WO2021000564A1 - Anti-reflective coated glass used for packaging solar assembly, and manufacturing method therefor - Google Patents

Abstract

Anti-reflective coated glass used for packaging a solar assembly, and a manufacturing method therefor. The method comprises: proportionally adding a silicon source to a certain amount of anhydrous ethanol, then adding a mixture of anhydrous ethanol, pure water, and an acid catalyst in a certain ratio, and stirring at room temperature and then standing so as to obtain a solution A; preparing a certain amount of nano-particles B; adding B having different proportions to the solution A so as to obtain coating materials having different refractive indexes used for manufacturing a coating; and in a mode that the refractive indexes gradually decrease from inside to outside, coating the coating materials having different refractive indexes on the surface of the glass used for packaging the solar assembly so as to form the anti-reflective coated glass used for packaging the solar assembly. The anti-reflective coated glass features high light transmittance, and can realize the enhancement of the light transmittance by means of a wide wavelength.

Description

Anti-reflection coated glass for solar module packaging and manufacturing method thereof Technical field

The invention relates to the technical field of glass for solar module packaging, in particular to an anti-reflection coated glass for solar module packaging and a manufacturing method thereof, in particular to a multi-layer anti-reflection coated glass with high light transmittance and high weather resistance for solar module packaging and其制造方法。 Its manufacturing method.

Background technique

In order to cope with the energy crisis and environmental pollution, new energy has been the focus of global attention. Solar energy is particularly concerned because of its cleanliness and environmental protection. Therefore, the solar cell industry is developing rapidly, and the issue facing people is how to further improve the conversion efficiency of solar energy. , Reduce the cost of solar equipment, so that the cost of solar cells is reduced to a level equivalent to conventional energy generation.

In China, the solar photovoltaic industry has developed rapidly at a doubling rate and has long become the world’s largest producer of solar cells. At present, China’s solar energy application market has also developed rapidly and has become the world’s largest photovoltaic application market. However, distributed photovoltaic applications The development of solar cells still relies on government subsidies and is therefore subject to many restrictions. In addition to policy reasons, the promotion and application of solar cells are affected mainly because of their high cost. Therefore, further reducing manufacturing costs is the large-scale application of solar cells The key, industry insiders said, improving the conversion efficiency of solar cells is one of the effective ways to reduce costs. It is understood that a 1% increase in conversion efficiency will reduce costs by 7%.

In order to improve the competitiveness of solar photovoltaic products, one of the most effective ways is to improve the conversion efficiency of solar cells; in addition to improving the conversion efficiency of the cells themselves through various technical means, they should also improve the packaging material-photovoltaic glass. Provide better solutions in terms of light transmittance and weather resistance. The current mainstream technical solution is to coat the surface of photovoltaic glass with an anti-reflection film, that is, use the sol-gel method to coat a layer of porous silica material on the surface of photovoltaic glass. In order to reduce the reflection in the specific band of the spectrum, thereby increasing the light transmittance of photovoltaic glass; the methods of coating the glass surface include roller coating, spraying, surface etching and aerosol methods, among which the roller coating method is easy to implement The most widely used application. At present, in order to meet the development needs of photovoltaic module manufacturers, major photovoltaic glass manufacturers strive to improve the level of AR coating technology, strive to obtain higher light transmittance, and effectively increase the power generation of photovoltaic modules;

Under the above-mentioned demand, people have successively developed a variety of photovoltaic glass coating technologies. For example, the Chinese patent (Patent No.: CN201010226020.2) discloses a photovoltaic glass coated with a toughened anti-reflection coating and a manufacturing method thereof; it includes a low-iron ultra-white embossed glass substrate and an anti-reflection coating. The iron ultra-white embossed glass substrate has a suede surface on one side and an embossed surface on the other side. The anti-reflection coating is plated on the suede surface of the low-iron ultra-white embossed glass substrate. The anti-reflection coating is anti-reflection The coating solution is applied to the suede surface of the low-iron ultra-white embossed glass substrate, and then the surface is dried, heated and pre-cured, and tempered to form nano-level dioxide on the suede surface of the low-iron ultra-white embossed glass substrate. Silicon film layer: The photovoltaic glass plated with a toughened anti-reflection film layer produced by this method has the characteristics of high power generation increment, high film hardness, good acid and alkali resistance, good weather resistance, and high film adhesion.

