CN102250404B - Packaging material - Google Patents

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CN102250404B
CN102250404B CN 201010183077 CN201010183077A CN102250404B CN 102250404 B CN102250404 B CN 102250404B CN 201010183077 CN201010183077 CN 201010183077 CN 201010183077 A CN201010183077 A CN 201010183077A CN 102250404 B CN102250404 B CN 102250404B
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photoluminescence
packaged material
material according
vinyl acetate
ethylene
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关旻宗
李明家
王文献
邱国展
李宗铭
叶芳耀
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Industrial Technology Research Institute ITRI
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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
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    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention provides a packaging material, which comprises 80-99.5 percent by weight (wt%) of ethylene-vinyl acetate copolymer and 0.5-20 percent by weight (wt%) of photoluminescent high molecules, wherein the ethylene-vinyl acetate copolymer and the photoluminescent high molecules are uniformly mixed. The packaging material can be applied to packaging of a solar cell; the damage to the ethylene-vinyl acetate copolymer by ultraviolet ray is reduced; and the light utilization rate of the solar cell can also be improved.

Description

Packaged material
Technical field
The present invention relates to packaged material, the particularly application of this packaged material in the package module of solar cell.
Background technology
First solar cell in 1954 by U.S.'s Bell Laboratory (Bell Lab) manufacturing, in order to provide remote districts the communication system power supply.But its efficient too low (only having 6%) and cost too high (357 dollars/watt) therefore lack commercial value.For overcoming poor efficiency, expensive, and the shortcoming such as work-ing life is short, many researchists propose many solutions in succession for many years, but how can't solve associated problem fully.
In order to intercept air and aqueous vapor to the impact of solar cell, and reduce environment to the destruction of chip, to increase its industry applications, can adopt package module.Above-mentioned package module must have good anti-UV, heat-resisting cracking, and the characteristic such as fast setting, to accord with the demands of the market and to use.
In 1970, U.S. NASA laboratory adopted ethylene-vinyl acetate copolymer (EVA) resin and polyvinyl butyral acetal (PVB) resin as package module.The EVA resin has the advantages such as low cost and high transparent, therefore has been widely used in solar cell.But anti-UV and the thermotolerance of EVA resin are bad, are deteriorated and can't continue to protect solar cell in use for some time.For addressing the above problem, US 6093757, WO06093936, JP 2000183382, US 7368655, EA0001908, and the patent such as US 5447576 solution is proposed.Above-mentioned solution mainly focus on add the UV absorption agent with the anti-UV that improves the EVA resin, add thermo-stabilizer with the resistance to thermal decomposition that improves the EVA resin and/or add resin promotor such as superoxide makes EVA resin fast setting and can not form light acid.Though such scheme can solve the problem of packaged material, but still can't further promote light conversion efficiency.
In JP2001007377, further at glass substrate outside coating one deck fluorescence dye, so that ultraviolet ray is converted to visible light.The above-mentioned practice also can promote light conversion efficiency except reducing the impact of ultraviolet ray on packaged material.Yet the above-mentioned practice can't promote the thermotolerance of internal layer packaged material, and processing procedure is complicated.On the other hand, outermost fluorescence dye layer may need extra packaged material protection, and this will increase processing procedure and relevant cost.
In sum, need at present a kind of packaged material badly, except having long work-ing life, also ultraviolet ray can be converted to visible light to improve the efficient of solar cell.
Summary of the invention
The invention provides a kind of packaged material, comprise that 80 weight percents (wt%) are to the ethylene-vinyl acetate copolymer of 99.5 weight percents (wt%); And 0.5 weight percent (wt%) to the photoluminescence polymer of 20 weight percents (wt%); Therein ethylene-vinyl acetate copolymer evenly mixes with the photoluminescence polymer; Wherein the high molecular structure of this photoluminescence is as follows:
Figure GSA00000116212300021
Wherein, D is fluorophor; R 1, R 2, R 3, R 4Independent separately, R 1, R 2, R 3For hydrogen or optional contain substituent C 1-6Alkyl, R 4Contain substituent C for choosing wantonly 1-6Alkylidene group; M is the positive integer of 1-5; N is 10～10,000.
Description of drawings
Fig. 1 is in one embodiment of the invention, the synoptic diagram of solar cell package module.
