CN116265554A - Photovoltaic packaging material and preparation method and application thereof - Google Patents

Photovoltaic packaging material and preparation method and application thereof Download PDF

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Publication number
CN116265554A
CN116265554A CN202111554405.6A CN202111554405A CN116265554A CN 116265554 A CN116265554 A CN 116265554A CN 202111554405 A CN202111554405 A CN 202111554405A CN 116265554 A CN116265554 A CN 116265554A
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Prior art keywords
vinyl acetate
diene
ethylene
packaging material
parts
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CN202111554405.6A
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Inventor
李元
郭清明
苗鲁滨
孔庆宁
黄冰艳
彭丽霞
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Canadian Solar Inc
Changshu Tegu New Material Technology CoLtd
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Changshu Tegu New Material Technology CoLtd
Atlas Sunshine Power Group Co Ltd
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Priority to CN202111554405.6A priority Critical patent/CN116265554A/en
Publication of CN116265554A publication Critical patent/CN116265554A/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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a photovoltaic packaging material, a preparation method and application thereof, wherein the packaging material comprises the following components in parts by weight: 100 parts of matrix resin and 0.1-2.6 parts of auxiliary agent; the matrix resin comprises a copolymer of ethylene, vinyl acetate and a diene; the diene includes any one or a combination of at least two of hexadiene, heptadiene or octadiene. The wettability and the thermal stability of the photovoltaic packaging material enable the material to have good adhesion performance with glass, the thermal stability of a glue film to be improved, delamination and deacidification can be effectively prevented, and the solar cell module can work normally and permanently.

Description

Photovoltaic packaging material and preparation method and application thereof
Technical Field
The invention relates to the technical field of photovoltaic modules, in particular to a photovoltaic packaging material, and a preparation method and application thereof.
Background
The packaging adhesive film plays a role in the assembly, namely packaging, namely ensuring that glass, a battery piece, the battery piece and a back plate can be glued into a whole. Secondly, the glue film is ensured to play a specified function. Although different packaging adhesive films have different functionalities, only one purpose is to reduce cost and enhance efficiency, and ensure that components of different types can normally work in corresponding environments.
The traditional packaging adhesive film is provided with an EVA adhesive film, and the EVA adhesive film is an ethylene-vinyl acetate copolymer and has the advantages of low melting point, good fluidity, high transparency, mature lamination process and the like, and is a main packaging material of the existing double-glass assembly.
CN107984658A discloses a high-efficiency EVA packaging adhesive film for shortening lamination time, and a preparation method and application thereof, and the preparation method of the disclosed EVA packaging adhesive film comprises the following steps: electron radiation is carried out on the transparent EVA adhesive film to obtain a pre-crosslinked transparent EVA adhesive film; electron radiation is carried out on the blocking EVA adhesive film to obtain a pre-crosslinked blocking EVA adhesive film; laminating the pre-crosslinked transparent EVA adhesive film and the pre-crosslinked blocking EVA adhesive film at 140-150 ℃ for 5-10 min to obtain the EVA packaging adhesive film. Under the condition that other additives are not added, the transparent EVA adhesive film and the blocking EVA adhesive film are pre-crosslinked through electronic radiation and then laminated, so that the laminating time can be effectively shortened, the reliability is not affected, appearance defects can be avoided, and the production cost is greatly reduced.
Although EVA adhesive film is the main packaging material of the double-glass assembly at present, as the EVA adhesive film is of a weaker polar structure, the bonding strength of the packaging adhesive film to glass and a backboard can be enhanced by adding a coupling agent. In addition, because of the polar structure of EVA, the water vapor transmission rate and water absorption rate are high, and the weather resistance is poor, for example, when the EVA is used on a dual-glass assembly, sealing treatment is required, however, water vapor still can penetrate in the normal use process. The vinyl acetate content of EVA for photovoltaic modules is typically 28-33%. Because the EVA resin is connected with the ester group on the main chain, the EVA resin can bring polarity to the resin, has the advantages of improving the compatibility among the auxiliary agents, preventing the auxiliary agents from coalescing, improving the vulcanization speed, and can be used together with the polar resin, and the EVA resin has the defect of decomposing into acid in the presence of water. In the photovoltaic module, along with the environment, acetic acid becomes a major quality problem of the photovoltaic module, such as silver grid line corrosion, bubbles become larger due to degradation of EVA molecular chains, and important causes of yellowing and the like caused by degradation of small molecules.
