Method for preparing photovoltaic water-based high diffuse reflection glass ink from ceramic white glaze

Abstract

The invention relates to the technical field of reflective inks and discloses a method for applying ceramic white glaze to prepare photovoltaic water-based highly diffuse reflective glass ink. The cost of the ceramic white glaze is 70% of that of a photovoltaic coating, which can save costs. The ceramic raw materials used contain modified high-boron frits, and more crystals with a tetrahedral structure are obtained through an oxidation reaction, resulting in higher mechanical properties. Highly reflective materials containing nano-scale grains are added to improve hardness and reflective properties. The water-based ink can be dispersed to improve coating properties and has high adhesion properties. The ink is refined and dispersed with the ceramic raw materials through a ball milling process. The prepared glass ink can effectively improve the photoelectric conversion rate of photovoltaic panels.

Description

Technical Field

[0001] The invention belongs to the technical field of reflective inks, and in particular relates to a method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze. Background Art

[0002] Glass ink is an ink that adheres firmly to glass through a printing process that includes high-temperature sintering and tempering. It has good color adhesion and durability and is widely used in glass products such as building curtain walls. Photovoltaic modules are composed of two pieces of glass: front glass and back glass. Sunlight passes through the back glass into the module cells, absorbing light energy and converting it into electrical energy. However, due to the effect of reflection, part of the sunlight entering the module will pass through the back glass to the outside, reducing the utilization of light energy. Therefore, white opaque glass ink with high reflectivity is often applied to the gaps between the silicon wafers of the back glass of the photovoltaic module. The higher the reflectivity of the glass ink, the less light intensity loss the glass receives, and the less affected the electrical performance of the module will be. However, many photovoltaic modules are installed outdoors, and the mechanical properties of the glass ink are required to be high. It needs to have strong adhesion, wear resistance, corrosion resistance, and not be easily damaged by aging, which affects the performance of the module. Pure white frit powder that can improve the photoelectric conversion rate is often used in the market, and frit powder is used as the main component of glaze, but the price is relatively high. The present invention now uses ceramic white glaze to replace the frit powder used for photovoltaics, and proposes a method for making photovoltaic water-based high diffuse reflective glass ink with ceramic white glaze for application in the white high reflective coating of the back panel of photovoltaic double-glass modules. Summary of the Invention

[0003] In view of the above problems, the object of the present invention is to provide a method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze.

[0004] The technical contents of the present invention are as follows:

[0005] The present invention provides a method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0006] Step 1: Weigh the ceramic raw materials according to the proportion and put them into the mixer to mix evenly;

[0007] The ceramic raw material comprises the following raw materials in parts by weight: 40-50 parts of modified high-boron frit, 12-16 parts of feldspar, 8-12 parts of quartz, 1-5 parts of zinc oxide, 8-12 parts of titanium dioxide, 4-8 parts of high reflective material, 3-7 parts of barium carbonate and 1-5 parts of kaolin;

[0008] The chemical composition of calcite is calcium carbonate, and it is a white transparent crystalline mineral with the highest birefringence and polarization properties;

[0009] Titanium dioxide is highly refractive and photoactive;

[0010] Titanium dioxide is titanium dioxide, which has high hiding power, high whiteness and large specific surface area;

[0011] Feldspar is the raw material of ceramics, which has the functions of dissolving, lowering melting temperature and resisting corrosion;

[0012] Barium carbonate improves transparency, refractive index and mechanical properties;

[0013] Kaolin can improve the fluidity and plasticity of materials and has good chemical properties;

[0014] The modified high-boron frit is prepared by adding 9-15 wt% zinc nitrate to the high-boron frit, then adding 30-50% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:8-10, performing low-heat treatment, and then drying. The low-heat treatment is performed at a temperature of 30-50° C. for 90-110 minutes.

