CN121203555A - Photovoltaic encapsulating films, their preparation methods and applications, and methods for recycling photovoltaic modules. - Google Patents
Photovoltaic encapsulating films, their preparation methods and applications, and methods for recycling photovoltaic modules.Info
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- CN121203555A CN121203555A CN202511411331.9A CN202511411331A CN121203555A CN 121203555 A CN121203555 A CN 121203555A CN 202511411331 A CN202511411331 A CN 202511411331A CN 121203555 A CN121203555 A CN 121203555A
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Abstract
The invention belongs to the technical field of photovoltaics, and provides a photovoltaic packaging adhesive film, a preparation method and application thereof, and a recovery method of a photovoltaic module. The photovoltaic packaging adhesive film comprises specific amounts of raw materials including matrix resin, low-temperature cross-linking agent, low-temperature catalyst, silane coupling agent, ultraviolet light stabilizer, organic peroxide initiator, auxiliary cross-linking agent and alcohol compound serving as reversible dynamic transesterification reaction group, wherein the matrix resin is EVA, POE and/or ethylene-butene copolymer, the low-temperature cross-linking agent is carboxylate cross-linking agent, bisoxazoline cross-linking agent and/or metal-organic ligand cross-linking agent with the reaction temperature below 150 ℃, and the low-temperature catalyst is polynuclear metal catalyst, solid acid resin catalyst, solid base catalyst and/or bimetallic MOF derivative catalyst with the reaction temperature below 150 ℃. The adhesive film can realize the recycling of the adhesive film and the photovoltaic module more efficiently and effectively, has wide adaptability, and has high crosslinking degree, peeling strength and PID resistance.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a photovoltaic packaging adhesive film, a preparation method and application thereof, and a recovery method of a photovoltaic module with the photovoltaic packaging adhesive film.
Background
The development background of the recyclable photovoltaic packaging adhesive film relates to a plurality of aspects, including the following aspects:
1. With the rapid development of the photovoltaic industry, along with the continuous increase of the global demand for renewable energy sources, photovoltaic power generation is widely applied as a clean energy source. The production and use of photovoltaic modules has also risen year by year. And the traditional photovoltaic packaging material can pollute the environment after being abandoned. Therefore, how to process and recycle the photovoltaic module after the service life is over is one of the important problems of industry concern.
2. The environmental awareness is improved, the global attention to sustainable development is increased, and enterprises and consumers pay more attention to the environmental influence of products. Thus, the use of recyclable materials is becoming a trend. By developing the recyclable photovoltaic packaging adhesive film, the waste of the photovoltaic module after the life cycle is finished can be reduced, and the burden on the environment is reduced.
3. The push of policies and regulations governments in many countries and regions have continually brought out relevant policies that support renewable energy and environmental materials, encouraging enterprises to develop and use recyclable materials. Along with the increase of the demand of recyclable materials, related industry standards and specifications are gradually established and perfected, and a basis is provided for popularization of recyclable photovoltaic packaging adhesive films.
4. Market demand-more and more consumers tend to choose environmental protection products, pushing the market demand for recyclable photovoltaic packaging adhesive films. Moreover, in the photovoltaic industry, competition between businesses has also prompted them to seek innovative and sustainable solutions to meet market demands and promote brand images. Therefore, with the deep penetration of the sustainable development concept, development and popularization of the recyclable photovoltaic packaging adhesive film will positively influence the future development of the photovoltaic industry.
The traditional photovoltaic packaging material is crosslinked through chemical covalent bonds, and the chemical covalent bonds have the characteristics of high bond energy, stable structure and irrecoverability after fracture. Therefore, once the traditional photovoltaic packaging adhesive film is heated, laminated, crosslinked and cured to form a polymer crosslinked network structure, the polymer crosslinked network structure is fixed and is difficult to change, so that the recovery treatment of the retired photovoltaic module is greatly limited.
Therefore, in recent years, a recyclable photovoltaic packaging film material having a dynamic covalent bond crosslinking structure as shown in publication No. CN115895508a has attracted attention. However, the adhesive film composition, the packaging adhesive film and the photovoltaic module provided by the prior art CN115895508a have at least the following drawbacks:
(1) The packaging adhesive film using the adhesive film composition is mainly of a reversible crosslinked network structure, the crosslinking degree of the adhesive film is low, the bonding stability is to be improved, and the PID resistance of the adhesive film and the photovoltaic module is poor.
(2) The reaction temperature of the catalyst and the cross-linking agent used in the adhesive film composition is high, so that when the packaging adhesive film is prepared by cross-linking and curing, higher heating lamination temperature (such as 150-200 ℃) is needed, so that the energy consumption during cross-linking and curing is high, and high efficiency, energy conservation and high recycling rate cannot be realized at the same time.
