CN115678376A - Photovoltaic antireflection coating liquid capable of being cured at normal temperature and super-hydrophilic photovoltaic antireflection glass - Google Patents
Photovoltaic antireflection coating liquid capable of being cured at normal temperature and super-hydrophilic photovoltaic antireflection glass Download PDFInfo
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Abstract
The invention discloses a photovoltaic antireflection coating liquid capable of being cured at normal temperature and super-hydrophilic photovoltaic antireflection glass, wherein the preparation of the coating liquid comprises the following steps: preparing organic-inorganic interpenetrating network component, adding nano TiO into organic-inorganic interpenetrating network component 2 Lithium salt, and the coating solution is formed by the nano TiO in the scheme 2 The addition of the (2) makes the microstructure of the film layer change under the illumination condition to provide super-hydrophilic micro areas for the coating,the film layer forms a super-hydrophilic structure and is nano TiO 2 The coating liquid can be cured at normal temperature, and the cured film layer has greatly improved weather resistance, hydrophilicity, antireflection, cementation and other properties.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a photovoltaic antireflection coating liquid capable of being cured at normal temperature and super-hydrophilic photovoltaic antireflection glass.
Background
Photovoltaic glass is an optimal packaging material for protecting crystalline silicon solar cells and has high transmittance per se. The conversion efficiency of the crystalline silicon cell can be improved by improving the optical characteristics, particularly the transmittance, of the photovoltaic glass. The photovoltaic glass antireflection film is also called a photovoltaic glass antireflection film, and is a protective film layer with antireflection and antireflection effects, which is coated on the surface of cover glass (photovoltaic glass) in a photovoltaic module. The photovoltaic cover plate glass can effectively improve the transmittance of sunlight on the photovoltaic cover plate glass, so that the power generation efficiency of a solar cell is improved. Before an effective photovoltaic glass antireflection coating is not invented, cover glass in a solar photovoltaic component is assembled in a bare chip mode, the installed capacity of the battery exceeds 300GW, and about 12 gigawatts of electric power is not effectively utilized compared with an assembly with an existing coating film.
The main problems of the prior coated glass are as follows:
firstly, the film layer of some coated glass is damaged and falls off, so that the generating efficiency is obviously reduced.
Secondly, the transmittance of the photovoltaic glass cannot meet the market demand.
Third, present solar energy component is applied to tiled power station and inclination power station more, and after long-time the use, the phenomenon that dirt such as dust accumulation or bird's droppings pile up appears in photovoltaic glass surface film layer easily because of electrostatic interaction, directly influences solar energy power generation's efficiency.
Fourth, the existing antireflection coating liquid on the market is difficult to be directly coated and constructed on the built photovoltaic power station because the template agent needs to be removed at high temperature to show the antireflection performance.
And fifthly, the film layer on the market is a hydrophobic film layer, for the south distributed photovoltaic power station, the angle of the solar module is low, the weather characteristics of rainy weather in the south and low-temperature and high-humidity weather in winter enable the surface of the film layer to be prone to dewing and the like, dust and dirt are easily formed by matching with accumulated dust, and the light transmittance is affected.
To this end, the department is intended to be based on the prior application of patent-publication No.: based on CN113480878A, a photovoltaic antireflection film which is super-hydrophilic and can be cured at normal temperature is developed as a target.
Disclosure of Invention
In order to solve at least one technical defect, the invention provides the following technical scheme:
the application document discloses a photovoltaic antireflection coating liquid capable of being cured at normal temperature, which comprises the following steps:
preparing an organic-inorganic interpenetrating network component: adding a high-molecular additive at least containing hydroxyl, amide or aldehyde groups into a silica sol solution prepared from alkoxysilane, and aging; wherein the silica sol solution contains silane coupling agent modified hollow silica nanoparticles, the mass ratio of the alkoxy silane to the modified hollow silica nanoparticles is (8) - (1) - (4), and the macromolecular additive accounts for 0.1% -20% of the alkoxy silane;
adding nano TiO into organic-inorganic interpenetrating network component 2 Forming a film coating solution by using lithium salt; wherein the nano TiO 2 The mass ratio of the particles to the modified hollow silica nanoparticles is 1.
