CN103214770B - Solar cell encapsulating film and preparation method thereof - Google Patents
Solar cell encapsulating film and preparation method thereof Download PDFInfo
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- CN103214770B CN103214770B CN201310140600.3A CN201310140600A CN103214770B CN 103214770 B CN103214770 B CN 103214770B CN 201310140600 A CN201310140600 A CN 201310140600A CN 103214770 B CN103214770 B CN 103214770B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a solar cell encapsulating film and a preparation method thereof. According to the encapsulating film, a fluorine-containing thin film is prepared in an extrusion tape-casting or film blowing way from the following raw materials: 40-55 parts of fluororesin which is added with a small amount of silane coupling agent, organic hyperoxide and a crosslinking catalyst; 10-45 parts of inorganic filler; 10-45 parts of modified resin; 0.05-1.0 part of lubricant; and 0-2 parts of functional assistant. The fluororesin is a copolymer of ethylene, tetrafluoroethylene, hexafluoropropylene and 1,2,2-trifluorostyrene; and the modified resin is polyacrylate, polymethyl methacrylate or polyethyl methacrylate. The invention also provides the preparation method of the solar cell encapsulating film. The solar cell protecting film prepared by the method is low in fluorine content and is excellent in anti-ultraviolet-aging characteristic, humidity-resistant performance and weather-proof performance; and simultaneously the mechanical performance of the film is enhanced.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly a kind of solar cell package film and preparation method thereof.
Technical background
Solar cell backboard is positioned at the back side of solar panel, plays protection and supporting role, need have reliable insulativity, water preventing ability, ageing-resistant performance to cell piece.Because backboard plays the vital role determining solar cell work-ing life in photovoltaic module, in recent years along with the rise of photovoltaic industry, backboard industry also becomes the focus that people pay close attention to.The structure that solar photovoltaic cell backplane is relatively more conventional at present has TPT structure and TPE structure, wherein T refers to the Tedlar film of E.I.Du Pont Company, composition is fluorinated ethylene propylene (PVF) film, P refers to polyethylene terephthalate (PET) film, E refers to ethylene-vinyl acetate resin (EVA) film, bonds between three-layer thin-film with suitable binding agent.TPT structure refers to PVF film/PET film/PVF membrane structure, and TPE structure refers to PVF film/PET film/eva film structure.But PVF processing difficulties, complicated process of preparation, cost is higher, and conventional PVF is monopolized by du pont company in the world.
For the deficiencies in the prior art, report is had to adopt other fluorine film to replace PVF film, such as CN101582459A(CN200910053911.X) provide a kind of take modified polyvinylidene fluoride alloy layer as the solar cell backboard of weathering protective layer, comprise the first bonding successively weathering layer, first adhesive linkage, structure enhancement layer, second adhesive linkage and the second weathering layer, first weathering layer and the second weathering layer are the polyblend alloy layer of polyvinylidene difluoride (PVDF) and inorganic materials, structure enhancement layer is polyethylene terephthalate layer, first adhesive linkage and the second adhesive linkage are urethane glue-lines, polyacrylic ester glue-line or epoxy adhesive layer.
In current most of modified polyvinylidene fluoride alloy layer, the content of fluoropolymer is higher, therefore, it is possible to ensure the performance of film, the high cost of film that causes of the content of fluoropolymer is higher.Be unfavorable for that suitability for industrialized production and mass market are applied.
Summary of the invention
For the deficiencies in the prior art, the invention provides solar cell package film that a kind of fluorine content is low, excellent property, cost are low and preparation method thereof.
