Packaging composite material, preparation method thereof and perovskite battery assembly

Abstract

The invention relates to the technical field of photovoltaic packaging materials, in particular to a packaging composite material, a preparation method thereof and a perovskite battery assembly. The packaging composite material is prepared from 5 to 25 parts of first EVA (Ethylene Vinyl Acetate) resin, 20 to 50 parts of second EVA resin, 5 to 20 parts of ethylene-acrylic acid copolymer, 10 to 30 parts of compound compatilizer, 1 to 10 parts of silane coupling agent, 0.05 to 0.5 part of modified inorganic filler and 0.05 to 0.5 part of antioxidant, the compound compatilizer is prepared from short-chain siloxane modified EVA resin, long-chain siloxane modified EVA resin and EBA resin according to the mass ratio of (5 to 30) to (5 to 40) to (1 to 15). The packaging composite material disclosed by the invention has good adhesive property, electrical property, damp heat resistance, ultraviolet aging resistance and low creep property, and meets the low-temperature packaging process requirements of the perovskite battery assembly.

Description

Technical Field

[0001] The present invention relates to the technical field of photovoltaic packaging materials, and in particular to a packaging composite material and a preparation method thereof, and a perovskite battery assembly. Background Art

[0002] Among many photovoltaic materials, perovskite has attracted much attention due to its excellent photoelectric conversion efficiency and cost-effectiveness. To achieve the commercial application of perovskite cells, one of the key links is the breakthrough of its packaging technology, which aims to improve the efficiency and stability of the cells.

[0003] Conventional cross-linked adhesive films are mostly made of high-molecular resins with high melting points and low melting points, with cross-linking agents and cross-linking aids. When used in lamination, the adhesive film will undergo a cross-linking reaction. Photovoltaic modules generally require a high temperature of more than 140°C, and the packaging time is generally as long as 20 to 30 minutes. If the packaging temperature is too high, it will have a great impact on the crystal structure and phase of perovskite, which will lead to a decrease in the efficiency of perovskite cells. In comparison, inorganic-based packaging materials have better heat resistance and moisture resistance, but they are more difficult to process and mass produce.

[0004] The patent application with publication number CN118667454A records a perovskite photovoltaic encapsulation material, which is prepared by processing polyvinyl butyral, terminal hydroxyl hyperbranched polycarbonate, functional copolymer and auxiliary agent, and has good resistance to wet heat aging, high temperature resistance and bonding performance. Wherein the melting point of polyvinyl butyral is above 165°C, and the melting point of polycarbonate is above 220°C. After being made into slurry, it is necessary to use ultraviolet light irradiation for curing. The patent application with publication number CN118064101A records a perovskite photovoltaic encapsulation material, which is prepared by using hyperbranched perfluoropolyether polyurethane acrylate polymer, epoxy hyperbranched polyborosiloxane, furoic acid allyl ester and auxiliary agent, and is prepared into slurry using solvent, and then cured by ultraviolet light irradiation. In the preparation of the above-mentioned encapsulation material, solvent recovery is difficult, mass production in the later stage is difficult, and the coating thickness is difficult to control. In addition, when using ultraviolet light for curing, the perovskite material is sensitive to ultraviolet light, and the film is easily destroyed under ultraviolet light, which accelerates the degradation of perovskite solar cells.

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

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

[0007] One object of the present invention is to provide a packaging composite material having good adhesion properties, low creep properties and excellent aging resistance, which can meet the low-temperature packaging process of perovskite battery components and can achieve mass production.

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

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

[0010] In order to achieve the above-mentioned object of the present invention, the present invention provides a packaging composite material on the one hand, comprising the following components in parts by weight:

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

[0012] The composite 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 number of main chain atoms of the short-chain siloxane is less than or equal to 8; the number of main chain atoms of the long-chain siloxane is greater than 8;

[0013] The VA content of the first EVA resin is lower than the VA content 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 of vinyl trimethoxy silane, vinyl triethoxy silane, triacetoxy vinyl silane, γ-aminopropyl triethoxy silane and γ-aminopropyl trimethoxy silane.

[0017] In a specific embodiment of the present invention, 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). Further, the long-chain siloxane includes at least one of γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, 3-glycidyloxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, vinylsilane oligomer and vinylsilane copolymer.

[0018] In a specific embodiment of the present invention, the modified inorganic filler is an inorganic filler modified by a silane coupling agent. Further, the modified inorganic filler is mainly prepared from 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 in a high-speed stirrer, 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 stirrer in 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 microbeads, nano-montmorillonite and nano-kaolin.

