Anti-PID type multilayer packaging adhesive film, preparation method thereof and photovoltaic module

Abstract

The invention relates to the technical field of photovoltaic materials, in particular to an anti-PID type multilayer packaging adhesive film, a preparation method thereof and a photovoltaic module. The anti-PID type multi-layer packaging adhesive film comprises a high light transmission layer, a polyamide layer and an anti-acid POE (Polyolefin Elastomer) layer, the anti-acid POE layer is prepared from the following raw materials: 100 parts of an ethylene-1-butene copolymer, 0.1 to 5 parts of amino silane, 0.1 to 5 parts of quaternized silane and 1 to 14 parts of a first auxiliary agent; the polyamide layer is mainly formed by in-situ reaction of amino silane and quaternized silane in the anti-acid POE layer with a first solution and a second solution in sequence; the first solution comprises trimesoyl chloride, 2-sodium sulfonate benzoyl chloride and a copper-based metal organic framework material; the second solution comprises N-(3-aminopropyl)-imidazole. The multilayer packaging adhesive film provided by the invention has good salt fog resistance, has good bonding strength with glass and a battery piece, and has excellent anti-PID (Potential Induced Degradation) performance.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic materials technology, and in particular to an anti-PID type multilayer encapsulating film, its preparation method, and a photovoltaic module. Background Technology

[0002] The construction of photovoltaic (PV) systems typically requires substantial space, and the ocean, with its vast area and abundant exploitable space resources, provides excellent natural conditions for the development of offshore PV. Furthermore, offshore PV facilities, being far from land, avoid the noise and light pollution generated during operation, thus minimizing the impact on residents' lives. Additionally, seawater resources can be used to establish PV water-cooling systems, effectively reducing the operating temperature of the modules and thereby increasing power generation. Therefore, promoting the construction of offshore PV systems has significant practical and strategic value.

[0003] However, the marine and terrestrial environments differ significantly, making it difficult for terrestrial photovoltaic modules to meet the requirements for marine use. The main influencing factor in the marine environment is seawater, whose chemical components corrode the encapsulating film. Simultaneously, driven by wind, the continuous erosion of the encapsulating film by seawater accelerates the corrosion process, leading to problems such as delamination and blistering. Ultimately, this allows moisture to enter the photovoltaic module, inducing potential-induced degradation (PID) in the photovoltaic module.

[0004] Common encapsulating films are mainly made of ethylene-vinyl acetate copolymer (EVA) or polyolefin elastomer (POE). EVA films, containing polar VA groups, have weak moisture barrier properties and are prone to hydrolysis and photothermal aging in high-temperature and high-humidity environments, leading to problems such as bubbling, delamination, and yellowing. This reduces material transmittance, module power generation efficiency, and shortens module lifespan. In contrast, POE molecules do not contain unsaturated bonds or other reactive functional groups, resulting in a more stable structure. POE films possess higher volume resistivity and superior moisture barrier performance, leading to modules with better anti-PID characteristics, lower leakage current, and good transmittance, thus significantly extending the lifespan of photovoltaic modules in outdoor environments. However, POE still suffers from insufficient salt spray resistance, making it unsuitable for harsh environments such as high salt spray, strong ultraviolet radiation, and high humidity at sea.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] The purpose of this invention is to provide an anti-PID type multilayer encapsulating film, its preparation method, and a photovoltaic module. The multilayer encapsulating film of this invention has good salt spray resistance, good adhesion strength to glass and solar cells, and excellent anti-PID performance.

