Encapsulation composite materials and their preparation methods and perovskite solar cell modules

Abstract

This invention relates to the field of photovoltaic encapsulation materials technology, and in particular to an encapsulation composite material, its preparation method, and a perovskite solar cell module. The encapsulation composite material comprises: 5-25 parts of a first EVA resin, 20-50 parts of a second EVA resin, 5-20 parts of an ethylene-acrylic acid copolymer, 10-30 parts of a compound compatibilizer, 1-10 parts of a silane coupling agent, 0.05-0.5 parts of a modified inorganic filler, and 0.05-0.5 parts of an antioxidant; the compound compatibilizer comprises short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of (5-30):(5-40):(1-15). The encapsulation composite material of this invention exhibits good adhesion, electrical properties, resistance to damp heat and ultraviolet aging, and low creep properties, meeting the requirements of low-temperature encapsulation processes for perovskite solar cell modules.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic encapsulation materials technology, and in particular to an encapsulation composite material, its preparation method, and a perovskite battery module. Background Technology

[0002] Among numerous photovoltaic materials, perovskite stands out for its superior photoelectric conversion efficiency and cost-effectiveness. A key factor in realizing the commercial application of perovskite solar cells lies in breakthroughs in their encapsulation technology, aimed at improving cell efficiency and stability.

[0003] Conventional cross-linked encapsulating films typically use high-melt-index, low-melting-point polymer resins, combined with cross-linking agents and cross-linking aids. During lamination, the film undergoes a cross-linking reaction. Photovoltaic modules generally require temperatures above 140°C, and encapsulation times are typically 20–30 minutes. Excessively high encapsulation temperatures significantly impact the crystal structure and phases of perovskite, leading to reduced efficiency in perovskite cells. In contrast, inorganic-based encapsulation materials offer better heat and moisture resistance, but they are more difficult to process and mass-produce.

[0004] Patent application CN118667454A discloses a perovskite photovoltaic encapsulation material, prepared using polyvinyl butyral, hydroxyl-terminated hyperbranched polycarbonate, functional copolymers, and additives. It exhibits good resistance to damp heat aging, high-temperature resistance, and adhesion. Polyvinyl butyral has a melting point above 165℃, and polycarbonate has a melting point above 220℃. After being prepared into a slurry, it requires ultraviolet light irradiation for curing. Patent application CN118064101A discloses another perovskite photovoltaic encapsulation material, prepared using hyperbranched perfluoropolyether polyurethane acrylate oligomers, epoxy-based hyperbranched polyborosiloxane, allyl furoate, and additives. It is prepared into a slurry using a solvent and then cured using ultraviolet light irradiation. In the preparation of the above encapsulation materials, solvent recovery is difficult, mass production is challenging, and the coating thickness is difficult to control. Furthermore, the use of ultraviolet light for curing makes perovskite materials quite sensitive to ultraviolet light. Under ultraviolet light, the thin film is easily damaged, which accelerates the degradation of perovskite solar cells.

[0005] Therefore, in the field of perovskite encapsulation, there is an urgent need for an encapsulation composite material that can meet the requirements of low-temperature encapsulation process for perovskite battery modules and can be mass-produced.

[0006] In view of this, the present invention is hereby proposed. Summary of the Invention

[0007] One object of the present invention is to provide an encapsulation composite material with good adhesion, low creep performance and excellent aging resistance, which can meet the low-temperature encapsulation process of perovskite battery modules and can be mass-produced.

[0008] Another object of the present invention is to provide a method for preparing encapsulated composite materials.

[0009] Another object of the present invention is to provide a perovskite battery module comprising the above-mentioned encapsulation composite material.

[0010] To achieve the above-mentioned objectives of the present invention, one aspect of the present invention provides an encapsulating composite material comprising the following components in parts by weight:

[0011] The mixture consists of 5-25 parts of the first EVA resin, 20-50 parts of the second EVA resin, 5-20 parts of the ethylene-acrylic acid copolymer, 10-30 parts of the compound compatibilizer, 1-10 parts of the silane coupling agent, 0.05-0.5 parts of the modified inorganic filler, and 0.05-0.5 parts of the antioxidant.