According to the scheme, the coupling agent modified hollow silica nanoparticles are added in the process of sol solution formed by hydrolyzing alkoxy silane, the silica nanoparticles and the sol solution are stably combined under the action of the coupling agent, and a high-molecular additive is used as an organic phase and interconnected with a silica sol inorganic network to form an interpenetrating network structure.
Nano TiO2 2 The addition of the nano TiO modified film enables the microstructure of the film layer to change under the illumination condition so as to provide super-hydrophilic micro areas for the coating, so that the film layer forms a super-hydrophilic structure, and the nano TiO modified film has nano TiO 2 Can enter the gaps between the hollow silicon dioxide nanospheres to improve the hardness of the coating.
The added lithium salt reduces the surface resistance of the film layer and increases the antistatic performance of the film layer.
The coating liquid prepared by the formula and the process can be cured at normal temperature, and the properties of weather resistance, hydrophilicity, antireflection, cementation and the like of the cured film layer are greatly improved.
Further, a polymer additive, and nano TiO 2 Are mixed with solvent and added to help the components to be distributed evenly.
For example, adding polymer additive in 5-15% solution, and adding nanometer TiO 2 Added as a dispersion in an amount of 10-30%, for example, an alcohol solvent.
Further, the polymer additive comprises one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl butyral. Preferably polyvinylpyrrolidone or polyvinyl butyral.
Further, the lithium salt comprises one or more of anhydrous lithium chloride, anhydrous lithium acetate, lithium tetrafluoroborate, lithium trichloroacetate, lithium trifluoromethanesulfonate, lithium hexafluorophosphate and lithium bistrifluoromethanesulfonylimide. Lithium trifluoroacetate, lithium trifluoromethanesulfonate or lithium hexafluorophosphate is preferred.
The mass ratio of the lithium salt to the hollow silica nanospheres is preferably 1.
Furthermore, the particle size of the modified hollow silicon dioxide nanosphere is 20-90nm, and the wall thickness is 3-20nm. Preferably, the particle size is 25-75nm and the wall thickness is 5-15nm.
The mass ratio of alkoxysilane to silane coupling agent-modified hollow silica nanoparticles is preferably 7.
Further, the nano TiO 2 The particle diameter is 5-30nm. For nano TiO 2 For example, rutile type, anatase type, or a mixed type of the two, and anatase type nano TiO is preferred 2 And (4) granulating. The preferred particle size is 5-20nm.
Preferably, nano TiO 2 The mass ratio of the particles to the hollow silica nanospheres is 1.
Further, in the preparation of the organic-inorganic interpenetrating network component, the mixture of alkoxysilane and hollow silica nanospheres modified by a silane coupling agent is subjected to acid catalysis reaction for 1-8h in an alcohol solvent to obtain a component A, and a high molecular additive is added into the component A and aged at 40-80 ℃ for at least 24h. Wherein the mass ratio of the alcohol solvent to the alkoxy silane is 5:1-25:1.
in the preparation of the coating solution, the alcohol solvent is preferably a lower alkanol, such as one or more of methanol, ethanol, n-propanol, isopropanol and isobutanol, and is preferably ethanol, n-propanol and isopropanol.
Further, the alkoxy silane comprises one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and isopropyl orthosilicate.
Further, nano TiO is added into the organic-inorganic interpenetrating network component 2 Then evenly stirring, then adding lithium salt and evenly stirring to form a film coating liquid.
The modification of the hollow silica nanoparticles was as follows: the preparation method of the hollow silica nanoparticles modified by the silane coupling agent comprises the steps of mixing the silane coupling agent and the hollow silica nanoparticles, adding the mixture into an alcohol solvent, and stirring for 2-8 hours at 40-100 ℃ to prepare the hollow silica nanoparticles modified by the silane coupling agent.
The amount of the silane coupling agent added is preferably 1% to 10% by mass of the alkoxysilane.
As the silane coupling agent, for example, one or more of gamma- (methacryloyloxy) propyltrimethoxysilane, gamma-aminopropyltriethoxysilane, octyltriethoxysilane, diethoxydimethylsilane, and gamma- (2, 3-epoxypropyl) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropyl) propyltrimethoxysilane, or gamma-aminopropyltriethoxysilane is preferable.
