CN103897487A - Fluorine modified epoxy resin-base ink for thin-film solar cells and preparation method thereof - Google Patents

Abstract

A fluorine-modified epoxy resin-based ink for thin-film solar cells and a preparation method thereof, comprising the following components in the following mass percentages: a solution of fluorine-modified epoxy resin-based resin (resin solid content 1-10%) 0.5- 5%; nano aluminum powder 0.0001-0.1%; viscosity regulator 0.1-1%; the balance is solvent. The products manufactured by the present invention are printed onto the upper surface of flexible or thin-film solar cells by using ink-jet printing technology, so as to directly improve the power generation efficiency of flexible or thin-film solar cells.

Description

Fluorine-modified epoxy resin-based ink for thin-film solar cells and preparation method thereof

technical field

The invention relates to a fluorine-modified epoxy resin-based inkjet printer ink for flexible or thin-film solar cells and a preparation method thereof. By using the ink to print on the light-incident surface of flexible or thin-film solar cells, the flexibility or thin-film can be directly improved. The efficiency of solar cells.

Background technique

Due to the special properties of fluorine atoms, fluorine-containing polymers form a helical structure in which F atoms surround the C-C main chain. The C-F bond is very stable, and the bond energy is 485 kJ/mol. The arrangement of fluorine atoms in the outer layer of the carbon skeleton is very tight, which can Form a shielding protection for the main chain and internal molecules. Protect the C-C main chain from being damaged by harsh environmental conditions and maintain a high degree of stability. The molecular side groups or side chains of organic fluoropolymer materials contain fluorine atoms with small steric hindrance and strong electrophilic ability, so that the surface free energy is very low, and it shows excellent waterproof, oil-proof and stain-resistant properties. Therefore, fluorocarbon coatings have some unique properties that are incomparable to other coatings, such as: excellent weather resistance, excellent chemical corrosion resistance, low friction, water repellency, oil repellency, non-combustibility, etc., making it widely used in many application fields It has been applied and has attracted more and more attention from people in the paint industry.

Epoxy resin has excellent adhesion, thermal stability, chemical resistance, insulation and mechanical strength, etc., and is widely used in coatings, adhesives and composite materials. Epoxy resin itself is difficult to dissolve in water, and it is not easy to disperse in water. There are currently three main methods to prepare water-based epoxy emulsion: mechanical method, phase inversion method (curing agent emulsification method) and chemical modification method. Compared with the first two methods, the chemical modification method has many advantages: No need to add emulsifier, high water and solvent resistance, small emulsion particle size (nano-scale), good storage stability, high curing degree, dense and uniform coating film. In recent years, the use of acrylic monomers to graft and modify epoxy resins does not consume epoxy groups and hydroxyl groups, and the obtained emulsions have small particle sizes and good emulsion stability. They have both high modulus and high strength of epoxy resins. , chemical resistance and excellent corrosion resistance, but also has the characteristics of acrylic resin gloss, fullness, and good weather resistance. Water-based epoxy resin has the advantages of excellent adhesion, high modulus, high strength, chemical resistance and corrosion resistance. Using epoxy resin to modify the fluorine-containing acrylate emulsion can improve the water resistance and water resistance of the coating. Solvent, adhesion and mechanical properties, while greatly reducing the cost of coatings without affecting the requirements of use. Wang Yifeng et al. prepared epoxy resin modified acrylate copolymer composite emulsion by physical blending method. Qin Zonggen et al. blended fluorine-containing emulsion with epoxy emulsion and found that the resin would self-stratify when forming a film. The coating film has excellent surface properties and good adhesion. (1. Wang Yuexin, Wang Jingke, Zhang Qian, Zhai He, Wang Fang, Modification of Epoxy Coatings by Fluorinated Copolymers with Epoxy Groups, Polymer Materials Science and Engineering, Issue 03, 2012. 2. Xu Xiaolong , Li Baosong, Wu Xuedong, Research on Hexafluorobutyl Methacrylate Grafted Epoxy Powder Coatings, "Coating Industry", Issue 4, 2010, pp. 56-59)

Among the projects of effective utilization of solar energy: photovoltaic utilization is the fastest growing and most dynamic research field in recent years. The production of general solar cells is mainly based on semiconductor materials, which use photoelectric materials to absorb light energy and generate photoelectric conversion reactions to generate electricity. According to the different materials used, solar cells can be divided into: 1. Silicon solar cells; 2. Solar cells made of inorganic salts such as gallium arsenide III-V compounds, cadmium sulfide, copper indium selenide and other multi-component compounds; 3. Solar cells made of functional polymer materials; 4. Nanocrystalline solar cells, etc.