[0012] The compound compatibilizer comprises short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of (5-30):(5-40):(1-15); wherein the short-chain siloxane has a main chain atom count of less than or equal to 8, and the long-chain siloxane has a main chain atom count of more than 8.

[0013] The VA content of the first EVA resin is lower than that of the second EVA resin.

[0014] In a specific embodiment of the present invention, the VA content in the first EVA resin is 14% to 20%; and the VA content in the second EVA resin is 20% to 28%.

[0015] In a specific embodiment of the present invention, the mass ratio of the first EVA resin to the second EVA resin is 1:(1-10).

[0016] In a specific embodiment of the present invention, the short-chain siloxane-modified EVA resin is mainly prepared from EVA resin, short-chain siloxane, and initiator in a mass ratio of 100:(1-10):(0.01-0.5). Further, the short-chain siloxane includes at least one selected from vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane.

[0017] In a specific embodiment of the present invention, the long-chain siloxane-modified EVA resin is mainly prepared from EVA resin, long-chain siloxane, and initiator in a mass ratio of 100:(1-10):(0.01-0.5). Further, the long-chain siloxane includes at least one selected from γ-glycidoxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane, 3-glycidoxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, vinylsilane oligomers, and vinylsilane copolymers.

[0018] In a specific embodiment of the present invention, the modified inorganic filler is an inorganic filler modified with a silane coupling agent. Further, the modified inorganic filler is mainly prepared by mixing an inorganic filler and a silane coupling agent in a mass ratio of 100:(5-10).

[0019] In a specific embodiment of the present invention, the preparation of the modified inorganic filler includes: mixing the inorganic filler and the silane coupling agent evenly in a high-speed mixer, then reacting at 140-150°C for 5-20 minutes, and cooling to room temperature to obtain the modified inorganic filler.

[0020] In another specific embodiment of the present invention, the preparation of the modified inorganic filler includes: mixing the inorganic filler and the silane coupling agent in a high-speed mixer in a certain proportion to obtain the modified inorganic filler.

[0021] In a specific embodiment of the present invention, the inorganic filler includes at least one of precipitated silica, fumed silica, magnesium hydroxide, aluminum hydroxide, glass microspheres, nano-montmorillonite, and nano-kaolin.

[0022] Another aspect of the present invention provides a method for preparing any of the above-described encapsulation composite materials, comprising the following steps: weighing each component in proportion, mixing them evenly, melting and extruding, and casting into a film.

[0023] In another aspect, the present invention provides a perovskite solar cell module comprising any of the encapsulation composite materials described above.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] (1) This invention uses EVA resin with different VA contents to compound with ethylene-acrylic acid copolymer. EVA with low VA content helps to improve the high temperature creep resistance of the material and can reduce the release of acetic acid during aging, slowing down the carrier density and increasing the volume resistivity. EVA with high VA content has a large number of polar groups that improve the mechanical properties of the material. The carboxyl groups randomly distributed in the molecular structure of ethylene-acrylic acid copolymer help to improve the adhesion and creep resistance of the material. At the same time, the presence of carboxyl groups and the hydrogen bonding in the system inhibit the crystallization of molecules and destroy the linear structure of the main chain, which can give full play to the toughness and optical properties of ethylene-acrylic acid copolymer and give the material better low temperature encapsulation performance.

[0026] (2) The present invention uses a compound compatibilizer made of short-chain siloxane modified EVA resin, long-chain siloxane modified EVA resin and EBA, which can improve the compatibility of the first EVA resin, the second EVA resin and the ethylene-acrylic copolymer, while improving the low-temperature toughness, adhesion and sealing performance of the material.

[0027] (3) A small amount of modified inorganic filler is added to the material of the present invention to improve the mechanical properties of the material.