Another example is the Chinese Patent (Patent No.: CN200910098519.7), which discloses a method for preparing an anti-reflection film on the surface of photovoltaic glass, which is characterized by including the following steps: ①preparation of inorganic-organic hybrid silica sol; ②coating film; ③hydrophobic treatment; ④ Curing treatment: Compared with the prior art, the advantages of the present invention are: the film base bonding force between the anti-reflection film and the substrate photovoltaic glass is stronger, and the anti-wiping performance of the anti-reflection film on the surface of the coated photovoltaic glass is improved; A layer of hydrophobic groups with low surface energy is formed on the surface of the anti-reflection film, thereby reducing the corrosion of the film's microstructure by moisture, and ensuring the long service life of the coated photovoltaic glass; the overall process cost of the present invention is low, the technical route is simple, and it is suitable for industrialization. Scale application.

However, the existing common AR coating technology development has encountered a bottleneck. The main problems are: ①The increase in light transmittance encounters a bottleneck; ②Wide wavelength anti-reflection cannot be achieved, especially the low transmittance of ultraviolet wavelength range, which cannot be improved. Well match the development needs of high-efficiency solar cells; ③The weather resistance is still insufficient, and there are still problems in special environmental applications such as seaside. To solve the above problems, more innovative technologies are needed to improve photovoltaic glass production technology. To this end, we have developed two or more layers of anti-reflection coated glass with high light transmittance and high weather resistance for solar module encapsulation, and we have mastered its unique manufacturing method.

Summary of the invention

The technical problem to be solved by the present invention is to provide an anti-reflective photovoltaic coated glass product with high light transmittance and high weather resistance prepared by a multilayer coating process in view of the above-mentioned deficiencies in the prior art. The anti-reflective photovoltaic coated glass The product has the characteristics of high light transmittance, and can realize wide-wavelength antireflection, especially in the infrared and ultraviolet bands. The transmittance is significantly improved, and the high weather resistance can pass more demanding weather resistance tests.

In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solution: an anti-reflective coating glass for solar module encapsulation, characterized in that: a first anti-reflective coating layer is plated on the textured surface of the glass substrate for solar module encapsulation, The first anti-reflection coating layer is coated with a second anti-reflection coating layer..., the n-1th anti-reflection coating layer is coated with an nth anti-reflection coating layer; The refractive index of the coating material of one anti-reflection coating layer is greater than the refractive index of the coating material of the second anti-reflection coating layer..., the refractive index of the coating material of the n-1th anti-reflection coating layer is greater than The refractive index of the coating material of the nth anti-reflection coating layer;

Preferably, n is 2 or greater than 2;

Preferably, the preparation process of the coating material includes the following steps: Step 1, the mixture of methyl orthosilicate and methyldiethoxysilane is diluted 2 times with absolute ethanol; then the volume ratio is 1:1: Add 0.1 of anhydrous ethanol, pure water, and acetic acid mixture slowly. After stirring for 2-3h at room temperature, let it stand for 1 day to obtain solution A; Step 2, use silica sol with a particle size of less than 20nm and a solid content of 40% to coat the nano Acrylic emulsion, wherein the mass ratio of silica sol and nano acrylic emulsion is 3:1 to obtain B; step 3, add X1% of B to solution A to obtain AB-1, and the corresponding film layer of this solution is the first layer Anti-reflection coating layer; add X2% of B to solution A to obtain AB-2, and the corresponding coating layer of this solution is the second anti-reflection coating layer; ..., add Xn% of B to solution A, Obtain AB-n, the corresponding film layer of the solution is the nth anti-reflection coating layer; where X1<X2...<Xn; Step 4, use AB-1 solution for the first coating, and then cure at 100°C After 1 minute, cool to below 40°C to obtain the first layer of anti-reflection coating; use AB-2 solution for the second coating, and then cure at 100°C for 1 minute, then cool to below 40°C to obtain the first layer Anti-reflective coating layer;..., use AB-n solution for the nth coating, and then cure at 100°C for 1 min; normal tempering to obtain multilayer anti-reflective coated glass;

