KR101630011B1 - Protecting film for solar cell and solar cell comprising the same - Google Patents
Protecting film for solar cell and solar cell comprising the same Download PDFInfo
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Abstract
The present invention provides a solar cell comprising a barrier film and a fluorine-based polymer layer, wherein the barrier film comprises at least one of a substrate layer and an organic-inorganic hybrid layer and an inorganic barrier layer formed on one surface of the substrate layer.
The protective film for a solar cell according to the present invention can prevent degradation of the efficiency of the solar cell module due to penetration of oxygen and water vapor into the barrier film and prevent degradation of the protective film by ultraviolet rays, Can be remarkably improved.
Description
A protective film for a solar cell and a solar cell including the same.
Recently, photovoltaic power generation using solar cells has attracted attention as a next-generation energy industry. Particularly, the energy source is clean, does not generate carbon dioxide generated when coal or petroleum is used, is very suitable for prevention of global warming, and has high utility value as an environmentally friendly alternative energy source.
Generally, a solar cell is manufactured from a semiconductor material that exhibits the effect of a plasma that emits electrons when the light is illuminated. When light is projected onto the semiconductor material, electrons with negative charge and holes with positive charge are generated, and electrons move to the cathode and holes move to the anode due to the difference in potential or charge. Solar cells are the devices that make electricity using electrons and holes that are gathered in the cathode and the anode.
In recent years, solar cells are mainly manufactured by appropriately combining monocrystalline silicon, polycrystalline silicon, and amorphous silicon thin film. By doing so, we are developing and commercializing solar cells with thinner solar cell thickness and higher efficiency.
The solar cell is installed in an external facility where the sun is directly lowered, such as an outer wall of a building or a roof, and the efficiency of the solar cell is increased. As a protective film for protecting the solar cell module due to exposure to such external environment for a long time, , Glass substrates having various advantages such as excellent gas barrier property, high light transmittance, high flatness, excellent heat resistance and chemical resistance were used.
However, since the glass substrate is weak against impact, it is easily broken, and the density is high, which is a serious disadvantage. Therefore, research is underway to replace the glass substrate with a plastic substrate.
When the glass substrate used as the solar cell protective film is replaced with a plastic substrate, the entire weight of the solar cell module can be lightened, design flexibility can be given, Lt; / RTI >
On the other hand, in order to use a plastic substrate as a protective film for a solar cell, the plastic substrate must have oxygen and water vapor barrier properties to prevent aging of the solar cell module, ultraviolet stability, a small linear expansion coefficient High dimensional stability, compatibility with process equipment used in conventional glass substrates, high mechanical strength, chemical resistance or high light transmittance that can withstand the etching process, small birefringence, and scratch resistance of the surface. In particular, oxygen and water vapor barrier properties and ultraviolet stability are required.
It is an object of the present invention to provide a protective film for a solar cell and a solar cell including the same, which can remarkably improve the efficiency and lifetime of the solar cell module.
The present invention provides a solar cell comprising a barrier film and a fluorine-based polymer layer, wherein the barrier film comprises at least one of a substrate layer and an organic-inorganic hybrid layer and an inorganic barrier layer formed on one surface of the substrate layer.
The protective film for a solar cell according to the present invention can prevent degradation of the efficiency of the solar cell module due to penetration of oxygen and water vapor into the barrier film and prevent degradation of the protective film by ultraviolet rays, Can be remarkably improved.
FIG. 1 shows an example of a protective film for a solar cell according to the present invention.
2A shows a structure of a solar cell element in which a barrier layer is laminated on a top surface of a base layer.
2B is a structure of a solar cell element in which a barrier layer is laminated on the lower surface of the base layer.
FIGS. 3 and 4 each show an example of a structure of a solar cell device according to the present invention.
FIG. 5 is a graph of light transmittance of the structures of FIGS. 2A and 2B. FIG.
FIG. 6 is a graph of light transmittance according to whether the polyester (PET) film and the fluorine (FEP) film are subjected to light transmittance and UV treatment.
The present invention relates to a protective film for a solar cell comprising a barrier film and a fluorine-based polymer layer, wherein the barrier film comprises at least one of a substrate layer, an organic-inorganic hybrid layer formed on one surface of the substrate layer, .