The product with the highest working efficiency in the prior art is based on III-V group semiconductor inorganic materials as raw materials. For example: gallium arsenide/germanium single-junction quantum well trap structure, its photoelectric conversion efficiency can reach >18%; and solar cells with multiple junction quantum well trap structure, such as: indium gallium phosphide/arsenide Gallium/germanium, its photoelectric conversion efficiency can be as high as >30%. At present, silicon is the most widely used, including amorphous silicon, with a photoelectric conversion efficiency of about 9%; polycrystalline silicon, with a photoelectric conversion efficiency of about 14%; and monocrystalline silicon, with a photoelectric conversion efficiency of about 17%. Although in terms of price, the group VI element Si is cheaper than the III-V group semiconductor GaAs, but its manufacturing price is still much more expensive than polymer organic solar cells; and in application, it is light in weight and has no risk of rupture. The fully plasticized organic solar cells can be realized by printing. In addition to lower prices, they are more suitable for the needs of portable electronic products, and can be used normally indoors or on cloudy days (this is something that silicon solar cells cannot achieve. ), making its practicability and market application breadth more enhanced.

Solar cells are a key technology that will advance cleaner energy production. But the cost of solar cells has reduced the economic competitiveness of solar technology. To overcome this problem, thin-film solar cells are currently widely used technology, which can greatly reduce the use of expensive semiconductor materials, but thin-film solar cells have low light absorption, and their performance is not as good as traditional solar cells.

Thin-film solar modules are composed of glass substrates, metal layers, transparent conductive layers, electrical functional boxes, adhesive materials, semiconductor layers, etc. Organic-inorganic composite solar cells are solar cells based on the organic conjugated polymer-inorganic nanocrystalline composite material system. Because organic polymer materials have good film-forming properties, the energy level structure and band gap are easy to adjust, they can be prepared by wet methods. Low-cost, large-area, flexible solar cell devices and inorganic nanocrystalline materials with high stability, high mobility, and the ability to construct ordered nanostructures have become research hotspots in the field of solar cells in recent years. Metal nanoparticles can guide light into solar cells better and prevent light from escaping. In conventional "thick-film" solar cells, nanoparticles have little effect because all light absorption is through the film, which depends on its thickness. For thin films, however, nanoparticles can do a lot. Their scattering increases the time that light stays in the film, bringing the overall light absorption to a level comparable to conventional solar cells.

Aluminum and silver nanoparticles in the visible part of the spectrum do a good job of focusing light into solar cells. But the optical resonance also causes the nanoparticles to absorb light, which means the solar cell will be less efficient. The resonance of silver nanoparticles is just in the key absorption spectrum part of solar cells, so the absorption of light is considerable. Aluminum nanoparticles resonate beyond critical spectral parts for solar cells. The loss of energy is small. In addition, aluminum particles are easily passivated. Although the shape and size will change, the properties of the nanoparticles will change little after passivation. Nanoparticles have uneven surfaces that scatter light more into a broad-spectrum wavelength range. This results in greater absorption, which increases the overall efficiency of the cell.

Inkjet printing technology can form thin film layers through the uniform deposition of liquid organic materials, so this technology can theoretically better solve the problem of large photoactivator size. A drop-on-demand process that deposits material in exactly the right amount and where it is needed. Since the inkjet system has a very high utilization rate of materials, manufacturing production costs can be reduced.

Contents of the invention

The purpose of this invention is to provide a flexible or thin-film solar cell with fluorine-modified epoxy resin-based inkjet printer ink and its preparation method, by using the ink to print on the surface of the light-incident surface of flexible or thin-film solar cells, directly improve Efficiency of flexible or thin film solar cells. And the flexible or thin-film solar cells treated with the ink have the effect of self-cleaning.

To achieve the above object, the technical scheme adopted in the present invention is as follows:

Fluorine-modified epoxy resin-based ink for thin film solar cells of the present invention comprises the following components in the following mass percentages:

Fluorine-modified epoxy resin-based resin solution (resin solid content 1-10%) 0.5-5%;

Nano aluminum powder 0.0001-0.1%;

Viscosity regulator 0.1-1%;

The balance is solvent.