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

[0023] Another aspect of the present invention provides a perovskite battery assembly, comprising any one of the above-mentioned packaging composite materials.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

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

[0026] (2) The present invention adopts 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 acid copolymer while improving the low-temperature toughness, bonding performance 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 packaging composite material of the present invention has good adhesion, electrical properties, moisture and heat resistance, UV aging resistance and low creep performance, and meets the low-temperature packaging process requirements of perovskite battery components. DETAILED DESCRIPTION

[0029] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be appreciated by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work, all belong to the scope of protection of the present invention. If specific conditions are not indicated in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0030] In the description of the present invention, it should be noted that the terms “first”, “second” and “third” are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0031] The packaging temperature of existing adhesive films is too high, which has a great impact on the crystal structure of perovskite, thus causing the performance of perovskite cells to deteriorate. Perovskite cell components need to have good adhesion, low creep performance and excellent aging resistance, and be able to meet the low-temperature packaging process requirements of perovskite components, and can realize mass production of packaging composite materials.

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

[0033] 5-25 parts of the first EVA resin, 20-50 parts of the second EVA resin, 5-20 parts of ethylene-acrylic acid copolymer, 10-30 parts of compound compatibilizer, 1-10 parts of silane coupling agent, 0.05-0.5 parts of modified inorganic filler and 0.05-0.5 parts of 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 number of main chain atoms of the short-chain siloxane is less than or equal to 8; the number of main chain atoms of the long-chain siloxane is greater than 8;

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

[0036] The present invention adopts ethylene-vinyl acetate copolymer (EVA) resin with different VA contents and ethylene-acrylic acid copolymer resin to compound, and the EVA resin with low VA content helps to improve the high temperature creep resistance of the material; and the EVA resin with low VA content can reduce the release of acetic acid during the aging process of the material, reduce the ions that can be dissociated and generated by the material, greatly slow down the carrier density of the material, and increase the volume resistivity of the material. A large number of polar groups in the EVA resin with high VA content improve the mechanical properties of the material. The randomly distributed carboxyl groups in the molecular structure of the ethylene-acrylic acid copolymer help to improve the bonding performance and creep resistance of the material. At the same time, the presence of the carboxyl group and the hydrogen bonding effect in the system inhibit the crystallization of the molecule and destroy the linear structure of the main chain, which can give full play to the toughness and optical properties of the ethylene-acrylic acid copolymer, and give the material more excellent low temperature packaging performance.

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

[0038] A small amount of modified inorganic filler is added to the material of the present invention, so as to improve the mechanical properties of the material while ensuring the light transmittance of the material.

[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 largest number of atoms in the corresponding siloxane substances. For example, in different embodiments, the number of main chain atoms of the short-chain siloxane of the present invention can be 3, 4, 5, 6, 7 or 8, etc.; the number of main chain atoms of the long-chain siloxane of the present invention can be 9, 10, 12, 14 or 16, etc.

[0040] In the packaging composite material of the present invention, each component is matched with each other in proportion to take into account good bonding performance, low creep performance and excellent aging resistance. For example, in different embodiments, in the packaging composite material, the amount of each component in parts by weight can be 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 a range consisting of any two of them;

[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 a range consisting of any two of them;

[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 two thereof;

[0044] The amount of the compound compatibilizer can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or a range consisting of any two of them;

[0045] The amount of the silane coupling agent can be 1 part, 3 parts, 5 parts, 8 parts, 10 parts or a range consisting of any two of them;

[0046] The amount of the modified inorganic filler can be 0.05 part, 0.1 part, 0.3 part, 0.4 part, 0.5 part or a range consisting of any two thereof;

[0047] The amount of the antioxidant can be 0.05 part, 0.1 part, 0.3 part, 0.4 part, 0.5 part or a range consisting of any two of them.

[0048] The shorter siloxane side chains in the short-chain siloxane-modified EVA resin can be interspersed in the molecular structure of the EVA resin matrix, which can solve the problem of stress concentration points caused by insufficient segment extension caused by the first EVA resin with low VA content; the longer siloxane side chains in the long-chain siloxane-modified EVA can further increase the entanglement in the EVA resin matrix, make the microstructure denser during the lamination process, reduce the water vapor permeability of the material, and increase the adhesion and creep resistance of the material. EBA has good reactivity, 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 properties. In the composite compatibilizer of the present invention, the mass ratio of the short-chain siloxane-modified EVA resin to the 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, 30:4 0 or a range consisting of any two thereof; the mass ratio of the short-chain siloxane-modified EVA resin to the 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 a range consisting of any two thereof. Further, the compound compatibilizer includes a short-chain siloxane-modified EVA resin, a long-chain siloxane-modified EVA resin and an 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] For example, in different embodiments, in the first EVA resin, the VA content may be 14%, 15%, 16%, 18%, 20% or a range consisting of any two thereof; in the second EVA resin, the VA content may be 20%, 22%, 24%, 25%, 26%, 28% or a range consisting of any two 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:(1-10), preferably 1:(1.5-4).

