A self-healing encapsulating film, its preparation method, and a perovskite solar cell

Abstract

This invention relates to the field of photovoltaic cell technology, and in particular to a self-healing encapsulating film, its preparation method, and perovskite solar cells. The self-healing encapsulating film provided by this invention comprises a first surface layer, a core layer, and a second surface layer sequentially arranged. The raw materials of the first surface layer include POE and monomers containing dynamic borate ester bonds. The raw materials of the core layer include a blend matrix of POE and PIB, hydrophobically modified nano-attapulgite, hydrophobically modified nano-silica, functionalized graphene, pH-responsive microcapsules A, and UV-resistant microcapsules B. The raw materials of the second surface layer include low-temperature modified EVA, maleic anhydride-grafted POE, a low-temperature peroxide crosslinking agent, an anti-hydrolysis agent, and a nano-acid absorber. The self-healing encapsulating film of this invention, through the synergistic effect of its components, possesses dual self-healing capabilities, low water vapor permeability, on-demand release of repair agents, and resistance to acetic acid corrosion.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic cell technology, and in particular to a self-healing encapsulating film, its preparation method, and a perovskite cell. Background Technology

[0002] Perovskite solar cells have achieved photoelectric conversion efficiencies exceeding 26%, while perovskite / silicon tandem cells have efficiency surpassed 34%. However, perovskite materials are highly sensitive to moisture and oxygen. EVA encapsulation requires lamination at temperatures above 130°C, where perovskite materials are prone to thermal decomposition, and the acetic acid released from EVA hydrolysis corrodes the electrodes. While POE encapsulation offers better heat resistance, its water vapor transmission rate (WVTR) is typically 1–10 g / m². 2 / day, while perovskite solar cells require WVTR < 0.1g / m 2 / day.

[0003] Traditional encapsulation materials generally lack self-healing capabilities and have high moisture permeability. While encapsulation materials employing dynamic bond self-healing have dynamic bonds distributed throughout the entire film, they cannot achieve pH-responsive active repair. Relying on a single external repair mechanism leads to the depletion of repair capabilities over time. EP polymer encapsulation materials, used only as a bulk coating, leave the active components constantly exposed, preventing on-demand release.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The primary objective of this invention is to provide a self-healing encapsulating film with dual self-healing capabilities, low water vapor permeability, on-demand release of repair agent, and resistance to acetic acid corrosion.

[0006] A second objective of this invention is to provide a method for preparing the aforementioned self-healing encapsulating film.

[0007] A third objective of this invention is to provide a perovskite battery.

[0008] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: This invention provides a self-healing encapsulating film, comprising a first surface layer, a core layer, and a second surface layer arranged sequentially. The raw material of the first surface layer, by mass parts, includes the following components: 65-85 parts of POE, 8-20 parts of monomer containing dynamic borate ester bonds, 0.3-1.2 parts of free radical crosslinking agent, and 0.6-1.9 parts of first auxiliary agent; The raw materials for the core layer, by mass, include the following components: 100 parts of blended matrix, 5-12 parts of hydrophobically modified nano-attapulgite, 5-10 parts of hydrophobically modified nano-silica, 0.5-2 parts of functionalized graphene, 5-12 parts of pH-responsive microcapsules A, 3-8 parts of UV-resistant microcapsules B, and 1-2.8 parts of a second auxiliary agent; the blended matrix includes POE and PIB in a mass ratio of (70-85):(15-30). The raw material for the second surface layer, by mass parts, includes the following components: 80-95 parts of low-temperature modified EVA, 5-20 parts of maleic anhydride grafted POE, 0.5-1.5 parts of low-temperature peroxide crosslinking agent, 1-3 parts of anti-hydrolysis agent, 2-6 parts of nano acid absorber, and 0.7-2 parts of third auxiliary agent.