[0007] To achieve the above-mentioned objectives of the present invention, the first aspect of the present invention provides an anti-PID type multilayer encapsulating film, comprising a high light transmittance layer, a polyamide layer disposed on the surface of the high light transmittance layer, and an acid-resistant POE layer disposed on the surface of the polyamide layer; The raw materials for preparing the acid-resistant POE layer include the following components by weight: 100 parts of ethylene-1-butene copolymer, 0.1-5 parts of aminosilane, 0.1-5 parts of quaternized silane, and 1-14 parts of the first auxiliary agent; The polyamide layer is mainly formed by the in-situ reaction of aminosilane and quaternized silane in the acid-resistant POE layer with the first solution and the second solution in sequence. The first solution contains pyromellitic benzoyl chloride, sodium 2-sulfonate benzoyl chloride, and a copper-based metal-organic framework material; the second solution contains N-(3-aminopropyl)-imidazolium.

[0008] In a specific embodiment of the present invention, the aminosilane includes at least one of γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-aminopropyltrimethoxysilane; the quaternized silane includes at least one of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0009] In a specific embodiment of the present invention, the ethylene-1-butene copolymer contains 75wt% to 80wt% ethylene.

[0010] In a specific embodiment of the present invention, the raw materials for preparing the high light transmittance layer include the following components by weight: 100 parts of EAA resin and 1 to 14 parts of the second additive.

[0011] In a specific embodiment of the present invention, the first additive and the second additive each independently include at least one of the following: peroxide crosslinking agent, co-crosslinking agent, silane coupling agent, silane oligomer, acrylate monomer, antioxidant, light stabilizer, and anti-acid agent.

[0012] In a specific embodiment of the present invention, the antacid includes at least one of zirconium hydrogen phosphate, magnesium hydroxide, and magnesium oxide.

[0013] In a specific embodiment of the present invention, the thickness of the high light transmittance layer is 150-250 μm, the thickness of the polyamide layer is 100-200 nm, and the thickness of the acid-resistant POE layer is 150-250 μm.

[0014] The second aspect of this invention provides a method for preparing an anti-PID type multilayer encapsulating film according to the first aspect of this invention, comprising the following steps: (a) The acid-resistant POE layer is prepared by extrusion casting according to the proportion of the acid-resistant POE layer; after at least one side of the acid-resistant POE layer is reacted with a first solution containing pyromellitic trimethylol chloride, sodium benzoyl 2-sulfonate and copper-based metal-organic framework material, a second solution containing N-(3-aminopropyl)-imidazolium is sprayed onto the surface after the reaction to react and obtain a polyamide layer; (b) Prepare the high-transmittance layer according to the proportion of the high-transmittance layer, extrude and cast to obtain the high-transmittance layer, and then coat it on the surface of the polyamide layer to obtain the anti-PID type multilayer encapsulation film.

[0015] In a specific embodiment of the present invention, in the first solution, the mass fraction of the pyromellitic trimethylolpropionate chloride is 0.05% to 0.2%, the mass fraction of the copper-based metal-organic framework material is 0.01% to 0.5%, and the mass fraction of the sodium 2-sulfonate benzoyl chloride is 0.04% to 0.06%. Further, the solvent of the first solution is n-hexane.

[0016] In a specific embodiment of the present invention, the mass fraction of N-(3-aminopropyl)-imidazole in the second solution is 1% to 3%. Further, the solvent of the second solution is ethanol.

[0017] In a specific embodiment of the present invention, the contact reaction includes: immersing at least one side of the acid-resistant POE layer in a first solution for more than 3 minutes, and then removing it and curing it at 50-70°C for 10-30 minutes.

[0018] In a specific embodiment of the present invention, after spraying a second solution containing N-(3-aminopropyl)-imidazole onto the surface, the surface is cured at 50-70°C for 10-30 minutes.