[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. For example, 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 two of them.

[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 by 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 of vinyl trimethoxy silane, vinyl triethoxy silane, triacetoxy vinyl silane, γ-aminopropyl triethoxy silane and γ-aminopropyl trimethoxy silane.

[0056] For example, in different embodiments, the mass ratio of EVA resin to short-chain siloxane can be 100:1, 100:3, 100:5, 100:8, 100:10 or a range consisting of any two 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 a range consisting of any two thereof.

[0057] In a specific embodiment of the present invention, 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). Further, the long-chain siloxane includes at least one of γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, 3-glycidyloxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, vinylsilane oligomer and vinylsilane copolymer.

[0058] For example, 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 a range consisting of any two 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 a range consisting of any two thereof.

[0059] In actual operation, the short-chain siloxane-modified EVA resin and the long-chain siloxane-modified EVA resin are mixed in proportion and granulated at a granulation temperature of 165 to 185°C.

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

[0061] In a specific embodiment of the present invention, the initiator used to prepare the short-chain siloxane-modified EVA resin and the long-chain siloxane-modified EVA resin can be a peroxide initiator, such as each independently selected from at least one of diisopropylbenzene peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, tert-butyl perbenzoate, tert-butyl peracetate and tert-butyl peroxy-3,5,5-trimethylhexanoate.

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

[0063] The present invention improves the uniformity of the inorganic filler dispersion in the resin matrix by silane modification of the inorganic filler, reduces the effect of inorganic filler agglomeration on the material transmittance, and gives full play to the improvement of the mechanical properties of the material by the inorganic filler. For example, in different embodiments, the mass ratio of the inorganic filler to the silane coupling agent in the modified inorganic filler can be 100:5, 100:6, 100:8, 100:9, 100:10 or a range consisting of any two of them.

[0064] In actual operation, the preparation method of the modified inorganic filler may include: mixing the inorganic filler and the silane coupling agent in a high-speed stirrer, then reacting at 140-150°C for 5-20 minutes, and cooling to room temperature to obtain the modified inorganic filler. Another preparation scheme of the modified inorganic filler may include: mixing the inorganic filler and the silane coupling agent in a high-speed stirrer according to a proportion to obtain the modified inorganic filler.

[0065] In the present invention, the silane coupling agent used in the encapsulation composite material and the silane coupling agent used in the modified inorganic filler can be independently selected from at least one of vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, octyltriethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide and vinyltri(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 microbeads, 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 one of the above-mentioned packaging composite materials, comprising the following steps: weighing each component in proportion, mixing evenly, melt-extruding, and casting into a film.

[0069] In actual operation, during melt extrusion and cast film forming, the temperature settings of each zone of the extruder are as follows: Zone I 65-110°C, Zone II 65-110°C, Zone III 70-115°C, Zone IV 70-115°C, Zone V 70-115°C, Zone VI 70-115°C, and die head 115°C.

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

[0071] Example 1

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

[0073] Among them, the VA content of the first EVA resin is 18%, and the VA content of the second EVA resin is 28%; the silane coupling agent is γ-aminopropyl trimethoxy silane, 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 with a high-speed stirrer, and then melt extruding and granulating with a twin screw. The temperature of melt granulation is: 80-85°C in zone I, 85-95°C in zone II, 100-120°C in zone III, 100-120°C in zone IV, 100-120°C in zone V, 100-120°C in zone VI, 100-120°C in zone VII, 100-120°C in zone VIII, 100-120°C in zone IX, and 110°C in the die.

