethyl alcohol and deionized water, then the annealing at 500 DEG C 0.5 h, has obtained nano-TiO2The substrate material of casing play.
Korea Research Inst. of Chemical Technology patent of invention US2016005547（2016-01-07）It discloses and a kind of preparing nanometer TiO2Titanium peroxide complex is thermally decomposed to yield the nano-TiO of average grain diameter 50nm by the method for framework film2Particle, by its with Terpinol mixing dispersion obtains nano-TiO2Lotion is screen printed onto on the compacted zone of electro-conductive glass, thickness about 600nm, 500 DEG C annealing 0.5 h, used TiCl at 60 DEG C4Aqueous solution processing is to improve nano-TiO2Skeleton surface layer, then 500 DEG C of 0.5 h of annealing, have obtained nano-TiO2The substrate material of casing play, nano-TiO2Skeleton surface layer is 40m2/ g。
Japan Ricoh company patent of invention US 2015279573（2015-10-01）It is open to prepare nano-TiO2Film uses Method, the 18NR-T type nano-TiOs made using Dyesol companies2Slurry is spin-coated on the compacted zone of electro-conductive glass, Thickness about 300nm, heated-air drying at 150 DEG C, then 0.5 h is made annealing treatment at 500 DEG C, obtain nano-TiO2The substrate of casing play Material.
The patent of invention CN104909404 of Tianjin Professional College（2015-09-16）Disclose a kind of sol-gel method Prepare stability nano-TiO2Colloid method is directly prepared for the good dichloride in anatase type TiO of translucency2Particle eliminates the reliance on height Warm processing procedure realizes nano-TiO2Turn crystalline substance, at present applicability of the test as perovskite light absorbing layer skeleton nano material.
Existing perovskite solar cell nanometer titanium dioxide casing play is needed by 500 DEG C or more high-temperature sintering process, system Standby complex process and of high cost, cannot apply on macromolecule transparent material, limit macromolecule membrane perovskite solar cell Development.
Invention content
It is an object of the present invention to provide a kind of perovskite solar cell nanometer TiO2Colloidal sol, using nuclear shell structure nano TiO2Grain Son solves nano-TiO2Contradiction between framework film adhesive force and hole content, and flexible molecule group is introduced in framework film, It is strong to further enhance film adhesion, to eliminate nano-TiO2The high-temperature sintering process of framework film inhales perovskite light It is good to receive material compatibility, can be used as perovskite solar cell light absorption layer framework material.
The principle of the present invention is the nano-TiO in small particle2Large-sized Nano-meter SiO_2 is added in colloidal sol2Colloidal sol and a small amount of The organic silicon nano resin sol of small particle, the nano-TiO of small particle2With large-sized Nano-meter SiO_22It is copolymerized, and wraps It is rolled in big grain diameter nano SiO2Particle surface forms nuclear shell structure nano TiO2Particle, the organic silicon nano resin of a small amount of small particle Further portion envelops nuclear shell structure nano TiO2Particle makes it adhere to substrate material surface securely and the shape that be combined with each other At nano-TiO2Framework film.Organic silicon nano resin of the present invention is a kind of self-curing adhesive containing active function groups, 150 DEG C or less can be adhered to substrate material surface with rapid curing.The small nanoparticle surface product of grain size is big, on substrate material Adhesive force is extremely strong, can be strongly adhered on substrate surface without sintering, but the nano-particle skeleton fenestra appearance that grain size is small Degree is too small, and core-shell structure nanometer particle can solve the contradiction between nano-particle adhesive force and hole content.Nuclear shell structure nano TiO2The hole content and surface area of framework film can pass through nano-TiO2, Nano-meter SiO_22With the pattern and grain of organic silicon nano particle Diameter controls.
Perovskite solar cell nanometer TiO of the present invention2Colloidal sol is by the nano-TiO that average grain diameter is 5nm2Colloidal sol, average grain diameter For the Nano-meter SiO_2 of 40nm2Colloidal sol, the organic silicon nano resin sol that average grain diameter is 10nm and solvent form, each group in colloidal sol Mass percent is as follows shared by point：
Average grain diameter is the nano-TiO of 5nm2 1.5%-5%
Average grain diameter is the Nano-meter SiO_2 of 40nm2 0.9%-3%
Average grain diameter is the organic silicon nano resin 0.6%-2% of 10nm
Balance of solvent.