[0028] (4) The encapsulation composite material of the present invention has good adhesion, electrical properties, resistance to damp heat and ultraviolet aging, and low creep properties, which meet the requirements of low temperature encapsulation process of perovskite battery modules. Detailed Implementation

[0029] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0030] In the description of this invention, it should be noted that the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0031] The excessively high encapsulation temperature of existing encapsulation films significantly impacts the crystal structure of perovskite, leading to degraded perovskite solar cell performance. Perovskite solar cell modules require encapsulation composite materials with excellent adhesion, low creep resistance, and superior aging resistance, while also meeting the low-temperature encapsulation process requirements for perovskite modules and enabling mass production.

[0032] Based on this, the present invention provides an encapsulating composite material comprising the following components in parts by weight:

[0033] The mixture consists of 5-25 parts of the first EVA resin, 20-50 parts of the second EVA resin, 5-20 parts of the ethylene-acrylic acid copolymer, 10-30 parts of the compound compatibilizer, 1-10 parts of the silane coupling agent, 0.05-0.5 parts of the modified inorganic filler, and 0.05-0.5 parts of the antioxidant.

[0034] The compound compatibilizer includes short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA in a mass ratio of (5-30):(5-40):(1-15); wherein the short-chain siloxane has a main chain atom count of less than or equal to 8, and the long-chain siloxane has a main chain atom count of more than 8.

[0035] The VA content of the first EVA resin is lower than that of the second EVA resin.

[0036] This invention employs a blend of ethylene-vinyl acetate copolymer (EVA) resins with varying VA contents and ethylene-acrylic acid copolymer resins. The low VA content of the EVA resin helps improve the material's high-temperature creep resistance; furthermore, it reduces acetic acid release during aging, decreases the number of ions that can dissociate, and significantly slows down the increase in carrier density, thus reducing the material's volume resistivity. The high VA content of the EVA resin, with its numerous polar groups, enhances the material's mechanical properties. The randomly distributed carboxyl groups in the ethylene-acrylic acid copolymer molecular structure help improve the material's adhesive and creep resistance properties. Simultaneously, the presence of carboxyl groups and hydrogen bonding in the system inhibits molecular crystallization and disrupts the linear structure of the main chain, fully leveraging the toughness and optical properties of the ethylene-acrylic acid copolymer and imparting superior low-temperature encapsulation performance.

[0037] The present invention uses a compound compatibilizer prepared by short-chain siloxane modified EVA resin, long-chain siloxane modified EVA resin and ethylene-butyl acrylate copolymer (EBA), which can improve the compatibility of the first EVA resin, the second EVA resin and the ethylene-acrylic copolymer, while improving the low-temperature toughness, adhesion and sealing performance of the material.

[0038] The material of this invention incorporates a small amount of modified inorganic filler to improve its mechanical properties while ensuring light transmittance.

[0039] It should be noted that the main chain of the short-chain siloxane and the main chain of the long-chain siloxane of the present invention refer to the chain with the most atoms in the corresponding siloxane. For example, in different embodiments, the number of atoms in the main chain of the short-chain siloxane of the present invention can be 3, 4, 5, 6, 7 or 8, etc.; the number of atoms in the main chain of the long-chain siloxane of the present invention can be 9, 10, 12, 14 or 16, etc.

[0040] In the encapsulation composite material of the present invention, the components are proportioned to achieve a balance of good adhesion, low creep performance, and excellent aging resistance. For example, in different embodiments, the amounts of each component in the encapsulation composite material, by weight, are as follows:

[0041] The amount of the first EVA resin can be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, or any combination thereof.

[0042] The amount of the second EVA resin can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any combination thereof.

[0043] The amount of ethylene-acrylic acid copolymer can be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, or any combination thereof;

[0044] The amount of the compound compatibilizer can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or any combination thereof;

[0045] The amount of silane coupling agent can be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, or any combination thereof;

[0046] The amount of modified inorganic filler can be 0.05 parts, 0.1 parts, 0.3 parts, 0.4 parts, 0.5 parts, or any combination thereof;

[0047] The amount of antioxidant can be 0.05 parts, 0.1 parts, 0.3 parts, 0.4 parts, 0.5 parts, or any combination thereof.