[0074] The short-chain siloxane-modified EVA resin is prepared by mixing EVA resin with a VA content of 28%, short-chain siloxane (vinyl trimethoxy silane) and diisopropylbenzene peroxide in a mass ratio of 100:5:0.02 and then extruding and granulating. The specific melt granulation temperatures are: 80-85°C in zone I, 85-95°C in zone II, 100-120°C in zone III, 120-140°C in zone IV, 165-185°C in zone V, 165-185°C in zone VI, 165-185°C in zone VII, 165-185°C in zone VIII, 120-140°C in zone IX and 110°C at the die head; the long-chain siloxane The alkyl-modified EVA resin is prepared by mixing EVA resin with a VA content of 28%, long-chain siloxane (γ-methacryloxypropyltrimethoxysilane) and diisopropylbenzene peroxide in a mass ratio of 100:5:0.02 and then extruding and granulating. The specific melt granulation temperatures are: 80-85°C in zone I, 85-95°C in zone II, 100-120°C in zone III, 120-140°C in zone IV, 165-185°C in zone V, 165-185°C in zone VI, 165-185°C in zone VII, 165-185°C in zone VIII, 120-140°C in zone IX and 110°C at the die head.

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

[0076] The method for preparing the packaging composite material of this embodiment comprises the following steps:

[0077] The first EVA resin, the second EVA resin, the ethylene-acrylic acid copolymer (EAA), the compound compatibilizer, the silane coupling agent, the modified inorganic filler and the antioxidant are weighed in the above proportions, mixed evenly in a high mixer, melt-extruded and cast into a film, wherein the temperature settings of each zone of the extruder include: 65-110°C in zone I, 65-110°C in zone II, 70-115°C in zone III, 70-115°C in zone IV, 70-115°C in zone V, 70-115°C in zone VI and 115°C in the die.

[0078] Example 2

[0079] This embodiment refers to the packaging composite material and preparation method thereof of Embodiment 1.

[0080] The packaging composite material of this embodiment includes the following components by weight: 10 parts of the first EVA resin, 40 parts of the 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 from 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 packaging composite material and preparation method thereof of Embodiment 1.

[0083] The packaging composite material of this embodiment includes the following components by weight: 25 parts of the first EVA resin, 25 parts of the 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 from 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 packaging composite material and preparation method thereof of Embodiment 1.

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

[0087] Example 5

[0088] This embodiment refers to the packaging composite material and preparation method thereof of Embodiment 1.

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

[0090] Example 6

[0091] This embodiment refers to the packaging composite material and preparation method thereof of Embodiment 1.

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

[0093] Example 7

[0094] This embodiment refers to the encapsulation composite material and preparation method thereof of Embodiment 1, with the only difference being that the amounts of the components of the encapsulation composite material and the amounts of the components of the compounded compatibilizer are different.

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

[0096] Example 8

[0097] This embodiment refers to the encapsulation composite material and preparation method thereof of Embodiment 1, with the only difference being that the amounts of the components of the encapsulation composite material and the amounts of the components of the compounded compatibilizer are different.

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

[0099] Example 9

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

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

[0102] Example 10

[0103] This embodiment refers to the packaging composite material and preparation method thereof of Example 4.

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

[0105] Embodiment 11

[0106] This embodiment refers to the packaging composite material and preparation method thereof of Example 4.

[0107] The composite compatibilizer of this embodiment is prepared from 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 packaging composite material and preparation method thereof of Example 4.

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

[0111] Embodiment 13

[0112] This embodiment refers to the packaging composite material and preparation method thereof of Example 4.

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

[0114] Embodiment 14

[0115] This embodiment refers to the packaging composite material and preparation method thereof of Example 4.

[0116] The packaging composite material of this embodiment includes the following components by weight: 5 parts of the first EVA resin, 40 parts of the 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 from short-chain siloxane-modified EVA resin, long-chain siloxane-modified EVA resin and EBA resin in a mass ratio of 20:30:10.

[0117] Embodiment 15

[0118] This embodiment refers to the packaging composite material and preparation method thereof of Example 4.

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

[0120] Example 16

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

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

[0123] Comparative Example 1

[0124] Comparative Example 1 refers to the packaging composite material and preparation method thereof of Example 4.

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

[0126] Comparative Example 2

[0127] Comparative Example 2 refers to the packaging composite material and preparation method thereof of Example 4, except that the amounts of the components of the compound compatibilizer are different.

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

[0129] Comparative Example 3

[0130] Comparative Example 3 refers to the packaging composite material and preparation method thereof of Example 4, except that the amounts of the components of the packaging composite material are different.

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

[0132] Comparative Example 4

[0133] Comparative Example 4 refers to the packaging composite material and preparation method thereof of Example 4, except that the amounts of the components of the packaging composite material are different.

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

[0135] Comparative Example 5

[0136] Comparative Example 5 refers to the encapsulation composite material and the preparation method thereof of Example 4, except that: the amounts of the components of the encapsulation composite material are different.

