CN103342856A - Preparation method of filler thermally conductive composite EVA (ethylene vinyl acetate copolymer) adhesive film for encapsulating solar cell - Google Patents
Preparation method of filler thermally conductive composite EVA (ethylene vinyl acetate copolymer) adhesive film for encapsulating solar cell Download PDFInfo
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- CN103342856A CN103342856A CN2013102852251A CN201310285225A CN103342856A CN 103342856 A CN103342856 A CN 103342856A CN 2013102852251 A CN2013102852251 A CN 2013102852251A CN 201310285225 A CN201310285225 A CN 201310285225A CN 103342856 A CN103342856 A CN 103342856A
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Abstract
The invention discloses a preparation method of a thermally conductive composite EVA (ethylene vinyl acetate copolymer) film for encapsulating a filler solar cell. The preparation method mainly comprises the following steps of: firstly, premixing EVA and a crosslinking curing agent, a coupling agent, an antioxidant, an ultraviolet light absorber and a stabilizer, then adding a thermally conductive material treated by the coupling agent, and evenly mixing under high-speed stirring; extruding the mixed material into a film by a double-screw extruder. The filler thermally conductive composite EVA adhesive film prepared by using the method can be used as a solar cell encapsulation hot melt adhesive, not only meets the requirements of crosslinking degree and transmittance in the industry, has higher thermal conductivity than that of the commercially available general adhesive film, and can effectively improve the thermal efficiency of solar cell modules, thereby slowing the aging rate so as to prolong the service life of the composite adhesive film.
Description
Technical field
The present invention relates to
A kind of filled-typeUsed for encapsulation of solar battery
The preparation method of EVA heat conduction compound cutanIn this method, by in the EVA glued membrane, adding the heat conduction compound cutan that heat conductive filler prepares filled-type.
Background technology
Packaged material ethylene-vinyl acetate copolymer (EVA) is along with the improvement demand of recent photovoltaic industry is increasing.Because domestic EVA product performance are more excellent, industry has proposed more and more higher requirement to EVA.At first be embodied in the most basic anti-xanthochromia aging resistance, this is the important performance index of solar cell.The anti-xanthochromia aging resistance of packaged material is bad, not only influences the outward appearance of battery component, the more important thing is the transmittance that can reduce assembly, reduces the generating efficiency of solar cell, and the serious meeting of xanthochromia directly causes solar cell to be scrapped.
By in EVA, adding suitable antiaging agent, antioxidant for example, ultraviolet absorbers, UV light stabilizing agent etc. can significantly be improved the ageing-resistant ability of EVA glued membrane.In the hydrothermal aging experiment of battery component, assembly is in the hot and humid environment, and in the ultraviolet light and aging process of the test, assembly envrionment temperature of living in is also very high, has reached general about 70 ℃.The solar cell of outdoor application, owing to constantly absorb sunlight, the temperature of component internal can constantly raise.And the temperature height is a major reason that causes packaged material aging.In the battery component, packaging adhesive film EVA and backboard all are the very poor polymkeric substance of heat dispersion.Given this, we consider the heat in the assembly is shifted away as soon as possible, thereby reduce the temperature of component internal, thereby improve the problem of aging of battery component.At present, thereby add heat conductivility very universal that heat conductive filler improves polymkeric substance in the polymer materials, in EVA, add the report that heat conductive filler improves the heat conductivility of EVA and rarely have.The present invention proposes a kind of preparation method of filled-type EVA film adhesive for solar cell package, characterizes the heat conductivility of matrix material by the thermal conductivity of measuring glued membrane.
Summary of the invention
The present invention proposes a kind of preparation method of filled-type thermally conductive EVA film adhesive for solar cell package, this method is by introducing homemade heat-conductive composite material, effectively improved the heat conductivility of glued membrane, reduced the temperature of component internal, slowed down the aging speed of glued membrane, improve the performance of battery component, prolonged time limit of service.Mainly comprise the steps:
(1) the multipolymer EVA with ethene-vinyl acetate is base material, and a certain amount of crosslinking and curing agent, coupling agent, oxidation inhibitor, ultraviolet absorbers, the steady agent of light and the pre-mixing in homogenizer of EVA particle is even;
(2) obtain the heat conductive filler powders A with the coupling agent treatment thermally conductive material, it is added in the product of step (1), high-speed stirring is evenly standby;
(3) product of step (2) being joined temperature is that blend is extruded in 80 ~ 95 ℃ of twin screw extruders, through operations such as casting film-forming, cooling, traction, rollings, obtains the purpose product;
Be benchmark in 100 g quality EVA, the quality of crosslinking and curing agent, coupling agent, oxidation inhibitor, ultraviolet absorbers and the steady agent of light is respectively: 0.6 ~ 0.9 g, 0.25 ~ 0.4 g, 0.1 ~ 0.2 g, 0.2 ~ 0.4 g and 0.1 ~ 0.4g; The quality of filler powder A is 2 ~ 3 g;
VA content is 28% among the described EVA, and melting index is 30g/10min/190 ℃;
Described crosslinking and curing agent is tert-butyl hydroperoxide carbonic acid-2-ethylhexyl and 2,5-dimethyl-2, a kind of in two (butyl peroxy) ethane of 5-;
Described oxidation inhibitor is a kind of in β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid and three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester;
Described ultraviolet absorbers is a kind of in Octabenzone and the 2-hydroxyl-4-methoxy benzophenone;
The steady agent of described light is a kind of in two (1,2,2,6,6-pentamethyl-piperidyl)-sebates or two (2,2,6,6-tetramethyl--4-piperidines) sebate;
Described coupling agent is a kind of in γ-An Bingjisanyiyangjiguiwan and the vinyltriethoxysilane.