(3) The adhesive film composition can only be used for preparing a photovoltaic packaging adhesive film (such as EVA packaging adhesive film) of a recyclable vinyl polar copolymer system, but cannot be used for preparing a recyclable POE packaging adhesive film, an EPE packaging adhesive film and the like, namely, the adhesive film composition is not suitable for the photovoltaic packaging adhesive film of the POE-containing system, so that the application and popularization of the adhesive film composition are limited.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a photovoltaic packaging adhesive film, a preparation method and application thereof, and a recovery method of a photovoltaic module with the photovoltaic packaging adhesive film.
Based on the above, the invention discloses a photovoltaic packaging adhesive film, which comprises the following raw materials in parts by weight:
100 parts of matrix resin, 5-10 parts of low-temperature cross-linking agent, 1-3 parts of low-temperature catalyst, 0.1-1 part of silane coupling agent, 0.05-0.5 part of ultraviolet light stabilizer, 0.1-1 part of organic peroxide initiator, 0.1-1 part of auxiliary cross-linking agent and 0-30 parts of alcohol compound serving as reversible dynamic transesterification reaction group;
the matrix resin is at least one of ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene-butene copolymer;
The low-temperature cross-linking agent is a cross-linking agent meeting the reaction temperature below 150 ℃ and is at least one of carboxylate cross-linking agent, bisoxazoline cross-linking agent and metal-organic ligand cross-linking agent;
The low-temperature catalyst is a catalyst meeting the reaction temperature below 150 ℃, and is a polynuclear metal catalyst, a solid acid resin catalyst, a solid base catalyst and a bimetallic MOF derivative catalyst.
Preferably, the low-temperature cross-linking agent is a cross-linking agent meeting the reaction temperature of 120-130 ℃, and the low-temperature cross-linking agent is beta-carboxyethyl acrylate;
the low-temperature catalyst is a catalyst meeting the reaction temperature of 120-130 ℃, and the low-temperature catalyst is a solid base catalyst CaO/MgO@CoFe 2O4.
Further preferably, the organic peroxide initiator is tert-butyl peroxy-2-ethylhexyl carbonate and the co-crosslinking agent is triallyl isocyanurate;
the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane, and the ultraviolet light stabilizer is sebacic acid bis-2, 6-tetramethyl piperidinol ester.
Further preferably, when the matrix resin is ethylene-vinyl acetate copolymer with VA content not less than 20%, no alcohol compound is required to be added in the raw material formulation of the photovoltaic packaging adhesive film.
Further preferably, when the matrix resin is ethylene-vinyl acetate copolymer with VA content less than 20%, or when the matrix resin contains ethylene-octene copolymer and/or ethylene-butene copolymer, 10-30 parts of alcohol compound is required to be added into the raw material formulation of the photovoltaic packaging adhesive film.
Further preferably, the alcohol compound is at least one of polyvinyl alcohol and hyperbranched polyvinyl alcohol.
The invention also discloses a preparation method of the photovoltaic packaging adhesive film, which comprises the steps of sequentially premixing, remelting and extruding, casting and forming films, cooling, slitting and rolling all raw materials weighed according to the formula amount, and obtaining the photovoltaic packaging adhesive film after a heating and laminating process in the preparation process of the photovoltaic module.
The invention also discloses application of the photovoltaic packaging adhesive film, which is applied to preparation of a photovoltaic module, and the application method comprises the following steps:
Sequentially laminating a photovoltaic front plate, a first packaging adhesive film, a photovoltaic cell, a second packaging adhesive film and a photovoltaic backboard in sequence from top to bottom, vacuumizing at a heating lamination temperature of less than 150 ℃, laminating at a low temperature, crosslinking and curing for 8-30 min to obtain a photovoltaic laminated piece, and performing post-treatment on the photovoltaic laminated piece to obtain a photovoltaic module;
The first packaging adhesive film and the second packaging adhesive film are both photovoltaic packaging adhesive films prepared by the preparation method
Preferably, in the application method, the temperature of heating lamination is 120-130 ℃, and the time of low-temperature lamination and crosslinking curing is 8-15 min;
The post-processing includes mounting a junction box on the back side of the photovoltaic laminate and fixedly mounting the photovoltaic laminate edge into the photovoltaic bezel.