In view of the above, it is important to develop a packaging film with excellent adhesion and good thermal stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photovoltaic packaging material, a preparation method and application thereof, wherein the wettability and the thermal stability of the photovoltaic packaging material enable the material to have good bonding performance with glass, the thermal stability of a glue film to be improved, delamination and deacidification can be effectively prevented, and the solar cell module can work normally and permanently.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a photovoltaic packaging material, which comprises the following components in parts by weight:
100 parts of matrix resin
0.1-2.6 parts of auxiliary agent;
the matrix resin comprises a copolymer of ethylene, vinyl acetate and a diene;
the diene includes any one or a combination of at least two of hexadiene, heptadiene, or octadiene, wherein typical but non-limiting combinations include: a combination of hexadiene and heptadiene, a combination of heptadiene and octadiene, a combination of hexadiene, heptadiene and octadiene, and the like.
In the invention, the matrix resin replaces the traditional ethylene-vinyl acetate copolymer with the copolymer of ethylene, vinyl acetate and diene, wherein the diene comprises any one or a combination of at least two of hexadiene, heptadiene and octadiene, the intermolecular acting force of the matrix resin is reduced, thus the viscosity is reduced, the processability is improved, the wettability of the adhesive film is improved, and further, the better bonding performance with glass is obtained.
In the invention, the weight part of the matrix resin is 100 parts.
The auxiliary agent is 0.1-2.6 parts by weight, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts and the like.
Preferably, the mass percentage of vinyl acetate is 5% -15%, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., based on 100% of the total mass of the three ethylene, vinyl acetate and diene.
In the invention, the mass percent of vinyl acetate in the reaction monomer of the copolymer is 5-15%, in this range, too high a ratio can lead to the increase of the polarity of the copolymer and the decrease of the moisture resistance, and too low a ratio can affect the crosslinking reaction of the copolymer and reduce the crosslinking degree.
Preferably, the mass percent of the diene is 15% -25%, such as 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, etc., based on 100% of the total mass of the ethylene, vinyl acetate and diene.
In the invention, in the reaction monomer of the copolymer, the mass percent of diene is 1-25%, the ratio in the range is too high, and the polarity of the copolymer is low to influence the crosslinking degree; too low a ratio decreases wettability and flexibility of the copolymer.
Preferably, the auxiliary agent comprises any one or a combination of at least two of a main crosslinking agent, a secondary crosslinking agent, a light stabilizer, a coupling agent or an ultraviolet absorber.
Preferably, the primary crosslinking agent comprises any one or a combination of at least two of tert-butyl peroxy (2-ethylhexyl) carbonate, tert-amyl peroxy (2-ethylhexyl) carbonate, or dicumyl peroxide, wherein typical but non-limiting combinations include: t-butyl peroxy (2-ethylhexyl) carbonate, t-amyl peroxy (2-ethylhexyl) carbonate, dicumyl peroxide, t-butyl peroxy (2-ethylhexyl) carbonate, t-amyl peroxy (2-ethylhexyl) carbonate, dicumyl peroxide, and the like.
Preferably, the co-crosslinking agent comprises any one or a combination of at least two of allyl diglycol dicarbonate, trimethylolpropane triacrylate or pentaerythritol triacrylate, wherein typical but non-limiting combinations include: a combination of allyl diglycol dicarbonate and trimethylolpropane triacrylate, a combination of trimethylolpropane triacrylate and pentaerythritol triacrylate, a combination of allyl diglycol dicarbonate, trimethylolpropane triacrylate and pentaerythritol triacrylate, and the like.
Preferably, the method comprises the steps of, the light stabilizer comprises a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol (light stabilizer 622) bis (2, 6-tetramethyl-4-piperidinyl) sebacate or poly { [6- [ (1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2, 6, -tetramethyl-piperidinyl) imino ] -1, 6-hexamethylenediyl [ (2, 6-tetramethyl-4-piperidinyl) imino ] } any one or a combination of at least two, wherein typical but non-limiting combinations include: the combination of light stabilizer 622 and bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (2, 6-tetramethyl-4-piperidinyl) sebacate and poly { [6- [ (]; 1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2, 6, -tetramethyl-piperidinyl) imino ] -1, 6-hexamethylenediyl [ (2, 6-tetramethyl-4-piperidinyl) imino ] }, and the like.