Preferably, the mass ratio of methyl orthosilicate and methyldiethoxysilane in step 1 is 2:1;

Preferably, the volume of the mixture of methyl orthosilicate and methyldiethoxysilane is X, the volume of the mixture of absolute ethanol, pure water, and acetic acid is Y, and X:Y is 2-4:1 ；

Preferably, the analytical purity of acetic acid described in step 1 is AR grade, and the purity is above 99.95%;

A method for preparing anti-reflection coated glass for solar module encapsulation, which is characterized in that it comprises the following steps: ① edging, ② cleaning, ③ first coating, ④ curing, ⑤ cooling..., ⑥ nth Sub-coating, ⑦ toughened;

Preferably, the coating process of the coating material can be one or a combination of roll coating, spray coating or aerosol coating process;

Preferably, each layer of coating process needs to be heated in a curing oven at 50°C-250°C for 30s-120s, and then through a cooling process of water cooling or air cooling or a combination of the two before the next layer of coating is performed.

Compared with the prior art, the present invention has the following advantages: the anti-reflective coated glass product for solar module encapsulation in the present invention has the following advantages compared with current conventional photovoltaic coated glass products: ①High light transmittance, 380-1100nm The light transmittance can reach more than 94.30%; ②Wide-wavelength anti-reflection can be realized, especially in the infrared and ultraviolet bands, the transmittance is obviously improved, and the visible transmittance curve is compared; ③High weather resistance, can pass more harsh weather resistance In the test, the transmittance of the HF40 test does not decrease by more than 1%.

The manufacturing method of anti-reflective coated glass for solar module encapsulation has the following characteristics:

In addition to the conventional coating process (such as roll coating), the present invention can also perfectly combine the aerosol coating process, further reducing the process difficulty of producing multilayer coating.

In the present invention, solidification and cooling processes are required after the coating before the last layer of coating, which effectively guarantees the adhesion of the coating and better guarantees the weather resistance of the coated glass product.

The anti-reflective coated glass product for solar module encapsulation described in the present invention has distinct characteristics and obvious application advantages, can effectively promote the improvement of the technical level of the industry, and can also make important contributions to the "cost reduction and efficiency increase" of photovoltaic modules. The manufacturing method described is simple and practical, has strong operability, and effectively guarantees the mass production of the product of the present invention.

Description of the drawings

Figure 1 is a product structure diagram of the anti-reflective photovoltaic coated glass in the present invention;

Figure 2 is a manufacturing process flow chart of the anti-reflective photovoltaic coated glass in the present invention;

Figure 3 is a comparison diagram of light transmittance curves of anti-reflection photovoltaic coated glass in the present invention;

Fig. 4 is a light transmittance curve of an implementation example of the anti-reflection photovoltaic coated glass in the present invention;

Figure 5 is an SEM image of the film in the present invention; where image (a) is an SEM image of a cross section of the film, and image (b) is an SEM image of the surface of the film;

Fig. 6 is a graph of HF40 test results of the anti-reflection photovoltaic coated glass in the present invention;

Detailed ways

The present invention will be further described below in conjunction with FIGS. 1-6 and specific embodiments.

