CN112980353B - Black high-reflection high-thermal-conductivity PID-resistant EVA (ethylene vinyl acetate) packaging adhesive film and preparation method and application thereof - Google Patents

Black high-reflection high-thermal-conductivity PID-resistant EVA (ethylene vinyl acetate) packaging adhesive film and preparation method and application thereof Download PDF

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CN112980353B
CN112980353B CN202110315771.XA CN202110315771A CN112980353B CN 112980353 B CN112980353 B CN 112980353B CN 202110315771 A CN202110315771 A CN 202110315771A CN 112980353 B CN112980353 B CN 112980353B
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eva
black
parts
resin
film
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CN112980353A (en
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杨同禄
张好宾
陈磊
纪文根
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Jiangsu Lushan New Material Co ltd
Guangzhou Lushan New Materials Co Ltd
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Jiangsu Lushan New Material Co ltd
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Priority to PCT/CN2022/082280 priority patent/WO2022199579A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/041—Provisions for preventing damage caused by corpuscular radiation, e.g. for space applications
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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 the technical field of packaging adhesive films, in particular to a black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film, and a preparation method and application thereof. The EVA packaging adhesive film is mainly prepared from the following components in parts by weight: 100 parts of EVA resin, 5-20 parts of master batch, 0.4-3 parts of initiator, 0.5-7 parts of auxiliary crosslinking agent, 1-5 parts of light stabilizer and 0.1-2 parts of antioxidant; the master batch is mainly prepared from 100: 1-8: 5-10: 1-6.5: 0.5 EVA resin, black pigment, high light reflection pigment, high heat conduction filler, coupling agent and tackifying resin. When the material is used for a black photovoltaic module, the temperature of the module can be obviously reduced, the CTM of the photovoltaic module is improved, and the power of the module is further improved; and when the black component is prepared and used by matching with the double-sided perc battery, the PID on the front side of the battery can be prevented.

Description

Black high-reflection high-thermal-conductivity PID-resistant EVA (ethylene vinyl acetate) packaging adhesive film and preparation method and application thereof
Technical Field
The invention relates to the technical field of packaging adhesive films, in particular to a black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film, and a preparation method and application thereof.
Background
The sunlight reaching the ground is mainly in the wave band range of 280-2500 nm. The crystalline silicon solar cell mainly absorbs sunlight with the wavelength of 400-1200 nm to generate a photovoltaic effect and generate current. Traditional crystal silicon photovoltaic module is mainly white subassembly, and the back collocation white backplate or white EVA glued membrane increase the transmission of light, promote the utilization efficiency of sunlight, promote subassembly generating efficiency. However, the color difference between the white back plate or the glue film and the crystalline silicon battery is large, which affects the beauty. Meanwhile, the roof of the distributed power station and other places cause certain light pollution due to white light reflection, and are limited by some regulations and regulations. For example, the panel of the solar module is required to be black, dark gray, dark blue with low chroma (chroma below 2) and other colors, and the frame can only adopt black or dark gray. Therefore, as the market becomes more aesthetically demanding, black photovoltaic modules are favored by more customers in the photovoltaic segment market. The black components are generally packaged and prepared by using a black back plate and a black aluminum frame.
However, in order to present a black appearance, the conventional black solar cell module needs to absorb almost all visible light and near infrared light, and has strong absorption in an infrared band, so that the absorption efficiency of the crystalline silicon cell on sunlight is reduced, the temperature of the module is greatly increased, and the power generation power of the module is reduced. The black subassembly is compared white ordinary subassembly or the transparent subassembly of dual glass, and the temperature is about 5~10 ℃ high. It is estimated that the power generation efficiency of the crystalline silicon battery decreases by about 0.4% for every 1 ℃ rise in temperature. Therefore, compared with the common white component, the black component has obvious power reduction which is about 2 to 6 percent lower.
In view of these problems, there is a battery back sheet in the prior art that improves the module function by increasing the reflectance of the infrared light black back sheet. However, since the back plate and the battery are separated by the packaging adhesive film, a large part of light is reflected to the back surface of the battery piece after being irradiated on the back plate, thereby reducing the utilization rate of light. The photovoltaic common white module is also used, although the white reflective backboard exists, the white reflective EVA packaging adhesive film is still used, and the power of the module can be obviously improved by about 1-2%.