The invention also discloses a recovery method of the photovoltaic module, which comprises the following steps:
S1, removing a post-processing component of a photovoltaic module to obtain a photovoltaic laminated piece;
S2, carrying out heat treatment on the photovoltaic laminated piece, wherein the heat treatment temperature is less than 150 ℃, and adopting laser to radiate a first packaging adhesive film and a second packaging adhesive film in the photovoltaic laminated piece to enable the first packaging adhesive film and the second packaging adhesive film to be melted, generate flow and be removed;
the photovoltaic module is the photovoltaic module obtained by the method.
Compared with the prior art, the invention at least comprises the following beneficial effects:
The photovoltaic packaging adhesive film with a double-network structure (free radical polymerization crosslinking network and reversible dynamic transesterification reaction network) of dynamic valence bond and covalent bond can be obtained through the mutual matching of a certain weight portion of raw material formulas such as matrix resin, low-temperature crosslinking agent, low-temperature catalyst, silane coupling agent, organic peroxide initiator, auxiliary crosslinking agent, alcohol compound (serving as a reversible dynamic transesterification reaction group) and the like, and through low-temperature lamination, crosslinking and curing. Therefore, (1) the crosslinking degree of the photovoltaic packaging adhesive film can be further improved on the basis of ensuring the high light transmittance (380-1100 nm) and the high bonding performance (high peeling strength) of the photovoltaic packaging adhesive film, and the PID resistance of the photovoltaic packaging adhesive film and the photovoltaic module can be further improved. (2) The dynamic valence bond can solve the problems of surface whitening and light transmittance reduction of the photovoltaic packaging adhesive film caused by surface scratch and abrasion, and is beneficial to improving the light transmittance stability and bonding stability of the photovoltaic packaging adhesive film. (3) Meanwhile, the reversible dynamic transesterification network is beneficial to improving the self-healing performance of the photovoltaic packaging adhesive film, improving the recycling rate of the photovoltaic packaging adhesive film and the photovoltaic component thereof and ensuring the high recycling rate of the photovoltaic packaging adhesive film and the photovoltaic component thereof. According to the recycling method disclosed by the invention, only the photovoltaic packaging adhesive film is subjected to low-temperature heat treatment, so that the photovoltaic cell piece, the photovoltaic front plate and the photovoltaic back plate of the photovoltaic module are not damaged, the removed photovoltaic packaging adhesive film can be recycled, and waste gas and waste liquid which pollute the environment are not generated. (4) In addition, the photovoltaic packaging adhesive film is matched with a low-temperature cross-linking agent, a low-temperature catalyst and the like, can realize recycling of the photovoltaic packaging adhesive film and the photovoltaic module more efficiently and energy-effectively, and reduces energy consumption. (5) The raw material formula of the photovoltaic packaging adhesive film can be used for preparing the recyclable EVA photovoltaic packaging adhesive film and also can be used for preparing the recyclable POE photovoltaic packaging adhesive film, and has wide adaptability.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
The invention discloses a photovoltaic packaging adhesive film which comprises the following raw materials in parts by weight:
100 parts of matrix resin, 5-10 parts of low-temperature cross-linking agent, 1-3 parts of low-temperature catalyst, 0.1-1 part of silane coupling agent, 0.05-0.5 part of ultraviolet light stabilizer, 0.1-1 part of organic peroxide initiator, 0.1-1 part of auxiliary cross-linking agent and 0-30 parts of alcohol compound.
Wherein, the matrix resin is selected from the matrix resins commonly used in photovoltaic packaging adhesive films in the market. The matrix resin is at least one of ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE) and ethylene-butene copolymer.
The upper limit of the operating temperature of most crystalline silicon photovoltaic modules is 85-90 ℃, and thin film photovoltaic modules (such as cadmium telluride) can withstand higher temperatures (such as 100 ℃). The reversible dynamic transesterification reaction temperature of the photovoltaic packaging adhesive film (namely the cross-linking curing temperature of the photovoltaic packaging adhesive film, because the cross-linking curing of the photovoltaic packaging adhesive film and the heating lamination of the photovoltaic module are synchronously carried out, the cross-linking curing temperature of the photovoltaic packaging adhesive film, namely the heating lamination temperature of the photovoltaic module is slightly higher than the operation temperature of the photovoltaic module, and the recycling of the photovoltaic module can be realized more efficiently and energy-effectively. Therefore, in order to realize high efficiency, energy saving and high recycling rate at the same time, the photovoltaic packaging adhesive film of the invention is matched with a low-temperature cross-linking agent and a low-temperature catalyst, and the specific types of the low-temperature cross-linking agent and the low-temperature catalyst are selected as follows:
wherein the low-temperature crosslinking agent is at least one of carboxylate crosslinking agent, bisoxazoline crosslinking agent and metal-organic ligand crosslinking agent.