Average grain diameter is the nano-TiO of 5nm2Colloidal sol in ethanol water, is hydrolyzed by butyl titanate with acetic acid catalysis It is obtained with polymerization, to prevent nano-TiO2Acetylacetone,2,4-pentanedione is added as complexing agent and stabilizer in particle coacervation and precipitation.Its conduct Shell particles can be wrapped in big grain diameter nano SiO2On particle, nuclear shell structure nano TiO is formed2Particle.
Average grain diameter is the Nano-meter SiO_2 of 40nm2Colloidal sol in ethanol water, is hydrolyzed by ethyl orthosilicate with ammonia-catalyzed It is obtained with polymerization, as nuclear shell structure nano TiO2The nuclear particle of particle.
Average grain diameter is the organic silicon nano resin sol of 10nm by organo-silicon coupling agent KH550, organo-silicon coupling agent Or mixtures thereof KH560, organo-silicon coupling agent KH570 are obtained in ethanol water with acetic acid catalysis hydrolysis and polymerization.It makees The nano-TiO of nucleocapsid is further partially retained in for adhesive2On particle, strong adhesive force is further enhanced.
Solvent is the aqueous solution of C2-C6 alcohol, C3-C6 ethers and acetylacetone,2,4-pentanedione, can be controlled by solvent volatility and concentration The stability of film forming speed and colloidal sol.Mass percentage concentration is that the nuclear shell structure nano TiO 2 sol of 3%-10% can be quick It dries, storage stability 3-12 months.
Raw material butyl titanate, ethyl orthosilicate, organo-silicon coupling agent KH550, organo-silicon coupling agent KH560, organosilicon Coupling agent KH570, acetic acid, ammonium hydroxide, solvent C 2-C6 alcohol, C3-C6 ethers and acetylacetone,2,4-pentanedione are commercially available chemical reagent.
It is a further object of the present invention to provide a kind of preparation method of perovskite solar cell nanometer titanium dioxide framework film, The technical solution taken includes small particle nano-TiO2Colloidal sol preparation, big grain diameter nano SiO2Colloidal sol preparation, organic silicon nano resin Solution preparation, nuclear shell structure nano TiO2Colloidal sol preparation, nuclear shell structure nano TiO2Colloidal sol film, nuclear shell structure nano TiO2Bone Frame film cures and evaluation, specific implementation step are：
（1）The acetic acid that absolute ethyl alcohol, deionized water and mass percentage concentration are 30% is separately added into glass reactor, It is 2-3 to make pH value of solution；The mass mixings such as butyl titanate and acetylacetone,2,4-pentanedione are uniform, it is added drop-wise in glass reactor solution, Being stirred continuously down makes butyl titanate be hydrolyzed at 5-10 DEG C is with polymerisation 1-2h, control material molar ratio：Metatitanic acid Four butyl esters：Acetylacetone,2,4-pentanedione：Deionized water：Acetic acid：Ethyl alcohol=1:0.3:4-40:0.2-1:20-50, reaction generate quality percentage The faint yellow nano-TiO of a concentration of 3%-5%2Colloidal sol, it is 5nm to measure nano-particle average grain diameter in colloidal sol；
（2）Absolute ethyl alcohol, deionized water and ammonium hydroxide are separately added into glass reactor, it is 10-11 to make pH value of solution；It will just Silester is added in glass reactor solution, and control material molar ratio is：Ethyl orthosilicate：Deionized water：Ammonium hydroxide：Ethyl alcohol= 1:4-40:0.2-1:20-50, be hydrolyzed at 10-30 DEG C with polymerisation 24-72 h, obtain Nano-meter SiO_22Alkalinity is molten Glue, heating reflux reaction 0.5-2 h deaminations, and make Nano-meter SiO_22Particle crystallization is grown up, and it is 30% then to use mass percentage concentration It is 2-3 that acetic acid, which adjusts colloidal sol pH, obtains the Nano-meter SiO_2 that mass percentage concentration is 5%-10%2Acidic sol is measured in colloidal sol and is received Rice corpuscles average grain diameter is 40nm；
（3）The acetic acid that absolute ethyl alcohol, deionized water and mass percentage concentration are 30% is separately added into glass reactor, It is 2-3 to make pH value of solution；Glass is added in organo-silicon coupling agent KH550, organo-silicon coupling agent KH560 or organo-silicon coupling agent KH570 In glass reactor solution, make its be hydrolyzed at room temperature with polymerisation 24-72 h, control material molar ratio be：Organosilicon Coupling agent：Deionized water：Acetic acid：Ethyl alcohol=1:3-30:0.2-1:20-50, it is 5%-10% that reaction, which generates mass percentage concentration, Organic silicon nano resin sol, it is 10nm to measure in colloidal sol nano-particle average grain diameter；