The patent application No. 201410120277.8 discloses a black infrared reflection type photovoltaic EVA film that can reduce the power loss of black photovoltaic modules. However, the special infrared reflection pigment is directly added in the scheme, so that the cost is high. The infrared reflectivity of 800-3300 nm is mainly improved, the average reflectivity is generally less than 45%, the reflectivity of 700-1200 nm in a near infrared region is lower, and the quantum efficiency (EQE) of the crystalline silicon battery is highest in 400-1200 nm. And the product has no high thermal conductivity and the temperature of the component is reduced little.
Meanwhile, with the development of perc double-sided battery technology, the cost of the double-sided perc battery is far lower than that of a common single-sided aluminum back field battery, and more existing single-sided power generation assemblies are still packaged by using low-cost double-sided perc batteries. However, when the conventional EVA packaging is used, the disappearance of the aluminum back field of the double-sided battery can bring about the PID generation on the front side of the battery to cause the power attenuation.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a black high-reflection high-thermal-conductivity PID-resistant EVA encapsulant film, so as to solve the technical problem that the black encapsulant film in the prior art cannot give consideration to the properties of high reflection, high thermal conductivity, PID resistance, etc.
The second purpose of the invention is to provide a preparation method of the black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film.
The third purpose of the invention is to provide the application of the black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film in packaging the crystalline silicon battery component.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film is mainly prepared from the following components in parts by weight:
100 parts of EVA resin, 5-20 parts of master batch, 0.4-3 parts of initiator, 0.5-7 parts of auxiliary crosslinking agent, 1-5 parts of light stabilizer and 0.1-2 parts of antioxidant;
the master batch is mainly prepared from EVA resin, black pigment, high-light-reflection pigment, high-heat-conductivity filler, coupling agent and tackifying resin in a mass ratio of 100: 1-8: 5-10: 1-6.5: 0.5-6.5;
the high light reflection pigment comprises any one or more of anthraquinone, phthalocyanine, indigo, thioindigo, quinacridone, perylene, dioxazine, isoindoline, indolinone ring and azomethine pigments.
In a specific embodiment of the present invention, the black pigment comprises any one or more of carbon black, iron chromium black, cobalt black, manganese iron black, manganese chromium nickel black, titanium iron black and aniline black.
In a specific embodiment of the present invention, the high thermal conductive filler includes any one or more of titanium dioxide, silica, zinc oxide, precipitated barium sulfate, talc, kaolin, quartz powder, and mica.
In a specific embodiment of the present invention, the coupling agent is a silane coupling agent. Further, the silane coupling agent includes any one or more of methacryloxy silane, aminopropyl triethoxysilane, and glycidyloxypropyl silane.
In a specific embodiment of the present invention, the tackifying resin is an acrylate tackifying resin. Further, the acrylate tackifying resin comprises epoxy acrylate and/or amino acrylate.
In a specific embodiment of the present invention, the auxiliary crosslinking agent comprises an acrylamide type auxiliary crosslinking agent and an acrylate type auxiliary crosslinking agent. Further, the mass ratio of the acrylamide auxiliary cross-linking agent to the acrylate auxiliary cross-linking agent is 1: 2-7.
In a specific embodiment of the present invention, the acrylamide-based co-crosslinking agent comprises methacrylamide and/or N-methylolacrylamide.
In a specific embodiment of the present invention, the acrylate-based co-crosslinking agent includes any one or more of cyanuric acid triacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, isopropyl methacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, and pentaerythritol triacrylate.
In a specific embodiment of the invention, the VA content of the EVA resin is 18wt% to 33 wt%; the melt index of the EVA resin is 3-25 g/10 min; the volume resistivity of the EVA resin is 1.0 multiplied by 1013～1.0×1017Ω·cm。
In a particular embodiment of the invention, the initiator is a peroxide-based initiator. Further, the peroxide initiator includes any one or more of benzoyl peroxide, lauroyl peroxide, cyclohexanone peroxide, bis (4-methylbenzoyl) peroxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, dicumyl peroxide, dicetyl peroxydicarbonate, t-hexyl peroxypivalate, cumyl peroxyneodecanoate, t-butyl peroxyisooctanoate, t-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (t-butyl peroxy) hexane, and di-t-butylperoxyisopropyl benzene.