Fig. 2 is in one embodiment of the invention, and end contains the high molecular excitation-emission collection of illustrative plates of photoluminescence of pyrenyl.
Fig. 3 is in one embodiment of the invention, and end contains the high molecular excitation-emission collection of illustrative plates of photoluminescence of naphthyl.
Nomenclature
10～solar cell package module;
11～packaged material;
13,15～substrate;
17～solar cell.
The embodiment of invention
The invention provides a kind of packaged material, comprise the ethylene-vinyl acetate copolymer (EVA) of 80～99.5 weight percents (wt%), and the photoluminescence polymer of 0.5～20 weight percent (wt%).If the part by weight of EVA too high (being that the high molecular part by weight of photoluminescence is excessively low) then can't be converted to visible light with the ultraviolet ray in the incident light effectively.If the part by weight of EVA excessively low (being that the high molecular part by weight of photoluminescence is too high) not only can't significantly increase ultraviolet turnover ratio, also can significantly promote cost.In one embodiment of this invention, the number-average molecular weight of EVA is between 5000～100000, and the mol ratio of the vinyl monomer among the EVA and Vinyl Acetate Monomer is between 60: 40～80: 20, and preferred ratio was between 65: 35～75: 25.If the molar ratio of vinyl monomer is too high, then can reduces the light transmission of EVA and follow property.If the molar ratio of Vinyl Acetate Monomer is too high, then can cause the water-absorbent of EVA too high.
Above-mentioned photoluminescence polymer evenly is mixed in the ethylene-vinyl acetate copolymer, can not be gathered into particle or be transferred to the mixture surface.For reaching mixed uniformly effect, the high molecular structure of photoluminescence is suc as formula 1:
In formula 1, D is the photoluminescence group; R 1, R 2, R 3, R 4Independent separately, R 1, R 2, R 3For hydrogen or optional contain substituent C 1-6Alkyl, R 4Contain substituent C for choosing wantonly 1-6Alkylidene group.M is the positive integer of 1-5, and n is 10～10,000.In formula 1, D is the photoluminescence gene, comprises for example pyrenyl (pyrene), anthryl (anthracene), naphthyl (naphthalene), flavones base (flavone), tonka bean camphor base (coumarin), perylene base (perylene), other photoluminescence group, the derivative of above-mentioned group or the combination of above-mentioned group.The effect of photoluminescence group D is to absorb the sunlight medium wavelength less than the ultraviolet ray of 400nm, and with visible light such as fluorescence or the phosphorescence of its conversion emit wavelength greater than 400nm.Thus, when surround lighting irradiation packaged material, except reducing the injury of ultraviolet ray to EVA, also can increase the efficiency of conversion of solar cell.
In formula l, the high molecular end of photoluminescence is photoluminescence group D, and its skeleton is polylactone, and its formation method is the ring-opening polymerization method.Be applicable to monomer of the present invention and can be caprolactone (caprolactone), valerolactone (valerolactone), butyrolactone (butyrolactone), propiolactone (propionolactone), lactic acid (lactic acid-) or second lactone (acetolactone), the carbon number of above-mentioned monomer will determine the size of m, and the substituting group of above-mentioned monomer will determine R 1With R 2Kind.The catalyzer of above-mentioned ring-opening polymerization can be stannous octoate (Sn (Oct) 2), and the part by weight of catalyzer and lactone will determine the high molecular polymerization degree n of photoluminescence (or molecular weight).In an embodiment of the present invention, the number-average molecular weight of photoluminescence polymer (Mn) is between 5,000 to 100,000.If the high molecular number-average molecular weight of photoluminescence is too high or too low, then can't evenly be mixed among the EVA.Reach than low haze in order to make packaged material have higher transmittance, the high molecular specific refractory power of photoluminescence is between 1.2 to 1.7.In order to make packaged material be easy to processing, the high molecular fusing point of above-mentioned photoluminescence is between 50 ℃ to 130 ℃.