The low temperature crosslinking agent is preferably a crosslinking agent satisfying a crosslinking temperature of 120 ℃, more preferably β -carboxyethyl acrylate. This is because the bisoxazoline-type crosslinking agent is suitable for the gradual reaction of an aqueous system at 120 ℃ and is not easily reacted with an alcoholic hydroxyl group. The metal-organic ligand cross-linking agent is more applied to polymer synthesis hydrogenation reaction, and has high price and high cost. The beta-carboxyethyl acrylate is applied to the photovoltaic packaging adhesive film, and can be used for modifying matrix resin of the photovoltaic packaging adhesive film, so that the toughness and the adhesiveness of the photovoltaic packaging adhesive film can be improved.
Wherein the low-temperature catalyst is a solid resin transesterification catalyst, preferably a catalyst meeting 120 ℃ reaction temperature, specifically a polynuclear metal catalyst (such as Ti-4 tetranuclear titanium catalyst) and a solid acid resin catalyst (such as Ti-4 tetranuclear titanium catalyst)T-62MP, amberlyst 39 WET), a solid base catalyst (e.g., caO/MgO@CoFe 2O4、KF/Fe3O4), a bimetallic MOF derivative catalyst (e.g., caFe-MOF derivative). The low-temperature catalyst is helpful for improving the effect of reversible dynamic transesterification of the photovoltaic packaging adhesive film.
The low-temperature catalyst is more preferably a solid base catalyst CaO/MgO@CoFe 2O4, and the solid base catalyst has the advantage of being used as a reaction catalyst and an antacid to promote the improvement of the PID resistance of the EPE adhesive film and the EVA adhesive film.
Among them, the silane coupling agent is preferably a silane coupling agent 570 (γ -methacryloxypropyl trimethoxysilane). The ultraviolet light stabilizer is preferably an ultraviolet light stabilizer 770 (bis-2, 6-tetramethylpiperidinol sebacate). The organic peroxide initiator is preferably the initiator TBEC (t-butylperoxy-2-ethylhexyl carbonate). The co-crosslinking agent is preferably triallyl isocyanurate (co-crosslinking agent TAIC).
Wherein the alcohol compound is at least one of polyvinyl alcohol and hyperbranched polyvinyl alcohol as the reversible dynamic transesterification reaction group.
The EVA, POE, EPE photovoltaic packaging adhesive films commonly used in the market are modified, so that the recoverability of the photovoltaic module is realized.
For the EVA photovoltaic packaging adhesive film taking EVA as matrix resin, the EVA resin has a large amount of carboxylic ester bonds and/or carboxyl groups, so that the EVA resin can realize the low-temperature crosslinking reaction of the EVA photovoltaic packaging adhesive film system under the combined action of a low-temperature crosslinking agent, a low-temperature catalyst, a silane coupling agent, an organic peroxide initiator and the like (without adding an alcohol compound), and the EVA photovoltaic packaging adhesive film system has a double-network structure (a free radical polymerization crosslinking network and a reversible dynamic transesterification reaction network).
It should be noted that when the VA content in the EVA resin is equal to or greater than 20%, an alcohol compound or a carboxylic acid ester compound may be optionally added as the reversible dynamic transesterification reaction group, whereas when the VA content in the EVA resin is less than 20%, a certain amount of an alcohol compound or a carboxylic acid ester compound may be added as the reversible dynamic transesterification reaction group. Preferably, the alcohol compound is at least one of polyvinyl alcohol and hyperbranched polyvinyl alcohol, and the carboxylic ester compound is beta-carboxyethyl acrylate.
For the POE photovoltaic packaging adhesive film (or the photovoltaic packaging adhesive film which takes the ethylene-butene copolymer as the matrix resin) which takes the POE as the matrix resin, since the matrix resin has no ester exchange reaction group, a certain amount of alcohol compounds (such as 10-30 parts of alcohol compounds) are added as reversible dynamic ester exchange reaction groups in addition to the low-temperature crosslinking agent, the low-temperature catalyst, the silane coupling agent, the organic peroxide initiator and the like to promote the formation of a reversible dynamic ester exchange reaction network.
For the EPE photovoltaic packaging adhesive film, a certain amount of alcohol compounds are required to be added into the POE layer as reversible dynamic transesterification reaction groups, and the EVA layer of the EPE photovoltaic packaging adhesive film has the same formula as the EVA photovoltaic packaging adhesive film.