[0015] The high-boron frit contains boron oxide, which can reduce the thermal expansion and curing temperature of the glaze, and improve the gloss and fastness. Zinc nitrate oxidation can promote the conversion of boron trioxide into boron tetroxide, enhancing the mechanical and reflective properties of the glass ink. Potassium dihydrogen phosphate solution acts as a buffer to control the degree of oxidation.

[0016] The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 9-11:3-5 at a solid-to-liquid ratio of 1:8-15 g / mL, dispersing the mixture in an organic silane coupling agent solution, and heating the mixture. The heating step is performed at a temperature of 80-90° C. for 60-80 minutes. The highly reflective material contains cubic nano-calcium carbonate and anatase titanium dioxide particles. The organic silane coupling agent can stably reduce the particles, resulting in higher hardness, chemically modifying the inorganic surface to increase material adhesion, reduce void defects in the material, and improve dispersibility, resulting in high reflective performance.

[0017] Step 2: Add water-based printing ink to the mixture at a solid-liquid ratio of 5-9:18 g / mL, stir and disperse, and obtain the finished ink after ball milling;

[0018] The water-based printing ink comprises a water-based resin, a dispersing and leveling agent, diethylene glycol, and an alcohol ether stabilizing solvent in a mass ratio of 11-13:22-26:1-3:10; the water-based resin is one of a water-based alkyd resin, a water-based polyurethane resin, and a water-based hydroxylated acrylic resin; and the alcohol ether stabilizing solvent is one of ethylene glycol ether, methanol ether, and propylene glycol ether;

[0019] The dispersing and leveling agent is ethylene carbonate added with polycarboxylate at a mass fraction of 10-20%;

[0020] The water-based ink is added with a resin intermediate, ethylene glycol, and a dispersing and leveling agent, which can reduce the surface tension of the ink, passivate interface defects, and improve mechanical properties;

[0021] The ball milling is performed by first performing low-speed ball milling and then high-speed ball milling; the ball milling adopts a planetary ball mill, first ball milling at a speed of 200-400 r / min for 40-60 minutes, and then ball milling at a speed of 800-1200 r / min for 10-20 minutes; the raw materials are fully mixed during the low-speed ball milling process, and then the high-speed ball milling promotes the stimulation of material properties and increases the number of performance crystals.

[0022] The beneficial effects of the present invention are as follows:

[0023] The present invention provides a method for preparing photovoltaic water-based high diffuse reflective glass ink using ceramic white glaze. The invention proposes applying the ceramic white glaze to the preparation of photovoltaic water-based high diffuse reflective glass ink, thereby saving costs. The cost of the ceramic white glaze is 70% of that of the photovoltaic coating. The ceramic raw materials used contain modified high-boron frits, which are oxidized to obtain more crystals with a tetrahedral structure, resulting in higher mechanical properties. Highly reflective materials containing nano-scale grains are added to improve hardness and reflective properties. Several raw materials in the water-based ink are compounded and can be mixed with the ceramic raw materials and refined and dispersed through a ball milling process. The prepared glass ink has high adhesion, thereby improving the solar energy utilization rate of photovoltaic panels and effectively increasing the photoelectric conversion rate of photovoltaic panels.

[0024] The glass ink provided by the present invention has good wear resistance, chemical corrosion resistance, good thermal expansion coefficient and gloss in its raw materials. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below through specific implementation cases. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. After reading the present invention, various equivalent modifications of the present invention by those skilled in the art are all within the scope of the claims attached to this application.

[0026] Unless otherwise specified, all raw materials and reagents in the present invention are raw materials and reagents from conventional markets.

[0027] Example 1

[0028] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0029] Step 1: put 45 parts of modified high-boron frit, 14 parts of feldspar, 10 parts of quartz, 3 parts of zinc oxide, 10 parts of titanium dioxide, 6 parts of high reflective material, 5 parts of barium carbonate and 3 parts of kaolin into a mixer and mix well;

[0030] The modified high-boron frit is prepared by adding 12 wt% zinc nitrate to the high-boron frit, then adding it to a 40% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:9, heating at a temperature of 40° C. for 100 minutes, and then drying.