Technical scheme of the present invention is as follows:
Solar cell package film, adopt the mode extruding curtain coating or blown film to make fluorine-contained film by following raw material, raw materials quality part is composed as follows:
Fluororesin 40-55 parts, in fluoro-resin quality, is added with silane coupling agent 0.5-4.5wt%, organo-peroxide 0.01-0.6wt%, crosslinking catalyst 0.01-0.8wt%;
Mineral filler 10-45 part, modified resin 10-45 part, lubricant 0.05-1.0 part, functional agent 0-2 part;
Described fluoro-resin is ethene, tetrafluoroethylene, R 1216 and 1,2, the multipolymer of 2-trifluorostyrene, described mineral filler is the oxide compound of titaniferous, aluminium, tin, element silicon, and described modified resin is polyacrylic ester, polymethylmethacrylate or polyethyl methacrylate; Described functional agent is one of oxidation inhibitor, antiaging agent, photostabilizer, light absorber or combination;
In the multipolymer of described ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, the mol ratio that ethene and tetrafluoroethylene sum account for multipolymer is 90-99.9%, and the mol ratio between ethene and tetrafluoroethylene is (30 ~ 70): (70 ~ 30); R 1216 and 1,2,2-trifluorostyrene sum mol ratio are in the copolymer 0.1-10%, and the mol ratio between R 1216 and 1,2,2-trifluorostyrene is (10 ~ 90): (90 ~ 10).
Preferably, in the multipolymer of described ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, tetrafluoroethylene molar content is 46 ~ 55%; Ethylene molar percentage composition is 36 ~ 44%; R 1216 molar content is 3 ~ 7%; 1,2,2-trifluorostyrene molar content is 1 ~ 7%.The molar content sum of ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene is 100%.
The multipolymer of described ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene can be prepared, as solution polymerization process, suspension polymerization, emulsion polymerization etc. by any one copolyreaction of prior art.Preferably, by ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene four kinds of monomers by proportioning mixing, adopt solution polymerization process to carry out the obtained multipolymer of copolyreaction in organic solvent, solvent is selected from the suitable reaction solvent of fluorocarbon solvent or fluorochloroparaffins and other.
Described silane coupling agent is selected from vinyltrimethoxy silane or vinyltriethoxysilane, described organo-peroxide is dicumyl peroxide (DCP) or dibenzoyl peroxide, and described crosslinking catalyst is one or more in dibutyltin dilaurate, lauric acid dibutyitin maleate, Bis(lauroyloxy)dioctyltin, Witco 1298 Soft Acid, dodecylbenzene sulfonation acetyl, toluenesulphonic acids, toluene sulfonation acetyl.
According to the present invention, preferably, described silane coupling agent is vinyltrimethoxy silane, and preferred content is 1.5-2.5wt%;
Described organo-peroxide is preferably dicumyl peroxide (DCP), and preferred content is 0.1-0.3wt%;
Described crosslinking catalyst is preferably dibutyltin dilaurate, and preferred content is 0.1-0.4wt%;
Described mineral filler is nano level titanium dioxide, silicon-dioxide or aluminium sesquioxide.
Described modification tree refers to for polymethylmethacrylate or polyethyl methacrylate, is preferably polymethylmethacrylate;
Described lubricant be stearic acid, butyl stearate, ethylene bis stearic acid amide, native paraffin, synthesis paraffin, polyethylene wax or polypropylene cured in any one or any several combination.
In described functional agent, oxidation inhibitor, photostabilizer, light absorber are all selected by this area routine.Oxidation inhibitor is selected from Hinered phenols, photostabilizer is selected from hindered amines, light absorber is selected from benzophenone class or benzotriazole category.Being preferably as follows further of described functional agent: antioxidant 1010, antioxidant 1076 or antioxidant BHT; Photostabilizer 770 or photostabilizer 622LD; Light absorber UV-P or light absorber UV-O.
Preferred further according to the present invention, solar cell package film, raw materials quality part is composed as follows:
Ethene-four fluo-copolymer 40-50 part, with ethene-tetrafluoro copolymer substance gauge, is added with dicumyl peroxide 0.1-0.3wt%, vinyltrimethoxy silane 1.5-2.5wt%; Dibutyltin dilaurate 0.1-0.4wt%;
TiO
210-40 part, polymethylmethacrylate 15-35 part, lubricant 0.1-1.0 part, functional agent 0.5-2 part.