[0019] A third aspect of the present invention provides a photovoltaic module, including an anti-PID type multilayer encapsulating film according to the first aspect of the present invention.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The acid-resistant POE layer of the encapsulating film of the present invention uses ethylene-1-butene copolymer as the main resin and introduces aminosilane and quaternized silane. Aminosilane and quaternized silane have the property of migrating to the surface in ethylene-1-butene copolymer. Aminosilane can react with trimesoyl chloride in situ to form a polyamide layer, which effectively retains metal ions. Furthermore, the quaternary ammonium ions introduced by quaternized silane can capture chloride ions through ion exchange. At the same time, since the polyamide layer is formed directly on the surface of the acid-resistant POE layer, it is tightly bonded to the acid-resistant POE layer, which effectively alleviates the problem of weak interfacial bonding caused by the polarity difference of the POE layer, thereby significantly improving the overall salt spray resistance of the encapsulating film. (2) In the formation of the polyamide layer of the present invention, a copper-based metal-organic framework material is introduced, which can fix chloride ions in the polyamide layer through coordination, ion exchange, physical adsorption and other means, thereby avoiding the corrosion of the battery cell by chloride ions; at the same time, sulfonic acid groups are introduced into the polyamide layer by sodium benzoyl 2-sulfonate, and sodium ions, magnesium ions and other substances in the film are fixed through electrostatic attraction, ion exchange and other means, further preventing their corrosion of the battery cell. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0022] Currently, in order to improve the weather resistance of POE films, additives such as crosslinking agents are usually introduced to increase the crosslinking density of POE films. However, since POE does not contain polar groups, its compatibility with polar additives is poor, which may lead to problems such as additive migration and precipitation, affecting the performance of POE films.

[0023] The first aspect of the present invention provides an anti-PID type multilayer encapsulating film, comprising a high light transmittance layer, a polyamide layer disposed on the surface of the high light transmittance layer, and an acid-resistant POE layer disposed on the surface of the polyamide layer; The raw materials for preparing the acid-resistant POE layer include the following components by weight: 100 parts of ethylene-1-butene copolymer, 0.1-5 parts of aminosilane, 0.1-5 parts of quaternized silane, and 1-14 parts of the first auxiliary agent; The polyamide layer is mainly formed by the in-situ reaction of aminosilane and quaternized silane in the acid-resistant POE layer with the first solution and the second solution in sequence; The first solution contains pyromellitic benzoyl chloride, sodium 2-sulfonate benzoyl chloride, and a copper-based metal-organic framework material; the second solution contains N-(3-aminopropyl)-imidazolium.

[0024] The acid-resistant POE layer of the encapsulating film of this invention uses ethylene-1-butene copolymer as the main resin and introduces aminosilane and quaternized silane. Aminosilane and quaternized silane have the property of migrating to the surface in the ethylene-1-butene copolymer. Aminosilane can react in situ with trimesoyl chloride to form a polyamide layer, effectively trapping metal ions. The quaternary ammonium ions introduced by the quaternized silane can capture chloride ions through ion exchange. Furthermore, N-(3-aminopropyl)-imidazolium is further grafted into the polyamide layer. N-(3-aminopropyl)-imidazolium is easily protonated under acidic conditions, carrying a positive charge, and can more efficiently trap sodium ions. Simultaneously, since the polyamide layer is formed directly on the surface of the acid-resistant POE layer in situ, it bonds tightly with the acid-resistant POE layer, effectively alleviating the problem of weak interfacial bonding caused by the polarity difference of the POE layer, thereby significantly improving the overall salt spray resistance of the encapsulating film.

[0025] In the formation of the polyamide layer of the present invention, a copper-based metal-organic framework material is introduced, which can fix chloride ions in the polyamide layer through coordination, ion exchange, physical adsorption and other means, thereby avoiding the corrosion of the battery cell by chloride ions; at the same time, sulfonic acid groups are introduced into the polyamide layer by sodium benzoyl 2-sulfonate, which fix sodium ions, magnesium ions and other substances in the film through electrostatic attraction, ion exchange and other means, further preventing their corrosion of the battery cell.

[0026] In some embodiments, the amount of aminosilane used in the acid-resistant POE layer is 0.1 to 5 parts per 100 parts by weight of ethylene-1-butene copolymer, specifically 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any combination thereof.

[0027] In some embodiments, the aminosilane includes at least one of γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-aminopropyltrimethoxysilane.