The preparation method of the photovoltaic packaging adhesive film comprises the steps of sequentially premixing, remelting and extruding, casting and forming films, cooling, slitting and rolling all the raw materials weighed according to the formula amount, and obtaining the photovoltaic packaging adhesive film with the double-network structure (a free radical polymerization cross-linking network and a reversible dynamic transesterification reaction network) through a heating lamination process in the preparation process of a photovoltaic module.
The application of the photovoltaic packaging adhesive film disclosed by the invention is that the photovoltaic packaging adhesive film is applied to the preparation of a photovoltaic module, and the application method comprises the following steps:
Sequentially laminating a photovoltaic front plate, a first packaging adhesive film, a photovoltaic cell, a second packaging adhesive film and a photovoltaic backboard from top to bottom, vacuumizing at a certain heating lamination temperature (120 ℃ and above and below 150 ℃), laminating at a low temperature and crosslinking and curing for 8-30 min (preferably 8-15 min) to obtain a photovoltaic laminated piece, mounting a junction box on the back surface of the photovoltaic laminated piece, and fixedly mounting the edge of the photovoltaic laminated piece into a photovoltaic frame to obtain the photovoltaic module. The first packaging adhesive film and the second packaging adhesive film are both photovoltaic packaging adhesive films with double-network structures, and the weight of the first packaging adhesive film and the weight of the second packaging adhesive film are 380 g.
In the application of the photovoltaic packaging adhesive film, the lamination temperature (namely the crosslinking curing temperature) is controlled to 120-130 ℃, so that the photovoltaic packaging adhesive film with a double-network structure (a free radical polymerization crosslinking network and a reversible dynamic transesterification reaction network) can be obtained, low-temperature crosslinking can be met, and energy consumption is saved.
The photovoltaic packaging adhesive film with the double-network structure is a photovoltaic packaging adhesive film capable of self-healing (namely self-repairing). This is mainly because:
the photovoltaic packaging adhesive film with the double-network structure contains a physical crosslinking structure or a dynamic covalent bond crosslinking structure (such as a reversible dynamic transesterification network structure) with lower bond energy, and the reversible dynamic transesterification network can endow the adhesive film with a self-repairing function (or a self-healing function).
In practice, the self-healable raw materials mainly comprise physical cross-linked structures of lower bond energy (physical cross-linking is generated by intermolecular interactions such as ionic bonds, electrostatic interactions, hydrogen bonds, metal coordination, guest-host interactions, etc.), and/or dynamic covalent cross-linked structures (dynamic covalent cross-linking belongs to chemical bonds, which are capable of converting a polymer structure from one macromolecule to another, and this conversion behaviour is reversible). Under the actions of temperature, illumination, solvent, pH and the like, the dynamic covalent bond can be reversibly broken and recombined, so that the polymer network structure crosslinked by the covalent bond is rearranged, when the action temperature is lower than the transition temperature of the covalent bond, the dynamic covalent bond presents a crosslinked network structure, and when the action temperature is higher than the transition temperature of the covalent bond, the dynamic covalent bond exchange reaction is violently generated, and the crosslinked network structure starts plastic flow under the assistance of external force (such as gravity assistance, airflow blowing assistance, liquid flushing assistance or scraper assistance). Common dynamic covalent bond reactions include transesterification, borate transesterification, disulfide/diselenide exchange, carbamate exchange, diels-Alder, siloxane exchange, olefin metathesis, imine exchange, and the like.
In addition, under the external stimulus such as heating, pressurizing, laser radiation and the like, the reversible dynamic transesterification reaction network can also promote the melting of the photovoltaic packaging adhesive film to carry out plastic flow, and after the melting flow of the photovoltaic packaging adhesive film is removed, each structure of the photovoltaic module is easily separated from each other, so that the disassembly and recycling of the photovoltaic module can be realized. Therefore, the photovoltaic packaging adhesive film with the double-network structure is also a recyclable photovoltaic packaging adhesive film, and can realize high recycling rate of the photovoltaic module.
Therefore, if certain external stimulus is given to the photovoltaic packaging adhesive film, the reversible recombination of dynamic covalent bonds (such as carboxylic ester bonds) can be realized, and the photovoltaic packaging adhesive film has a self-healing function and can also realize the recycling of the photovoltaic packaging adhesive film and the whole photovoltaic module.
When the photovoltaic module is recycled by heating, light radiation equipment (such as laser radiation equipment) is vertically arranged at the gaps between the photovoltaic front plate (such as photovoltaic glass) and the photovoltaic cell and between the photovoltaic backboard and the photovoltaic cell, so that the photovoltaic packaging adhesive film is easier to melt and flow under the actions of heating, laser radiation and gravity and separate from the photovoltaic module, and the photovoltaic module is disassembled, thereby achieving the recycling purpose.