In a specific embodiment of the present invention, the light stabilizer is a hindered amine light stabilizer. Further, the hindered amine-based light stabilizer includes any one or more of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate, bis (2,2,6, 6-tetramethyl-4-piperidine) sebacate, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] and bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate.
In a particular embodiment of the invention, the antioxidant comprises any one or more of tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The invention also provides a preparation method of the black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film, which comprises the following steps:
the mixture of EVA resin, master batch, initiator, auxiliary crosslinking agent, light stabilizer and antioxidant is subjected to melt extrusion, tape casting to form a film, and then irradiation pre-crosslinking treatment is performed;
the preparation method of the master batch comprises the following steps: and extruding and granulating the mixture of the EVA resin, the black pigment, the high-light reflection pigment, the high-heat-conductivity filler, the coupling agent and the tackifying resin.
In a specific embodiment of the present invention, in the preparing of the master batch, the preparing of the mixture includes:
uniformly mixing EVA resin, black pigment, high-light reflection pigment and high-heat-conductivity filler to obtain a premix; and uniformly mixing the coupling agent, the tackifying resin and the premix at 50-60 ℃ to obtain the mixture.
In a specific embodiment of the present invention, the melt extrusion temperature is 70 to 100 ℃.
In a specific embodiment of the present invention, the degree of crosslinking of the pre-crosslinking is 5% to 30%.
The invention also provides an application of any black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film in preparation of a crystalline silicon battery assembly or an amorphous silicon battery assembly.
In a specific embodiment of the present invention, the crystalline silicon battery module includes at least one of a single-sided Perc battery module and a double-sided Perc battery module.
In a specific embodiment of the present invention, the amorphous silicon battery module is a flexible module.
Compared with the prior art, the invention has the beneficial effects that:
(1) the EVA packaging adhesive film has high light reflectivity, the reflectivity in the range of 700-1200 nm exceeds 45%, and the EVA packaging adhesive film has high thermal conductivity;
(2) when the EVA packaging adhesive film is used for a black photovoltaic module, compared with a common black light resistance module, the EVA packaging adhesive film can obviously reduce the temperature of the module by 5-20 ℃, improve the CTM of the photovoltaic module, further improve the power of the module, and actually improve the power by about 4% -5%; when the black component is prepared and used by matching the double-sided perc battery, the PID on the front side of the battery can be prevented, and the combination of a POE packaging adhesive film and a black back plate can be replaced;
(3) the EVA packaging adhesive film has high blackness, has the advantage of no glue overflow after EB irradiation, and can meet the requirement of aesthetic sense.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film is mainly prepared from the following components in parts by weight:
100 parts of EVA resin, 5-20 parts of master batch, 0.4-3 parts of initiator, 0.5-7 parts of auxiliary crosslinking agent, 1-5 parts of light stabilizer and 0.1-2 parts of antioxidant;
the master batch is mainly prepared from EVA resin, black pigment, high-light-reflection pigment, high-heat-conductivity filler, coupling agent and tackifying resin in a mass ratio of 100: 1-8: 5-10: 1-6.5: 0.5-6.5;
the high light reflection pigment comprises any one or more of anthraquinone, phthalocyanine, indigo, thioindigo, quinacridone, perylene, dioxazine, isoindoline, indolinone ring and azomethine pigments.
In a preferred embodiment of the present invention, the anthraquinone is at least one of RSN Rebate blue, KN-R Brilliant blue and Brilliant blue RAW; the phthalocyanine is at least one of cobalt phthalocyanine and phthalocyanine blue BGS; the indigo is hardened indigo.
As in the different embodiments, the amount of the master batch may be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc. compared to 100 parts of the EVA resin in the raw material components of the packaging adhesive film; the amount of the initiator may be 0.4 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.; the co-crosslinking agent may be used in an amount of 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, etc.; light stabilizers can be used in amounts of 1 part, 2 parts, 3 parts, 4 parts, 5 parts, and the like; antioxidants can be used in amounts of 0.1 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, and the like.