[0028] In some embodiments, the amount of quaternized silane used in the acid-resistant POE layer is 0.1 to 5 parts per 100 parts by weight of ethylene-1-butene copolymer, specifically 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any combination thereof.

[0029] In some embodiments, the quaternized silane includes dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0030] In this invention, introducing appropriate amounts of aminosilane and quaternized silane into the acid-resistant POE layer helps to improve adhesive strength, salt spray resistance, and PID resistance. If the amount of aminosilane or quaternized silane is too low, it is insufficient to form a sufficiently dense polyamide layer, which cannot effectively retain sodium ions, etc.; if the amount of aminosilane or quaternized silane is too high, it will lead to excessive cross-linking of the polyamide layer, affecting its compatibility with the acid-resistant POE layer, which is detrimental to the improvement of salt spray resistance, PID resistance, etc.

[0031] In some embodiments, the ethylene content in the ethylene-1-butene copolymer is 75 wt% to 80 wt%. Adjusting the ethylene content in the ethylene-1-butene copolymer to meet the above conditions is more conducive to the migration of aminosilanes and quaternized silanes in the acid-resistant POE layer, thereby ensuring the formation of the polyamide layer.

[0032] In some embodiments, the antacid includes at least one of zirconium hydrogen phosphate, magnesium hydroxide, and magnesium oxide. Zirconium hydrogen phosphate can capture small amounts of free sodium ions in the film; magnesium oxide and magnesium hydroxide can neutralize acidic substances in the film during aging, preventing corrosion of the battery cells.

[0033] In some embodiments, the raw materials for preparing the high-transmittance layer include the following components by weight: 100 parts of EAA resin and 1 to 14 parts of a second additive.

[0034] In some embodiments, the first and second additives each independently include at least one of the following: a peroxide-based crosslinking agent, a co-crosslinking agent, a silane coupling agent, a silane oligomer, an acrylate monomer, an antioxidant, a light stabilizer, and an anti-acid agent. Further, the first and second additives each independently include, by weight, 0.4–0.8 parts of a peroxide-based crosslinking agent, 0.3–0.7 parts of a co-crosslinking agent, 0.1–5 parts of a silane coupling agent, 0.1–5 parts of a silane oligomer, 0.6–1 part of an acrylate monomer, 0.1–0.5 parts of an antioxidant, 0.05–0.09 parts of a light stabilizer, and 0.2–1 part of an anti-acid agent.

[0035] In some embodiments, the peroxide crosslinking agent includes at least one of disuccinic acid peroxide, tert-butyl peracetate, tert-butyl peroxyisopropyl carbonate, and tert-butyl peroxybenzoate.

[0036] In some embodiments, the co-crosslinking agent includes at least one of triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, and di(trimethylolpropane)tetraacrylate.

[0037] In some embodiments, the silane coupling agent includes γ Methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane.

[0038] In some embodiments, the silane oligomer includes at least one of methacryloxysilane oligomer, vinyltriethoxysilane oligomer, vinyltrimethoxysilane oligomer, and epoxysilane oligomer.

[0039] In some embodiments, the acrylate monomers include at least one of pentaerythritol diacrylate, tris(propoxy)propanetriol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, and dipentaerythritol hexaacrylate.

[0040] In some embodiments, antioxidants include β-oxidants. (3,5) Second Uncle Ding Ji 4 1,4-hydroxyphenyl)propionate n-octadecyl alcohol ester, tetra[β-hydroxyphenyl]propionate (3,5) Second Uncle Ding Ji 4 [Hydroxyphenyl]propionate] pentaerythritol ester and tris[2,4] At least one of di-tert-butylphenyl]phosphite.

[0041] In some implementations, the light stabilizer includes UV... 328, UV 531, UV 1164 and UV At least one of 329.