The invention relates to a recovery method of a photovoltaic module, which comprises the following steps:
s1, removing the photovoltaic frame and the junction box of the photovoltaic module to obtain the photovoltaic laminated piece.
S2, carrying out heat treatment on the photovoltaic laminated piece, wherein the heat treatment temperature is 120-130 ℃, and adopting laser to radiate a first packaging adhesive film and a second packaging adhesive film in the photovoltaic laminated piece, so that the first packaging adhesive film and the second packaging adhesive film are melted to generate flow and removed, and the photovoltaic cell and the rest of the constituent structures of the photovoltaic module can be recovered.
In step S2, the laser is a laser (common laser includes continuous laser and femto-second laser) that can be absorbed by the organic bonded photovoltaic packaging adhesive film. The fluid flow of the photovoltaic packaging adhesive film can be assisted by air flow blowing, liquid flushing and the like.
Under certain stimulus (heating and/or radiation), the photovoltaic packaging adhesive film can be melted, so that the photovoltaic module can be easily separated, the photovoltaic packaging adhesive film can be recycled, other structures of the photovoltaic module can be recycled under the condition of not damaging, the recycling rate of the whole photovoltaic module can be improved, and the recycling cost is reduced. In addition, laminated air bubbles are a big pain point of many photovoltaic modules at present. The recyclable photovoltaic packaging adhesive film has a reversible dynamic network structure, can repair laminated bubbles and improves the qualification rate of the produced photovoltaic modules.
Specific examples of a photovoltaic packaging adhesive film, a preparation method and application thereof, and a recovery method of a photovoltaic module with the photovoltaic packaging adhesive film are given below:
Example 1
The photovoltaic packaging adhesive film of the embodiment comprises the following raw materials in parts by weight:
100 parts of EVA resin (VA content is 30%, zhejiang petrochemical Co., ltd.), 10 parts of beta-carboxyethyl acrylate, 1 part of solid base catalyst CaO/MgO@CoFe 2O4, 0.3 part of silane coupling agent 570,0.1 parts of ultraviolet stabilizer 770,0.3 parts of initiator TBEC and 0.25 part of auxiliary cross-linking agent TAIC.
The preparation method of the photovoltaic packaging adhesive film comprises the steps of premixing, remelting and extruding, casting and forming films, cooling, slitting and rolling all raw materials weighed according to the formula amount in sequence at 50 ℃, and obtaining the photovoltaic packaging adhesive film with the double-network structure (a free radical polymerization cross-linking network and a reversible dynamic transesterification reaction network) through a heating and laminating process in the preparation process of the photovoltaic module.
The application of the photovoltaic packaging adhesive film in the embodiment applies the photovoltaic packaging adhesive film to the preparation of a photovoltaic module, and the application method comprises the following steps:
And sequentially laminating front plate glass (toughened glass), a first packaging adhesive film, a photovoltaic cell (Suzhong) piece, a second packaging adhesive film and back plate glass (toughened glass) from top to bottom, vacuumizing at a heating lamination temperature of 120 ℃, laminating at a low temperature and curing for 9 minutes to obtain a photovoltaic laminated piece, mounting a junction box on the back surface of the photovoltaic laminated piece, and fixedly mounting the edge of the photovoltaic laminated piece into a photovoltaic frame to obtain the photovoltaic module of the embodiment. The first packaging adhesive film and the second packaging adhesive film are both photovoltaic packaging adhesive films with double-network structures, which are prepared by the embodiment, and the first packaging adhesive film and the second packaging adhesive film are both 380 g in weight.
The recovery method of the photovoltaic module of the embodiment comprises the following steps:
s1, removing the photovoltaic frame and the junction box of the photovoltaic module to obtain the photovoltaic laminated piece.
S2, placing the photovoltaic laminated piece into a heating box for heat treatment, wherein the heat treatment temperature is 120 ℃, and continuously irradiating the first packaging adhesive film and the second packaging adhesive film in the photovoltaic laminated piece by laser with the laser wave band of 1064nm to enable the first packaging adhesive film and the second packaging adhesive film to be melted, flow and removed, so that the photovoltaic cell can be recovered.
Example 2
The photovoltaic packaging adhesive film, the preparation method and the application thereof, and the recovery method of the photovoltaic module in this embodiment refer to embodiment 1, and the difference from embodiment 1 is that:
In the application of the photovoltaic packaging adhesive film of the embodiment, the back plate glass is changed into a white back plate (specifically, an FFC white back plate is prepared by coating modified PTFE on the two sides of a PET substrate), and the rest is the same as that of the embodiment 1.