In a specific embodiment of the present invention, the black pigment comprises any one or more of carbon black, iron chromium black, cobalt black, manganese iron black, manganese chromium nickel black, titanium iron black and aniline black.
In a specific embodiment of the present invention, the high thermal conductive filler includes any one or more of titanium dioxide, silica, zinc oxide, precipitated barium sulfate, talc, kaolin, quartz powder, and mica. Furthermore, the average particle size of the high-thermal-conductivity filler is 0.1-0.3 μm.
In a specific embodiment of the present invention, the coupling agent is a silane coupling agent. Further, the silane coupling agent includes any one or more of methacryloxy silane, aminopropyl triethoxysilane, and glycidyloxypropyl silane.
In a specific embodiment of the present invention, the tackifying resin is an acrylate tackifying resin. Further, the acrylate tackifying resin comprises epoxy acrylate and/or amino acrylate.
In a specific embodiment of the invention, the mass ratio of the EVA resin, the black pigment, the high light reflectance pigment, the high thermal conductivity filler, the coupling agent and the tackifying resin in the masterbatch is 100: 2: 8 (2: 8) to 6: 10 (2: 6.5) to (2: 6.5), preferably 100: 4: 8 (4: 8) to (8: 10) to (3: 6.5) to (3.5: 6.5).
In various embodiments, the mass ratio of EVA resin, black pigment, specular reflection pigment, high thermal conductivity filler, coupling agent and adhesion promoting resin in the masterbatch can be 100: 2, 100: 3, 100: 4: 8: 3.5, 100: 5: 4: 5, 100: 6: 8: 6, etc.
In a specific embodiment of the present invention, the auxiliary crosslinking agent comprises an acrylamide type auxiliary crosslinking agent and an acrylate type auxiliary crosslinking agent. Furthermore, the mass ratio of the acrylamide auxiliary cross-linking agent to the acrylate auxiliary cross-linking agent is 1: 2-7, so that the cross-linking rate and the cross-linking density can be further adjusted.
For example, in various embodiments, the mass ratio of the acrylamide auxiliary crosslinking agent to the acrylate auxiliary crosslinking agent can be 1: 2, 1: 3, 1: 4, 1: 5, 1: 6, or 1: 7.
According to the invention, the amide group is introduced into the system, so that the corrosion to the battery piece can be reduced by neutralizing acidity, and meanwhile, the amide group can form a complex pairing with sodium ions migrated in glass, and the sodium ions are further migrated to the surface of the battery piece to prevent the PID phenomenon, so that POE can not be used in the packaging of the black component and the double-sided perc battery, and the requirement of PID resistance can still be met.
In a specific embodiment of the present invention, the acrylamide-based co-crosslinking agent comprises methacrylamide and/or N-methylolacrylamide.
In a specific embodiment of the present invention, the acrylate-based co-crosslinking agent includes any one or more of cyanuric acid triacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, isopropyl methacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, and pentaerythritol triacrylate.
In a specific embodiment of the invention, the VA content of the EVA resin is 18wt% to 33 wt%; the melt index of the EVA resin is 3-25 g/10 min; the volume resistivity of the EVA resin is 1.0 multiplied by 1013～1.0×1017Omega cm. The EVA resin adopting the above conditions can be further convenient to process and meet the performance requirement.
Specifically, the EVA resin in the packaging adhesive film and the EVA resin in the master batch both meet the above requirements, and the EVA resin in the packaging adhesive film and the EVA resin in the master batch may be two different EVA resins meeting the above requirements, or may also meet the same EVA resin meeting the above requirements.
As in the various embodiments, the VA content of the EVA resin may be 18wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 33wt%, and so forth; the melt index of the EVA resin (test conditions are 190 ℃, 2.16kg) can be 3g/10min, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min and the like; the EVA resin may have a volume resistivity of 1.0X 1013Ω·cm、5.0×1013Ω·cm、1.0×1014Ω·cm、5.0×1014Ω·cm、1.0×1015Ω·cm、5.0×1015Ω·cm、1.0×1016Ω·cm、5.0×1016Ω·cm、1.0×1017Ω · cm, and the like.