The application provides super hydrophilic photovoltaic antireflection glass, which takes photovoltaic glass as a substrate, and a film coating liquid prepared by any scheme is solidified on at least one surface of the substrate to form a film layer. The method for coating the coating solution on the glass substrate, etc. can be freely selected according to the prior art.
Preferably, the thickness of the film layer is 40 to 300nm, more preferably 50 to 150nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the components are optimized, the coating liquid forming process is designed, the prepared coating liquid can be cured at normal temperature, the formed film layer is hydrophilic, the performances of antireflection, cementation and the like are greatly improved, the glass substrate is particularly suitable for forming a film on a glass substrate, and the film layer is high in stability.
2. The invention provides photovoltaic antireflection glass, wherein a film coating liquid is coated on a photovoltaic glass substrate to form a film layer, and nano TiO is irradiated by light 2 The film layer forms a super-hydrophilic structure, and the accumulation of impurities and the like on the film layer can be greatly reduced by matching with the antistatic effect of the lithium salt.
Drawings
FIG. 1: transmittance of the photovoltaic glasses of examples 1-7 before and after coating was compared;
FIG. 2 is a schematic diagram: transmittance of the photovoltaic glass of comparative examples 1-5 was compared before and after coating;
FIG. 3: the transmittance of the photovoltaic glass in examples 1-7 was compared after the coated and illuminated photovoltaic glass was subjected to a double 85 test;
FIG. 4: after the coated and illuminated photovoltaic glass is subjected to a double 85 test, the transmissivity of the photovoltaic glass in the comparative examples 1-5 is compared;
FIG. 5: after the coated and illuminated photovoltaic glass is subjected to a salt spray test, the transmittance of the photovoltaic glass in the embodiments 1-7 is compared;
FIG. 6: after the coated and illuminated photovoltaic glass is subjected to a salt spray test, the transmittance of the photovoltaic glass in comparative examples 1-5 is compared;
FIG. 7: after the coated and illuminated photovoltaic glass is subjected to high and low temperature tests, the transmittance of the photovoltaic glass in examples 1-7 is compared;
FIG. 8: after the coated and illuminated photovoltaic glass is subjected to high and low temperature tests, the transmissivity of the photovoltaic glass in the comparative examples 1-5 is compared;
FIG. 9: hydrophilicity test plots of photovoltaic glass coatings after illumination in examples 1-7;
FIG. 10: hydrophilicity of photovoltaic glass coatings after illumination in comparative examples 1-5 are shown.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
The materials are added according to the proportion in the table 1, and the specific method is as follows:
1. preparation of coating solution
Preparing an organic-inorganic interpenetrating network component:
synthesizing hollow silicon dioxide nanospheres modified by a silane coupling agent; uniformly mixing gamma-aminopropyltriethoxysilane and hollow silicon dioxide nano-spheres, adding the mixture into an ethanol solvent, and stirring the mixture for 6 hours at the temperature of 60 ℃, wherein the gamma-aminopropyltriethoxysilane accounts for the ratio;
step (2), component A: mixing tetraethoxysilane with the modified hollow silica nano-spheres prepared in the step (1) according to the mass ratio of 4 to 1, adding the mixture into a 4/5 total ethanol solvent, and stirring the mixture for 3 hours under the action of a hydrochloric acid catalyst;
step (3), component C: dissolving polyvinylpyrrolidone in the rest ethanol solvent, and stirring for 6 hours to obtain a component C;
and (4) mixing the solution A obtained in the step (2) with the component C obtained in the step (3), stirring for 24 hours at room temperature, and aging in an oven at 60 ℃ for 3 days to obtain a component B.
Step (5) mixing the component B obtained in the step (4) with nano TiO 2 And stirring the dispersion liquid for 4 hours at room temperature, adding lithium salt, and uniformly stirring to obtain the final coating liquid colloid.
2. Glass plate coating film layer
Pretreating a photovoltaic glass substrate (model 60 × 3mm, manufacturer: qiBin) on a solar cell by using a glass cleaning solution of the Shenzhen far bank, cleaning by using clear water after pretreatment, and naturally drying after cleaning;
loading the prepared photovoltaic antireflection coating liquid into coating equipment; and placing the device on a treated photovoltaic glass substrate, coating at a blade coating speed of 3m/min, naturally drying the coated film, and then performing illumination treatment, wherein the thickness of the film layer is 106nm.