The preparation method of solar cell package film of the present invention, step is as follows:
(1) divide two groups by fluoro-resin, respectively with silane coupling agent and organo-peroxide through extrusion mechanism for pellet A, with crosslinking catalyst through extrusion mechanism for pellet B, make fluoro-resin content sum in pellet A, pellet B be the total amount of fluoro-resin in proportioning raw materials.In pellet A and pellet B, the mass ratio of fluoro-resin is (90 ~ 98): (2 ~ 10).
(2) pellet A and pellet B is mixed, then mix with mineral filler, modified resin, lubricant and functional agent through extruding curtain coating or blown film mode makes fluorine-contained film, and within 9 ~ 11 hours, complete crosslinked through 85 ± 5 DEG C of water-baths.
Preferably, the thickness making fluorine-contained film is 20-40 μm.
Preferred further according to the present invention, the preparation method of solar cell package film, raw materials quality part is composed as follows:
Ethene-four fluo-copolymer 40-50 part, with ethene-tetrafluoro copolymer substance gauge, is added with dicumyl peroxide 0.1-0.3wt%, vinyltrimethoxy silane 1.5-2.5wt%; Dibutyltin dilaurate 0.1-0.4wt%;
TiO
210-40 part, polymethylmethacrylate 15-35 part, lubricant 0.1-1.0 part, functional agent 0.5-2 part.
Get ethene-four fluo-copolymer 95% with silane coupling agent and organo-peroxide through double-screw extruding pelletizing, obtain pellet A; 5% and the crosslinking catalyst of getting ethene-four fluo-copolymer, through double-screw extruding pelletizing, obtain pellet B; Will pellet A and pellet B set with mineral filler, modification refer to, lubricant and functional agent mix through extruding curtain coating or blown film mode that to make thickness be 20-40 μm of fluorine-contained film, and within 10 hours, complete crosslinked through 85 ± 5 DEG C of water-baths.
Ethene of the present invention, tetrafluoroethylene, R 1216 and 1,2, the multipolymer of 2-trifluorostyrene is a kind of ETFE (tetrafluoroethylene-ethylene copolymer) fluoroplastics of modification, the ETFE of this modification has excellent mechanical property, chemical resistant properties and ageing-resistant performance, and adhesion property is good, it is the preferred material of solar cell package film weathering layer.
Protecting solar cell film provided by the invention; under the condition melt extruded, polymkeric substance is made to complete grafting process by interpolation silane coupling agent, organo-peroxide; then under crosslinking catalyst effect, complete the crosslinking reaction of polymkeric substance; make fluorine film under lower content, still have excellent anti-ultraviolet ageing characteristic, excellent moisture-proof, weather resistance; improve the mechanical strength of film simultaneously; and cost-saving, there is very important meaning to solar cell industry.Silane coupling agent has the silicoorganic compound of special construction, it very easily produces firmly chemical bond with inorganic materials, good combination can be produced with organic polymer material again, give material mechanical property, electric property, water tolerance, thermotolerance and preservative property etc. better.
Embodiment
Below by specific embodiment, the invention will be further described, but be not limited only to this.Material per-cent in embodiment is mass percent.Raw material in embodiment is commercial products.
Embodiment 1:
Solar cell package film, raw materials quality part forms: fluorine resin 53 parts, nano level TiO
227 parts, powder, polymethylmethacrylate (PMMA) 18 parts, polyethylene wax 1.0 parts, functional agent 1.0 parts, this functional agent is by 0.3 part of antioxidant 1010,0.3 part of photostabilizer, 770,0.4 part of light absorber UV-P; Making film thickness is 30 μm.