In a particular embodiment of the invention, the initiator is a peroxide-based initiator. Further, the peroxide initiator includes any one or more of benzoyl peroxide, lauroyl peroxide, cyclohexanone peroxide, bis (4-methylbenzoyl) peroxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, dicumyl peroxide, dicetyl peroxydicarbonate, t-hexyl peroxypivalate, cumyl peroxyneodecanoate, t-butyl peroxyisooctanoate, t-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (t-butyl peroxy) hexane, and di-t-butylperoxyisopropyl benzene.
In a specific embodiment of the present invention, the light stabilizer is a hindered amine light stabilizer. Further, the hindered amine-based light stabilizer includes any one or more of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate, bis (2,2,6, 6-tetramethyl-4-piperidine) sebacate, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] and bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate.
In a particular embodiment of the invention, the antioxidant comprises any one or more of tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The invention also provides a preparation method of the black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film, which comprises the following steps:
the mixture of EVA resin, master batch, initiator, auxiliary crosslinking agent, light stabilizer and antioxidant is subjected to melt extrusion, tape casting to form a film, and then irradiation pre-crosslinking treatment is performed;
the preparation method of the master batch comprises the following steps: and extruding and granulating the mixture of the EVA resin, the black pigment, the high-light reflection pigment, the high-heat-conductivity filler, the coupling agent and the tackifying resin.
In a specific embodiment of the present invention, in the preparing of the master batch, the preparing of the mixture includes: uniformly mixing EVA resin, black pigment, high-light reflection pigment and high-heat-conductivity filler to obtain a premix; and uniformly mixing the coupling agent, the tackifying resin and the premix at 50-60 ℃ to obtain the mixture.
The coupling agent, the tackifying resin and the rest components are mixed to prepare master batches, and the compatibility of each component in the master batches is increased to ensure the dispersion uniformity.
In a specific embodiment of the invention, the extrusion granulation comprises: extruding at 100-200 ℃, cooling, drawing and granulating the extrudate to obtain the master batch.
In a specific embodiment of the present invention, the melt extrusion temperature is 70 to 100 ℃.
In practical operation, in the preparation of the packaging adhesive film, the mixture is subjected to melt extrusion at 70-100 ℃ in a single-screw extrusion casting machine, embossing, cooling, traction film forming and irradiation pre-crosslinking treatment.
In a particular embodiment of the invention, the irradiation is electron beam EB irradiation.
In a specific embodiment of the present invention, the degree of crosslinking of the pre-crosslinking is 5% to 30%.
The invention also provides an application of any black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film in preparation of a crystalline silicon battery assembly or an amorphous silicon battery assembly.
In a specific embodiment of the present invention, the crystalline silicon battery module includes at least one of a single-sided Perc battery module and a double-sided Perc battery module.
In a specific embodiment of the present invention, the amorphous silicon battery module is a flexible module.
In practical operation, when the packaging adhesive film is used for preparing a crystalline silicon battery assembly, the packaging adhesive film can be subjected to laminating treatment by a vacuum laminating machine at 140-150 ℃, so that crosslinking and curing can be completed, and black EVA (ethylene vinyl acetate) glue overflow to the front surface of a battery piece can be avoided.
Example 1
The embodiment provides a black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film and a preparation method thereof, wherein the packaging adhesive film comprises the following raw materials:
100 parts of EVA resin, 20 parts of master batch, 3 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 3 parts of bis (2,2,6, 6-tetramethyl-4-piperidine) sebacate, 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 5 parts of auxiliary crosslinking agent; the auxiliary crosslinking agent consists of trihydroxy methyl propane trimethyl acrylate and N-hydroxymethyl acrylamide in the mass ratio of 1: 5;
the master batch comprises the following raw materials: EVA resin at a mass ratio of 100: 8: 10: 6, nigrosine, hardened indigo (disodium 3,3 ' -dioxo-2, 2 ' -biindolyl-5, 5 ' -disulfonate), titanium dioxide, gamma-methacryloxypropyl trimethoxysilane and epoxy acrylate tackifying resin.
The EVA resin in the packaging adhesive film and the master batch is as follows: VA content 28 wt%, melt index 25g/10min, volume resistivity 1.0X 1015Omega cm EVA resin.