Example 2
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are referred to the table 2.
Example 3
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are shown in the table 2.
Example 4
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are shown in the table 2.
Example 5
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are shown in the table 2.
Example 6
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are shown in the table 2.
Example 7
The materials are added according to the material proportion in the table 1, the specific steps are carried out according to the example 1, and the parameters in each step are shown in the table 2.
TABLE 1 proportion of materials added
Wherein: parts by weight: according to the mass;
ethyl orthosilicate: the content is 99 percent;
coupling agent: gamma-aminopropyl triethoxysilane, content 97%;
ethanol: the content is 99 percent;
isopropyl alcohol: the content is 99 percent;
hydrochloric acid: content 3.34%, commercially available high-concentration hydrochloric acid was diluted with deionized water to a content of 3.34%;
polymer additive solution: mixing polyvinylpyrrolidone with ethanol, wherein the content is 10%;
nanosphere: hollow silicon dioxide nanospheres with the particle size of 75nm and the wall thickness of 15nm.
Nano TiO2 dispersion liquid: anatase type nano TiO 2 Mixing with ethanol, and the particle size is as follows: 10-20nm containingThe amount is 20%.
Lithium salt: lithium trifluoroacetate: the content is as follows: 97 percent.
TABLE 2 parameter setting in the procedure
In addition, ethanol can be added according to needs, such as adding 3/5 in the step 2.
Comparative example 1
Compared with the example 1, the difference is that the rutile type nano TiO is in the material 2 And (4) dispersing.
Comparative example 2
The difference compared to example 1 is that the material is free of silane coupling agent.
Comparative example 3
The difference compared to example 1 is that the material is free of polymeric additives.
Comparative example 4
The difference from example 1 is that after stirring for 24hr in step 4, the next preparation was carried out without aging.
Comparative example 5
The difference compared to example 1 is that the material is free of lithium salts.
The photovoltaic antireflection glass prepared in the examples and the comparative examples is subjected to performance detection after illumination.
Test example 1 measurement of transmittance
And (3) detecting an instrument: an ultraviolet-visible spectrophotometer model Hitachi-U4100;
the detection method comprises the following steps: putting the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating into a spectrophotometer;
the photovoltaic glass was tested for transmittance before and after coating, as shown in fig. 1-2.
Test example 2-double 85 test
A detection instrument: a high-low temperature damp-heat test box with the model GDS-100L;
the detection method comprises the following steps: and (3) placing the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating into a high-low temperature damp-heat test box. Wherein the program set constant temperature 85 deg.C, constant humidity 85%, run for 120h, test transmittance as shown in figures 3-4.
Test example 3 salt spray test
And (3) detecting an instrument: a salt spray corrosion test chamber with the model of YWX/Q-250L;
the detection method comprises the following steps: and putting the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating into a salt spray corrosion test box. The salt spray test was carried out for 48h at a salt spray concentration of 5% and a temperature of 35 c, and the transmission was measured as shown in fig. 5-6.
Test example 4 high and Low temperature cycle test
And (3) detecting an instrument: a high-low temperature damp-heat test chamber with the model GDS-100L;
the detection method comprises the following steps: and (3) placing the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating into a high-low temperature damp-heat test box. Wherein the program is set to high temperature of 85 ℃ and kept for 3h; keeping the temperature at-40 ℃ for 3h; the transmittance was tested after 20 cycles as shown in fig. 7-8.
Test example 5 hydrophobic detection
A detection instrument: contact angle measuring instrument, model: SDC-200S
The detection method comprises the following steps: the water drop angle tester is started, the computer connected with the water drop angle tester is used for placing photovoltaic glass coated with a photovoltaic antireflection coating which is super-hydrophilic and can be solidified at normal temperature on the sample table, then manual dropping liquid (automatic dropping liquid) dropping liquid standard is 1-2 microliters, and then the sample table is lifted to enable the photovoltaic glass to be connected to water drops. And finally clicking the frozen measuring scale to move the displayed measuring scale to the left or right or up or down by clicking a shortcut button, wherein the measuring scale is tangent to the edge of the liquid drop. Then clicking the downward moving measuring scale to coincide the intersection point with the edge of the liquid drop, clicking the left-handed button to intersect the measuring scale with one side of the liquid drop, and clicking to calculate the contact angle, as shown in fig. 9-10.