Preferably, the coupling agent comprises any one or a combination of at least two of vinyltrimethoxysilane, vinylmethyldimethoxysilane, or vinyltriisopropenoxysilane, wherein typical but non-limiting combinations include: a combination of vinyltrimethoxysilane and vinylmethyldimethoxysilane, a combination of vinylmethyldimethoxysilane and vinyltriisopropyloxysilane, a combination of vinyltrimethoxysilane, vinylmethyldimethoxysilane and vinyltriisopropyloxysilane, and the like.
Preferably, the ultraviolet light absorber comprises any one or a combination of at least two of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazin-4-one or 2' - (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, wherein typical but non-limiting combinations include: combinations of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole and 2,2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazin-4-one, combinations of 2,2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazin-4-one and 2' - (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, combinations of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazin-4-one and 2' - (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, and the like.
Preferably, the weight fraction of the primary crosslinker is from 0.4 to 0.7 parts, e.g., 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, etc.
Preferably, the co-crosslinking agent is present in an amount of 0.2 to 0.6 parts by weight, for example 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, etc.
Preferably, the light stabilizer is present in an amount of 0.1 to 0.5 parts by weight, for example 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts.
Preferably, the coupling agent is present in an amount of 0.1 to 0.3 parts by weight, such as 0.15 parts, 0.2 parts, 0.25 parts, etc.
Preferably, the ultraviolet absorber is present in an amount of 0.1 to 0.5 parts by weight, for example 0.15 parts, 0.2 parts, 0.25 parts, etc.
As a preferable technical scheme, the photovoltaic packaging material comprises the following components in parts by weight:
Figure BDA0003418690840000051
Figure BDA0003418690840000061
the matrix resin comprises a copolymer of ethylene, vinyl acetate and hexadiene;
the mass percentage of the vinyl acetate structural unit is 5% -15% based on 100% of the total mass of the copolymer of ethylene, vinyl acetate and hexadiene; the mass percentage of hexadiene structural units is 15% -25%.
In a second aspect, the present invention provides a method for preparing the photovoltaic packaging material according to the first aspect, the method comprising the following steps:
mixing and processing a copolymer of ethylene, vinyl acetate and diene with an auxiliary agent to obtain the photovoltaic packaging material;
the diene includes any one or a combination of at least two of hexadiene, heptadiene or octadiene.
Preferably, the processing means include extrusion, casting, cooling, slitting and coiling.
Preferably, the temperature of the extrusion is 85-95 ℃, e.g., 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, etc.
Preferably, the preparation method of the copolymer of ethylene, vinyl acetate and diene comprises the following steps:
polymerizing ethylene, vinyl acetate and diene to obtain a copolymer of ethylene, vinyl acetate and diene;
preferably, the vinyl acetate is 5% -15% by mass, e.g. 6%, 8%, 10%, 12%, 14% etc., based on 100% by mass of the total of ethylene, vinyl acetate and diene.
In the preparation of the invention, the mass percent of vinyl acetate in the comonomer is 5-15%, the too high proportion in the range can lead to the increase of the polarity of the copolymer and the decrease of the moisture resistance, the too low proportion can influence the crosslinking reaction of the copolymer, and the crosslinking degree is reduced.
The vinyl acetate content of the conventional EVA is 28-33%, the water vapor transmittance of the EVA is 35%, and the vinyl acetate can be decomposed into acetic acid, so that the risk of corrosion of the double-sided battery piece exists.
Preferably, the mass percent of the diene is 15% -25%, such as 16%, 18%, 20%, 22%, 24%, etc., based on 100% of the total mass of the ethylene, vinyl acetate and diene.
In the preparation process, in the comonomer, the mass percentage of the diene is 15-25%, the ratio in the range is too high, and the polarity of the copolymer is low to influence the crosslinking degree; too low a ratio decreases wettability and flexibility of the copolymer.
Preferably, the polymerization temperature is from 100℃to 120℃such as 102℃104℃106℃108℃110℃112℃114℃116℃118℃etc.
Preferably, the polymerization time is 1-2 hours, such as 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, etc.
In a third aspect, the present invention provides a photovoltaic module comprising the photovoltaic packaging material of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The wettability and the thermal stability of the photovoltaic packaging material enable the material to have good bonding performance with glass, the thermal stability of the adhesive film to be improved, delamination can be effectively prevented, the solar cell module can work normally and permanently, corrosion of a cell piece can be prevented, the product quality is high, and the stability is high. The vinyl acetate content of the conventional EVA is 28-33%, the water vapor transmittance of the EVA is 35%, and the vinyl acetate can be decomposed into acetic acid, so that the risk of corrosion of the double-sided battery piece exists.