The preparation method of the black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film comprises the following steps:
(1) mixing EVA resin, aniline black, indigo pigment and titanium dioxide in the master batch raw materials in a mixing kettle at room temperature for about 30min until the mixture is uniform to form a first mixture; adding a methacryloxy silane coupling agent and an epoxy acrylate tackifying resin in the master batch raw material into the first mixture at a feeding speed of 60-70 g/min, and then heating, stirring and mixing at 50-60 ℃ for 40-50 min until the mixture is completely dried to form a second mixture; and mixing and extruding the second mixture by a double-screw granulator, controlling the extrusion temperature to be 150-160 ℃, and cooling, drawing and granulating the extrudate to prepare master batches.
(2) Weighing the raw materials of the packaging adhesive film according to the proportion, heating, stirring and mixing at 40-50 ℃ for 70-100 min until the mixture is completely dried to form a third mixture; adding the third mixture into a single-screw extrusion casting machine, extruding at 90-100 ℃, and respectively embossing, cooling, drawing, cutting edges and rolling to obtain a film material, wherein the thickness of the film material is 0.5 mm; and then, subjecting the film material to electron beam EB irradiation treatment, wherein the pre-crosslinking degree is 5% -10%, so as to obtain the black high-reflection high-thermal-conductivity anti-PID EVA packaging adhesive film.
Example 2
The present example refers to the black high-reflection high-thermal conductivity anti-PID EVA encapsulant film of example 1 and the preparation method thereof, and the difference is only that: the master batch has different raw material components.
The masterbatch of this example was prepared from EVA resin, nigrosine, hardened indigo, titanium dioxide, gamma-methacryloxypropyltrimethoxysilane, and an epoxy acrylate tackifying resin at a mass ratio of 100: 1: 5: 1: 0.5.
Example 3
The present example refers to the black high-reflection high-thermal conductivity anti-PID EVA encapsulant film of example 1 and the preparation method thereof, and the difference is only that: the master batch has different raw material components.
The masterbatch of this example was prepared from EVA resin, nigrosine, hardened indigo, titanium dioxide, gamma-methacryloxypropyltrimethoxysilane, and an epoxy acrylate tackifying resin at a mass ratio of 100: 4: 8: 3.5.
Comparative example 1
Comparative example 1 referring to the black high-reflection high-thermal-conductivity anti-PID EVA encapsulant film of example 1 and the preparation method thereof, the difference is: the master batch has different raw material components.
The master batch of comparative example 1 was prepared from EVA resin, nigrosine, gamma-methacryloxypropyltrimethoxysilane, and epoxy acrylate tackifying resin at a mass ratio of 100: 8: 6.
Comparative example 2
Comparative example 2 referring to the black high-reflection high-thermal-conductivity anti-PID EVA encapsulant film of example 1 and the preparation method thereof, the difference is: the master batch has different raw material components.
The master batch of comparative example 2 was prepared from EVA resin, nigrosine, titanium dioxide, gamma-methacryloxypropyltrimethoxysilane, and epoxy acrylate tackifying resin at a mass ratio of 100: 8: 10: 6.
Comparative example 3
Comparative example 3 referring to the black high-reflection high-thermal-conductivity anti-PID EVA encapsulant film of example 1 and the preparation method thereof, the difference is: the master batch has different raw material components.
The master batch of comparative example 3 was prepared from EVA resin, nigrosine, hardened indigo, gamma-methacryloxypropyltrimethoxysilane, and epoxy acrylate tackifying resin at a mass ratio of 100: 8: 6.
Comparative example 4
An EVA adhesive packaging film (manufacturer: LuShan, model: 1050G7) is commercially available.
Comparative example 5
Another EVA adhesive packaging film is commercially available (manufacturer: LuShan, model: S103).