[0031] The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 10:4 at a solid-liquid ratio of 1:12 g / mL, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane, and heating the mixture at 85° C.

[0032] The water-based printing ink comprises a water-based alkyd resin in a mass ratio of 12:23:2:10, ethylene carbonate with a mass fraction of 15% of polycarboxylate, diethylene glycol and ethylene glycol ether;

[0033] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 7:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 300 r / min for 50 minutes, and then at a speed of 1000 r / min for 15 minutes.

[0034] Example 2

[0035] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0036] Step 1: put 40 parts of modified high-boron frit, 12 parts of feldspar, 8 parts of quartz, 1 part of zinc oxide, 8 parts of titanium dioxide, 4 parts of high reflective material, 3 parts of barium carbonate and 1 part of kaolin into a mixer and mix well;

[0037] The modified high-boron frit is prepared by adding 9 wt% zinc nitrate to the high-boron frit, then adding it to a 30% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:8, heating at a temperature of 30° C. for 90 minutes, and then drying.

[0038] The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 9:3 at a solid-liquid ratio of 1:8 g / mL, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane, and heating the mixture at 80° C. for 60 minutes.

[0039] The water-based printing ink comprises a water-based polyurethane resin, a water-based hydroxy acrylic resin, ethylene carbonate with a mass fraction of 10% of polycarboxylate, diethylene glycol and methanol ether in a mass ratio of 11:22:1:10;

[0040] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 5-9:18 g / mL, stir and disperse, and obtain finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 200 r / min for 40-60 minutes, and then at a speed of 800 r / min for 10-20 minutes.

[0041] Example 3

[0042] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0043] Step 1: put 50 parts of modified high-boron frit, 16 parts of feldspar, 12 parts of quartz, 5 parts of zinc oxide, 12 parts of titanium dioxide, 8 parts of high reflective material, 7 parts of barium carbonate and 5 parts of kaolin into a mixer and mix well;

[0044] The modified high-boron frit is prepared by adding 15 wt% zinc nitrate to the high-boron frit, then adding 50% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:10, heating at 50° C. for 110 minutes, and then drying.

[0045] The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 11:5 at a solid-liquid ratio of 1:15 g / mL, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane, and heating the mixture at 90° C. for 80 minutes.

[0046] The water-based printing ink comprises a water-based hydroxy acrylic resin in a mass ratio of 13:26:3:10, ethylene carbonate with a mass fraction of 20% of polycarboxylate added, diethylene glycol and propylene glycol ether;

[0047] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 9:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 400 r / min for 60 minutes, and then at a speed of 1200 r / min for 20 minutes.

[0048] Example 4

[0049] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0050] Step 1: put 42 parts of modified high-boron frit, 14 parts of feldspar, 9 parts of quartz, 2 parts of zinc oxide, 9 parts of titanium dioxide, 5 parts of high reflective material, 4 parts of barium carbonate and 2 parts of kaolin into a mixer and mix well;

[0051] The modified high-boron frit is prepared by adding 11 wt% zinc nitrate to the high-boron frit, then adding it to a 35% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:9, heating at a temperature of 35°C for 95 minutes, and then drying to obtain

[0052] The highly reflective material is prepared by mixing calcite and titanium dioxide particles in a mass ratio of 10:3, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane at a solid-liquid ratio of 1:10 g / mL, and heating the mixture at 85° C. for 65 minutes.

[0053] The water-based printing ink comprises a water-based alkyd resin in a mass ratio of 12:23:2:10, ethylene carbonate with a mass fraction of 13% of polycarboxylate, diethylene glycol and ethylene glycol ether;

[0054] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 6:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 250 r / min for 45 minutes, and then at a speed of 900 r / min for 15 minutes.