With the agent of fluorine resin quality, add silane coupling agent vinyl Trimethoxy silane 2.3wt%, dicumyl peroxide (DCP) 0.2wt%; Crosslinking catalyst dibutyltin dilaurate 0.3wt%;
Described fluorine resin is the multipolymer (modification ETFE) of ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, and in multipolymer, tetrafluoroethylene composition molar content is 49%; Ethene composition molar content is 43.5%; R 1216 Component molar content is 5.8%; Trifluorostyrene Component molar percentage composition is 3.7%.
Preparation method is as follows:
(1) by the 95wt% of fluoro-resin and silane coupling agent and organo-peroxide through double-screw extruding pelletizing, obtain pellet A.
(2) by the 5wt% of fluoro-resin and crosslinking catalyst through double-screw extruding pelletizing, obtain pellet B.
(3) pellet A, pellet B and mineral filler, modification are set refer to, through extruding curtain coating or blown film mode, to make thickness be 30 μm of fluorine-contained films according to above-mentioned ratio for lubricant and functional agent etc., and within 10 hours, completes crosslinked through 85 ± 5 DEG C of water-baths
Embodiment 2: as described in Example 1, difference is: the composition changing the multipolymer of main component ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene in fluorine film, and with nano level TiO
2the mass ratio (as table 1) of powder, polymethylmethacrylate (PMMA).In the multipolymer of the present embodiment, tetrafluoroethylene composition accounts for molar content is 50.6%; It is 36.8% that ethene composition accounts for molar content; R 1216 content accounts for 6.8%; It is 5.8% that trifluorostyrene composition accounts for molar content.
Embodiment 3: as described in Example 1, difference is: the composition changing the multipolymer of main component ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene in fluorine film, and nano level TiO
2the mass ratio (as table 1) of powder, polymethylmethacrylate (PMMA).In the multipolymer of the present embodiment, tetrafluoroethylene composition accounts for molar content is 54.3%; It is 41.4% that ethene composition accounts for molar content; It is 3.2% that R 1216 composition accounts for molar content, and it is 1.3% that trifluorostyrene composition accounts for molar content.
Comparative example 1: reference sample 1, does not add silane coupling agent, organo-peroxide and crosslinking catalyst, other compositions and preparation method identical with embodiment 1, in fluorine film, the mass ratio of material is as shown in table 1 below.
Material ratio in table 1, fluorine film
Standard detection in fluorine film according to the form below 2 prepared by above embodiment 1-3 and reference sample 1 is known, and this fluorine film mechanical property is excellent, and ageing-resistant performance is good, the results are shown in table 2.
Note: described fluorine film refers to the fluorine protecting solar cell film of the present invention's low fluorine protecting solar cell film or comparative example.Lower same.
Table 2, product performance
Embodiment 4:
Solar cell package film, raw materials quality part forms: multipolymer 48 parts and the mineral filler SiO of fluorine resin ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene
230 parts, polymethylmethacrylate (PMMA) 20 parts, 0.7 part, lubricant paraffin, functional agent 1.3 parts, making film thickness is 25 μm.Functional agent is 0.3 part of antioxidant 1076,0.2 part of photostabilizer 622LD and 0.2 part of light absorber UV-O.
Each monomer ratio in the multipolymer of fluorine resin ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene is identical with embodiment 1.
Preparation process as embodiment 1, difference be pellet A add silane coupling agent be vinyltriethoxysilane 1.8wt%, organo-peroxide is dicumyl peroxide (DCP) 0.3wt%; At the crosslinking catalyst dibutyltin dilaurate 0.2t% that pellet B adds.
Embodiment 5:
Solar cell package film, raw materials quality part forms: multipolymer 44 parts and the mineral filler Al of fluorine resin ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene
2o
332 parts, polymethylmethacrylate (PMMA) 22 parts, lubricant chlorinatedpolyethylene 0.5 part, functional agent 1.5 parts, making film thickness is 20 μm.Functional agent is the mixing of 0.5 part of antioxidant BHT, 0.5 part of photostabilizer, 770,0.5 part of light absorber UV-O.Each monomer ratio in the multipolymer of ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene is identical with embodiment 1.