Experimental example 1
In order to illustrate the performances of different packaging adhesive films by comparison, the following performances are tested, and the test method of each test item is as follows:
and (3) testing the crosslinking degree: testing by referring to a method in GB/T29848 2018 ethylene-vinyl acetate copolymer (EVA) adhesive film for photovoltaic module packaging;
and (3) volume resistivity test: testing is carried out according to GB/T1410-200 test method for volume resistivity and surface resistivity of solid insulating materials;
and (3) testing the peel strength: according to the test of GB/T2790 + 1995 adhesive 180-degree peel strength test method, TPT back plates are adopted for all back plates of peel strength, and photovoltaic glass is adopted for glass;
and (3) reflectivity testing: testing the reflectivity of 700 nm-1200 nm by using an ultraviolet visible spectrophotometer lambda 950;
the conventional means well known by photovoltaic module technicians is adopted to test the temperature rise, the power consumption and the PID test of the photovoltaic module according to the standards IEC 61215 and IEC61730, and all the batteries used for preparing the module are TW single-crystal perc double-sided batteries.
The test results are shown in table 1, and the test objects corresponding to the specific test items are respectively: the thickness and volume resistivity test object is a laminated single adhesive film; the crosslinking degree and the peeling strength test objects are the crosslinking degree of the adhesive film and the strength of the adhesive film and the glass/back plate after lamination; the light reflectivity, assembly temperature rise, power boost and PID attenuation test object is a laminated assembly sample; preparing a component: the assembly was assembled by welding the cells → laminating glass, EVA, cell string, back sheet → laminating (laminating condition: 145 ℃ C., evacuating 5min, holding pressure for 10 min).
Table 1 results of different performance tests:
Figure BDA0002991397140000151
as can be seen from the above table, compared with the common adhesive film component, the black high-reflection high-thermal-conductivity PID-resistant EVA packaging adhesive film or the prepared component has no obvious influence on various performances, and can meet the component requirements.
Compared with the common black component prepared by the black back plate, the reflectivity of the component prepared by the adhesive film of the embodiment 1 is obviously better, is higher by 46.7% than that of the component prepared by the comparative example 4, the temperature rise of the component is smaller, the PID resistance is more excellent, the power is obviously improved, and the improvement is about 4.8%.
The white components prepared in comparative example 1 and comparative example 5 have more excellent PID resistance of the component prepared in example 1 of the invention, and the component prepared in comparative example 5 has poor PID resistance, and the power attenuation of the white components exceeds the control standard of 5% in the industry. Therefore, when the common transparent EVA is matched with the perc single crystal double-sided battery to prepare the single glass assembly, the PID resistance of the single glass assembly is a hidden danger. The black module produced in example 1 according to the invention has a lower power attenuation, only 0.91%, than the white module of comparative example 5.
In comparison with example 1 and comparative example 1, the addition of the high light reflection pigment and the high heat conduction material significantly increases the reflectivity, decreases the temperature of the assembly, and increases the power.
In comparative example 1, comparative example 2 and comparative example 3, the reflectance was remarkably reduced without adding the high light reflective pigment in comparative example 2, and the temperature of the assembly was remarkably increased without adding the high thermal conductive material in comparative example 3. The power of the modules corresponding to both comparative examples 2 and 3 was significantly lower than the module corresponding to example 1.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (20)

1. The black high-reflection high-heat-conduction anti-PID EVA packaging adhesive film is characterized by being mainly prepared from the following components in parts by weight:
100 parts of EVA resin, 5-20 parts of master batch, 0.4-3 parts of initiator, 0.5-7 parts of auxiliary crosslinking agent, 1-5 parts of light stabilizer and 0.1-2 parts of antioxidant;
the master batch is mainly prepared from EVA resin, black pigment, high-light-reflection pigment, high-heat-conductivity filler, coupling agent and tackifying resin in a mass ratio of 100: 1-8: 5-10: 1-6.5: 0.5-6.5;
the high light reflection pigment comprises any one or more of anthraquinone, phthalocyanine, indigo, thioindigo, quinacridone, perylene, dioxazine, isoindoline, indolinone ring and azomethine pigments;
the high heat conduction filler is titanium dioxide.
2. The EVA adhesive packaging film of claim 1, wherein the black pigment comprises one or more of carbon black, iron chromium black, cobalt black, manganese iron black, manganese chromium nickel black, titanium iron black and aniline black.
3. The EVA adhesive packaging film of claim 1, wherein the coupling agent is a silane coupling agent; the tackifying resin is acrylate tackifying resin.