The fluorine-modified epoxy resin refers to perfluoroalkyl ethyl acrylate with epoxy groups, perfluoroalkyl ethyl acrylate with epoxy groups containing nano-montmorillonite, One or more of nano-powder hexafluorobutyl methacrylate epoxy resin, bisphenol A epoxy-hexafluorobutyl methacrylate resin, bisphenol A epoxy-perfluoroalkyl ethyl acrylate resin A mix of species.

The viscosity regulator is N-methyl-2-pyrrolidone or poly-3-methylthiophene.

The solvent is one or more of alcohols, esters, ethers, amines, amides, ketones or hydrocarbons.

Preferably, the ink contains at least 20% of ketones, 20% of esters, and 10% of ethers, accounting for the mass percentage of the ink.

The alcohol is methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, or one or more of the above-mentioned fluorinated alcohols.

The ketone is one or more of acetone, cyclohexanone, methyl ethyl ketone, methyl isopropyl ketone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, and N-methylpyrrolidone.

The ester is alcohol ether ester, methyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate, propyl acetate, butyl acetate, methyl propionate, or ethyl propionate, diol One or more of ether acetate and butyl glycol acetate.

The ether is one or more of diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, ethylene glycol ether or ethylene glycol methyl ether.

Fluorine-modified epoxy resin-based ink for thin film solar cells of the present invention comprises the following steps:

(1) Mix fluorine-modified epoxy resin solution, viscosity modifier and solvent, process it in a high-speed emulsifier for 10-60 minutes at a speed of 10,000-100,000 rpm, and process it into a uniformly mixed emulsion;

(2) After the processing of the above mixed emulsion is completed, under the same processing speed environment, within 10-20 minutes, add the nano-aluminum powder continuously in batches;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered through a filter with a mesh size of 300 mesh or above to obtain a fluorine-modified epoxy for flexible or thin-film solar cells. Resin-based inkjet printer ink.

In order to meet the above industrial needs, we invented the fluorine-modified epoxy resin-based nano-aluminum powder ink. The ink can be used not only on the backlight of thin-film solar cells, but also on the surface of the light incident film of thin-film solar cells through inkjet printing equipment. absorption efficiency. Improve the power generation efficiency of solar cells.

Nano-metal aluminum particles are easy to passivate, although the shape and size will change, the properties of the nanoparticles change little after passivation. Nanoparticles have uneven surfaces that scatter light more into a broad-spectrum wavelength range. This results in greater absorption, which increases the overall efficiency of the cell. Scattering by the metallic aluminum nanoparticles increases the time that light stays in the film, bringing the overall light absorption to a level comparable to conventional solar cells. The performance of the thin film solar cell processed by using the thin film of the present invention is 3-15% higher than that of the thin film solar cell not processed by the thin film. Thin-film solar cells After using the thin film, the metallic aluminum nanoparticles can guide light into the solar cell and prevent light from escaping. Solve the problem that in traditional "thick film" solar cells, nanoparticles have little effect and all light absorption must rely on thickness to solve the problem.

Detailed ways

Example 1

(1) Add 0.5Kg of perfluoroalkylethyl acrylate solution (resin solid content 10%) with epoxy groups, 0.1Kg of viscosity modifier (N-methyl-2-pyrrolidone), 99.3995Kg N, Mix N-dimethylformamide, process it in a high-speed emulsifier for 10-60 minutes at a speed of 10,000-100,000 rpm, and process it into a uniformly mixed emulsion;

(2) Add 0.005Kg of acetone nano-aluminum powder in batches and continuously within 10-20 minutes at the same processing speed after the processing of the above mixed emulsion;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; (5) The above emulsion is filtered with a filter screen of more than 300 mesh to obtain a fluorine-modified epoxy resin for flexible or thin-film solar cells Inkjet printer ink.

The ink of this embodiment is tested according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standards respectively. The quality inspection indicators of the ink, such as specific gravity, PH value, surface tension, viscosity, conductivity, etc., have been tested, and the test results are in line with the national standard. Pour the ink to be tested into a cold-resistant packaging bottle, put it in a low-temperature incubator at (-20± 1)°C for 24 hours, and then take it out. After returning to room temperature, test its printing performance. Test results: Its reducibility is good, no deterioration, no taste. the

Example 2

(1) 2Kg of perfluoroalkylethyl acrylate solution containing epoxy groups containing nano-montmorillonite (resin solid content 8%), 0.3Kg of viscosity modifier (N-methyl-2-pyrrolidone) 1. Prepare a solution with 10Kg ethanol, 20Kg acetone, and 67.6999Kg glycol ether acetate, process it in a high-speed emulsifier for 10-60 minutes at a speed of 10000-100000 rpm, and process it into a uniformly mixed emulsion;

(2) Add 0.0001Kg of acetone nano-aluminum powder in batches and continuously within 10-20 minutes under the same processing speed environment after the above mixed emulsion is processed;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a filter screen of more than 300 mesh to obtain a fluorine-modified epoxy resin inkjet printer for flexible or thin-film solar cells ink.