The manufacturing method of the anti-reflection coated glass for solar module encapsulation in this application is as follows:

Step 1. Dilute the mixture of methyl orthosilicate and methyldiethoxysilane twice with absolute ethanol; then slowly add a mixture of absolute ethanol, pure water and acetic acid with a volume ratio of 1:1:0.1. After stirring for 2-3 hours at room temperature, let it stand for 1 day to obtain solution A; the mass ratio of the methyl orthosilicate and methyl diethoxysilane is 2:1; the methyl orthosilicate and methyl The volume of the mixture of diethoxysilane is X, the volume of the mixture of absolute ethanol, pure water, and acetic acid is Y, and X:Y is 2:1; the analytical purity of acetic acid is AR grade, with a purity of 99.95% the above;

Step 2: Coating the nano acrylic emulsion with silica sol with a particle size of less than 20 nm and a solid content of 40%, wherein the mass ratio of the silica sol to the nano acrylic emulsion is 3:1 to obtain B;

Step 3. Add 1% of B to solution A to obtain AB-1. The refractive index of this solution is 1.50;

Step 4. Add 5% of B to solution A to obtain AB-2. The refractive index of the corresponding film of this solution is 1.45;

Step 5. Add 10% of B to solution A to obtain AB-3, the refractive index of the corresponding film of this solution is 1.39;

Step 6, adding 50% of B to solution A to obtain AB-4, the refractive index of the corresponding film of this solution is 1.30;

Step 7. Add 50% of B to solution A to obtain AB-5. The refractive index of the film corresponding to this solution is 1.24;

Step 8. According to the above production method, use AB-1 solution for the first coating, then solidify at 100°C for 1 min, and then cool to below 40°C;

Step 9. According to the above production method, use the AB-2 solution for the second coating, then solidify at 100°C for 1 min, and cool to below 40°C;

Step 10. According to the above production method, use the AB-3 solution for the third coating, then solidify at 100°C for 1 min, and cool to below 40°C;

Step 11. According to the above manufacturing method, use AB-4 solution for the fourth coating, then cure at 100°C for 1 min, and cool to below 40°C;

Step 12. According to the above production method, use AB-5 solution for the fifth coating, and then cure at 100°C for 1 min;

Step 13, normal tempering, to obtain a double-layer high-transmittance coating product.

Figure 1 is the product structure diagram of the anti-reflective photovoltaic coated glass obtained in the above embodiment; Figure 2 is the manufacturing process flow chart of the anti-reflective photovoltaic coated glass in the above embodiment; Figure 3 is the reduction in the above embodiment The light transmittance curve comparison diagram of the reflective photovoltaic coated glass, which is compared with the light transmittance curve of the original sheet and the coated glass obtained by the single-layer coating process; Figure 4 is the implementation of the anti-reflective photovoltaic coated glass in the above embodiment The light transmittance curve of the example is compared with the light transmittance curve of the original glass; Figure 5 is the SEM image of the film layer of the anti-reflective photovoltaic coated glass in the above embodiment, where Figure (a) is the film cross section Figure (b) is the SEM image of the surface of the film; Figure 6 is the HF40 test result of the anti-reflective photovoltaic coated glass in the above embodiment.

Compared with the prior art, the present invention has the following advantages: the anti-reflective coated glass product for solar module encapsulation in the present invention has the following advantages compared with current conventional photovoltaic coated glass products: ①High light transmittance, 380-1100nm The light transmittance can reach more than 94.30%; ②Wide-wavelength anti-reflection can be realized, especially in the infrared and ultraviolet bands, the transmittance is obviously improved, and the visible transmittance curve is compared; ③High weather resistance, can pass more harsh weather resistance In the test, the transmittance of the HF40 test does not decrease by more than 1%.

The manufacturing method of anti-reflective coated glass for solar module encapsulation has the following characteristics:

In addition to the conventional coating process (such as roll coating), the present invention can also perfectly combine the aerosol coating process, further reducing the process difficulty of producing multilayer coating.

In the present invention, solidification and cooling processes are required after the coating before the last layer of coating, which effectively guarantees the adhesion of the coating and better guarantees the weather resistance of the coated glass product.

The anti-reflective coated glass product for solar module encapsulation described in the present invention has distinct characteristics and obvious application advantages, can effectively promote the improvement of the technical level of the industry, and can also make important contributions to the "cost reduction and efficiency increase" of photovoltaic modules. The manufacturing method described is simple and practical, has strong operability, and effectively guarantees the mass production of the product of the present invention.