Although the photoluminescence polymer in the above-mentioned packaged material can reduce ultraviolet ray to the infringement of EVA, but still ultraviolet ray can't be converted to visible light fully.For the life-span that increases packaged material and the processibility of improving encapsulation procedure, can further add additive such as resin promotor, thermo-stabilizer or above-mentioned being incorporated in the packaged material of 0.1～5 weight percent (wt%).Resin promotor is generally superoxide such as benzoyl peroxide, dicumyl peroxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane or above-mentioned combination.Above-mentioned resin promotor can produce free radical when being heated makes EVA crosslinked, and make originally thermoplastic packaged material becomes thermoset after encapsulation.Thus, the packaged material after the encapsulation will can because of thermally denature, can effectively not protect the assembly of its encapsulation such as solar cell not damaged by air or aqueous vapor.On the other hand, above-mentioned thermo-stabilizer such as butylated hydroxytoluene, sebacic acid two (2,2,6, the 6-tetrabutyl-4-piperidyl) ester or above-mentioned combination can be stablized EVA because of free radical or the light acid of being heated or the irradiation ultraviolet radiation scission of link produces, and avoid the acid of these free radicals or light to destroy solar module.
In an embodiment of the present invention, above-mentioned mixed packaged material 11 is formed at substrate 13 and 15 after, solar cell 17 is placed between the packaged material 11 of two plate bases 13 and 15, add hot pressing and namely form solar cell package module 10, as shown in Figure 1.Substrate 13 can be transparent material such as glass, plastics or resin.Substrate 15 can be reflective material such as metal.Solar cell 17 can be as main solar battery chip take silicon substrate.
Compare with known packaged material EVA, the present invention contains the high molecular mixture of photoluminescence can be converted to visible light with ultraviolet ray, not only can promote the light utilization efficiency of the solar cell of its encapsulation, can also reduce ultraviolet damage EVA and increases assembly life-span.On the other hand, the present invention grafts to the photoluminescence group can be terminal with the mixed uniformly polylactone of EVA, rather than with the direct blending of photoluminescence small molecules in EVA.Via experiment showed, that other polymer such as polystyrene can't evenly be mixed among the EVA, the transparence that this can increase the mist degree of mixture and reduce mixture.In addition, if the photoluminescence small molecules is blended directly among the EVA, because the photoluminescence small molecules can't be dissolved in the EVA resin and can only have the EVA resin by dispersing mode, will make small molecules assemble (aggregate) even shift (migrate) to the mixture surface, on the contrary deteriorated packaged material character and reduce assembly life-span.
For above and other objects of the present invention, feature and advantage can be become apparent, below enumerate a plurality of embodiment and also be described in detail below by reference to the accompanying drawings.
Embodiment
Embodiment 1
Get 80,90,98, and the ethylene-vinyl acetate copolymer (DupontD150 of 99 weight percents (wt%), VA content:32%) respectively with 20,10,2, and the polycaprolactone (source is shown in preparation example 1B) of 1 weight percent (wt%) with toluene (Tedia, 99%) mixes as solvent, afterwards by rotary coating (Spin coating) on glass make film after, it is as shown in table 1 to survey respectively its mist degree and transmissivity.As shown in Table 1, even the consumption of polycaprolactone is promoted to 10wt%, film still has high-transmission rate and low haze, and the expression polycaprolactone can effectively be dispersed in the ethylene-vinyl acetate copolymer.
Table 1
Embodiment 1a Embodiment 1b Embodiment 1c Embodiment 1d
The EVA weight ratio 99 98 90 80
The PCL weight ratio 1 2 10 20
Transmissivity (%) 91.29 91.81 91.74 91.14
Mist degree (%) 1.28 0.82 0.86 0.36
Comparative example 1
Get 90,98, and the ethylene-vinyl acetate copolymer (DupontD150) of 99 weight percents (wt%) respectively with 10,2, and the polystyrene (Acros MW=250000) of 1 weight percent (wt%) mix, by rotary coating (spin coating) on glass make film after, it is as shown in table 2 to survey respectively its mist degree and transmissivity.As shown in Table 2, when the consumption of polystyrene is promoted to 10wt%, the mist degree of film will significantly improve, and the expression polystyrene can't effectively be dispersed in the ethylene-vinyl acetate copolymer.
Embodiment 1 and comparative example 1 are compared as can be known, are not that all polymers all can as polylactone, can effectively be scattered in the ethylene-vinyl acetate copolymer.Based on above-mentioned comparison, the present invention will adopt polylactone as the high molecular skeleton of photoluminescence, and further grafting photoluminescence group.