[0048] In short-chain siloxane-modified EVA resin, the shorter siloxane branches can be intercalated into the molecular structure of the EVA resin matrix, solving the stress concentration problem caused by insufficient chain extension in the first EVA resin with low VA content. In long-chain siloxane-modified EVA, the longer siloxane branches can further increase the entanglement in the EVA resin matrix, making the microstructure denser during lamination, reducing the material's water vapor permeability, and increasing the material's adhesion and creep resistance. EBA has good reactivity, a high melting point, good heat-sealing performance, and good low-temperature impact resistance. The addition of an appropriate amount of EBA can improve the compatibility of the first EVA resin, the second EVA resin, and the ethylene-acrylic acid copolymer, and provide the material with good low-temperature toughness, adhesion, and sealing performance. In the compound compatibilizer of the present invention, the mass ratio of short-chain siloxane-modified EVA resin to long-chain siloxane-modified EVA resin can be 5:5, 5:10, 5:20, 5:30, 5:40, 10:5, 10:15, 10:30, 20:5, 20:10, 30:5, 30:10, 30:20, or 30:4. The range is 0 or any combination thereof; the mass ratio of short-chain siloxane-modified EVA resin to EBA resin can be 5:1, 10:1, 20:1, 30:1, 5:5, 10:5, 20:5, 30:5, 5:10, 30:10, 5:15, 10:15, 20:15 or any combination thereof. Further, the compatibilizer includes short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin and EBA resin in a mass ratio of (10–30):(20–40):(5–10).

[0049] In a specific embodiment of the present invention, the preparation of the compound compatibilizer includes: weighing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin and EBA resin in proportion, and performing melt extrusion granulation.

[0050] In a specific embodiment of the present invention, the VA content in the first EVA resin is 14% to 20%; and the VA content in the second EVA resin is 20% to 28%.

[0051] In different embodiments, the VA content in the first EVA resin can be 14%, 15%, 16%, 18%, 20%, or any combination thereof; the VA content in the second EVA resin can be 20%, 22%, 24%, 25%, 26%, 28%, or any combination thereof.

[0052] In a specific embodiment of the present invention, the mass ratio of the first EVA resin to the second EVA resin is 1:(1 to 10), preferably 1:(1.5 to 4).

[0053] By further adjusting the mass ratio of the first EVA resin to the second EVA resin, the mechanical strength, creep resistance, and aging resistance of the encapsulated composite material can be improved. In different embodiments, the mass ratio of the first EVA resin to the second EVA resin can be 1:1, 1:2, 1:3, 1:4, 1:5, or any combination thereof.

[0054] In a specific embodiment of the present invention, the ethylene-acrylic acid copolymer includes at least one of ethylene-methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-acrylic acid copolymer (EAA).

[0055] In a specific embodiment of the present invention, the short-chain siloxane-modified EVA resin is mainly prepared from EVA resin, short-chain siloxane, and initiator in a mass ratio of 100:(1-10):(0.01-0.5). Further, the short-chain siloxane includes at least one selected from vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane.

[0056] In different embodiments, the mass ratio of EVA resin to short-chain siloxane can be a range of 100:1, 100:3, 100:5, 100:8, 100:10, or any combination thereof; the mass ratio of EVA resin to initiator can be a range of 100:0.01, 100:0.1, 100:0.2, 100:0.3, 100:0.5, or any combination thereof.

[0057] In a specific embodiment of the present invention, the long-chain siloxane-modified EVA resin is mainly prepared from EVA resin, long-chain siloxane, and initiator in a mass ratio of 100:(1-10):(0.01-0.5). Further, the long-chain siloxane includes at least one selected from γ-glycidoxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane, 3-glycidoxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, vinylsilane oligomers, and vinylsilane copolymers.

[0058] In different embodiments, the mass ratio of EVA resin to long-chain siloxane can be 100:1, 100:3, 100:5, 100:8, 100:10, or any combination thereof; the mass ratio of EVA resin to initiator can be 100:0.01, 100:0.1, 100:0.2, 100:0.3, 100:0.5, or any combination thereof.