（4）The Nano-meter SiO_2 that mass percentage concentration is 5%-10% is first added in glass reactor2Acidic sol and solvent, The nano-TiO of 3%-5% is added dropwise again2Colloidal sol is stirred to react 4-8 h at 40-50 DEG C, its copolymerization is made to form nuclear shell structure nano TiO2Colloidal sol is cooled to room temperature, adds the organic silicon nano resin sol of 5%-10%, continues to be stirred to react 8-12 h, obtain Mass percentage concentration is the organic silicon nano TiO 2 sol of 3%-10%；
（5）With needle tubing by organic silicon nano TiO2Colloidal sol drops in the 100mm ╳ 100mm fluorine-doped tin dioxides of compacted zone It in Conducting Glass, is coated with uniformly with bar spreader, controls wet-film thickness 3000-5000 nm, caudacoria is dried in solvent volatilization Layer thickness was 200-600nm, then with 110-150 DEG C of heated-air drying 30 minutes, so that colloidal sol is fully cured, forms surface and uniformly receive Rice TiO2Framework film；
（6）Measure nano-TiO2Framework film surface area is 40-60m2/ g, to substrate material surface adhesive force level-one, it is seen that light Transmitance 70%-85%, is tested by damp heat test.
Beneficial effects of the present invention are embodied in：
（1）Nano-TiO of the present invention2Group containing flexible molecule in framework film, film adhesion is strong, can remove nano-TiO from2's High-temperature sintering process；
（2）Nano-TiO of the present invention2Framework film is nucleocapsid, is solved between the adhesive force of framework film and hole content Contradiction；
（3）Nano-TiO of the present invention2Organic silicon nano resin portion wraps up nano-TiO in framework film2Surface reduces its light Catalytic capability is applied in perovskite solar cell and its chemical stability can be improved；
（4）Nano-TiO of the present invention2Skeleton film surface has certain hydrophobicity, is not easy to adsorb the moisture in air, applies To its moisture-resistance can be improved in perovskite solar cell.
Specific implementation mode
Embodiment 1
Absolute ethyl alcohol 10.4g, deionized water 4g and mass percentage concentration are separately added into 100mL glass reactors is 30% acetic acid 4g (20mmol), it is 2-3 to make pH value of solution；By butyl titanate 6.8g (20mmol) and acetylacetone,2,4-pentanedione solvent 6.8g (68mmol) be uniformly mixed, be added drop-wise in glass reactor solution, make under constant stirring butyl titanate at 5-10 DEG C into Row hydrolysis and polymerisation 1-2h, reaction generate the faint yellow nano-TiO that mass percentage concentration is 5%2Colloidal sol 32g, measures colloidal sol Middle nano-particle average grain diameter is 5nm.
It is 25% ammonium hydroxide that absolute ethyl alcohol 20g, deionized water 4g and percentage concentration are separately added into 100mL glass reactors 0.4g (6mmol), it is 10-11 to make pH value of solution；Ethyl orthosilicate 5.3g (20mmol) is added in glass reactor solution, Be hydrolyzed at 10-30 DEG C with polymerisation 24-72 h, obtain Nano-meter SiO_22Alkaline sol, heating reflux reaction 0.5-2 h Deamination and make Nano-meter SiO_22Particle crystallization is grown up, and it is 2-3 that the acetic acid for being then 30% with mass percentage concentration, which adjusts colloidal sol pH, is obtained The Nano-meter SiO_2 for being 5% to mass percentage concentration2Acidic sol 24g, it is 40nm to measure nano-particle average grain diameter in colloidal sol.
Absolute ethyl alcohol 17.6g, deionized water 2g and mass percentage concentration are separately added into 100mL glass reactors is 30% acetic acid 2g (10mmol), it is 2-3 to make pH value of solution；Organo-silicon coupling agent KH560 2.4g (10mmol) are added drop-wise to glass In reactor solution, make its be hydrolyzed at room temperature with polymerisation 24-72 h, reaction generate mass percentage concentration be 10% Organic silicon nano resin sol 24g, it is 10nm to measure in colloidal sol nano-particle average grain diameter.