(2) The peeling strength of the packaging material DH2000 is between 109 and 202N/cm, the peeling strength of the packaging material DH2000 is between 83 and 195N/cm, the peeling strength is not obviously attenuated, the light transmittance is above 90%, and the further formed photovoltaic module does not or slightly suffers from delamination, bubbles and corrosion.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a photovoltaic packaging material, which comprises the following components in parts by weight:
Figure BDA0003418690840000081
the matrix resin is a terpolymer of ethylene, vinyl acetate and hexadiene.
The preparation method of the photovoltaic packaging material comprises the following steps:
(1) Mixing and polymerizing ethylene, vinyl acetate and hexadiene with mass percentages of 70%, 12% and 18% respectively to obtain a terpolymer of ethylene, vinyl acetate and hexadiene;
(2) And (3) blending and extruding the terpolymer, the main crosslinking agent, the auxiliary crosslinking agent, the light stabilizer, the coupling agent and the ultraviolet absorber in an extruder, controlling the temperature at 90 ℃, and carrying out casting, cooling, slitting and coiling procedures on the extrudate to obtain the photovoltaic packaging material.
Example 2
The embodiment provides a photovoltaic packaging material, which comprises the following components in parts by weight:
Figure BDA0003418690840000082
Figure BDA0003418690840000091
the matrix resin is a terpolymer of ethylene, vinyl acetate and hexadiene.
The preparation method of the photovoltaic packaging material comprises the following steps:
(1) Mixing 65%, 15% and 20% of ethylene, vinyl acetate and hexadiene respectively, and polymerizing to obtain a terpolymer of ethylene, vinyl acetate and hexadiene;
(2) And (3) blending and extruding the terpolymer, the main crosslinking agent, the auxiliary crosslinking agent, the light stabilizer, the coupling agent and the ultraviolet absorber in an extruder, controlling the temperature at 90 ℃, and carrying out casting, cooling, slitting and coiling procedures on the extrudate to obtain the photovoltaic packaging material.
Example 3
The embodiment provides a photovoltaic packaging material, which comprises the following components in parts by weight:
Figure BDA0003418690840000092
the matrix resin is a terpolymer of ethylene, vinyl acetate and hexadiene.
The preparation method of the photovoltaic packaging material comprises the following steps:
(1) Mixing ethylene, vinyl acetate and hexadiene with mass percent of 80%, 10% and 10% respectively, and polymerizing to obtain a terpolymer of ethylene, vinyl acetate and hexadiene;
(2) And (3) blending and extruding the terpolymer, the main crosslinking agent, the auxiliary crosslinking agent, the light stabilizer, the coupling agent and the ultraviolet absorber in an extruder, controlling the temperature at 90 ℃, and carrying out casting, cooling, slitting and coiling procedures on the extrudate to obtain the photovoltaic packaging material.
Examples 4 to 7
Examples 4 to 7 differ from example 1 in the mass percentages of ethylene, vinyl acetate and hexadiene, in particular as follows:
example 4: when three monomers are prepared, the mass percentage of vinyl acetate is 5%, the mass percentage of hexadiene is 18%, ethylene is 100%, and the rest is the same as that of the example 1;
example 5: when three monomers are prepared, the mass percentage of vinyl acetate is 15%, the mass percentage of hexadiene is 18%, and the mass percentage of ethylene is 100%, and the rest is the same as that of the example 1;
example 6: when three monomers are prepared, the mass percentage of vinyl acetate is 3%, the mass percentage of hexadiene is 18%, ethylene is 100%, and the rest is the same as that of the example 1;
example 7: when three monomers were prepared, the mass percentage of vinyl acetate was 18%, the mass percentage of hexadiene was 18%, ethylene was 100%, and the rest was the same as in example 1.
Examples 8 to 11
Examples 4-7 differ from example 1 in the mass percent of ethylene, vinyl acetate and hexadiene, and the further terpolymers formed differ in the respective structural unit ratios as follows:
example 8: when three monomers are prepared, the mass percentage of hexadiene is 15%, the mass percentage of vinyl acetate is 12%, ethylene is 100%, and the rest is the same as that of the example 1;
example 9: when three monomers are prepared, the mass percentage of hexadiene is 25%, the mass percentage of vinyl acetate is 12%, ethylene is 100%, and the rest is the same as that of the example 1;
example 10: when three monomers are prepared, the mass percentage of hexadiene is 10%, the mass percentage of vinyl acetate is 12%, ethylene is 100%, and the rest is the same as that of the example 1;
example 11: when three monomers were prepared, the mass percentage of hexadiene was 30%, the mass percentage of vinyl acetate was 12%, ethylene was 100%, and the rest was the same as in example 1.