[0059] In practice, short-chain siloxane-modified EVA resin and long-chain siloxane-modified EVA resin are prepared separately in proportion, mixed, and then granulated. The granulation temperature can be 165–185℃.

[0060] The EVA resin used to prepare short-chain siloxane-modified EVA resin and long-chain siloxane-modified EVA resin can be the same as the second EVA resin, with a VA content of 28% and a melt index of 25 g / 10 min.

[0061] In specific embodiments of the present invention, the initiators used to prepare short-chain siloxane-modified EVA resin and long-chain siloxane-modified EVA resin can be peroxide initiators, such as those independently selected from at least one of dicumyl peroxide, di-tert-butyl peroxide, dicumyl hydrogen peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide, benzoyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peracetate, and tert-butyl peroxide-3,5,5-trimethylhexanoate.

[0062] In a specific embodiment of the present invention, the modified inorganic filler is an inorganic filler modified with a silane coupling agent. Further, the modified inorganic filler is mainly prepared by mixing an inorganic filler and a silane coupling agent in a mass ratio of 100:(5-10).

[0063] This invention, by modifying inorganic fillers with silane, improves the uniformity of inorganic filler dispersion in the resin matrix, reduces the impact of inorganic filler agglomeration on material transmittance, and fully leverages the role of inorganic fillers in enhancing the mechanical properties of the material. For example, in different embodiments, the mass ratio of inorganic filler to silane coupling agent in the modified inorganic filler can be within the range of 100:5, 100:6, 100:8, 100:9, 100:10, or any combination thereof.

[0064] In practice, the preparation method of modified inorganic fillers may include: mixing inorganic fillers and silane coupling agents uniformly in a high-speed mixer, then reacting at 140–150°C for 5–20 min, and cooling to room temperature to obtain modified inorganic fillers. Another preparation method of modified inorganic fillers may include: mixing inorganic fillers and silane coupling agents uniformly in a high-speed mixer according to a specified ratio to obtain modified inorganic fillers.

[0065] In this invention, the silane coupling agent used in the encapsulation composite material and the silane coupling agent used in the modified inorganic filler can each be independently selected from at least one of vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, octyltriethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide and vinyltris(2-methoxyethoxy)silane.

[0066] In a specific embodiment of the present invention, the inorganic filler includes at least one of precipitated silica, fumed silica, magnesium hydroxide, aluminum hydroxide, glass microspheres, nano-montmorillonite, and nano-kaolin.

[0067] In a specific embodiment of the present invention, the antioxidant includes at least one of antioxidant 1035, antioxidant 168, antioxidant 1010 and antioxidant 1098.

[0068] Another aspect of the present invention provides a method for preparing any of the above-mentioned encapsulation composite materials, comprising the following steps: weighing each component in proportion, mixing them evenly, melting and extruding, and casting into a film.

[0069] In actual operation, the temperature settings of each zone of the extruder in melt extrusion and casting are as follows: Zone I 65~110℃, Zone II 65~110℃, Zone III 70~115℃, Zone IV 70~115℃, Zone V 70~115℃, Zone VI 70~115℃, and the die head 115℃.

[0070] Another aspect of the present invention provides a perovskite battery module, comprising any of the above-mentioned encapsulation composite materials.

[0071] Example 1

[0072] This embodiment provides an encapsulation composite material comprising the following components by weight: 5 parts of first EVA resin, 45 parts of second EVA resin, 10 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.6 parts of silane coupling agent, 0.18 parts of modified inorganic filler, and 0.18 parts of antioxidant.

[0073] The first EVA resin has a VA content of 18%, and the second EVA resin has a VA content of 28%. The silane coupling agent is γ-aminopropyltrimethoxysilane, and the antioxidant is 1010. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 5:30:10 using a high-speed mixer, followed by melt extrusion granulation using a twin-screw extruder. The melt granulation temperatures are: Zone I 80–85℃, Zone II 85–95℃, Zone III 100–120℃, Zone IV 100–120℃, Zone V 100–120℃, Zone VI 100–120℃, Zone VII 100–120℃, Zone VIII 100–120℃, Zone IX 100–120℃, and die head 110℃.