The protective film for a solar cell according to the present invention can form at least one of an organic-inorganic hybrid layer and an inorganic barrier layer on the upper surface of a substrate layer, Can be realized.
The barrier film may include a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, and an organic-inorganic hybrid layer formed on an upper surface of a substrate layer are sequentially laminated. When the inorganic barrier layer is laminated on the upper surface of the organic-inorganic hybrid layer, the inorganic barrier layer can be laminated on the planarized surface, and the adhesion between the inorganic barrier layer and the organic-inorganic hybrid layer is excellent, do. Further, when the organic-inorganic hybrid layer is further laminated on the upper surface of the inorganic barrier layer, the inorganic barrier layer can be protected from external physical contact or the inorganic barrier layer can be compensated for, thereby further improving the gas barrier property. Furthermore, since the modulus of the inorganic barrier layer itself is high and the linear expansion coefficient is small, the mechanical properties of the entire barrier layer can be improved.
The protective film for a solar cell may include an adhesive layer formed between the barrier film and the fluorine-based polymer layer. The adhesive layer may be used for bonding a barrier film of a multilayer structure and a fluoropolymer film. Specific examples of the adhesive layer include at least one of ethylene vinyl acetate (EVA), polyvinyl butyral (PVB) and polybenzimidazole May be used, but is not limited thereto.
The adhesive layer may be dissolved in a solvent to prepare a coating solution, and then the film may be formed into a film and laminated on the base layer. In some cases, it may be coated on a substrate without a separate adhesive layer.
There may be two-roll reverse coating, three-roll reverse coating, flow coating, gravure coating, microgravure coating, die coating, curtain coating, bar coating, dip coating and the like as non-limiting examples of the coating method.
The base layer may include at least one of a single polymer, two or more polymer blends, and a polymer composite material containing an organic or inorganic additive. Examples of the polymer forming the substrate layer include polymers such as polynorbornene, aromatic fluorene polyester, polyethersulfone, bisphenol A polyolsulfone, polyimide, polyethylene terephthalate, polyethylene naphthalene, polyarylate, polycarbonate and cyclic olefin copolymer May be used.
The base layer may be a structure in which a nanomaterial is dispersed in a polymer. Such polymer composites include polymer-clay nanocomposites, because of the small particle size of the clay (<1 micron) and large aspect ratios, resulting in a smaller amount of polymeric clay than conventional composites such as glass fibers Physical properties such as mechanical properties, heat resistance, gas barrier properties and dimensional stability can be improved. That is, in order to improve the physical properties, it is important that the clay layer of the layered structure is peeled off and dispersed well in the polymer matrix. The polymer-clay composite satisfies this requirement.
The polymer and the clay that can be used in the polymer-clay composite are not particularly limited. In one embodiment, the polymer is selected from the group consisting of polystyrene, polymethacrylate, polyethylene terephthalate, polyethylene naphthalene, polyarylate, polycarbonate, cyclic olefin copolymer, polynorbornene, aromatic fluorene polyester, A polyimide, an epoxy resin, and a polyfunctional acrylate. The clay may also include at least one of laponite, montmorillonite, saponite hortolite, bastelite, bentonite, nontronite, vermiculite, ilite, muscovite, mica and fluorinated mica.
The thickness of the base layer is not particularly limited and may be, for example, in the form of a film or a sheet having a thickness of 10 to 2000 mu m, 50 to 1500 mu m, or 100 to 1000 mu m. The base layer may be prepared by a solution casting method or a film extrusion process, and it is preferable to anneal for several seconds to several minutes in the vicinity of the glass transition temperature in order to minimize deformation after the production. After the annealing, the surface of the plastic film is coated with a primer or a plasma treatment using corona, argon, oxygen, nitrogen or carbon dioxide, an ultraviolet-ozone treatment, or an ion beam treatment method in which a reactive gas is introduced, Processing can be performed.
The barrier film may include a base layer, an organic-inorganic hybrid layer, and an inorganic barrier layer, and is not particularly limited as long as it can block oxygen or moisture from the outside. Further, it may be prepared from a composition further comprising an appropriate filler, a solvent and a polymerization catalyst, as the case may be.