[0042] In some embodiments, the thickness of the high-transmittance layer is 150–250 μm, specifically 150 μm, 170 μm, 190 μm, 210 μm, 220 μm, 250 μm, or any combination thereof; the thickness of the polyamide layer is 100–200 nm, specifically 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, or any combination thereof; the thickness of the acid-resistant POE layer is 150–250 μm, specifically 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, or any combination thereof.

[0043] In some embodiments, the thickness of the anti-PID type multilayer encapsulating film is 300 to 500 μm, specifically 300 μm, 350 μm, 400 μm, 450 μm, 500 μm or any combination thereof.

[0044] The second aspect of this invention provides a method for preparing an anti-PID type multilayer encapsulating film according to the first aspect of this invention, comprising the following steps: (a) The acid-resistant POE layer is prepared by extrusion casting according to the proportion of the acid-resistant POE layer; after at least one side of the acid-resistant POE layer is reacted with a first solution containing pyromellitic benzoyl chloride, sodium 2-sulfonate benzoyl chloride and copper-based metal-organic framework material, a second solution containing N-(3-aminopropyl)-imidazolium is sprayed onto the surface after the reaction to react and obtain a polyamide layer. (b) Prepare the high-transmittance layer according to the proportion of the high-transmittance layer, extrude and cast to obtain the high-transmittance layer, and then coat it on the surface of the polyamide layer to obtain the anti-PID type multilayer encapsulation film.

[0045] In some embodiments, the mass fraction of pyromellitic trimethylol chloride in the first solution is 0.05% to 0.2%, specifically within the range of 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, or any combination thereof; the mass fraction of copper-based metal-organic framework material is 0.01% to 0.5%, specifically within the range of 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.1%, 0.3%, 0.5%, or any combination thereof. The inventors of this invention have found that adding too little copper-based metal-organic framework material does not significantly improve the anti-PID effect, while adding too much can lead to defects such as holes in the polyamide layer formed by interfacial polymerization, affecting density and significantly reducing the anti-PID effect; the mass fraction of sodium benzoyl 2-sulfonate is 0.04% to 0.06%, specifically within the range of 0.04%, 0.045%, 0.05%, 0.055%, 0.06%, or any combination thereof. Furthermore, the solvent of the first solution is n-hexane. It is understood that the copper-based metal-organic framework material exists in a suspended dispersion form in the first solution.

[0046] In some embodiments, the mass fraction of N-(3-aminopropyl)-imidazole in the second solution is 1% to 3%, specifically 1%, 1.5%, 2%, 2.5%, 3%, or any combination thereof. Further, the solvent of the second solution is ethanol.

[0047] In some embodiments, the contact reaction includes immersing at least one side of the acid-resistant POE layer in a first solution for at least 3 minutes, such as 3 to 5 minutes, and then removing it and curing it at 50 to 70°C for 10 to 30 minutes.

[0048] In some embodiments, after spraying a second solution containing N-(3-aminopropyl)-imidazolium onto the surface, a curing reaction is carried out at 50–70°C for 10–30 min. Further, the spraying amount of the second solution is 5–10 g / m². 2 Specifically, it can be 5g / m2 6g / m 2 7g / m 2 8g / m 2 9g / m 2 10g / m 2 Or a range consisting of any two of them.

[0049] In some embodiments, in the extrusion casting process of step (a), the temperature is set to 90°C in zone 1, 90°C in zone 2, and 90°C in zone 3 of the screw; 95°C in zone 1 and 95°C in zone 2 of the melt pump; and 95°C in zone 1, 95°C in zone 2, and 95°C in zone 3 of the die. In the extrusion casting process of step (b), the temperature is set to 95°C in zone 1, 95°C in zone 2, and 95°C in zone 3 of the screw; 100°C in zone 1 and 100°C in zone 2 of the melt pump; and 100°C in zone 1, 100°C in zone 2, and 100°C in zone 3 of the die.

[0050] In some embodiments, the coating process includes: attaching a high-transmittance layer to an acid-resistant POE layer having a polyamide layer formed thereon, wherein the high-transmittance layer and the polyamide layer are bonded together by pressing with a rubber roller.