[0074] Short-chain siloxane-modified EVA resin is prepared by extrusion granulation of EVA resin with 28% VA content, short-chain siloxane (vinyltrimethoxysilane), and dicumyl peroxide in a mass ratio of 100:5:0.02. The specific melt granulation temperatures are: Zone I 80–85℃, Zone II 85–95℃, Zone III 100–120℃, Zone IV 120–140℃, Zone V 165–185℃, Zone VI 165–185℃, Zone VII 165–185℃, Zone VIII 165–185℃, Zone IX 120–140℃, and die head 110℃; long-chain siloxane... The alkyl-modified EVA resin is prepared by extrusion granulation of EVA resin with 28% VA content, long-chain siloxane (γ-methacryloyloxypropyltrimethoxysilane), and dicumyl peroxide in a mass ratio of 100:5:0.02. The specific melt granulation temperatures are: Zone I 80-85℃, Zone II 85-95℃, Zone III 100-120℃, Zone IV 120-140℃, Zone V 165-185℃, Zone VI 165-185℃, Zone VII 165-185℃, Zone VIII 165-185℃, Zone IX 120-140℃, and die head 110℃.

[0075] The modified inorganic filler is prepared by mixing fumed silica and γ-aminopropyltrimethoxysilane in a high-speed mixer at a mass ratio of 100:8 for 10-15 min, then placing the mixture in an oven and reacting it at 140-150℃ for 10-15 min, followed by cooling.

[0076] The preparation method of the encapsulation composite material in this embodiment includes the following steps:

[0077] Weigh the first EVA resin, the second EVA resin, ethylene-acrylic acid copolymer (EAA), compound compatibilizer, silane coupling agent, modified inorganic filler, and antioxidant according to the above proportions. Mix them evenly in a high-speed mixer, then melt-extrude and cast into a film. The temperature settings of each zone of the extruder are as follows: Zone I 65-110℃, Zone II 65-110℃, Zone III 70-115℃, Zone IV 70-115℃, Zone V 70-115℃, Zone VI 70-115℃, and die head 115℃.

[0078] Example 2

[0079] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1.

[0080] The encapsulation composite material of this embodiment includes the following components by weight: 10 parts of first EVA resin, 40 parts of second EVA resin, 13 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.72 parts of silane coupling agent, 0.186 parts of modified inorganic filler, and 0.186 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0081] Example 3

[0082] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1.

[0083] The encapsulation composite material of this embodiment includes the following components by weight: 25 parts of first EVA resin, 25 parts of second EVA resin, 15 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0084] Example 4

[0085] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1.

[0086] The encapsulation composite material of this embodiment comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0087] Example 5

[0088] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1.

[0089] The encapsulation composite material of this embodiment includes the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 20 parts of compound compatibilizer, 3.4 parts of silane coupling agent, 0.17 parts of modified inorganic filler, and 0.17 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 30:30:10.

[0090] Example 6

[0091] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1.

[0092] The encapsulation composite material of this embodiment comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 10:40:5.

[0093] Example 7

[0094] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1, with the only difference being the amount of each component of the encapsulation composite material and the amount of each component of the compatibilizer.

[0095] The encapsulation composite material of this embodiment comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:20:5.

[0096] Example 8

[0097] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 1, with the only difference being the amount of each component of the encapsulation composite material and the amount of each component of the compatibilizer.

[0098] The encapsulation composite material of this embodiment comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:20:10.

[0099] Example 9

[0100] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 8, the only difference being that the preparation method of the modified inorganic filler is different.

[0101] The method for preparing the modified inorganic filler in this embodiment includes: weighing fumed silica and γ-aminopropyltrimethoxysilane in proportion and mixing them directly in a high-speed mixer for 10-15 minutes to obtain the modified inorganic filler.

[0102] Example 10

[0103] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0104] The compatibilizer in this embodiment is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 5:40:10.

[0105] Example 11

[0106] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0107] The compatibilizer in this embodiment is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 30:5:10.

[0108] Example 12

[0109] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0110] The compound compatibilizer in this embodiment is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 10:20:10.