4. The EVA adhesive packaging film of claim 3, wherein the silane coupling agent comprises any one or more of methacryloxy silane, aminopropyl triethoxysilane, and glycidylethoxypropyl silane;
the acrylate tackifying resin comprises epoxy acrylate and/or amino acrylate.
5. The EVA packaging film according to any one of claims 1 to 4, wherein the mass ratio of the EVA resin, the black pigment, the high light reflection pigment, the high thermal conductive filler, the coupling agent and the tackifying resin in the masterbatch is 100: 2 to 8: 6 to 10: 2 to 6.5.
6. The EVA packaging adhesive film of claim 5, wherein the mass ratio of the EVA resin, the black pigment, the high light reflection pigment, the high thermal conductive filler, the coupling agent and the tackifying resin in the masterbatch is 100: 4 to 8: 8 (4 to 8: 8) (3 to 6.5: 6.5).
7. The EVA adhesive packaging film of claim 1, wherein the auxiliary crosslinking agent comprises an acrylamide auxiliary crosslinking agent and an acrylate auxiliary crosslinking agent;
the mass ratio of the acrylamide auxiliary cross-linking agent to the acrylate auxiliary cross-linking agent is 1: 2-7.
8. The EVA adhesive packaging film of claim 7, wherein the acrylamide auxiliary crosslinker comprises methacrylamide and/or N-methylol acrylamide;
the acrylate auxiliary crosslinking agent comprises one or more of cyanuric acid triacrylate, isocyanuric triacrylate, trihydroxymethyl propane triacrylate, isopropyl methacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trihydroxymethyl propane trimethacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate and pentaerythritol triacrylate.
9. The EVA adhesive film for packaging according to claim 1, wherein the EVA resin has a VA content of 18wt% to 33 wt%.
10. The EVA adhesive film for packaging according to claim 9, wherein the EVA resin has a melt index of 3-25 g/10 min.
11. The EVA adhesive film for packaging according to claim 9, wherein the EVA resin has a volume resistivity of 1.0 x 1013~1.0×1017Ω·cm。
12. The EVA adhesive packaging film of claim 1, wherein the initiator is a peroxide initiator; the light stabilizer is a hindered amine light stabilizer;
the antioxidant comprises any one or more of tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
13. The EVA adhesive packaging film of claim 12, the hindered amine light stabilizer comprises any one or more of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate, bis (2,2,6, 6-tetramethyl-4-piperidine) sebacate, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] and bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate;
the peroxide initiator comprises any one or more of benzoyl peroxide, lauroyl peroxide, cyclohexanone peroxide, bis (4-methylbenzoyl) peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, dicumyl peroxide, dicetyl peroxydicarbonate, tert-hexyl peroxypivalate, cumyl peroxyneodecanoate, tert-butyl peroxyisooctanoate, tert-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane and di-tert-butylperoxyisopropylbenzene.
14. The method for preparing the EVA adhesive packaging film of any one of claims 1-13, comprising the following steps:
the mixture of EVA resin, master batch, initiator, auxiliary crosslinking agent, light stabilizer and antioxidant is subjected to melt extrusion, tape casting to form a film, and then irradiation pre-crosslinking treatment is performed;
the preparation method of the master batch comprises the following steps: and extruding and granulating the mixture of the EVA resin, the black pigment, the high-light reflection pigment, the high-heat-conductivity filler, the coupling agent and the tackifying resin.
15. The preparation method of the EVA adhesive packaging film of claim 14, wherein the degree of crosslinking of the pre-crosslinking is 5-30%.
16. The preparation method of the EVA adhesive packaging film of claim 14, wherein the melt extrusion temperature is 70-100 ℃.
17. The method for preparing the EVA adhesive packaging film of claim 14, wherein the extrusion granulation comprises: extruding at 100-200 ℃, cooling, drawing and granulating the extrudate.
18. Use of the EVA encapsulant film of any of claims 1-13 in the manufacture of amorphous silicon cell modules or crystalline silicon cell modules.
19. The use of claim 18, wherein the crystalline silicon cell assembly comprises at least one of a single-sided Perc cell assembly and a double-sided Perc cell assembly.
20. Use according to claim 18, wherein the amorphous silicon cell component is a flexible component.
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