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

[0138] Comparative Example 6

[0139] Comparative Example 6 refers to the packaging composite material and preparation method thereof of Example 4, except that the amounts of the components of the compound compatibilizer are different.

[0140] The compound compatibilizer of Comparative Example 6 is 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 packaging composite material and preparation method thereof of Example 4, except that the amounts of the components of the compound compatibilizer are different.

[0143] The compound compatibilizer of Comparative Example 7 is 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 packaging composite materials of different embodiments and comparative examples was tested. The testing method is as follows. The test results are shown in Tables 1 and 2.

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

[0147] Creep resistance test: Take 10cm×20cm glass, 10cm×10cm glass and 10cm×10cm adhesive film, laminate and bond the two glasses with the adhesive film, and then put them vertically into a 125℃ oven, and record the slip distance of the 10cm×10cm glass in 168h.

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

[0149]

[0150]

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

[0152]

[0153]

[0154] Note: The yellowing value of the film is the yellowing value of the film after aging minus the yellowing value of the film in the initial test.

[0155] It can be seen from the above test results that the packaging composite material of the present invention exhibits high peel strength, electrical properties, excellent moisture and heat resistance and UV aging resistance adhesion properties and low aging yellowing value, as well as low creep performance of the film. In Comparative Example 1, EAA was not added, and the corresponding aging adhesion force was low, indicating that the addition of EAA in combination with the remaining components can significantly improve the adhesion performance of the packaging composite material. The compound compatibilizer in Comparative Example 2 does not contain EBA, and the adhesion performance and anti-creep effect are significantly reduced. In Comparative Example 3, no compound compatibilizer was added, resulting in poor compatibility between different materials and poor overall performance. In Comparative Example 4, the amount of compound compatibilizer added was reduced, and the adhesion performance of the film was reduced. In Comparative Example 5, the amount of compound compatibilizer added was increased, and the amount of siloxane-modified resin increased, resulting in a decrease in the aging performance of the film. The compound compatibilizers in Comparative Examples 6 and 7 are prepared by using only a single short-chain siloxane-modified EVA and a single long-chain siloxane-modified EVA and EBA resin, which have poor effects on improving the compatibility between different materials, and have poor bonding properties 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, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements 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. A packaging composite material, characterized in that: It includes the following components by weight: 5-25 parts of the first EVA resin, 20-50 parts of the second EVA resin, 5-20 parts of ethylene-acrylic acid copolymer, 10-30 parts of compound compatibilizer, 1-10 parts of silane coupling agent, 0.05-0.5 parts of modified inorganic filler and 0.05-0.5 parts of antioxidant; The composite 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 number of main chain atoms of the short-chain siloxane is less than or equal to 8; the number of main chain atoms of the long-chain siloxane is greater than 8; The VA content of the first EVA resin is lower than the VA content of the second EVA resin.

2. The packaging composite material according to claim 1, characterized in that: The VA content of the first EVA resin is 14% to 20%; the VA content of the second EVA resin is 20% to 28%.

3. The packaging 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).

4. The packaging composite material according to claim 1, characterized in that: 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); Preferably, the short-chain siloxane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

5. The packaging composite material according to claim 1, characterized in that: 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); Preferably, the long-chain siloxane includes at least one of γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, 3-glycidyloxypropyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, vinylsilane oligomers and vinylsilane copolymers.

6. The packaging composite material according to claim 1, characterized in that: The compound compatibilizer comprises 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).

7. The packaging composite material according to claim 1, characterized in that: The modified inorganic filler is an inorganic filler modified by a silane coupling agent; Preferably, the modified inorganic filler is mainly prepared from an inorganic filler and a silane coupling agent in a mass ratio of 100:(5-10); Preferably, the preparation of the modified inorganic filler comprises: mixing the inorganic filler and the silane coupling agent uniformly in a high-speed stirrer, then reacting at 140-150° C. for 5-20 minutes, 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 the silane coupling agent in a high-speed stirrer in proportion to obtain the modified inorganic filler.

8. The packaging composite material according to claim 1, characterized in that: The inorganic filler comprises at least one of precipitated silica, fumed silica, magnesium hydroxide, aluminum hydroxide, glass microbeads, nano-montmorillonite and nano-kaolin.

9. A method for preparing a packaging composite material, characterized in that: The method comprises the following steps: preparing the components of the packaging composite material according to any one of claims 1 to 8, mixing them uniformly, melting and extruding them, and casting them into films.

10. A perovskite battery assembly, characterized in that: The encapsulation composite material comprises the encapsulation composite material according to any one of claims 1 to 8.

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