[0111] Example 13

[0112] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0113] The compatibilizer in this embodiment is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 30:40:5.

[0114] Example 14

[0115] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0116] The encapsulation composite material of this embodiment comprises the following components by weight: 5 parts of first EVA resin, 40 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0117] Example 15

[0118] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4.

[0119] The encapsulation composite material of this embodiment comprises the following components by weight: 10 parts of first EVA resin, 35 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0120] Example 16

[0121] This embodiment refers to the encapsulation composite material and its preparation method in Embodiment 4, with the only difference being the amount of each component in the encapsulation composite material.

[0122] The encapsulation composite material of this embodiment includes the following components by weight: 25 parts of first EVA resin, 20 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 30 parts of compound compatibilizer, 3.8 parts of silane coupling agent, 0.19 parts of modified inorganic filler, and 0.19 parts of antioxidant. The compound compatibilizer is prepared by mixing short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of 20:30:10.

[0123] Comparative Example 1

[0124] Comparative Example 1 refers to the encapsulation composite material and its preparation method in Example 4.

[0125] The encapsulation composite material of Comparative Example 1 comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of compound compatibilizer, 2.6 parts of silane coupling agent, 0.13 parts of modified inorganic filler and 0.13 parts of antioxidant.

[0126] Comparative Example 2

[0127] Comparative Example 2 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component of the compatibilizer are different.

[0128] The compatibilizer of Comparative Example 2 was prepared by mixing short-chain siloxane-modified EVA resin and long-chain siloxane-modified EVA resin in a mass ratio of 20:30.

[0129] Comparative Example 3

[0130] Comparative Example 3 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component in the encapsulation composite material are different.

[0131] The encapsulation composite material of Comparative Example 3 comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 2.6 parts of silane coupling agent, 0.13 parts of modified inorganic filler, and 0.13 parts of antioxidant.

[0132] Comparative Example 4

[0133] Comparative Example 4 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component in the encapsulation composite material are different.

[0134] The encapsulation composite material of Comparative Example 4 comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 5 parts of compound compatibilizer, 2.8 parts of silane coupling agent, 0.14 parts of modified inorganic filler and 0.14 parts of antioxidant.

[0135] Comparative Example 5

[0136] Comparative Example 5 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component in the encapsulation composite material are different.

[0137] The encapsulation composite material of Comparative Example 5 comprises the following components by weight: 15 parts of first EVA resin, 30 parts of second EVA resin, 20 parts of ethylene-acrylic acid copolymer (EAA), 35 parts of compound compatibilizer, 4 parts of silane coupling agent, 0.2 parts of modified inorganic filler and 0.2 parts of antioxidant.

[0138] Comparative Example 6

[0139] Comparative Example 6 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component of the compatibilizer are different.

[0140] The compatibilizer of Comparative Example 6 was prepared from short-chain siloxane-modified EVA resin and EBA resin in a mass ratio of 50:10.

[0141] Comparative Example 7

[0142] Comparative Example 7 refers to the encapsulation composite material and its preparation method in Example 4, the difference being that the amounts of each component of the compatibilizer are different.

[0143] The compatibilizer of Comparative Example 7 was prepared from long-chain siloxane-modified EVA resin and EBA resin in a mass ratio of 50:10.

[0144] Experimental Example

[0145] The performance of the encapsulated composite materials in different embodiments and comparative examples was tested. The test methods are as follows, and the test results are shown in Tables 1 and 2.

[0146] The performance of the films prepared in different embodiments and comparative examples was tested according to the standard GB / T 29848-2018.

[0147] Creep resistance test: Take a 10cm×20cm glass, a 10cm×10cm glass, and a 10cm×10cm adhesive film. Laminate and bond the two glass pieces together with the adhesive film, and then place them vertically in a 125℃ oven. Record the sliding distance of the 10cm×10cm glass after 168 hours.

[0148] Table 1 Performance test results of different encapsulation composite materials

[0149]

[0150]

[0151] Table 2 Performance test results of different encapsulated composite materials

[0152]

[0153]

[0154] Note: The yellowing value of the film is the yellowing value tested after the film has aged, minus the yellowing value tested initially.