[0051] A third aspect of the present invention provides a photovoltaic module, including an anti-PID type multilayer encapsulating film according to the first aspect of the present invention.

[0052] In some implementations, photovoltaic modules include offshore photovoltaic modules.

[0053] Example 1 This embodiment provides a method for preparing an anti-PID type multilayer encapsulating film, including the following steps: (1) By weight, weigh 100 parts of POE resin (LF675, LG Chem), 0.5 parts of aminosilane (γ-aminopropyltriethoxysilane, Boiling Point Chemical, FD550), 0.5 parts of quaternized silane (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, Dow Corning, DC-5700), 0.6 parts of tert-butylperoxy-2-ethylhexyl carbonate, 0.5 parts of triallyl isocyanurate, 0.3 parts of silane (570), 0.5 parts of silane oligomer (3130t, Kaistar), and acrylate monomers. 0.7 parts of GM66 (Guojing Chemical), 0.2 parts of antioxidant (antioxidant 1010, BASF), 0.07 parts of light stabilizer (UV-328, Lianlong), 0.3 parts of magnesium hydroxide, and 0.2 parts of zirconium hydrogen phosphate were stirred in a high-speed mixing tank for 4 hours. The mixture was then fed into an extruder with the following temperatures set: screw zone 1: 90℃, zone 2: 90℃, zone 3: 90℃; melt pump zone 1: 95℃, zone 2: 95℃; die zone 1: 95℃, zone 2: 95℃, zone 3: 95℃. The extrusion and winding process yielded an acid-resistant POE layer with a thickness of 210μm.

[0054] (2) Immerse one side of the acid-resistant POE layer obtained in step (1) in a hexane solution containing 0.1 wt% trimesoyl chloride, 0.05 wt% sodium benzoyl 2-sulfonate and 0.2 wt% copper-based metal-organic framework material (SIFSIX-2-Cu-i) for 3 min, then remove and air dry naturally, and then place it in an oven at 60°C for 15 min to cure; then remove it and spray a 2.5% N-(3-aminopropyl)-imidazole ethanol solution evenly on its surface, with a spraying amount of about 5-10 g / m 2 (e.g., approximately 8g / m) 2 Then, it is air-dried naturally and then cured in an oven at 60°C for 10 minutes. This results in a polyamide layer with an average thickness of approximately 150 nm forming on the surface of one layer of the acid-resistant POE layer.

[0055] (3) By weight, weigh 100 parts of EAA resin (EA200, Dow), 0.6 parts of tert-butylperoxy-2-ethylhexyl carbonate, 0.5 parts of triallyl isocyanurate, 0.4 parts of silane (570), 0.5 parts of silane oligomer (3130t, Kaistar), 0.9 parts of acrylate monomer (GM66, Guojing Chemical), 0.1 parts of antioxidant (antioxidant 1010, BASF), 0.07 parts of light stabilizer (UV-328, Lianlong), and magnesium hydroxide. 0.3 parts and 0.2 parts of zirconium hydrogen phosphate were stirred in a high-speed mixing tank for 4 hours and then fed into an extruder. The temperature was set as follows: screw zone 1 95℃, zone 2 95℃, zone 3 95℃; melt pump zone 1 100℃, zone 2 100℃; die zone 1 100℃, zone 2 100℃, zone 3 100℃, screw speed 65r / min. The extrusion and winding were carried out to obtain a high light transmittance layer (thickness of 190μm) and then pressed by a rubber roller to coat the polyamide layer surface of step (2) to obtain an anti-PID type multilayer encapsulation film.

[0056] Example 2 group This embodiment group refers to the preparation method of the anti-PID type multilayer encapsulating film in Example 1, the only difference being: in step (1), the amount of aminosilane and quaternized silane is different, the specific differences are as follows: Example 2a: 0.1 parts aminosilane, 0.1 parts quaternized silane; Example 2b: 5 parts aminosilane, 5 parts quaternized silane.