In one embodiment, the organic-inorganic hybrid layer may be a partial hydrolyzate of a composition comprising an organosilane and a metal alkoxide.
Further, it may be prepared from a composition further comprising an appropriate filler, a solvent and a polymerization catalyst, as the case may be.
The organosilane may be at least one compound selected from compounds represented by the following formulas (1) to (3). When one kind of organosilane compound is used, crosslinking is preferable.
[Chemical Formula 1]
(R 1 ) m -Si-X ( 4-m )
(2)
(R 1 ) m -O-Si-X ( 4-m )
(3)
(R 1 ) m -HR 2 -Si-X ( 4-m )
In the above Formulas 1 to 3,
R 1 is an alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl, halogen, amino, amide, aldehyde, ketone, An alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, a sulfonic acid group, a phosphoric acid group, an acryloxy group, a methacryloxy group, an epoxy group or a vinyl group,
R 2 is hydrogen or alkyl having 1 to 12 carbon atoms,
X is hydrogen, halogen, alkoxy of 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl or -N (R 3 ) 2 ,
R 3 is hydrogen or alkyl having 1 to 12 carbon atoms,
m is an integer of 1 to 3;
Examples of the organosilane include, but are not limited to, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, Phenyldiethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane , Triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, di Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimoxysilane, n- (2-aminoethyl) Methoxy silane, 3-amine phosphine 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
The metal alkoxide may be at least one selected from the compounds represented by the following general formula (4).
[Chemical Formula 4]
M- (R 4 ) z
In Formula 4,
M is at least one of aluminum, zirconium and titanium,
R 4 is halogen, alkyl having 1 to 12 carbon atoms, alkoxy, acyloxy or hydroxyl group,
and z is an integer of 3 or 4.
In the organic-inorganic hybrid layer, the content of the organosilane may be 20 to 99.99 parts by weight, 50 to 99 parts by weight, or 70 to 99 parts by weight based on the total weight of the composition for producing the organic-inorganic hybrid layer. The content of the metal alkoxide may be 0.01 to 80 parts by weight, 0.01 to 70 parts by weight, or 20 to 70 parts by weight based on the total weight of the composition for producing the organic-inorganic hybrid layer.
The amount of the filler, solvent and catalyst to be added to the organic-inorganic hybrid layer is not particularly limited, as it is added as needed. The filler may be selected from the group consisting of metal, glass powder, diamond powder, silicon oxide, clay, calcium phosphate, magnesium phosphaf, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, Silicate, and the like. As the solvent, a solvent used for a conventional partial hydrolysis reaction may be used. For example, distilled water may be used. Also, the catalyst is not particularly limited, and for example, aluminum butoxide and / or zirconium propoxide may be used.
Wherein the inorganic barrier layer is made of a material selected from the group consisting of SiO x wherein x is an integer of 1 to 3, SiO x N y wherein x and y are each an integer of 1 to 3, Al 2 O 3 , TiO 2 , SnO 2, and ITO And at least one kind of inorganic substance.
A method of forming the inorganic barrier layer constituting the barrier film can be formed by coating a transparent inorganic material having a high density or a thin metal film of a nanometer unit on the upper surface of the organic-inorganic hybrid layer by physical or chemical methods. As the deposition coating method, a sputtering method, a chemical vapor deposition method, an ion plating method, an atomic layer deposition method, a plasma chemical vapor deposition method, a sol-gel method and the like can be used. The thickness of the formed inorganic barrier layer may be 5 to 1000 nm, 5 to 500 nm, 20 to 500 nm, or 50 to 200 nm.
The inorganic barrier layer may further include a filler, a solvent, a catalyst and the like, if necessary. The amount of the filler, the solvent, the catalyst, and the like is not particularly limited, as it is added as needed.
In one embodiment, the fillers include metal, glass powder, diamond powder, silicon oxide, clay, calcium phosphate, magnesium phosphaf, , Barium hydroxide, and aluminum silicate may be used.