[0155] The test results above show that the encapsulation composite material of the present invention exhibits high peel strength, electrical properties, excellent resistance to damp heat and UV aging, low yellowing value, and low film creep performance. Comparative Example 1, which did not contain EBA, showed lower aging adhesion, indicating that adding EBA in combination with the other components significantly improves the adhesion performance of the encapsulation composite material. Comparative Example 2, which did not contain EBA in its compatibilizer, showed significantly reduced adhesion and creep resistance. Comparative Example 3, which did not contain a compatibilizer, resulted in poor compatibility between different materials and deteriorated overall performance. In Comparative Example 4, reducing the amount of compatibilizer reduced the film's adhesion performance. In Comparative Example 5, increasing the amount of compatibilizer increased the amount of siloxane-modified resin, leading to a decrease in the film's aging performance. The compatibilizers in Comparative Examples 6 and 7 were prepared by using EVA modified with a single short-chain siloxane and EVA modified with a single long-chain siloxane with EBA resin. They had poor effect on improving the compatibility between different materials, and poor adhesion and creep resistance.

[0156] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An encapsulated composite material, characterized in that, Includes the following components by weight: The mixture consists of 5-25 parts of the first EVA resin, 20-50 parts of the second EVA resin, 5-20 parts of the ethylene-acrylic acid copolymer, 10-30 parts of the compound compatibilizer, 1-10 parts of the silane coupling agent, 0.05-0.5 parts of the modified inorganic filler, and 0.05-0.5 parts of the antioxidant. The compound compatibilizer includes short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin and EBA resin in a mass ratio of (5-30):(5-40):(1-15). The VA content of the first EVA resin is lower than that of the second EVA resin; the VA content of the first EVA resin is 14% to 20%; and the VA content of the second EVA resin is 20% to 28%. The short-chain siloxane modified EVA resin is mainly prepared from EVA resin, short-chain siloxane and initiator in a mass ratio of 100:(1-10):(0.01-0.5); the short-chain siloxane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane. The long-chain siloxane modified EVA resin is mainly prepared by EVA resin, long-chain siloxane and initiator in a mass ratio of 100:(1-10):(0.01-0.5); the long-chain siloxane includes at least one of γ-glycidoxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane, 3-glycidoxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane and hexadecyltriethoxysilane.

2. The encapsulation composite material according to claim 1, characterized in that, The mass ratio of the first EVA resin to the second EVA resin is 1:(1~10).

3. The encapsulation composite material according to claim 1, characterized in that, The compound compatibilizer includes short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin, and EBA resin in a mass ratio of (10-30):(20-40):(5-10).

4. The encapsulation composite material according to claim 1, characterized in that, The modified inorganic filler is an inorganic filler modified with a silane coupling agent.

5. The encapsulation composite material according to claim 4, characterized in that, The modified inorganic filler is mainly prepared by inorganic filler and silane coupling agent in a mass ratio of 100:(5-10).

6. The encapsulation composite material according to claim 5, characterized in that, The preparation of the modified inorganic filler includes: mixing the inorganic filler and silane coupling agent evenly in a high-speed mixer, then reacting at 140-150℃ for 5-20 min, and cooling to room temperature to obtain the modified inorganic filler; Alternatively, the preparation of the modified inorganic filler includes: mixing the inorganic filler and silane coupling agent in a high-speed mixer in a certain proportion to obtain the modified inorganic filler.

7. The encapsulation composite material according to claim 1, characterized in that, The inorganic filler includes at least one of precipitated silica, fumed silica, magnesium hydroxide, aluminum hydroxide, glass microspheres, nano-montmorillonite, and nano-kaolin.

8. A method for preparing encapsulated composite materials, characterized in that, The process includes the following steps: dispensing the components of the encapsulation composite material according to any one of claims 1 to 7, mixing them evenly, melting and extruding them, and casting them into a film.

9. A perovskite solar cell module, characterized in that, Includes the encapsulation composite material as described in any one of claims 1 to 7.

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