Table 2
Comparative example 1a Comparative example 1b Comparative example 1c
The EVA weight ratio 99 98 90
The PS weight ratio 1 2 10
Transmissivity (%) 91.27 91.02 91.55
Mist degree (%) 2.5 2.82 9.5
Preparation example 1A
Get the 1-pyrenyl butanols (1-pyrenebutanol of 0.09g, Aldrich), the stannous octoate (Aldrich) of the caprolactone of 18g (Tokyo changes into TCI purity 98%) and 0.1g is dissolved in 20mL toluene (Tedia, 99%) in, be heated to 130 ℃ and carry out ring-opening polymerization 8 hours suc as formula 2, namely form 7g photoluminescence polymer (productive rate 70%), recording its number-average molecular weight by GPC is 8139, its fusing point is between 55 ℃ to 60 ℃, its specific refractory power is between 1.52 to 1.48, and its film absorption spectrum and fluorescence emission spectrum take centre wavelength 340nm as the excitation light source gained are as shown in Figure 2.
Preparation example 1B
Getting the caprolactone (TCI) of 18g and the stannous octoate (Aldrich) of 0.1g is dissolved in the 20mL toluene, being heated to 130 ℃ carries out ring-opening polymerization and namely formed 15g polycaprolactone polymer (productive rate 83%) in 8 hours, recording its number-average molecular weight by GPC is 8500, and its fusing point is between 55 ℃ to 60 ℃.
Preparation example 2
Getting the naphthyl derivatives (structure is suc as formula shown in the compd B in 3) of 0.1g, the caprolactone of 10g and the stannous octoate of 0.1g is dissolved in the 20mL toluene, be heated to 130 ℃ and carry out ring-opening polymerization 8 hours suc as formula 3, namely form 6.5g photoluminescence polymer (productive rate 65%), recording its number-average molecular weight by GPC is 7140, its fusing point is between 55 ℃ to 60 ℃, its specific refractory power is between 1.51 to 1.48, and its film absorption spectrum and fluorescence emission spectrum take centre wavelength 340nm as the excitation light source gained are as shown in Figure 3.
Figure GSA00000116212300071
Embodiment 2
Weight percent according to table 3, get respectively 90,98, and the ethylene-vinyl acetate copolymer (Dupont D150) of 99 weight percents (wt%) and respectively with after the product of 10,2 and 1 weight percent (wt%) preparation example 1A Chinese style 2 is dissolved in toluene and mixes, rotary coating (spin coating) is at the film of making on glass, then, it is as shown in table 3 to survey respectively its mist degree and transmissivity.As shown in Table 3, even the product consumption of preparation example 1A Chinese style 2 is promoted to 10wt%, film still has high-transmission rate and low haze, and the product of expression preparation example 1A Chinese style 2 can effectively be scattered in the ethylene-vinyl acetate copolymer.
Table 3
Comparative example 2a Comparative example 2b Comparative example 2c
The EVA weight ratio 99 98 90
The weight ratio of formula 2 products 1 2 10
Transmissivity (%) 91.34 91.71 91.63
Mist degree (%) 0.81 0.81 0.51
Comparative example 2
The ethylene-vinyl acetate copolymer (Dupont D150) of getting 90 weight percents (wt%) mixes with the 3-hydroxyflavone (Aldrich 3-Hydroxyflavone) of 10 weight percents (wt%), rotary coating (spin coating) on glass make film after, it is as shown in table 4 to survey respectively its mist degree and transmissivity.By table 3 (embodiment 2c) and table 4 (comparative example 2) as can be known, even 3-hydroxyflavone is identical with the consumption of formula 2 products, micromolecular 3-hydroxyflavone still can't be scattered among the ethylene-vinyl acetate copolymer suc as formula the product in 2 is equally effective.Thus, the film that contains fluorescent small molecule will significantly atomize and not be suitable for the encapsulation solar cell.