Example 3
The photovoltaic packaging adhesive film of the embodiment comprises the following raw materials in parts by weight:
100 parts of POE resin (ethylene-octene copolymer, 14g/10min of high-melt-index ethylene-octene copolymer: 4.8g/10min of low-melt-index ethylene-octene copolymer are mixed according to a weight ratio of 1:1, dow chemical), 10 parts of beta-carboxyethyl acrylate, 1 part of solid base catalyst CaO/MgO@CoFe 2O4, 0.3 part of silane coupling agent 570,0.1 parts of ultraviolet stabilizer 770,0.45 parts of initiator TBEC,0.35 part of auxiliary cross-linking agent TAIC and 10 parts of polyvinyl alcohol.
The preparation method of the photovoltaic packaging adhesive film, the application of the photovoltaic packaging adhesive film and the recovery method of the photovoltaic module of the embodiment refer to embodiment 1, and the difference from embodiment 1 is that:
in the application of the photovoltaic packaging adhesive film of the embodiment, the curing time (i.e. the low-temperature lamination time) is changed to 14 minutes.
Comparative example 1
The photovoltaic packaging adhesive film of the comparative example, the preparation method and the application thereof, and the recovery method of the photovoltaic module are all referred to example 1, and the difference from example 1 is that:
The raw material formulation of the photovoltaic packaging adhesive film of the comparative example is free of an initiator TBEC and a crosslinking assistant TAIC, and the rest is the same as that of the example 1, so that the photovoltaic packaging adhesive film with the single network structure (reversible dynamic transesterification reaction network) of the comparative example is obtained after a heating lamination process in the preparation process of the photovoltaic module.
Performance testing
Performance tests were performed on the photovoltaic packaging adhesive films and photovoltaic modules prepared in examples 1 to 3 and comparative example 1, and the test results are shown in table 1 below:
TABLE 1
From the data in table 1, it can be seen that:
The raw material formula of the photovoltaic packaging adhesive film can be used for preparing the recyclable EVA photovoltaic packaging adhesive film (as in examples 1-2) and the recyclable POE photovoltaic packaging adhesive film, namely the raw material formula of the photovoltaic packaging adhesive film can be suitable for preparing the photovoltaic packaging adhesive films of different resin systems, and has wide adaptability.
In addition, when the raw material formula of the photovoltaic packaging adhesive film is used for preparing the photovoltaic packaging adhesive film (especially EVA photovoltaic packaging adhesive film), the photovoltaic packaging adhesive film has high light transmittance (380-1100 nm), crosslinking degree and peeling strength.
Further, the recovery rate of the whole cell of the photovoltaic module prepared by adopting the EVA photovoltaic packaging adhesive film (example 1-2) or the POE photovoltaic packaging adhesive film (example 3) can be about 98.5%, the recovery rate of the whole cell is high, and the PID resistance of the photovoltaic module is good.
In addition, in the process of recycling the photovoltaic module, after the melt flow of the photovoltaic packaging adhesive film is removed, all structures of the photovoltaic module are separated from each other, so that not only the battery piece but also other structures including the photovoltaic packaging adhesive film can be recycled, and the recycling rate of the photovoltaic module is high.
Compared with the photovoltaic packaging adhesive film with a double-network structure in the embodiment 1, the crosslinking degree and the peeling strength of the photovoltaic packaging adhesive film with the single-network structure in the comparative example 1 are obviously reduced, and the PID resistance of the photovoltaic module prepared by adopting the photovoltaic packaging adhesive film with the single-network structure in the comparative example 1 is obviously deteriorated.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the invention.
While the foregoing has been provided to illustrate the principles and embodiments of the present invention, specific examples have been provided herein to assist in understanding the principles and embodiments of the present invention, and are intended to be in no way limiting, for those of ordinary skill in the art will, in light of the above teachings, appreciate that the principles and embodiments of the present invention may be varied in any way.
Claims (10)
1. The photovoltaic packaging adhesive film is characterized by comprising the following raw materials in parts by weight:
100 parts of matrix resin, 5-10 parts of low-temperature cross-linking agent, 1-3 parts of low-temperature catalyst, 0.1-1 part of silane coupling agent, 0.05-0.5 part of ultraviolet light stabilizer, 0.1-1 part of organic peroxide initiator, 0.1-1 part of auxiliary cross-linking agent and 0-30 parts of alcohol compound serving as reversible dynamic transesterification reaction group;
the matrix resin is at least one of ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene-butene copolymer;
The low-temperature cross-linking agent is a cross-linking agent meeting the reaction temperature below 150 ℃ and is at least one of carboxylate cross-linking agent, bisoxazoline cross-linking agent and metal-organic ligand cross-linking agent;
The low-temperature catalyst is a catalyst meeting the reaction temperature below 150 ℃, and is a polynuclear metal catalyst, a solid acid resin catalyst, a solid base catalyst and a bimetallic MOF derivative catalyst.