As the solvent, a solvent used in a conventional partial hydrolysis reaction may be used. For example, distilled water may be used. The catalyst is also not particularly limited, but aluminum butoxide or zirconium propoxide may be used.
The fluorine-based polymer layer includes a fluorine-containing copolymer, and the fluorine-containing copolymer includes a monomer containing a fluorine atom; And a copolymer of a monomer containing a hydroxyl group or an epoxy group.
The fluorine-based compound for producing the fluorine-based polymer layer may include a fluorine-containing copolymer. The fluorine-containing copolymer includes a monomer containing a fluorine atom; And a monomer containing a hydroxyl group or an epoxy group, and may be produced by adding an ethylenically unsaturated monomer, if necessary, but is not limited thereto.
Examples of the fluorine atom-containing monomer include tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, volatile alkyl vinyl ether, fluoroalkoxy alkyl vinyl ether, Ether, perfluoro alkoxyvinyl ether, and fluorine-containing methacrylic ester, or a combination thereof.
Examples of the monomer containing a hydroxyl group or an epoxy group include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyethyl aryl ether, hydroxybutylaryl Ether, glycerol monoallyl ether, allyl alcohol, and hydroxyethyl methacrylate, or a combination of two or more thereof.
The content of the fluorine-containing compound may be 0.5 to 10 parts by weight, or 0.5 to 5 parts by weight, based on the total weight of the fluoropolymer layer-forming composition.
The fluorine-based polymer layer may be prepared by dissolving a fluorine-based compound in a solvent to prepare a fluorine coating solution, and then the film may be formed into a film form and laminated on the adhesive layer.
In the fluorine coating solution, the solvent may be selected from the group consisting of perfluoro pentane, perfluoro hexane, perfluorocarbons such as perfluoro octane, methyl nonafluoroisobutyl ether, methyl Perfluoropolyethers such as methyl nonafluorobutyl ether and the like, 1-chloro-1,2,2-trifluorocyclobutane, 1-chloro-2,3, 4-trifluorobenzene, chlorofluorobenzene, and dichlorofluorobenzene. However, the fluorinated solvents may be used alone or in combination of two or more. have.
In one embodiment of the present invention, the protective film for a solar cell may include at least one of a UV stabilizer and an ultraviolet absorber. For example, one or more of a UV stabilizer and an ultraviolet absorber may be contained in at least one of the base layer, the organic-inorganic hybrid layer and the inorganic barrier layer constituting the barrier film. Alternatively, one or more of an ultraviolet stabilizer and an ultraviolet absorber may be contained in the adhesive layer or the fluoropolymer layer in the protective film for the solar cell. In some cases, the barrier film may further include a separate coating layer formed on one or both sides of the barrier film, and the coating layer may include at least one of a UV stabilizer and an ultraviolet absorber.
The ultraviolet stabilizer may be when the maximum absorption peak is in the range of 340 to 430 nm, 340 to 400 nm, or 360 to 400 nm. When the maximum absorption peak of the ultraviolet stabilizer is present within the above wavelength range, it is possible to prevent the ultraviolet absorbing ability from being lowered, to realize a high visible light transmittance and an excellent color.
The ultraviolet stabilizer may further include a radical scavenger (HALS) compound.
The radical scavenger may include a structure represented by the following formula (a).
(A)
In the above formula (a)
R 5 is CH 2 ,
n is from 1 to 16,
R 6 is hydrogen; A halogen atom, a cyano group or an alkyl group having 1 to 16 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an aryl group having 6 to 20 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an alkoxy group having 1 to 16 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an aryloxy group having 6 to 20 carbon atoms in which a nitro group is substituted or unsubstituted.
In the case of the radical scavenger represented by the above formula (a), the ultraviolet absorber has an ultraviolet ray absorbing ability mainly at 340 nm or less, and the ultraviolet absorber has a synergistic effect with the ultraviolet absorber.
The ultraviolet absorber disperses excited electron energy by ultraviolet absorption into heat energy, stabilizes it, and terminates free radicals. In addition, it can be used in combination with a radical scavenger which has the function of removing radicals to stop photooxidation and decompose peroxides.
The ultraviolet absorber may include a structure of the following formulas (b) to (c).