[0057] Example 3 Group This embodiment group refers to the preparation method of the anti-PID type multilayer encapsulating film in Example 1, the only difference being: in step (1), the specific type of POE is different, the specific differences are as follows: Example 3a: The POE resin was POE69147 (Wanhua), and the ethylene content was 74.5 wt%. Example 3b: The POE resin was UL1488 (Dushanzi Petrochemical), and the ethylene content was 81.4 wt%.

[0058] Comparative Example 1 This comparative example group refers to the preparation method of the anti-PID type multilayer encapsulating film in Example 1, the only difference being: in step (1), the amounts of aminosilane and quaternized silane are different, the specific differences are as follows: Comparative Example 1a: 0 parts aminosilane, 1 part quaternized silane; Comparative Example 1b: 1 part aminosilane, 0 parts quaternized silane; Comparative Example 1c: 0 parts aminosilane, 0 parts quaternized silane; Comparative Example 1d: 0.05 parts aminosilane, 0.05 parts quaternized silane; Comparative Example 1e: 6 parts aminosilane and 6 parts quaternized silane.

[0059] Comparative Example 2 This comparative example group refers to the preparation method of the anti-PID type multilayer encapsulating film in Example 1, the only difference being: in step (2), the content of pyromellitic trimethylol chloride, sodium benzoyl 2-sulfonate or copper-based metal-organic framework material in the solution is different, the specific differences are as follows: Comparative Example 2a: The solution did not contain sodium benzoyl 2-sulfonate; Comparative Example 2b: The solution does not contain copper-based metal-organic framework materials.

[0060] Comparative Example 3 This comparative example refers to the preparation method of the anti-PID type multilayer encapsulating film in Example 1, the only difference being: in step (1), the specific type of POE is different, as follows: The POE resin is POE 8813V (SK Chemicals, South Korea).

[0061] Experimental Example To compare and illustrate the performance of different encapsulation films, the following tests were conducted, and the test results are shown in Table 1.

[0062] 1. Transmittance: The transmittance of the encapsulating film at 280–380 nm and 380–1100 nm was measured using a Shimadzu UV6800S ultraviolet spectrophotometer.

[0063] 2. Initial, DH2000h, and Salt Spray Aging 1000h Performance Tests: According to GB / T 29848-2018 "Ethylene-Vinyl Acetate Copolymer (EVA) Film for Photovoltaic Module Encapsulation," the initial peel strength, peel strength after DH2000h, and peel strength after 1000h salt spray aging were tested between the encapsulation film and glass in the module. The initial power, power after DH2000h, and power after 1000h salt spray aging of the module were also tested, and the power degradation rate was calculated. Salt spray aging was conducted according to GB / T 2423.17-2024 for a duration of 1000h. The component fabrication process includes: stacking glass, upper adhesive film, solar cell, lower adhesive film, and lower glass, followed by dual-cavity lamination. The lamination parameters include: first cavity, vacuuming for 360s, pressure of -70kPa, temperature of 115℃, for 120s; second cavity, pressure of -30kPa, temperature of 145℃, for 15min. Both the upper and lower adhesive films are the adhesive films to be tested in this invention (high-transmittance layer bonded to glass), and the solar cells are TOPCON solar cells. 3. PID192h Module Power Attenuation Rate: The PID192h power attenuation rate of the above modules was tested according to IEC TS 62804-2025.