The specific embodiments described herein are merely examples to illustrate the spirit of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or additions to the specific embodiments described or use similar alternatives, but they will not deviate from the spirit of the present invention or exceed the definition of the appended claims. Range.

In summary, only the preferred technical solutions of the present invention are embodied by those skilled in the art, and some possible changes to some parts of them by those skilled in the art all embody the principles of the present invention and should be within the technical scope of the present invention.

Claims (9)

1. An anti-reflection coating glass for solar module packaging, characterized in that: a first anti-reflection coating layer is plated on the textured surface of a glass substrate for solar module packaging, and a first anti-reflection coating layer is plated on the first anti-reflection coating layer. Two-layer anti-reflection coating layer..., the n-1th anti-reflection coating layer is coated with an n-th anti-reflection coating layer; the refractive index of the coating material of the first anti-reflection coating layer is greater than that of all The refractive index of the coating material of the second anti-reflection coating layer..., the refractive index of the coating material of the n-1th anti-reflection coating layer is greater than the refraction of the coating material of the nth anti-reflection coating layer rate.
2. The anti-reflective coated glass for solar module packaging according to claim 1, wherein n is 2 or greater than 2.
3. The anti-reflective coated glass for solar module encapsulation according to claim 1 or 2, wherein the preparation process of the coated material includes the following steps:

   Step 1. Dilute the mixture of methyl orthosilicate and methyldiethoxysilane twice with absolute ethanol; then slowly add a mixture of absolute ethanol, pure water and acetic acid with a volume ratio of 1:1:0.1. After stirring for 2-3h at room temperature, let it stand for 1 day to obtain solution A;

   Step 2: Coating the nano acrylic emulsion with silica sol with a particle size of less than 20 nm and a solid content of 40%, wherein the mass ratio of the silica sol to the nano acrylic emulsion is 3:1 to obtain B;

   Step 3. Add X1% of B to solution A to obtain AB-1, and the corresponding film layer of this solution is the first anti-reflection coating layer;

   Add X2% of B to solution A to obtain AB-2, and the corresponding film layer of this solution is the second anti-reflection coating layer;

   ..., add Xn% of B to solution A to obtain AB-n, and the corresponding film layer of this solution is the nth anti-reflection coating layer;

   Among them, X1<X2...<Xn;

   Step 4. Use AB-1 solution for the first coating, then cure at 100°C for 1 min, and then cool to below 40°C to obtain the first anti-reflection coating layer;

   Use AB-2 solution for the second coating, and then cure at 100°C for 1 min, and then cool to below 40°C to obtain the first anti-reflection coating layer;

   ..., use AB-n solution for the nth coating, and then cure at 100°C for 1 min; normal tempering to obtain multilayer anti-reflection coated glass.
4. The anti-reflection coated glass for solar module encapsulation according to claim 3, wherein the mass ratio of methyl orthosilicate and methyldiethoxysilane in step 1 is 2:1.
5. The anti-reflective coated glass for solar module encapsulation according to claim 4, wherein the volume of the mixture of methyl orthosilicate and methyldiethoxysilane is X, and the absolute ethanol, The volume of the mixture of pure water and acetic acid is Y, and X:Y is 2-4:1.
6. The anti-reflective coated glass for solar module encapsulation according to claim 3 or 4, wherein the acetic acid in step 1 is AR grade with a purity of 99.95% or more.
7. A method for preparing the anti-reflection coated glass for solar module encapsulation according to any one of claims 1 to 6, characterized in that it comprises the following steps:

   ① Edging

   ②Cleaning

   ③The first coating

   ④ curing

   ⑤Cooling

   ...

   ⑥The nth coating

   ⑦ Tempered.
8. A preparation method according to claim 4, characterized in that: the coating process of the coating material can select one or a combination of roll coating, spray coating or aerosol coating process.
9. A preparation method according to claim 4 or 5, characterized in that: after each layer of coating process, it needs to be heated in a curing oven at 50°C-250°C for 30s-120s, and then subjected to water cooling or air cooling or both. After the combined cooling process, the next layer of coating is performed.

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