[Formula b]
(C)
In the above formula (b)
R < 7 > and R < 10 > are independently hydrogen; A hydroxy group; halogen; A halogen atom, a cyano group or an alkyl group having 1 to 16 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an aryl group having 6 to 20 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an alkoxy group having 1 to 16 carbon atoms in which a nitro group is substituted or unsubstituted; Or an aryloxy group having 6 to 20 carbon atoms in which a halogen, cyano group or nitro group is substituted or unsubstituted,
In the above formula (c)
Z is hydrogen or a chlorine substituent,
R 11 and R 12 are independently hydrogen; halogen; An alkyl group having 1 to 16 carbon atoms in which a halogen atom, a halogen atom, a cyano group or a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an aryl group having 6 to 20 carbon atoms in which a nitro group is substituted or unsubstituted; A halogen atom, a cyano group or an alkoxy group having 1 to 16 carbon atoms in which a nitro group is substituted or unsubstituted; Or an aryloxy group having 6 to 20 carbon atoms in which a halogen, cyano group or nitro group is substituted or unsubstituted.
For example, the compound of formula (b) may have the structure of formula (b-1).
[Formula b-1]
For example, the compound of formula (c) may have the structure of formula (c-1) or (c-2)
[Formula c-1]
[Formula c-2]
As one example, LA 67 (manufactured by Adeka Co.) or the like can be used as the ultraviolet stabilizer. Examples of the ultraviolet absorber include Tinuvin 1577, 2- (4,6-Diphenyl-1,3,5-triazin-2-yl) -5- [(hexyl) oxy] -phenol, (Tinuvin 326, 2-2-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole) and Tinuvin 328 hydroxyphenyl) benzotriazole (manufactured by Ciba-Geigy) may be used alone or in combination. In addition, a variety of commercially available UV stabilizers and absorbents may be used.
The content of the ultraviolet absorber and the stabilizer may be 0.01 to 50 parts by weight based on 100 parts by weight of each film to which the ultraviolet absorber and / or stabilizer is added. The above content range can prevent the ultraviolet absorber and / or the stabilizer from exhibiting an effective effect and at the same time absorbing absorption in the visible region and affecting optical characteristics. For example, when the ultraviolet absorber and / or stabilizer is added to the pressure-sensitive adhesive layer, if the content is too high, the physical properties of the pressure-sensitive adhesive may be affected.
The bonding method of each layer constituting the protective film may be performed by a pressure-sensitive adhesive having the same composition as that of the pressure-sensitive adhesive layer described above, or a thermal bonding method, but is not limited thereto. In this case, when the pressure-sensitive adhesive is used, the content thereof is not particularly limited, but the thickness of the pressure-sensitive adhesive layer formed may be in the range of 0.1 to 75 탆, 0.5 to 50 탆, 0.1 to 30 탆, or 0.5 to 30 탆.
The present invention also provides a solar cell comprising the protective film for a solar cell.
In the solar cell according to the present invention, the space around the solar cell arranged in series or in parallel is filled with a filler composed of a thermosetting plastic (ethylene vinyl acetate copolymer), and the protective film for a solar cell according to the present invention And the back surface is protected by the back sheet. However, the present invention is not limited thereto.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. This is for the purpose of illustration only and is not intended to limit the scope of the invention.
1 is a schematic view showing a laminated structure of a protective film for a solar cell according to an embodiment of the present invention.
1, the
Hereinafter, the present invention will be described in more detail by way of examples. The embodiments of the present invention are only for the detailed description of the present invention and are not intended to limit the scope of the present invention.
Example One
A barrier film, an adhesive layer, and a fluorine-based polymer layer.
Specifically, the barrier film has a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, and an organic-inorganic hybrid layer are sequentially laminated on the upper surface of the substrate layer. Specifically, the barrier film includes a substrate layer using a polyester (PET) film having a thickness of 50 占 퐉; An organic-inorganic hybrid layer using a partial hydrolyzate of a composition comprising an organosilane of Formula 5 and a metal alkoxide of Formula 6; And it was prepared using an inorganic barrier layer containing SiO 2.
