CN104152015A - Polyester paint for flexible or thin film solar cell and preparation method thereof - Google Patents
Polyester paint for flexible or thin film solar cell and preparation method thereof Download PDFInfo
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- CN104152015A CN104152015A CN201310174504.0A CN201310174504A CN104152015A CN 104152015 A CN104152015 A CN 104152015A CN 201310174504 A CN201310174504 A CN 201310174504A CN 104152015 A CN104152015 A CN 104152015A
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Abstract
The invention discloses polyester paint for a flexible or thin film solar cell and a preparation method thereof, and the polyester paint comprises the following components by weight: 8-12% of a polyester resin solution (with the solid content of polyester resin in the solution being 1-10%); 0.0001-0.1% of nano aluminum powder; 0.1-1% of a viscosity regulator; and the balance of a solvent. The polyester paint coats the surface of the flexible or thin film solar cell by spraying, silk screen printing and printing and other technologies to directly improve the power generation efficiency of the flexible or thin film solar cell.
Description
Technical field
The present invention relates to a kind of flexibility or thin-film solar cells coating and preparation method thereof, by using this coating to form one deck transparent coatings on the surface of flexibility or thin-film solar cells incidence surface, directly improve the efficiency of flexibility or thin-film solar cells.
Background technology
Polyester, by polyvalent alcohol and polyprotonic acid polycondensation and polymkeric substance general name, comprise saturated polyester and unsaturated polyester etc.Polyester molecule structure height symmetry, has certain crystalline orientation ability, so have higher film-forming properties and formability.Mainly refer to polyethylene terephthalate (PET), also comprise traditionally the line style thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylester.A class excellent performance, broad-spectrum engineering plastics.Also can be made into trevira and polyester film.Polyester has good optical property and weathering resistance, and amorphous polyester plastics has good optical transparence.Polyester plastics has good abrasion performance frictional property and dimensional stability and electrical insulating property in addition.PBT is similar to PET molecular chain structure, and most of character is also the same, and just molecular backbone chain has become four by two methylene radical, so molecule is submissiveer, processing characteristics is better.When synthesizing polyester resin, if introduce some other compositions by chemical reaction, can have the performance that vibrin does not possess originally, reach and improve and outstanding certain performance object, reach special application performance requirement, using at present more is epoxy, vinylformic acid, silicone modified polyester resin.Unsaturated polyester has two kinds of self-vulcanizing and thermofixations: 1. self-vulcanizing, in the above-mentioned unsaturated polyester ester solution making, add respectively initiator (such as benzoyl peroxide, Cyclohexanone peroxides etc.) and promotor (as N, accelerine, cobalt salt), make polyester liquid at room temperature first form gel, then be cured.2. thermofixation, can only add benzoyl peroxide initiator, is heated to 100 DEG C of left and right and solidifies.No matter be self-vulcanizing or thermofixation, its reaction is all that the elementary free radical first being produced by decomposition of initiator causes styrene polymerization, form the living radical of oligomer, and then be connected on the two keys on unsaturated polyester main chain, carry out crosslinking copolymerization reaction.In addition, also can use the hardening with radiation such as ultraviolet ray, electron beam, gamma-rays.
Effectively utilizing in the middle of project of sun power: solar photovoltaic utilization is research field with fastest developing speed in the last few years, most active.The making of general solar cell is mainly taking semiconductor material as basis, opto-electronic conversion reaction generating occurs after utilizing photoelectric material to absorb luminous energy.According to the difference of material therefor, solar cell can be divided into: 1, silicon solar cell; 2, taking inorganic salt if the multi-element compounds such as gallium arsenide III-V compound, Cadmium Sulfide, copper indium diselenide are as the solar cell of material; 3, the solar cell of preparing with functional high molecule material; 4, nano-crystalline solar battery etc.
What prior art working efficiency was the highest is taking III-V family semiconductor inorganic materials as raw-material product.For example: the quantum well of the single junction type of gallium arsenide/germanium falls into crystal structure, and its photoelectric transformation efficiency can reach >18 %; For example, and multiple junction quantum well falls into the solar cell of crystal structure: InGaP/gallium arsenide/germanium, its photoelectric transformation efficiency can be up to >30 %.Most widely used at present, taking silicon as main: comprise non-crystalline silicon, photoelectric transformation efficiency approximately 9 %; Polysilicon, photoelectric transformation efficiency approximately 14 %; Silicon single crystal, photoelectric transformation efficiency approximately 17 %.Although in price, VI family elements Si is more cheap than III-V family semiconductor GaAs, the price of its manufacture, compared with polymer organic solar batteries, or expensive many; And in application, the light weight again overall plasticization organic solar batteries of the anxiety of crack-free can be realized via the processing of printing, except price reduces, be more suitable for the demand of portable electronic product, and indoor or cloudyly all can normally use (this is that siliceous solar cell is beyond one's reach), its practicality and market application range are promoted more.