Test example 6 hardness test
And (3) detecting an instrument: portable pencil mar experiment appearance, the model: model QHQ-A.
The detection method comprises the following steps: the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating is placed on a table top, a pencil is always ensured to form a 45-degree included angle with a measured coating by three points of contact with the measured surface (two points are two wheels, and one point is a pencil lead), and a pencil hardness tester is pushed to move by force horizontally, so that the test process can be completed, and the deformation resistance of the coating can be measured. Identified by the pencil designation, the test results are shown in table 3.
Table 3: coating hardness test results
Test example 7 surface resistance test
Testing the instrument: SIMCO surface resistance tester, model: ST-4
The test method comprises the following steps: after a power switch is turned on, ST-4 is placed on the photovoltaic glass coated with the super-hydrophilic and normal-temperature-curable photovoltaic antireflection coating, a START key is pressed to START testing, and after 10 seconds, the measured value can be displayed on a liquid crystal display. The measurement value was set to an index of 10. The test results are shown in table 4.
Table 4: test results of surface resistance of coating
As can be seen from the detection results in fig. 1-10, table 3 and table 4, the film layer prepared by the present method has excellent properties in the aspects of transmittance, hardness, high and low temperature resistance, salt spray resistance, etc., and the addition of lithium salt improves the comprehensive properties of the film layer again.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The photovoltaic antireflection coating liquid capable of being cured at normal temperature is characterized by comprising the following steps of:
preparing an organic-inorganic interpenetrating network component: adding a high-molecular additive at least containing hydroxyl, amide or aldehyde groups into a silica sol solution prepared from alkoxysilane, and aging; wherein the silane coupling agent-modified hollow silica nanoparticles are contained in the silica sol solution, the mass ratio of the alkoxy silane to the modified hollow silica nanoparticles is (8) - (1);
adding nano TiO into organic-inorganic interpenetrating network component 2 Forming a film coating solution by using lithium salt; wherein the nano TiO is 2 The mass ratio of the particles to the modified hollow silica nanoparticles is (1).
2. The normal-temperature-curable photovoltaic antireflection coating solution according to claim 1, wherein: polymer additive and nano TiO 2 Are mixed with a solvent and then added.
3. The normal-temperature-curable photovoltaic antireflection coating solution according to claim 1, wherein: the polymer additive comprises one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl butyral.
4. The photovoltaic antireflection coating solution capable of being cured at normal temperature according to claim 1, wherein: the lithium salt comprises one or more of anhydrous lithium chloride, anhydrous lithium acetate, lithium tetrafluoroborate, lithium trichloroacetate, lithium trifluoromethanesulfonate, lithium hexafluorophosphate and lithium bistrifluoromethanesulfonylimide.
5. The photovoltaic antireflection coating solution capable of being cured at normal temperature according to claim 1, wherein: the particle size of the modified hollow silicon dioxide nanosphere is 20-90nm, and the wall thickness is 3-20nm.
6. The normal-temperature-curable photovoltaic antireflection coating solution according to claim 1, wherein: the nano TiO 2 The particle size is 5-30nm.
7. The normal-temperature-curable photovoltaic antireflection coating solution according to claim 1, wherein: in the preparation of the organic-inorganic interpenetrating network component, a mixture of alkoxysilane and hollow silica nanospheres modified by a silane coupling agent is subjected to acid catalytic reaction for 1-8h in an alcohol solvent to obtain a component A, and a high-molecular additive is added into the component A and is aged for at least 24h at 40-80 ℃.
8. The normal-temperature-curable photovoltaic antireflection coating solution according to claim 1, wherein: the alkoxy silane comprises one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and isopropyl orthosilicate.
9. The photovoltaic antireflection coating solution capable of being cured at normal temperature according to claim 1, wherein: adding nano TiO into organic-inorganic interpenetrating network component 2 Then evenly stirring, then adding lithium salt and evenly stirring to form a film coating liquid.
10. The utility model provides a super hydrophilic type photovoltaic antireflection glass which characterized in that: the photovoltaic glass is taken as a substrate, and the coating liquid according to any one of the claims 1-9 is cured on at least one surface of the substrate to form a film layer.
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