Described thermally conductive material is ZnO and Al
2O
3The mixing agent, the preparation method of described heat conductive filler powders A is: coupling agent is dissolved in the acetone soln of capacity, adds, 55 ℃ of heating in water bath 3h, fully after the magnetic agitation in 100 ℃ of vacuum-drying 48h;
In 100 g heat conductive filler powders A, the quality of described coupling agent is 1.5 ~ 3 g; The quality of described ZnO is 75 ~ 90 g; Described Al
2O
3Quality be 10 ~ 25 g.
Innovation part of the present invention is to add the heat conductive filler powders A in the sun power packaged material EVA that requires the comparison harshness, under the prerequisite that satisfies the required degree of crosslinking of packaging EVA and stripping strength, promote its ageing resistance by the heat conductivility that improves EVA, improve the efficient of assembly.
Embodiment
Embodiment one:
Be that 1.5% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with mass fraction, add fully dry ZnO(75%) and Al
2O
3(25%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 1;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.6 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.25 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.2 part of 2-hydroxyl-4-methoxy benzophenone, 0.2 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 2 parts of A1, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E-1;
Embodiment two:
Be that 1.5% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(80%) and Al2O3(20%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 2;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.8 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.3 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.3 part of 2-hydroxyl-4-methoxy benzophenone, 0.2 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 2 parts of A2, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E-2;
Embodiment three:
Be that 2% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(85%) and Al2O3(15%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 3;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.6 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.25 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.2 part of 2-hydroxyl-4-methoxy benzophenone, 0.4 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 3 parts of A3, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E-3;
Embodiment four:
Be that 1.5% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(90%) and Al
2O
3(10%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 4;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.6 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.3 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.3 part of 2-hydroxyl-4-methoxy benzophenone, 0.3 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 3 parts of A4, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package A5;
Embodiment five:
Be that 3% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(75%) and Al
2O
3(25%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 5;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.8 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.4 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.4 part of 2-hydroxyl-4-methoxy benzophenone, 0.2 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add the heat conductive filler of 2 parts of preparations in stuff and other stuff, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E5;
Embodiment six:
Be that 3% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(85%) and Al2O3(15%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 6;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.8 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.4 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.4 part of 2-hydroxyl-4-methoxy benzophenone, 0.25 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 2 parts of A6, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E6;
Embodiment seven:
Be that 3% vinyl silicane coupling agent is dissolved in the acetone soln of capacity with massfraction, add fully dry ZnO(90%) and Al
2O
3(10%), 55 ℃ of heating in water bath 3h, fully 100 ℃ of vacuum-drying 48h after the magnetic agitation can get heat conductive filler powders A 7;
In mass fraction, with the multipolymer (EVA) of 100 parts of ethene-vinyl acetates, 0.9 part of tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 0.4 part of γ-An Bingjisanyiyangjiguiwan homogenizer pre-mixing; 0.1 part of three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester, 0.3 part of 2-hydroxyl-4-methoxy benzophenone, 0.2 part of two (1,2,2,6,6-pentamethyl-piperidyl)-sebate are added in the above premixture, high-speed stirring mixes again; Add 4 parts of A7, stir again; The mixture that obtains is extruded through the twin screw extruder blend, and forcing machine production temperature is controlled at 80 ~ 95 ℃, by curtain coating, cooling, traction, winding process, obtains EVA film adhesive for solar cell package E7.
With the thermal conductivity of each glued membrane that obtains more than the measurement of thermal conductivity tester, as shown in table 1.