Preparation process as embodiment 1, difference be pellet A add silane coupling agent be vinyltriethoxysilane 2.0wt%, organo-peroxide is dicumyl peroxide (DCP) 0.1wt%; Crosslinking catalyst dibutyltin dilaurate 0.3wt% is added at pellet B;
Comparative example 2: reference sample 2 does not add silane coupling agent, organo-peroxide and crosslinking catalyst, other compositions are identical with embodiment 4.
Standard detection in fluorine film according to the form below 3 prepared by above embodiment 4-5 and reference sample 2 is known, and this fluorine film mechanical property is excellent, and ageing-resistant performance is good, the results are shown in table 3.
Table 3, product performance
Claims (10)
1. solar cell package film, adopt the mode extruding curtain coating or blown film to make fluorine-contained film by following raw material, raw materials quality part is composed as follows:
Fluororesin 40-55 parts, in fluoro-resin quality, is added with silane coupling agent 0.5-4.5wt%, organo-peroxide 0.01-0.6wt%, crosslinking catalyst 0.01-0.8wt%;
Mineral filler 10-45 part, modified resin 10-45 part, lubricant 0.05-1.0 part, functional agent 0-2 part;
Described fluoro-resin is ethene, tetrafluoroethylene, R 1216 and 1,2, the multipolymer of 2-trifluorostyrene, described mineral filler is the oxide compound of titaniferous, aluminium, tin, element silicon, and described modified resin is polyacrylic ester, polymethylmethacrylate or polyethyl methacrylate; Described functional agent is one of oxidation inhibitor, antiaging agent, photostabilizer, light absorber or combination;
In the multipolymer of described ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, the mol ratio that ethene and tetrafluoroethylene sum account for multipolymer is 90-99.9%, and the mol ratio between ethene and tetrafluoroethylene is (30 ~ 70): (70 ~ 30); R 1216 and 1,2,2-trifluorostyrene sum mol ratio are in the copolymer 0.1-10%, and the mol ratio between R 1216 and 1,2,2-trifluorostyrene is (10 ~ 90): (90 ~ 10).
2. solar cell package film as claimed in claim 1, is characterized in that, in the multipolymer of described ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, tetrafluoroethylene molar content is 46 ~ 55%; Ethylene molar percentage composition is 36 ~ 44%; R 1216 molar content is 3 ~ 7%; 1,2,2-trifluorostyrene molar content is 1 ~ 7%.
3. solar cell package film as claimed in claim 1, it is characterized in that described silane coupling agent is selected from vinyltrimethoxy silane or vinyltriethoxysilane, described organo-peroxide is dicumyl peroxide (DCP) or dibenzoyl peroxide, and described crosslinking catalyst is one or more in dibutyltin dilaurate, lauric acid dibutyitin maleate, Bis(lauroyloxy)dioctyltin, Witco 1298 Soft Acid, dodecylbenzene sulfonation acetyl, toluenesulphonic acids, toluene sulfonation acetyl.
4. solar cell package film as claimed in claim 1, it is characterized in that described silane coupling agent is vinyltrimethoxy silane, content is 1.5-2.5wt%.
5. solar cell package film as claimed in claim 1, it is characterized in that described organo-peroxide is dicumyl peroxide (DCP), content is 0.1-0.3wt%.
6. solar cell package film as claimed in claim 1, it is characterized in that described crosslinking catalyst is dibutyltin dilaurate, content is 0.1-0.4wt%.
7. solar cell package film as claimed in claim 1, is characterized in that described mineral filler is nano level titanium dioxide, silicon-dioxide or aluminium sesquioxide; Described modification tree refers to for polymethylmethacrylate or polyethyl methacrylate; Described lubricant be stearic acid, butyl stearate, ethylene bis stearic acid amide, native paraffin, synthesis paraffin, polyethylene wax or polypropylene cured in any one or any several combination.