Example 12
This example differs from example 1 in that in the preparation of the terpolymer hexadiene was replaced by an equal mass of heptadiene, the remainder being the same as example 1.
Example 13
This example differs from example 1 in that in the preparation of the terpolymer hexadiene was replaced with equal mass of octadiene, the remainder being the same as in example 1.
Example 14
The embodiment provides a photovoltaic packaging material, which comprises the following components in parts by weight:
Figure BDA0003418690840000111
the matrix resin is a terpolymer of ethylene, vinyl acetate, hexadiene and octadiene.
The preparation method of the photovoltaic packaging material comprises the following steps:
(1) Mixing ethylene, vinyl acetate, hexadiene and octadiene with mass percentages of 68%, 12%, 15% and 5%, and performing high-pressure bulk polymerization to obtain a tetrapolymer of ethylene, vinyl acetate, hexadiene and octadiene;
(2) And (3) blending and extruding the quadripolymer, a main crosslinking agent, an auxiliary crosslinking agent, a light stabilizer, a coupling agent and an ultraviolet absorber in an extruder, controlling the temperature at 95 ℃, and carrying out casting, cooling, slitting and coiling procedures on the extrudate to obtain the photovoltaic packaging material.
Comparative example 1
This comparative example differs from example 1 in that the terpolymer of ethylene, vinyl acetate and hexadiene was replaced by an equal mass of ethylene-vinyl acetate copolymer, the mass ratio of vinyl acetate building blocks being 28%, commercially available from Han Hua under the designation E282PV.
Comparative example 2
This comparative example differs from example 1 in that in the preparation of the terpolymer hexadiene was replaced by equal mass of pentadiene, the remainder being the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that in the preparation of the terpolymer hexadiene was replaced by equal mass of nonadiene, the remainder being the same as in example 1.
Performance testing
The photovoltaic packaging materials described in examples 1 to 14 and comparative examples 1 to 3 were subjected to the following test:
(1) Peel strength: after the photovoltaic packaging material is laminated with glass, the peeling strength is tested before and after DH2000 (85 ℃ C. &85% RH) (the temperature is 85 ℃ C. Times.humidity is 85%. Times.2000 h), and the attenuation degree is observed;
(2) Appearance: laminating the photovoltaic packaging material and the battery piece to form a photovoltaic module, and observing the edge of the photovoltaic module and the corrosion degree of the battery piece after DH 2000;
the edge of the assembly is marked as grade I, and the assembly is sequentially divided into grade I, grade II, grade III and grade IV from light to heavy according to the severity of bubbles and delamination;
the corrosion-free battery piece is marked as 1 grade, and is divided into a grade I, a grade II, a grade III and a grade IV in sequence from light to heavy according to the corrosion phenomenon of the battery piece, and the specific table is shown in table 1.
TABLE 1
Figure BDA0003418690840000131
(3) Transmittance: after DH2000 (85 ℃ C. &85% RH), the test method is a UV method (380 nm-1100 nm).
The test results are summarized in table 2.
TABLE 2
Figure BDA0003418690840000132
Figure BDA0003418690840000141
Figure BDA0003418690840000151
As can be seen from analysis of the data in Table 2, the peel strength of the packaging material DH2000 of the invention is between 109 and 202N/cm, the peel strength of the packaging material DH2000 is between 83 and 195N/cm, the peel strength is not obvious in attenuation, the light transmittance is above 90%, and further formed photovoltaic modules are free or slightly free of delamination, bubbles and corrosion.
As can be seen from analysis of comparative example 1 and example 1, the performance of comparative example 1 is inferior to that of example 1, and it is proved that the photovoltaic packaging material of the invention replaces the traditional ethylene-vinyl acetate copolymer with a copolymer of ethylene, vinyl acetate and C6-C8 diene, thereby being more beneficial to the improvement of the performance of the photovoltaic module.
From an analysis of comparative examples 2-3 and examples 1 and 12-13, comparative examples 2-3 are inferior to examples 12-13 in performance, and it is proved that among the copolymers of ethylene, vinyl acetate and diene, the diene selected from hexadiene, heptadiene and octadiene forms a photovoltaic encapsulating material which is superior in performance, that is, hexadiene is preferred, in example 2.