[Chemical Formula 5]
(R 1 ) 2 -Si-X 2
In Formula (5), R 1 is an alkyl group having 6 carbon atoms, X is an alkoxy group having 6 carbon atoms, and m is an integer of 1 to 3.
[Chemical Formula 6]
Al- (R 4 ) 3
In Formula (6), R 4 is an alkyl group having 6 carbon atoms.
A pressure-sensitive adhesive layer comprising ethylene vinyl acetate (EVA) is laminated on the barrier film, and a fluorine-based polymer layer containing a copolymer of tetrafluoroethylene monomer and hydroxyethyl vinyl ether is adhered thereon to protect A film was prepared.
Further, an adhesive layer containing ethylene vinyl acetate was laminated on the lower surface of the above-prepared protective film to prepare a module with a solar cell element as shown in FIG. 2A.
Example 2
A barrier film, an adhesive layer, and a fluorine-based polymer layer.
Specifically, the barrier film has a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, and an organic-inorganic hybrid layer are sequentially laminated on the lower surface of the substrate layer. Specifically, the barrier film includes a substrate layer using a polyester (PET) film having a thickness of 50 占 퐉; An organic-inorganic hybrid layer using a partial hydrolyzate of a composition comprising an organosilane of Formula 5 and a metal alkoxide of Formula 6; And it was prepared using an inorganic barrier layer containing SiO 2.
A pressure-sensitive adhesive layer comprising ethylene vinyl acetate (EVA) is laminated on the upper surface of the barrier film, and a fluorine-based polymer layer containing a copolymer of tetrafluoroethylene monomer and hydroxyethyl vinyl ether is adhered thereon A protective film was prepared.
In addition, an adhesive layer containing ethylene vinyl acetate was laminated on the lower surface of the above-prepared protective film to prepare a module with a solar cell element as shown in FIG. 2B.
Example 3
A module with a solar cell element was fabricated in the same manner as in Example 1 except that the structure of the barrier film was changed.
Specifically, the structure of the barrier film was formed as shown in FIG. 3 in such a structure that an organic-inorganic hybrid layer and an inorganic barrier layer were sequentially laminated on the upper surface of the substrate layer.
Example 4
A module with a solar cell element was fabricated in the same manner as in Example 1 except that the structure of the barrier film was changed.
Specifically, the structure of the barrier film is formed as shown in FIG. 4 by forming a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, an organic-inorganic hybrid layer and an inorganic barrier layer are sequentially laminated on the upper surface of the base layer.
Experimental Example 1: Evaluation of water resistance and adhesiveness of protective film for solar cell
The solar cell elements with the protective films prepared in Examples 1 and 2 were contacted with water at 120 ° C for 96 hours. Thereafter, the state of adhesion between the solar cell element and the protective film was observed.
As a result, no delamination occurred inside the protective film. Thus, it was confirmed that the protective film for a solar cell according to the present invention is excellent in water resistance and adhesion.
Experimental Example 2: For protective film for solar cell Light transmittance evaluation
The solar cell elements with the protective films prepared in Example 1 and Example 2 were treated in water at 120 ° C for 96 hours and then peeled off only the protective film and the light transmission characteristics were compared using a UV3600 spectrometer of Shimadzu Corporation . The results are shown in Fig.
Referring to FIG. 5, it can be seen that the protective film of Example 1 exhibits a light transmittance of 70% or more in the visible light region. The light transmittance was improved by about 10% as compared with the protective film of Example 2.
Experimental Example 3: Fluorine The polymer layer Light resistance evaluation
The light resistance of the polyester film and the fluoropolymer layer was compared and evaluated. The fluorine-based polymer layer used was a fluorinated ethylene copolymer (FEP, Flourinated Ethylene Propylene Copolymer).
The thicknesses of the polyester film and the fluorine-based polymer layer were respectively 50 탆, and the experiment was divided into the case of treating ultraviolet ray and the case of not treating ultraviolet ray as shown in Table 1 below. The ultraviolet treatment was carried out by using a UV3600 spectrophotometer of Shimadzu Co. for UV treatment (Quick UV treatment, QUV) on the film at 0.6 W / m 2 and 60 ° C for 100 hours. The results of the measurement of the light transmittance are shown in Fig.