Table 4
Comparative example 2
The EVA weight ratio 90
3-hydroxyl brass weight ratio 10
Transmissivity (%) 91.25
Mist degree (%) 4
Embodiment 3 (solar cell prepares and module package with encapsulating film)
Get EVA resin micelle 90 grams and restrain (suc as formula 2) first with single screw mixing machine (star's metal Co., Ltd. with photoluminescence polymer 10, L/D is than 20) under 80 ℃, carry out blend, get afterwards 50 g of resins through mixing and carry out the pressing film forming with pressing machine, obtain the encapsulating film of 200mm * 200mm * 0.65mm.Get in addition the MCLA2D encapsulating film as a comparison of allocating voluntarily in EVA encapsulating film (available from Mitsui) and laboratory, its thickness is 0.6mm～1mm.The resin promotor of containing EVA (available from Dupont) Yu the 3.95g of 100g in the composition of MCLA2D, and resin promotor comprises the Octabenzone (available from Acros) of 0.6g, the sebacic acid two (2 of 0.6g, 2,6, the 6-tetrabutyl-4-piperidines) 2 of ester (available from Acros), 0.8g, 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane (available from ACROS), and the triallyl isocyanate (available from Acros) of 1.95g.
Get above-mentioned packaged material (as Fig. 1 11) be formed at substrate (as Fig. 1 13 and 15) upper after, with solar module (as Fig. 1 17) place vacuum pressing device to add hot pressing, to finish the encapsulating structure module.Solar module after the above-mentioned encapsulation is carried out circuit measuring with it, and it is as shown in table 5 to measure its assembly property.
Table 5
Figure GSA00000116212300091
As shown in Table 5, mix the photoluminescence polymer of EVA except can increasing its transparence, also can further promote light conversion efficiency.
Although the present invention discloses several preferred embodiments as above; but these embodiment limit the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; all can do to change arbitrarily and retouching, so protection scope of the present invention should be as the criterion with the scope that appending claims defines.

Claims (12)

1. packaged material comprises:
The ethylene-vinyl acetate copolymer of 80～99.5 % by weight; And
0.5 the photoluminescence polymer of～20 % by weight;
Wherein, this ethylene-vinyl acetate copolymer evenly mixes with this photoluminescence polymer;
Wherein the high molecular structure of this photoluminescence is as follows:
Wherein D is the photoluminescence group;
R 1, R 2, R 3, R 4Independent separately, R 1And R 2Be hydrogen, and R 3For hydrogen or optional contain substituent C 1-6Alkyl, R 4Contain substituent C for choosing wantonly 1-6Alkylidene group;
M is positive integer 1-5; And
N is 10～10,000,
Wherein, this photoluminescence group is pyrenyl, anthryl, naphthyl, flavones base, tonka bean camphor Ji, perylene base, the derivative of above-mentioned group or the combination of above-mentioned group.
2. packaged material according to claim 1, wherein, the number-average molecular weight of this ethylene-vinyl acetate copolymer is 5000～100000.
3. packaged material according to claim 1, wherein, the high molecular photoluminescence group of this photoluminescence absorbing wavelength is less than the ultraviolet ray of 400nm, and transmitted wave is grown up in the visible light of 400nm; Wherein this visible light is comprised of fluorescence (Fluorescence) or phosphorescence (Phosphorescence).
4. packaged material according to claim 1, wherein, the high molecular number-average molecular weight of this photoluminescence is 5000～100000.
5. packaged material according to claim 1, wherein, the high molecular specific refractory power of this photoluminescence is 1.2～1.7.
6. packaged material according to claim 1, wherein, the high molecular fusing point of this photoluminescence is 50 ℃～130 ℃.
7. packaged material according to claim 1, wherein, in this ethylene-vinyl acetate copolymer, the mol ratio of vinyl monomer and Vinyl Acetate Monomer is 60: 40～80: 20.
8. packaged material according to claim 1 wherein also comprises the additive of 0.1～5 % by weight.
9. packaged material according to claim 8, wherein, this additive comprises resin promotor, thermo-stabilizer or above-mentioned combination.
10. packaged material according to claim 9, wherein, this resin promotor comprises benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane or above-mentioned combination.
11. packaged material according to claim 9, wherein, this thermo-stabilizer comprises butylated hydroxytoluene, sebacic acid two (2,2,6, the 6-tetrabutyl-4-piperidyl) ester or above-mentioned combination.
12. packaged material according to claim 1, it is used for the encapsulation solar cell.
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CN103872162B (en) * 2014-03-18 2017-04-12 连云港神舟新能源有限公司 Low-working-temperature solar cell module
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