Absolute ethyl alcohol 46g is first added in 100mL glass reactors, the nanometer that mass percentage concentration is 5% is then added SiO2Acidic sol 18g adds the faint yellow nano-TiO that mass percentage concentration is 5%2Colloidal sol 30g is stirred at 40-50 DEG C 4-8 h are reacted, its copolymerization is made to form nuclear shell structure nano TiO2Colloidal sol is cooled to room temperature, adds 10% organic silicon nano tree Liposoluble glue 6g continues to be stirred to react 8-12 h, obtains nano-TiO2Mass percentage concentration is 1.5%, Nano-meter SiO_22Quality percentage is dense 100 g of colloidal sol that degree is 0.9% and organic silicon nano resin quality percentage concentration is 0.6%.
With needle tubing by the organic silicon nano TiO of preparation2Colloidal sol drops in the 100mm ╳ 100mm fluorine doped titanium dioxides of compacted zone In tin Conducting Glass, uniform, control wet-film thickness 3000-5000 nm are coated with bar spreader, after solvent volatilization is dried Thicknesses of layers was 200-600nm, then with 110-150 DEG C of heated-air drying 30 minutes, so that colloidal sol is fully cured, it is uniform to form surface Nano-titanium dioxide framework film.The nano-TiO of preparation2Framework film surface area is 40-60m2/ g, in the attachment of substrate material surface Power level-one, it is seen that light transmission rate 70%-85% has passed through damp and hot test, the nano-titanium dioxide framework film prepared with high temperature sintering Performance is suitable, meets perovskite solar cell light-absorption layer and prepares requirement.
Embodiment 2
By PbI2Reagent 46.1g（100mmol）And CH3NH3I reagents 15.9g（100mmol）200g dimethyl formyls are added In amine solvent, at 60-70 DEG C at stir 12 h, obtain CH3NH3PbI3Light absorbing layer coating fluid.Light absorbing layer is applied with needle tubing The nano-TiO that cloth drop is prepared in embodiment 12On framework film, it is coated with uniformly with stainless steel wire rod coating device, is placed on vacuum hand Dry solvent volatilization in casing, light absorbing layer thickness reaches 500-600nm, finally uses 90-110 DEG C of heated-air drying 30 minutes, Light absorbing layer sheet resistance is reduced rapidly, and color becomes black by rufous rapidly, forms smooth surface and covering is uniform black Color perovskite light absorbing layer.

Claims (6)

1. a kind of perovskite solar cell nanometer TiO2Colloidal sol, it is characterized in that using nuclear shell structure nano TiO2Particle solves shape At nano-TiO2Contradiction between framework film adhesive force and hole content, and flexible molecule base is introduced in the framework film of formation Group, further enhances the adhesive force to form film layer, to eliminate the nano-TiO to be formed2The high-temperature sintering process of framework film, It can be used as perovskite solar cell light absorption layer framework film and form colloidal sol, by the nano-TiO that average grain diameter is 5nm2Colloidal sol is averaged Grain size is the Nano-meter SiO_2 of 40nm2Colloidal sol, the organic silicon nano resin sol that average grain diameter is 10nm and solvent composition, each component Shared mass percent is as follows：
Average grain diameter is the nano-TiO of 5nm2 1.5%-5%
Average grain diameter is the Nano-meter SiO_2 of 40nm2 0.9%-3%
Average grain diameter is the organic silicon nano resin 0.6%-2% of 10nm
Balance of solvent.
2. perovskite solar cell nanometer TiO as described in claim 12Colloidal sol, it is characterized in that average grain diameter is 5nm's in colloidal sol Nano-TiO2Colloidal sol is obtained in ethanol water with acetic acid catalysis hydrolysis and polymerization by butyl titanate, is wrapped up as shell particles In big grain diameter nano SiO2On particle, nuclear shell structure nano TiO is formed2Particle.
3. perovskite solar cell nanometer TiO as described in claim 12Colloidal sol, it is characterized in that average grain diameter is 40nm's in colloidal sol Nano-meter SiO_22Colloidal sol is obtained in ethanol water with ammonia-catalyzed hydrolysis and polymerization by ethyl orthosilicate, is received as nucleocapsid Rice TiO2The nuclear particle of particle.
4. perovskite solar cell nanometer TiO as described in claim 12Colloidal sol, it is characterized in that average grain diameter is 10nm's in colloidal sol Organic silicon nano resin sol is by organo-silicon coupling agent KH550, organo-silicon coupling agent KH560, organo-silicon coupling agent KH570 in second It is obtained with acetic acid catalysis hydrolysis and polymerization in alcohol solution, it is further partially retained in the nano-TiO of nucleocapsid2Particle On, further enhance the adhesive force of framework film.