Referring to FIG. 6, there was no change in the light transmittance of the tetrafluoroethylene-hexafluoropropylene copolymer (FEP) used as the fluoropolymer layer when exposed to ultraviolet light. However, it was found that the light transmittance of the polyester film was lowered at 320 to 400 nm, which is the wavelength of ultraviolet ray A. In addition, it was found that the fluorine-based polymer layer had a relatively excellent light transmittance over the entire wavelength range.
As a result, it was found that the protective film according to the present invention did not deteriorate the efficiency by ultraviolet rays and was excellent in durability.
Experimental Example 4: Solar cell efficiency evaluation
The efficiency of the solar cell including the protective film prepared in Example 1 and Example 2 was evaluated. Specifically, the photovoltaic devices with the protective films prepared in Examples 1 and 2 were treated for 96 hours in water at 120 ° C., and the efficiency versus efficiency before the treatment was evaluated. .
Referring to Table 2, through this, It was confirmed that the efficiency reduction when the protective film including the barrier film having the structure in which the organic-inorganic hybrid layer, the inorganic barrier layer and the organic-inorganic hybrid layer are sequentially laminated on the upper surface of the substrate layer was attached to the solar cell . Specifically, it was confirmed that there was no reduction in efficiency when treated for 48 hours.
100: Protection film for solar cell
10: substrate layer
20: Organic-Inorganic Hybrid Layer
30: inorganic barrier layer
40: Adhesive layer
50: Fluorine-based polymer layer
60: barrier film
70: Solar cell element
Claims (14)
Protective films for solar cells,
A barrier film and a fluorine-based polymer layer,
The barrier film comprises a substrate layer; And a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, and an organic-inorganic hybrid layer formed on one surface of the substrate layer are sequentially laminated,
The organic-inorganic hybrid layer, the inorganic barrier layer and the organic-inorganic hybrid layer are formed on the opposite side of the solar cell element with respect to the base layer,
Wherein the inorganic barrier layer comprises at least one of SiO x (where x is an integer of 1 to 3) and SiO x N y (where x and y are each an integer of 1 to 3).
Wherein the barrier film comprises a structure in which an organic-inorganic hybrid layer, an inorganic barrier layer, and an organic-inorganic hybrid layer formed on an upper surface of a substrate layer are sequentially laminated.
And a pressure-sensitive adhesive layer formed between the barrier film and the fluorine-based polymer layer.
Wherein the base layer comprises at least one of a single polymer, at least two polymer blends, and a polymer composite material containing an organic or inorganic additive.
Wherein the base layer is a polymer-clay nanocomposite in which the clay nanomaterial is dispersed in a polymer matrix.
Wherein the organic-inorganic hybrid layers are a partial hydrolyzate of a composition comprising an organosilane and a metal alkoxide.
The organic-inorganic hybrid layers comprise, based on the total weight of the composition for preparing the organic-inorganic hybrid layer, 20 to 99.99 parts by weight of the organosilane compound and 0.01 to 80 parts by weight of the metal alkoxide compound, battery.
The fluorine-based polymer layer includes a fluorine-containing copolymer,
The fluorine-containing copolymer includes a monomer containing a fluorine atom; And a copolymer of a monomer containing a hydroxyl group or an epoxy group.
The fluorine atom-containing monomer is at least one member selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, alkylated vinyl vinyl ether, alkoxyalkyl vinyl fluoride, Containing alkoxyvinyl ether, and a fluorine-containing methacrylic acid ester.
The monomer containing a hydroxyl group or an epoxy group is preferably a hydroxyethyl vinyl ether, a hydroxypropyl vinyl ether, a hydroxybutyl vinyl ether, a hydroxypentyl vinyl ether, a hydroxyhexyl vinyl ether, a hydroxyethyl aryl ether, a hydroxybutyl aryl ether, Glycerol monoallyl ether, allyl alcohol, and hydroxyethyl methacrylate ester.
The content of the fluorine-containing copolymer is 0.5 to 10 parts by weight based on the total weight of the composition for forming the fluorine-based polymer layer.
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