[0009] Furthermore, it includes at least one of the following features (1) to (3); (1) The monomer containing dynamic borate ester bonds includes resorcinol bis(p-boronate phenyl) ether; (2) The free radical crosslinking agent includes dicumyl peroxide; (3) The first additive, by mass parts, includes the following components: 0.2 to 0.5 parts of antioxidant, 0.1 to 0.4 parts of light stabilizer and 0.3 to 1 part of interfacial coupling agent.

[0010] Further, the pH-responsive microcapsule A includes a core material and a first shell layer and a second shell layer sequentially disposed on the surface of the core material; the core material includes an EP polymer and a lead scavenging agent in a mass ratio of 1:(0.3~0.6); the first shell layer includes polyurea and / or polyurethane; the second shell layer includes a pH-responsive polyelectrolyte composite layer.

[0011] Preferably, the lead-capturing agent comprises citric acid and polyacrylic acid in a mass ratio of 1:(0.3~0.6).

[0012] Preferably, the pH-responsive polyelectrolyte composite layer comprises sodium alginate and chitosan.

[0013] Preferably, the pH-responsive microcapsule A has a particle size of 10-30 μm, the thickness of the first shell layer is 1.5-2.5 μm, and the thickness of the second shell layer is 0.5-1.5 μm.

[0014] Furthermore, the anti-UV microcapsule B includes a core material and a shell layer disposed on the surface of the core material; the core material includes an ultraviolet absorber and a hindered amine light stabilizer in a mass ratio of (1.8~2.2):1; the shell layer includes melamine-formaldehyde resin.

[0015] Preferably, the particle size of the UV-resistant microcapsule B is 5~20μm.

[0016] Furthermore, it includes at least one of the following features (1) to (6); (1) The hydrophobically modified nano-attapulgite includes nano-attapulgite that has been hydrophobically modified with a silane coupling agent; (2) The hydrophobically modified nano-attapulgite is fibrous and has an aspect ratio of 15~30; (3) The hydrophobically modified nano-silica includes nano-silica that has been hydrophobically modified with a silane coupling agent; (4) The hydrophobically modified nano-silica is spherical particles with a particle size of 20~50nm; (5) The functionalized graphene includes graphene surface-treated with a silane coupling agent; (6) The second additive, by mass parts, includes the following components: 0.5 to 1.5 parts of irradiation crosslinking agent, 0.2 to 0.5 parts of antioxidant and 0.3 to 0.8 parts of interfacial coupling agent.

[0017] Furthermore, it includes at least one of the following features (1) to (5); (1) The low-temperature peroxide crosslinking agent includes TBEC; (2) The anti-hydrolysis agent includes a carbodiimide anti-hydrolysis agent; (3) The nano acid absorbent comprises nano CaO and nano MgO in a mass ratio of 1:(1~2); (4) The particle size of the nano acid absorbent is 30~80nm; (5) The third auxiliary agent, by mass parts, includes the following components: 0.2 to 0.5 parts of antioxidant and 0.5 to 1.5 parts of silane coupling agent.

[0018] Furthermore, it includes at least one of the following features (1) to (3); (1) The thickness of the first surface layer is 80~120μm; (2) The thickness of the core layer is 200~320μm; (3) The thickness of the second surface layer is 60~100μm.

[0019] The present invention also provides a method for preparing the self-healing encapsulating film as described above, comprising the following steps: S1. The premixed first surface layer material, the premixed core layer material and the premixed second surface layer material are co-extruded and cast to obtain a semi-finished film. S2. The semi-finished adhesive film is pre-crosslinked to obtain the self-healing encapsulating adhesive film.

[0020] Further, the pre-crosslinking treatment includes: under ultraviolet light with a wavelength of 320~400nm, at a concentration of 200~500mJ / cm². 2 The irradiation dose is used to irradiate the semi-finished film, so that the gel content in the semi-finished film is 30%~50%.