The ink of this embodiment is tested according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standards respectively. The quality inspection indicators of the ink, such as specific gravity, PH value, surface tension, viscosity, conductivity, etc., have been tested, and the test results are in line with the national standard. Pour the ink to be tested into a cold-resistant packaging bottle, put it in a low-temperature incubator at (-20± 1)°C for 24 hours, and then take it out. After returning to room temperature, test its printing performance. Test results: Its reducibility is good, no deterioration, no taste. the

Example 3

(1) Mix 3Kg of hexafluorobutyl methacrylate epoxy resin solution (resin solid content 5%) containing nanopowder, 0.8Kg of viscosity modifier (N-methyl-2-pyrrolidone), 25Kg of methyl ethyl Mix ketone, 31.15Kg ethylene glycol ethyl ether, and 20Kg butyl acetate, process it in a high-speed emulsifier for 10-60 minutes at a speed of 10,000-100,000 rpm, and process it into a uniformly mixed emulsion;

(2) Add 0.05Kg of acetone nano-aluminum powder in batches and continuously within 10-20 minutes under the same processing speed after the processing of the above mixed emulsion is completed;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a filter screen of more than 300 mesh to obtain a fluorine-modified epoxy resin inkjet printer for flexible or thin-film solar cells ink.

The ink of this embodiment is tested according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standards respectively. The quality inspection indicators of the ink, such as specific gravity, PH value, surface tension, viscosity, conductivity, etc., have been tested, and the test results are in line with the national standard. Pour the ink to be tested into a cold-resistant packaging bottle, put it in a low-temperature incubator at (-20± 1)°C for 24 hours, and then take it out. After returning to room temperature, test its printing performance. Test results: Its reducibility is good, no deterioration, no taste. the

Example 4

(1) Mix 4Kg of bisphenol A epoxy-hexafluorobutyl methacrylate resin solution (resin solid content 3%), 1Kg of viscosity regulator (poly-3-methylthiophene), and 20Kg of butyl glycol acetic acid Esters, 10Kg butanol, 20Kg tetrahydrofuran are prepared into a solution, mixed with 44.9 Kg ethyl propionate, processed in a high-speed emulsifier for 10-60 minutes at a speed of 10000-100000 rpm, and processed into a uniformly mixed emulsion;

(2) Add 0.1Kg of acetone nano-aluminum powder continuously in small amounts in batches within 10-20 minutes after the processing of the above mixed emulsion is completed at the same processing speed;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a filter screen of more than 300 mesh to obtain a fluorine-modified epoxy resin inkjet printer for flexible or thin-film solar cells ink.

The ink of this embodiment is tested according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standards respectively. The quality inspection indicators of the ink, such as specific gravity, PH value, surface tension, viscosity, conductivity, etc., have been tested, and the test results are in line with the national standard. Pour the ink to be tested into a cold-resistant packaging bottle, put it in a low-temperature incubator at (-20± 1)°C for 24 hours, and then take it out. After returning to room temperature, test its printing performance. Test results: Its reducibility is good, no deterioration, no taste. the

Example 5

(1) Mix 5Kg of bisphenol A epoxy-perfluoroalkyl ethyl acrylate resin solution (resin solid content 1%), 0.6Kg of viscosity modifier (poly-3-methylthiophene), and 10Kg of N,N-dimethyl Formamide, 20Kg acetone, 20Kg tetrahydrofuran, and 44.92Kg butyl acetate are prepared into a solution, processed in a high-speed emulsifier for 10-60 minutes at a speed of 10,000-100,000 rpm, and processed into a uniformly mixed emulsion;

(2) Add 0.08Kg of acetone nano-aluminum powder in batches and continuously within 10-20 minutes at the same processing speed after the processing of the above mixed emulsion is completed;

(3) The above emulsion is fully emulsified for 10-30 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a filter screen of more than 300 mesh to obtain a fluorine-modified epoxy resin inkjet printer for flexible or thin-film solar cells ink.