[0055] Example 5

[0056] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0057] Step 1: put 50 parts of modified high-boron frit, 15 parts of feldspar, 11 parts of quartz, 4 parts of zinc oxide, 11 parts of titanium dioxide, 7 parts of high reflective material, 6 parts of barium carbonate and 4 parts of kaolin into a mixer and mix well;

[0058] The modified high-boron frit is prepared by adding 14 wt% zinc nitrate to the high-boron frit, then adding 45% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:9, performing low-heat treatment, and then drying. The low-heat treatment is performed at a temperature of 45° C. for 105 minutes.

[0059] The highly reflective material is prepared by mixing calcite and titanium dioxide particles in a mass ratio of 10:4 at a solid-liquid ratio of 1:14 g / mL, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane, and heating the mixture at 85° C. for 75 minutes.

[0060] The water-based printing ink comprises a water-based alkyd resin, a water-based polyurethane resin, a water-based hydroxy acrylic resin, ethylene carbonate with a mass fraction of 18% of polycarboxylate, diethylene glycol and methanol ether in a mass ratio of 12:25:2:10;

[0061] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 8:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 350 r / min for 55 minutes, and then at a speed of 1100 r / min for 20 minutes.

[0062] Example 6

[0063] A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, comprising the following steps:

[0064] Step 1: put 40 parts of modified high-boron frit, 16 parts of feldspar, 8 parts of quartz, 5 parts of zinc oxide, 8 parts of titanium dioxide, 8 parts of high reflective material, 3 parts of barium carbonate and 5 parts of kaolin into a mixer and mix well;

[0065] The modified high-boron frit is prepared by adding 9 wt% zinc nitrate to the high-boron frit, then adding 30% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:10, performing low-heat treatment, and then drying. The low-heat treatment is performed at a temperature of 50° C. for 90 minutes.

[0066] The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 11:3 at a solid-liquid ratio of 1:15 g / mL, dispersing the mixture in γ-glycidyloxypropyltrimethoxysilane, and heating the mixture at 80° C. for 80 minutes.

[0067] The water-based printing ink comprises a water-based alkyd resin, a water-based polyurethane resin, a water-based hydroxy acrylic resin, ethylene carbonate with a mass fraction of 10% of polycarboxylate, diethylene glycol and propylene glycol ether in a mass ratio of 11:26:1:10;

[0068] Step 2: Add aqueous printing ink to the mixture at a solid-liquid ratio of 9:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; the ball milling adopts a planetary ball mill, first at a speed of 400 r / min for 40 minutes, and then at a speed of 1200 r / min for 10 minutes.

[0069] Comparative Example 1

[0070] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses an equal amount of high-boron frit instead of the modified high-boron frit, and the other contents remain unchanged.

[0071] Comparative Example 2

[0072] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 uses an equal amount of calcite to replace the high-reflective material, and the other contents remain unchanged.

[0073] Comparative Example 3

[0074] The difference between Comparative Example 3 and Example 1 is that the ball milling process in preparation step 2 of Comparative Example 3 adopts low-speed ball milling, and the ball milling time remains unchanged.

[0075] Comparative Example 4

[0076] The difference between Comparative Example 4 and Example 1 is that the water-based printing ink in Comparative Example 4 does not contain a leveling dispersant.

[0077] 1. The glass inks prepared in the examples and comparative examples were printed on photovoltaic glass using a screen printing process, and the reflective properties of the obtained glass were tested.

[0078] Table 1 Reflective properties of glass

[0079]

[0080] As can be seen from Table 1, the glass ink prepared by the present invention has high reflective properties. In Comparative Examples 1 and 2, the tetrahedral grains and nano-scale grains of the highly reflective material in the modified high-boron frit are numerous and highly dispersed, which can improve the reflective properties of the glass ink. As can be seen from Comparative Examples 3 and 4, the water-based printing ink containing a resin intermediate and a leveling stabilizer can improve the surface properties of the ink, and the use of an accelerated ball milling process can stimulate the growth of highly reflective grains of the ceramic raw material. Compared with conventional processes and general printing inks, the prepared glass ink has stronger reflective properties.