8. solar cell package film as claimed in claim 1, is characterized in that, in described functional agent, oxidation inhibitor is selected from antioxidant 1010, antioxidant 1076 or antioxidant BHT; Photostabilizer is selected from photostabilizer 770 or photostabilizer 622LD; Light absorber is selected from light absorber UV-P or light absorber UV-O.
9. solar cell package film as claimed in claim 1, it is characterized in that, raw materials quality part is composed as follows:
Multipolymer 40-50 part of ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, with the copolymer substance gauge of ethene, tetrafluoroethylene, R 1216 and 1,2,2-trifluorostyrene, be added with dicumyl peroxide 0.1-0.3wt%, vinyltrimethoxy silane 1.5-2.5wt%; Dibutyltin dilaurate 0.1-0.4wt%;
TiO
210-40 part, polymethylmethacrylate 15-35 part, lubricant 0.1-1.0 part, functional agent 0.5-2 part.
10. the preparation method of the solar cell package film described in any one of claim 1 ~ 9, step is as follows:
(1) divide two groups by fluoro-resin, respectively with silane coupling agent and organo-peroxide through extrusion mechanism for pellet A, with crosslinking catalyst through extrusion mechanism for pellet B, make fluoro-resin content sum in pellet A, pellet B be the total amount of fluoro-resin in proportioning raw materials; In pellet A and pellet B, the mass ratio of fluoro-resin is (90 ~ 98): (2 ~ 10);
(2) pellet A and pellet B is mixed, then mix with mineral filler, modified resin, lubricant and functional agent through extruding curtain coating or blown film mode makes fluorine-contained film, and within 9 ~ 11 hours, complete crosslinked through 85 ± 5 DEG C of water-baths; The thickness making fluorine-contained film is 20-40 μm.
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| CN103467651B (en) * | 2013-10-09 | 2015-04-29 | 昆山天洋热熔胶有限公司 | Method for preparing anti-scratch coating material for solar cell backplanes |
| CN104479270B (en) * | 2014-12-31 | 2017-09-12 | 广东玉兰集团股份有限公司 | A kind of aqueous, environmental protective resin, preparation method and application |
| KR102477337B1 (en) * | 2015-01-23 | 2022-12-13 | 아크론 폴리머 시스템즈, 인코포레이티드 | Fluoropolymer-based polymer blend, polymer film and polarizer protective film |
| CN105097972B (en) * | 2015-09-01 | 2017-04-12 | 北京铂阳顶荣光伏科技有限公司 | Preparation method and application for solar cell protective film |
| CN105754273B (en) * | 2016-03-11 | 2018-04-20 | 安徽金兑新材料科技有限公司 | A kind of polymer/nanometer film for obstructing steam and preparation method thereof |
| CN111393599A (en) * | 2018-12-13 | 2020-07-10 | 北京汉能光伏投资有限公司 | Fluorine modified thermoplastic polyurethane composite material and preparation method thereof, solar cell module and preparation method thereof |
| CN110690307B (en) * | 2019-10-30 | 2022-09-09 | 杭州福斯特应用材料股份有限公司 | Transparent back plate for photovoltaic module and preparation method thereof |
| CN113512286A (en) * | 2021-04-25 | 2021-10-19 | 苏州频发机电科技有限公司 | High-wear-resistance and anti-aging polyurethane tire |
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| ES2453972T3 (en) * | 2008-10-16 | 2014-04-09 | Solvay Specialty Polymers Italy S.P.A. | Opaque fluoropolymer composition comprising white pigments for solar cell photovoltaic elements |
| CN101508841B (en) * | 2009-03-17 | 2012-02-08 | 武汉理工大学 | Flexible polymer dielectric material for electrical condenser and preparation thereof |
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