Solar cell is a gordian technique, can advance more clean Energy production.But the Cost Problems of solar cell, has reduced the economic competitiveness of heliotechnics.For overcoming this problem, thin-film solar cells is the technology of current widespread use, can reduce in a large number the usage quantity of expensive semiconductor material, but the absorbing amount of thin-film solar cells is lower, and Performance Ratio is not gone up traditional solar cell.
Thin-film solar module is to be made up of glass substrate, metal level, transparency conducting layer, electrical function box, glueing material, semiconductor layer etc.Organic and inorganic composite solar battery is the solar cell based on organic conjugate polymer-inorganic nano-crystal composite system, because of while tool organic polymer material good film-forming property, level structure and band gap are easy to regulate, can prepare low cost, big area, flexible solar battery device and inorganic nano-crystal material high stability by wet method, high mobility, can construct the advantages such as ordered nano-structure, and become the study hotspot of area of solar cell in recent years.Metal nanoparticle can direct light enter solar cell better, prevents light escape.In traditional " thick film " solar cell, nanoparticle does not have any effect, is all by this film because all light absorbs, and this just relies on its thickness.But for film, nanoparticle just can be brought into play great role.Their scattering has increased light and has rested on the time in film, makes the light of overall absorption reach a kind of level, and traditional solar cell can match in excellence or beauty.
Aluminium and Nano silver grain are in the frequency spectrum of visible part, and focused ray enters solar cell well.But optical resonance also can cause nanoparticle absorb light, this efficiency that just means solar cell can be lower.Nano grain of silver sub-resonance is just in time in the crucial absorption spectrum part of solar cell, so the absorption of light is appreciable.Aluminum nanoparticles resonance has exceeded the crucial spectra part of solar cell.Loss to energy is less, and in addition, aluminum particulate is easy to passivation, although can change shape and size, after passivation, nanoparticle attribute change is very little.Nanoparticle has rough surface, and scattered beam can enter wide spectrum wavelength region more.This can bring larger absorption, thereby improves the whole efficiency of battery.
Coating, stamp and printing technology can form thin film layer by the uniform deposition of liquid organic materials, and therefore, this technology can solve large photoactivation thing dimensional problem in theory better.Coating as required, stamp and typography, can be accurately by deposition of material in position in the desired amount.Because coating, stamp and print system are very high to the utilization ratio of material, can reduce manufacture production cost.
Summary of the invention
The object of this invention is to provide a kind of flexibility or thin-film solar cells polyester coating and preparation method thereof, by using this coating coating, stamp and being printed on flexibility or the surface of thin-film solar cells incidence surface, directly improve the efficiency of flexibility or thin-film solar cells.And flexibility or thin-film solar cells that tool was processed through this coating have self-cleaning effect.
For achieving the above object, the technical solution used in the present invention is as follows:
Flexibility of the present invention or thin-film solar cells polyester coating, comprises following component by weight percentage:
The solution (in solution, alkyd resin solid content is 1-10%) 8 ~ 12% of alkyd resin;
Nanometer aluminium powder 0.0001-0.1%;
Viscosity-controlling agent 0.1-1%;
Surplus is solvent.
Described alkyd resin is any one in unsaturated polyester resin or unsaturated polyester resin and epoxy resin, polyacrylic acid, polyacrylic ester, organic-silicon-modified resin.
Unsaturated thermoplasticity, the thermosetting resin of described alkyd resin for being made through polycondensation by diprotic acid (or acid anhydrides) and dibasic alcohol.Unsaturated dibasic acid or acid anhydrides have MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE and tetrahydronaphthalic anhydride etc.Monounsaturated dicarboxylic acid or acid anhydrides are Tetra hydro Phthalic anhydride, m-phthalic acid and hexanodioic acid.Dibasic alcohol is propylene glycol, glycol ether and dipropylene glycol.There are vinylbenzene, methyl methacrylate and Phthalic acid, diallyl ester as the vinyl monomer of linking agent.The solution of this polyester in liquid ethylene base monomer (as the mixture of 18%～40% vinylbenzene or vinylbenzene and methyl methacrylate) is through crosslinking curing, and becomes three dimensional structure.Polyesterification polycondensation is to carry out at 190～220 DEG C, until reach the acid number (or viscosity) of expection, after polyesterification contracting reaction finishes, adds while hot a certain amount of vinyl monomer, is made into the liquid of thickness.
Described alkyd resin is unsaturated polyester, comprises adjacent benzene type, metaphenylene, p-phenyl, bisphenol A-type, halo unsaturated polyester, vinyl ester type etc.The trade mark as 191,196,199,2608,902A3, Xm-1, Xm-2,197,3301,323.Polyester resin solution used in the present invention can directly be ordered to manufacturer.