The ink of this embodiment is tested according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standards respectively. The quality inspection indicators of the ink, such as specific gravity, PH value, surface tension, viscosity, conductivity, etc., have been tested, and the test results are in line with the national standard. Pour the ink to be tested into a cold-resistant packaging bottle, put it in a low-temperature incubator at (-20± 1)°C for 24 hours, and then take it out. After returning to room temperature, test its printing performance. Test results: Its reducibility is good, no deterioration, no taste. the

The ink formula is simple, easy to manufacture, easy to master the process, only need stirring machinery, ultrasonic dispersion and filtering machinery can be industrialized production, easy to meet quality standards.

Example 7

Mix fluorine-modified epoxy resin-based resin solution, acetone, glycol ether acetate, ethyl acetate, cyclohexanone and ethylene glycol ether according to the ratio of 0.5:20:10:20:29.3:20, Process in a high-speed emulsifier at a speed of 20,000rpm for 20 minutes, and process it into a uniform mixed emulsion; after the above mixed emulsion is processed, under the same processing speed environment, the nano-aluminum powder with a weight percentage of 0.2 is divided into batches within 20 minutes Add in a small amount continuously; the above emulsion is fully emulsified for 20 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a 1000-mesh filter to obtain the required fluorine-modified epoxy resin-based inkjet for flexible or thin-film solar cells Printer ink and method for its preparation.

Example 7

Fluorine-modified epoxy resin-based resin solution, acetone, glycol ether acetate, butyl glycol acetate, cyclohexanone and methoxypropanol according to the ratio of 0.5:20:10:20: 29.4: 20 mixed, processed in a high-speed emulsifier at a speed of 100,000 rpm for 10 minutes, and processed into a uniform mixed emulsion; after the above mixed emulsion was processed, the weight percentage was 0.1 within 10 minutes under the same processing speed environment The nano-aluminum powder is continuously added in small batches; the above emulsion is fully emulsified for 10 minutes after the nano-aluminum powder is completely added; the above emulsion is filtered with a 500-mesh filter to obtain the required fluorine-modified flexible or thin-film solar cells Epoxy resin-based inkjet printer ink and a preparation method thereof.

The fluorine-modified epoxy resins used in the examples of the present invention were purchased from Yongzhou Lida Resin Raw Materials Co., Ltd.

Claims (10)

1. a fluorine modified epoxy base ink for thin-film solar cells, is characterized in that, comprises the following component of following mass percent:

Solution (resin solid content 1-10%) 0.5-5% of fluorine modified epoxy base resin;

Nanometer aluminium powder 0.0001-0.1%;

Viscosity-controlling agent 0.1-1%;

Surplus is solvent.

2. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described fluorine modified epoxy refers to the polyacrylic acid perfluoro alkyl ethyl of epoxide group, containing one or more the mixing in the polyacrylic acid perfluoro alkyl ethyl with epoxide group of nano imvite, Hexafluorobutyl mathacrylate epoxy resin containing nano-powder, dihydroxyphenyl propane epoxy-Hexafluorobutyl mathacrylate resin, dihydroxyphenyl propane epoxy-vinylformic acid perfluoro alkyl ethyl resin.

3. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described viscosity-controlling agent is METHYLPYRROLIDONE or poly-3 methyl thiophene.

4. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described solvent is one or more in alcohol, ester, ether, amine, acid amides, ketone or hydrocarbon.

5. fluorine modified epoxy base ink for thin-film solar cells according to claim 1 is characterized in that: in described ink, contain ketone, ester and ether simultaneously.

6. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, or one or more in the fluorinated alohol of above-mentioned alcohol.

7. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, it is characterized in that: described ketone is acetone, cyclohexanone one or more in methylethylketone, first isopropyl acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N-Methyl pyrrolidone.

8. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described ester is one or more in alcohol ether-ether, methyl acetate, ethyl acetate, acetic acid 1-methoxyl group-2-propyl ester, propyl acetate, butylacetate, methyl propionate or ethyl propionate, glycol ethers acetic ester, butyl glycol acetate.

9. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described ether is one or more in diethyl ether, dipropyl ether, tetrahydrofuran (THF), dioxan, ethylene glycol ethyl ether or ethylene glycol monomethyl ether.

10. fluorine modified epoxy base ink for thin-film solar cells claimed in claim 1, is characterized in that: comprise the steps:

(1) by fluorine modified epoxy solution, viscosity-controlling agent and solvent, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;

(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by nanometer aluminium powder in batches trace add continuously;

(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; The one flexibility that both must need after strainer filterings more than 300 orders or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer for above emulsion.