The thermal conductivity of table 1 embodiment sample and commercially available sample
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Commercially available 1 | Commercially available 2 |
| Thermal conductivity (W/m/K) | 0.54 | 0.62 | 0.61 | 0.75 | 0.58 | 0.71 | 0.66 | 0.32 | 0.40 |
Claims (2)
1. the preparation method of a filled-type solar cell packaging EVA heat conduction compound cutan is characterized in that comprising the steps:
(1) the multipolymer EVA with ethene-vinyl acetate is base material, and a certain amount of crosslinking and curing agent, coupling agent, oxidation inhibitor, ultraviolet absorbers, the steady agent of light and the pre-mixing in homogenizer of EVA particle is even;
(2) use the coupling agent treatment thermally conductive material, obtain the heat conductive filler powders A, it is added in the product of step (1), high-speed stirring is even, and is standby;
(3) product of step (2) being joined temperature is that blend is extruded in 80 ~ 95 ℃ of twin screw extruders, through operations such as casting film-forming, cooling, traction, rollings, obtains the purpose product;
Be benchmark in 100g EVA, the quality of crosslinking and curing agent, coupling agent, oxidation inhibitor, ultraviolet absorbers and the steady agent of light is respectively: 0.6 ~ 0.9 g, 0.25 ~ 0.4 g, 0.1 ~ 0.2 g, 0.2 ~ 0.4 g and 0.1 ~ 0.4 g; The quality of heat conductive filler powders A is 2 ~ 3 g;
VA content is 28% among the described EVA, and melting index is 30g/10min/190 ℃;
Described crosslinking and curing agent is tert-butyl hydroperoxide carbonic acid-2-ethylhexyl and 2,5-dimethyl-2, a kind of in two (butyl peroxy) ethane of 5-;
Described oxidation inhibitor is a kind of in β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid and three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid ester;
Described ultraviolet absorbers is a kind of in Octabenzone and the 2-hydroxyl-4-methoxy benzophenone;
The steady agent of described light is a kind of in two (1,2,2,6,6-pentamethyl-piperidyl)-sebates or two (2,2,6,6-tetramethyl--4-piperidines) sebate;
Described coupling agent is a kind of in γ-An Bingjisanyiyangjiguiwan and the vinyltriethoxysilane.
2. according to claim 1, it is characterized in that described thermally conductive material is ZnO and Al
2O
3Mixture, the preparation method of heat conductive filler powders A is: coupling agent is dissolved in the acetone soln of capacity, adds thermally conductive material, and in 55 ℃ of heating in water bath 3h, fully after the magnetic agitation in 100 ℃ of vacuum-drying 48h;
In 100 g heat conductive filler powders A, the quality of described coupling agent is 1.5 ~ 3 g, and the quality of described ZnO is 75 ~ 90 g, described Al
2O
3Quality be 10 ~ 25 g.
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Cited By (8)
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| CN105023963A (en) * | 2015-07-28 | 2015-11-04 | 宁波贝达新能源科技股份有限公司 | Silicon solar module |
| CN105140323A (en) * | 2015-07-28 | 2015-12-09 | 宁波贝达新能源科技股份有限公司 | Efficient silicon solar module |
| CN105778792A (en) * | 2016-04-07 | 2016-07-20 | 江苏省特种设备安全监督检验研究院 | EVA packaging adhesive film containing graphene and preparation method thereof |
| CN107286449A (en) * | 2017-05-18 | 2017-10-24 | 江苏东昇光伏科技有限公司 | A kind of EVA material used for solar batteries and preparation method thereof |
| CN107603515A (en) * | 2017-09-04 | 2018-01-19 | 常州斯威克光伏新材料有限公司 | A kind of eutectic refers to white EVA photovoltaics glued membrane |
| CN109337596A (en) * | 2018-08-17 | 2019-02-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the thermally conductive compound cutan of EVA |
| CN112409942A (en) * | 2020-11-19 | 2021-02-26 | 杭州福斯特应用材料股份有限公司 | Heat dissipation type packaging adhesive film and preparation method thereof |
| CN115491152A (en) * | 2022-10-10 | 2022-12-20 | 上海润势科技有限公司 | Heat-conducting packaging adhesive film and preparation method thereof |
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| CN105023963A (en) * | 2015-07-28 | 2015-11-04 | 宁波贝达新能源科技股份有限公司 | Silicon solar module |
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| CN105778792A (en) * | 2016-04-07 | 2016-07-20 | 江苏省特种设备安全监督检验研究院 | EVA packaging adhesive film containing graphene and preparation method thereof |
| CN107286449A (en) * | 2017-05-18 | 2017-10-24 | 江苏东昇光伏科技有限公司 | A kind of EVA material used for solar batteries and preparation method thereof |
| CN107603515A (en) * | 2017-09-04 | 2018-01-19 | 常州斯威克光伏新材料有限公司 | A kind of eutectic refers to white EVA photovoltaics glued membrane |
| CN109337596A (en) * | 2018-08-17 | 2019-02-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the thermally conductive compound cutan of EVA |
| CN112409942A (en) * | 2020-11-19 | 2021-02-26 | 杭州福斯特应用材料股份有限公司 | Heat dissipation type packaging adhesive film and preparation method thereof |
| CN112409942B (en) * | 2020-11-19 | 2022-05-31 | 杭州福斯特应用材料股份有限公司 | Heat dissipation type packaging adhesive film and preparation method thereof |
| CN115491152A (en) * | 2022-10-10 | 2022-12-20 | 上海润势科技有限公司 | Heat-conducting packaging adhesive film and preparation method thereof |
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Application publication date: 20131009 |