Described solvent is one or more in alcohol, ester, ether, amine, acid amides, ketone or hydrocarbon.
Be preferably and in ink, at least contain that to account for ink mass percent be 20% ketone, 20% ester, 10% ether.
Described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, or one or more in the fluorinated alohol of above-mentioned alcohol.
Described ketone is acetone, cyclohexanone, one or more in methylethylketone, first isopropyl acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N-Methyl pyrrolidone.
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.
Described ether is one or more in diethyl ether, dipropyl ether, tetrahydrofuran (THF), dioxan, ethylene glycol ethyl ether or ethylene glycol monomethyl ether.
Described viscosity-controlling agent is METHYLPYRROLIDONE or poly-3 methyl thiophene.
In coating of the present invention, can also add other conventional additives such as tensio-active agent, PH conditioning agent, sanitas.
The preparation method of polyester coating for flexibility of the present invention or thin-film solar cells, comprises the steps:
(1) by the polyester resin solution of formula ratio, 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;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
Polyester type nanometer aluminium powder coating of the present invention, this coating is by coating, stamp and printing equipment, both can be used in the backlight place of thin-film solar cells, also can be used in the light inlet film surface of thin-film solar cells, also can be used in the middle layer of thin-film solar cells, improve the efficiency of light absorption of solar cell simultaneously.Improve the generating efficiency of solar cell.
Nano metal aluminum particulate is easy to passivation, although can change shape and size, after passivation, nanoparticle attribute change is very little.Nanoparticle has rough surface, and scattered beam can enter wide spectrum wavelength region more.This can bring larger absorption, thereby improves the whole efficiency of battery.The scattering of metallic aluminium nanoparticle has increased light and has rested on the time in film, makes the light of overall absorption reach a kind of level, and traditional solar cell can match in excellence or beauty.The unsaturated polyester coating of our invention, this coating both can be used in the backlight place of thin-film solar cells, also can be used in the light inlet film surface of thin-film solar cells, also can be used in the middle layer of thin-film solar cells simultaneously.Through using the thin-film solar cells of unsaturated polyester coating of the present invention to improve 3-15% than untapped thin-film solar cells performance.Metallic aluminium nanoparticle in coating can direct light enter solar cell preferably, prevents light escape.Solve in traditional " thick film " solar cell, nanoparticle does not have any effect and all essential problems that relies on thickness solution of light absorption.
Embodiment
embodiment 1
(1) by 8Kg polyester resin solution (vibrin the solid content 10%) (trade mark 191, Zhong Qiao macromolecular material industrial corporation of Wenzhou City), viscosity-controlling agent (METHYLPYRROLIDONE) 0.1Kg, 20 Kg N, dinethylformamide, 20Kg acetone, 20Kg tetrahydrofuran (THF), 31.895Kg butylacetate mix, 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 0.005Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
By the ink of above-mentioned the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
embodiment 2
(1) by 9Kg polyester resin solution (vibrin the solid content 5%) (trade mark 196, Zhong Qiao macromolecular material industrial corporation of Wenzhou City), viscosity-controlling agent (METHYLPYRROLIDONE) 0.3Kg, 30Kg propyl carbinol, 30Kg acetone, 30.699Kg glycol ethers acetic ester mix, 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 0.0001Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
By the coating of above-mentioned the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of coating, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.
embodiment 3
(1) by 10Kg polyester resin solution (vibrin the solid content 1%) (trade mark 2608, Bayer Bitterfeld GmbH), viscosity-controlling agent (METHYLPYRROLIDONE) 0.8Kg, mix with 15Kg methyl ethyl ketone, 10Kg ethylene glycol ethyl ether, 64.15Kg butylacetate, 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 0.05Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
embodiment 4
(1)by 11Kg polyester resin solution (vibrin solid content 8%) (Xm-1, Wuxi City A Erzi Chemical Co., Ltd.), viscosity-controlling agent (poly-3 methyl thiophene) 1Kg, 70 Kg butyl glycol acetates, 17.9Kg butanols mix, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) above mix emulsion fluid machine after with under same processing rotating speed environment, in 10-20 minute by 0.1Kg acetone nanometer aluminium powder in batches trace add continuously;
(3 above emulsions are after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute;
(4 above emulsions with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
embodiment 5
(1) by 12Kg polyester resin solution (vibrin solid content 2%) (3301, Jinan auxiliary chemicals company limited), viscosity-controlling agent (poly-3 methyl thiophene) 0.6Kg, 10KgN, dinethylformamide, 20Kg acetone, 57.32Kg butylacetate mix, 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 0.08Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
embodiment 6
Alkyd resin solution, acetone, glycol ethers acetic ester, ethyl acetate, cyclohexanone and ethylene glycol ethyl ether are mixed according to described ratio 10:20:10:20:29.3:20, in emulsify at a high speed device, process 20 minutes with rotating speed 20000rpm, be processed into even mix emulsion fluid; After above mix emulsion fluid machines, with under same processing rotating speed environment, the nanometer aluminium powder that was 0.2 by weight percent in 20 minutes in batches trace adds continuously; Above emulsion after nanometer aluminium powder adds completely, more fully emulsified 20 minutes; The flexibility that both must need after 1000 object strainer filterings or thin-film solar cells polyester coating for above emulsion.