[0081] 2. The mechanical properties of the prepared ink were tested. The glass inks prepared in the examples and comparative examples were first printed on glass by screen printing, and then chemically tempered and packaged to obtain tempered photovoltaic glass. Ordinary tempered glass on the market was used for comparison, and various performance tests were performed on the glass. The adhesion test standard was GB / T9286-1988, and the impact performance test standard was GB / T 39814-2021. The test results are shown in Table 2.

[0082] Table 2 Mechanical properties of glass ink

[0083]

[0084]

[0085] As can be seen from Table 2, the glass ink prepared by the present invention has good mechanical properties. Compared with the comparative example, it is more resistant to wear, impact, aging and corrosion, and has good adhesion and thermal expansion coefficient. As can be seen from Comparative Examples 1 and 2, the high-reflective material added by the present invention contains composite grains and the surface is modified with organic silane to improve chemical properties such as surface viscosity, and the tetrahedral grain structure of the modified high-boron frit can improve the comprehensive mechanical properties of the glass ink. As can be seen from Comparative Examples 3 and 4, the water-based printing ink of the present invention is compounded with several organic solvents, and its dispersibility and thickening properties make the prepared glass ink have good printing performance and strong adhesion. The ball milling process can improve the comprehensive properties of the glass ink through physical energy.

[0086] In summary, the present invention applies ceramic raw materials to the preparation of photovoltaic water-based glass ink, which reduces the preparation cost of traditional glass ink. The prepared glass ink has high diffuse reflection performance, has good mechanical properties when printed on glass, and is not easy to damage the performance of photovoltaic modules.

Claims

1. A method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze, characterized in that: The following steps are involved: Step 1: Weigh the ceramic raw materials according to the proportion and put them into the mixer to mix evenly; The ceramic comprises the following raw materials in parts by weight: 40-50 parts of modified high-boron frit, 12-16 parts of feldspar, 8-12 parts of quartz, 1-5 parts of zinc oxide, 8-12 parts of titanium dioxide, 4-8 parts of high reflective material, 3-7 parts of barium carbonate and 1-5 parts of kaolin; The modified high-boron frit is prepared by adding 9-15wt% zinc nitrate to the high-boron frit, then adding 30-50% potassium dihydrogen phosphate aqueous solution at a solid-liquid ratio of 1:8-10, performing low-temperature treatment, and then drying. The low heat treatment is performed at a temperature of 30-50° C. for 90-110 minutes; The highly reflective material is obtained by mixing calcite and titanium dioxide particles in a mass ratio of 9-11:3-5 at a solid-liquid ratio of 1:8-15 g / mL, dispersing the mixture in an organic silane coupling agent solution, and then heating the mixture. The heating is performed at a temperature of 80-90° C. for 60-80 minutes; Step 2: Add water-based printing ink to the mixture at a solid-liquid ratio of 5-9:18 g / mL, stir and disperse, and obtain the finished ink after ball milling; The water-based printing ink comprises a water-based resin, a dispersing and leveling agent, diethylene glycol and an alcohol ether stabilizing solvent in a mass ratio of 11-13:22-26:1-3:10; the water-based resin is one of a water-based alkyd resin, a water-based polyurethane resin and a water-based hydroxy acrylic resin.

2. The method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze according to claim 1, characterized in that: The alcohol ether stabilizing solvent is one of ethylene glycol ether, methanol ether and propylene glycol ether.

3. The method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze according to claim 1, characterized in that: The dispersing and leveling agent is ethylene carbonate added with polycarboxylate at a mass fraction of 10-20%.

4. The method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze according to claim 1, characterized in that: The ball milling is performed first at a low speed and then at a high speed.

5. The method for preparing photovoltaic water-based high diffuse reflective glass ink from ceramic white glaze according to claim 1, characterized in that: The ball milling adopts a planetary ball mill, and the ball milling is first performed at a rotation speed of 200-400 r / min for 40-60 min, and then at a rotation speed of 800-1200 r / min for 10-20 min.

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