[0064] Table 1 Test results of different encapsulating films

[0065] The test results above show that the multilayer encapsulation film of the present invention has good salt spray resistance, good adhesion strength with glass and battery cells, and excellent anti-PID performance.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A PID-resistant multilayer encapsulating film, characterized in that, It includes a high light transmittance layer, a polyamide layer disposed on the surface of the high light transmittance layer, and an acid-resistant POE layer disposed on the surface of the polyamide layer; The raw materials for preparing the acid-resistant POE layer include the following components by weight: 100 parts of ethylene-1-butene copolymer, 0.1-5 parts of aminosilane, 0.1-5 parts of quaternized silane, and 1-14 parts of the first auxiliary agent; The polyamide layer is mainly formed by the in-situ reaction of aminosilane and quaternized silane in the acid-resistant POE layer with the first solution and the second solution in sequence. The first solution contains pyromellitic benzoyl chloride, sodium 2-sulfonate benzoyl chloride, and a copper-based metal-organic framework material; the second solution contains N-(3-aminopropyl)-imidazolium.

2. The anti-PID type multilayer encapsulating film according to claim 1, characterized in that, The aminosilane includes at least one of γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-aminopropyltrimethoxysilane; The quaternized silane includes dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

3. The anti-PID type multilayer encapsulating film according to claim 1, characterized in that, In the ethylene-1-butene copolymer, the ethylene content is 75wt% to 80wt%.

4. The anti-PID type multilayer encapsulating film according to claim 1, characterized in that, The raw materials for preparing the high-transmittance layer include the following components by weight: 100 parts of EAA resin and 1-14 parts of the second additive; Preferably, the first additive and the second additive each independently include at least one of the following: peroxide crosslinking agent, co-crosslinking agent, silane coupling agent, silane oligomer, acrylate monomer, antioxidant, light stabilizer, and anti-acid agent; Preferably, the antacid agent includes at least one of zirconium hydrogen phosphate, magnesium hydroxide, and magnesium oxide.

5. The anti-PID type multilayer encapsulating film according to claim 1, characterized in that, It has at least one of the following characteristics: (1) The thickness of the high-transmittance layer is 150-250 μm; (2) The thickness of the polyamide layer is 100-200 nm; (3) The thickness of the acid-resistant POE layer is 150-250 μm.

6. The method for preparing the anti-PID type multilayer encapsulating film according to any one of claims 1 to 5, characterized in that, Includes the following steps: (a) The acid-resistant POE layer is prepared by extrusion casting according to the proportion of the acid-resistant POE layer; after at least one side of the acid-resistant POE layer is reacted with a first solution containing pyromellitic trimethylol chloride, sodium benzoyl 2-sulfonate and copper-based metal-organic framework material, a second solution containing N-(3-aminopropyl)-imidazolium is sprayed onto the surface after the reaction to react and obtain a polyamide layer; (b) Prepare the high-transmittance layer according to the proportion of the high-transmittance layer, extrude and cast to obtain the high-transmittance layer, and then coat it on the surface of the polyamide layer to obtain the anti-PID type multilayer encapsulation film.

7. The preparation method according to claim 6, characterized in that, The first solution has at least one of the following characteristics: (1) The mass fraction of the pyromellitic trimethylol chloride is 0.05% to 0.2%; (2) The mass fraction of the copper-based metal-organic framework material is 0.01% to 0.5%; (3) The mass fraction of the sodium benzoyl chloride 2-sulfonate is 0.04% to 0.06%; (4) The solvent of the first solution is n-hexane.

8. The preparation method according to claim 6, characterized in that, The second solution has at least one of the following characteristics: (1) The mass fraction of the N-(3-aminopropyl)-imidazole is 1% to 3%; (2) The solvent of the second solution is ethanol.

9. The preparation method according to claim 6, characterized in that, The contact reaction includes: immersing at least one side of the acid-resistant POE layer in a first solution for more than 3 minutes, and then removing it and curing it at 50-70°C for 10-30 minutes; Preferably, after spraying the surface with a second solution containing N-(3-aminopropyl)-imidazolium, the surface is cured at 50-70°C for 10-30 minutes.

10. A photovoltaic module, characterized in that, This includes the anti-PID type multilayer encapsulating film according to any one of claims 1 to 5 or the anti-PID type multilayer encapsulating film prepared by the preparation method according to any one of claims 6 to 9.

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