embodiment 7
Alkyd resin solution, acetone, glycol ethers acetic ester, butyl glycol acetate, cyclohexanone and methoxypropanol are mixed according to described ratio 12:20:10:20:29.4:20, in emulsify at a high speed device, process 10 minutes with rotating speed 100000 rpm, be processed into even mix emulsion fluid; After above mix emulsion fluid machines, with under same processing rotating speed environment, the nanometer aluminium powder that was 0.1 by weight percent in 10 minutes in batches trace adds continuously; Above emulsion after nanometer aluminium powder adds completely, more fully emulsified 10 minutes; The one flexibility that both must need after 500 object strainer filterings or thin-film solar cells polyester coating for above emulsion.
Claims (10)
1. a flexibility or thin-film solar cells polyester coating, is characterized in that, comprises following component by weight percentage:
The solution (in solution, alkyd resin solid content is 1-10%) 8 ~ 12% of alkyd resin;
Nanometer aluminium powder 0.0001-0.1%;
Viscosity-controlling agent 0.1-1%;
Surplus is solvent.
2. flexibility according to claim 1 or thin-film solar cells polyester coating, is characterized in that: described alkyd resin is any one in unsaturated polyester resin or unsaturated polyester resin and epoxy resin, polyacrylic acid, polyacrylic ester, organic-silicon-modified resin.
3. flexibility according to claim 1 or thin-film solar cells polyester coating, is characterized in that: described solvent is one or more in alcohol, ester, ether, amine, acid amides, ketone or hydrocarbon.
4. flexibility according to claim 1 or thin-film solar cells polyester coating, is characterized in that: in described ink, contain ketone, ester and ether simultaneously.
5. flexibility according to claim 3 or thin-film solar cells polyester coating, 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.
6. according to the flexibility described in claim 3 or 4 or thin-film solar cells polyester coating, 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.
7. according to the flexibility described in claim 3 or 4 or thin-film solar cells polyester coating, it 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.
8. according to the flexibility described in claim 3 or 4 or thin-film solar cells polyester coating, it 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.
9. flexibility according to claim 1 or thin-film solar cells polyester coating, is characterized in that: described viscosity-controlling agent is METHYLPYRROLIDONE or poly-3 methyl thiophene.
10. the preparation method of polyester coating for flexibility claimed in claim 1 or thin-film solar cells, is characterized in that: comprise the steps:
(1) by the polyester resin solution of formula ratio; Viscosity-controlling agent and solvent are processed 10-60 minute in emulsify at a high speed device, and 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;
(4) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells polyester coating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310174504.0A CN104152015A (en) | 2013-05-13 | 2013-05-13 | Polyester paint for flexible or thin film solar cell and preparation method thereof |
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| CN201310174504.0A CN104152015A (en) | 2013-05-13 | 2013-05-13 | Polyester paint for flexible or thin film solar cell and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393973A (en) * | 2017-05-31 | 2017-11-24 | 浙江工业大学 | Preparation method using self-assembled nanometer ball as GaAs solar battery surface antireflection layers |
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| CN102876179A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院化学研究所 | Coating for aluminum plate base used in ink-jet printing direct-to-plate, and preparation method and application thereof |
| CN103073948A (en) * | 2012-12-31 | 2013-05-01 | 中原工学院 | Ink of polycarbonate ink-jet printer for flexible or thin-film solar battery and preparation method of same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102876179A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院化学研究所 | Coating for aluminum plate base used in ink-jet printing direct-to-plate, and preparation method and application thereof |
| CN103073948A (en) * | 2012-12-31 | 2013-05-01 | 中原工学院 | Ink of polycarbonate ink-jet printer for flexible or thin-film solar battery and preparation method of same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107393973A (en) * | 2017-05-31 | 2017-11-24 | 浙江工业大学 | Preparation method using self-assembled nanometer ball as GaAs solar battery surface antireflection layers |
| CN107393973B (en) * | 2017-05-31 | 2020-12-01 | 浙江工业大学 | Preparation method of GaAs solar cell surface antireflection layer by using self-assembled nanospheres |
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