5. perovskite solar cell nanometer TiO as described in claim 12Colloidal sol, it is characterized in that in colloidal sol solvent be C2-C6 alcohol, The aqueous solution of C3-C6 ethers and acetylacetone,2,4-pentanedione.
6. a kind of preparation method of perovskite solar cell nanometer titanium dioxide framework film, it is characterized in that the technical solution packet taken Include small particle nano-TiO2Colloidal sol preparation, big grain diameter nano SiO2Prepared by colloidal sol, prepared by organic silicon nano resin solution, nucleocapsid knot Structure nano-TiO2Colloidal sol preparation, nuclear shell structure nano TiO2Colloidal sol film, nuclear shell structure nano TiO2Framework film cures and evaluation, Specific implementation step is：
（1）It is separately added into the acetic acid that absolute ethyl alcohol, deionized water and mass percentage concentration are 30% in glass reactor, makes molten Liquid pH is 2-3；The mass mixings such as butyl titanate and acetylacetone,2,4-pentanedione are uniform, it is added drop-wise in glass reactor solution, continuous Make under stirring butyl titanate be hydrolyzed at 5-10 DEG C with polymerisation 1-2h, control material molar ratio be：Four fourth of metatitanic acid Ester：Acetylacetone,2,4-pentanedione：Deionized water：Acetic acid：Ethyl alcohol=1:0.3:4-40:0.2-1:20-50, reaction generate mass percentage concentration For the faint yellow nano-TiO of 3%-5%2Colloidal sol, it is 5nm to measure nano-particle average grain diameter in colloidal sol；
（2）Absolute ethyl alcohol, deionized water and ammonium hydroxide are separately added into glass reactor, it is 10-11 to make pH value of solution；By positive silicic acid Ethyl ester is added in glass reactor solution, and control material molar ratio is：Ethyl orthosilicate：Deionized water：Ammonium hydroxide：Ethyl alcohol=1: 4-40:0.2-1:20-50, be hydrolyzed at 10-30 DEG C with polymerisation 24-72 h, obtain Nano-meter SiO_22Alkaline sol, Heating reflux reaction 0.5-2 h deaminations, and make Nano-meter SiO_22Particle crystallization is grown up, and it is 30% second then to use mass percentage concentration It is 2-3 that acid, which adjusts colloidal sol pH, obtains the Nano-meter SiO_2 that mass percentage concentration is 5%-10%2Acidic sol measures nanometer in colloidal sol Average particle size is 40nm；
（3）It is separately added into the acetic acid that absolute ethyl alcohol, deionized water and mass percentage concentration are 30% in glass reactor, makes molten Liquid pH is 2-3；It is anti-that glass is added in organo-silicon coupling agent KH550, organo-silicon coupling agent KH560 or organo-silicon coupling agent KH570 Answer in device solution, make its be hydrolyzed at room temperature with polymerisation 24-72 h, control material molar ratio be：Organosilicon is coupled Agent：Deionized water：Acetic acid：Ethyl alcohol=1:3-30:0.2-1:20-50, it is having for 5%-10% that reaction, which generates mass percentage concentration, Machine silicon nano-resin colloidal sol, it is 10nm to measure nano-particle average grain diameter in colloidal sol；
（4）The Nano-meter SiO_2 that mass percentage concentration is 5%-10% is first added in glass reactor2Acidic sol and solvent, then drip Add the nano-TiO of 3%-5%2Colloidal sol is stirred to react 4-8 h at 40-50 DEG C, its copolymerization is made to form nuclear shell structure nano TiO2It is molten Glue is cooled to room temperature, adds the organic silicon nano resin sol of 5%-10%, continues to be stirred to react 8-12 h, obtains quality hundred Divide the nano-TiO of a concentration of 3%-10%2Colloidal sol；
（5）With needle tubing by organic silicon nano TiO2Colloidal sol drops in the 100mm ╳ 100mm fluorine-doped tin dioxide conduction glass of compacted zone It on glass substrate, is coated with uniformly with bar spreader, controls wet-film thickness 3000-5000 nm, rear thicknesses of layers is dried in solvent volatilization For 200-600nm, then with 110-150 DEG C of heated-air drying 30 minutes, so that colloidal sol is fully cured, form the uniform nano-TiO in surface2 Framework film；
（6）Measure nano-TiO2Framework film surface area is 40-60m2/ g, to substrate material surface adhesive force level-one, it is seen that light penetrates Rate 70%-85%, is tested by damp heat test.
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