2. The photovoltaic packaging adhesive film according to claim 1, wherein the low-temperature crosslinking agent is a crosslinking agent meeting a reaction temperature of 120-130 ℃, and the low-temperature crosslinking agent is beta-carboxyethyl acrylate;
the low-temperature catalyst is a catalyst meeting the reaction temperature of 120-130 ℃, and the low-temperature catalyst is a solid base catalyst CaO/MgO@CoFe 2O4.
3. The photovoltaic packaging adhesive film according to claim 1 or 2, wherein the organic peroxide initiator is tert-butyl peroxy-2-ethylhexyl carbonate, and the auxiliary crosslinking agent is triallyl isocyanurate;
the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane, and the ultraviolet light stabilizer is sebacic acid bis-2, 6-tetramethyl piperidinol ester.
4. The photovoltaic packaging adhesive film according to claim 1 or 2, wherein when the matrix resin is ethylene-vinyl acetate copolymer with VA content not less than 20%, no alcohol compound is required to be added in the raw material formulation of the photovoltaic packaging adhesive film.
5. The photovoltaic packaging adhesive film according to claim 1 or 2, wherein when the matrix resin is ethylene-vinyl acetate copolymer with VA content of <20%, or when the matrix resin contains ethylene-octene copolymer and/or ethylene-butene copolymer, 10-30 parts of alcohol compound is required to be added into the raw material formulation of the photovoltaic packaging adhesive film.
6. The photovoltaic packaging film according to claim 1 or 2, wherein the alcohol compound is at least one of polyvinyl alcohol and hyperbranched polyvinyl alcohol.
7. The method for preparing the photovoltaic packaging adhesive film according to any one of claims 1 to 6, which is characterized by comprising the steps of sequentially premixing raw materials weighed according to the formula amount, remelting and extruding, casting and forming a film, cooling, slitting and rolling, and obtaining the photovoltaic packaging adhesive film after a heating and laminating process in the preparation process of a photovoltaic module.
8. The application of the photovoltaic packaging adhesive film is characterized in that the photovoltaic packaging adhesive film is applied to the preparation of a photovoltaic module, and the application method comprises the following steps:
Sequentially laminating a photovoltaic front plate, a first packaging adhesive film, a photovoltaic cell, a second packaging adhesive film and a photovoltaic backboard in sequence from top to bottom, vacuumizing at a heating lamination temperature of less than 150 ℃, laminating at a low temperature, crosslinking and curing for 8-30 min to obtain a photovoltaic laminated piece, and performing post-treatment on the photovoltaic laminated piece to obtain a photovoltaic module;
the first packaging adhesive film and the second packaging adhesive film are both photovoltaic packaging adhesive films prepared by the preparation method of claim 7.
9. The application of the photovoltaic packaging adhesive film according to claim 8, wherein the temperature of the heating lamination is 120-130 ℃, and the time of low-temperature lamination and crosslinking curing is 8-15 min;
The post-processing includes mounting a junction box on the back side of the photovoltaic laminate and fixedly mounting the photovoltaic laminate edge into the photovoltaic bezel.
10. A method of recycling a photovoltaic module, comprising:
S1, removing a post-processing component of a photovoltaic module to obtain a photovoltaic laminated piece;
S2, carrying out heat treatment on the photovoltaic laminated piece, wherein the heat treatment temperature is less than 150 ℃, and adopting laser to radiate a first packaging adhesive film and a second packaging adhesive film in the photovoltaic laminated piece to enable the first packaging adhesive film and the second packaging adhesive film to be melted, generate flow and be removed;
The photovoltaic module is the photovoltaic module obtained in claim 8 or 9.
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| CN202511411331.9A CN121203555A (en) | 2025-09-29 | 2025-09-29 | Photovoltaic encapsulating films, their preparation methods and applications, and methods for recycling photovoltaic modules. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN121271465A (en) * | 2025-12-10 | 2026-01-06 | 苏州弘道新材料有限公司 | A self-healing EVA film and its preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN121271465A (en) * | 2025-12-10 | 2026-01-06 | 苏州弘道新材料有限公司 | A self-healing EVA film and its preparation method |
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