Analysis of examples 4-7 shows that examples 6-7 perform less well than examples 4-5, demonstrating that the photovoltaic encapsulant material formed with the ethylene, vinyl acetate and C6-C8 diene copolymers has better properties with the vinyl acetate building blocks in the terpolymer in the range of 5% -15% by mass.
Analysis of examples 8-11 shows that examples 10-11 perform less well than examples 8-9, demonstrating that the photovoltaic encapsulant material formed with the copolymer of ethylene, vinyl acetate and C6-C8 diene has better properties with the mass ratio of C6-C8 diene structural units in the terpolymer ranging from 15% to 25%. In addition, the results of example 3 also help demonstrate this conclusion.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The photovoltaic packaging material is characterized by comprising the following components in parts by weight:
100 parts of matrix resin
0.1-2.6 parts of auxiliary agent;
the matrix resin comprises a copolymer of ethylene, vinyl acetate and a diene;
the diene includes any one or a combination of at least two of hexadiene, heptadiene or octadiene.
2. The photovoltaic packaging material according to claim 1, wherein the mass percentage of vinyl acetate is 5% -15% based on the total mass of the ethylene, vinyl acetate and diene is 100%;
preferably, the mass percentage of the diene is 15-25% based on 100% of the total mass of the ethylene, the vinyl acetate and the diene.
3. The photovoltaic packaging material of claim 1 or 2, wherein the auxiliary agent comprises any one or a combination of at least two of a primary crosslinking agent, a secondary crosslinking agent, a light stabilizer, a coupling agent, or an ultraviolet absorber.
4. The photovoltaic encapsulation material of claim 3, wherein the primary crosslinking agent comprises any one or a combination of at least two of t-butyl peroxy (2-ethylhexyl) carbonate, t-amyl peroxy (2-ethylhexyl) carbonate, or dicumyl peroxide;
preferably, the auxiliary crosslinking agent comprises any one or a combination of at least two of allyl diglycol dicarbonate, trimethylolpropane triacrylate or pentaerythritol triacrylate;
preferably, the method comprises the steps of, the light stabilizer comprises a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol bis (2, 6-tetramethyl-4-piperidinyl) sebacate or poly { [6- [ (1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2, 6, -tetramethyl-piperidinyl) imino ] -1, 6-hexamethylenediyl [ (2, 6-tetramethyl-4-piperidinyl) imino ] };
preferably, the coupling agent comprises any one or a combination of at least two of vinyltrimethoxysilane, vinylmethyldimethoxysilane or vinyltriisopropenoxysilane;
preferably, the ultraviolet light absorber comprises any one or a combination of at least two of 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazin-4-one or 2' - (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole.
5. The photovoltaic packaging material according to claim 3 or 4, wherein the weight part of the main crosslinking agent is 0.4-0.7 part;
preferably, the weight part of the auxiliary cross-linking agent is 0.2-0.6 part;
preferably, the weight part of the light stabilizer is 0.1-0.5 part;
preferably, the weight part of the coupling agent is 0.1-0.3 part;
preferably, the weight part of the ultraviolet absorber is 0.1-0.5 part.
6. A method of preparing the photovoltaic packaging material of any of claims 1-5, comprising the steps of:
mixing and processing a copolymer of ethylene, vinyl acetate and diene with an auxiliary agent to obtain the photovoltaic packaging material;
the diene includes any one or a combination of at least two of hexadiene, heptadiene or octadiene.
7. The method of claim 6, wherein the processing comprises extrusion, casting, cooling, slitting, and winding;
preferably, the temperature of the extrusion is 85-95 ℃.
8. The method according to claim 6 or 7, wherein the method for producing the copolymer of ethylene, vinyl acetate and diene comprises the steps of:
polymerizing ethylene, vinyl acetate and diene to obtain a copolymer of ethylene, vinyl acetate and diene;
preferably, the mass percentage of the vinyl acetate is 5% -15% based on 100% of the total mass of the ethylene, the vinyl acetate and the diene;
preferably, the mass percentage of the diene is 15% -25% based on 100% of the total mass of the ethylene, the vinyl acetate and the diene.
9. The method of claim 8, wherein the polymerization temperature is 100-120 ℃;
preferably, the polymerization time is 1 to 2 hours.
10. A photovoltaic module comprising the photovoltaic packaging material of any one of claims 1-5.
CN202111554405.6A 2021-12-17 2021-12-17 Photovoltaic packaging material and preparation method and application thereof Pending CN116265554A (en)

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