[0021] The present invention also provides a perovskite battery, comprising the self-healing encapsulating film as described above.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: The self-healing encapsulation film of this invention achieves multiple healings of repeated minor damage and on-demand active repair of penetrating damage through the dual synergy of intrinsic dynamic covalent bond self-healing in the first surface layer and external repair by pH-responsive microcapsules A in the core layer. A three-dimensional labyrinthine diffusion barrier is constructed by combining a blended matrix of POE and PIB with a three-mode barrier filler system of fibers, spheres, and sheets, giving the film low water vapor permeability. The second surface layer utilizes a three-in-one synergy of a low-temperature peroxide crosslinking agent, an anti-hydrolysis agent, and a nano-acid absorber to achieve low-temperature lamination at 100-120°C to avoid thermal decomposition of perovskite, inhibiting acetic acid generation at the source and capturing acetic acid in situ, thus solving the problem of acetic acid corrosion in EVA-based encapsulation. When used for encapsulation of perovskite batteries, it improves the long-term stability, self-healing performance, lead leakage suppression capability, resistance to damp heat aging, resistance to ultraviolet aging, and encapsulation adhesion reliability of perovskite batteries. Detailed Implementation

[0023] 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.

[0024] In some embodiments of the present invention, a self-healing encapsulating film is provided, comprising a first surface layer, a core layer, and a second surface layer disposed sequentially. The raw material for the first surface layer, by mass parts, includes the following components: 65-85 parts of POE, 8-20 parts of monomers containing dynamic borate ester bonds, 0.3-1.2 parts of free radical crosslinking agent, and 0.6-1.9 parts of first auxiliary agent; The raw materials for the core layer, by mass, include the following components: 100 parts of blended matrix, 5-12 parts of hydrophobically modified nano-attapulgite, 5-10 parts of hydrophobically modified nano-silica, 0.5-2 parts of functionalized graphene, 5-12 parts of pH-responsive microcapsules A, 3-8 parts of UV-resistant microcapsules B, and 1-2.8 parts of a second auxiliary agent; the blended matrix includes POE and PIB in a mass ratio of (70-85):(15-30); The raw materials for the second surface layer, by mass parts, include: 80-95 parts of low-temperature modified EVA, 5-20 parts of maleic anhydride grafted POE, 0.5-1.5 parts of low-temperature peroxide crosslinking agent, 1-3 parts of anti-hydrolysis agent, 2-6 parts of nano acid absorber, and 0.7-2 parts of third auxiliary agent.

[0025] The self-healing encapsulating film of the present invention constructs a dual self-healing system with functional layers: the first surface layer is provided with dynamic borate ester bonds for intrinsic self-healing, which can cope with repeated minor damage without consuming repair agents; the core layer is provided with pH-responsive microcapsules A for external active repair, which can cope with penetrating damage and chemical triggering of water vapor intrusion; the two mechanisms are complementary in space and function.

[0026] A barrier core layer synergistically constructed with a blended matrix of POE and PIB and fillers was developed. The matrix of the core layer was a blend of PIB and POE, while hydrophobically modified nano-attapulgite, hydrophobically modified nano-silica and functionalized graphene were introduced to form a barrier.

[0027] The introduction of pH-responsive microcapsule A utilizes a pH-responsive mechanism driven by a weakly acidic environment to precisely achieve a protective strategy of on-demand release, which is significantly different from conventional non-pH-responsive external repair systems.

[0028] The second surface layer is a low-temperature acid absorption and synergistic protection, which adopts a three-in-one strategy of low-temperature peroxide crosslinking agent, anti-hydrolysis agent and nano acid absorber to inhibit the generation of acetic acid from the source and capture residual acetic acid in situ, synergistically solving the problem of acetic acid corrosion in EVA-based encapsulation, and providing a complete technical path for low-temperature encapsulation of components.

[0029] In the self-healing encapsulating film of the present invention, the first surface layer has intrinsic self-healing (repeated healing) and water and oxygen barrier functions; the core layer has a three-mode barrier network, pH-triggered active repair and lead adsorption functions; the second surface layer can achieve low-temperature lamination (100~120℃) and has acetic acid inhibition and capture functions.

[0030] In some embodiments of the present invention, the raw materials of the first surface layer, typically but not limitingly, may include, for example, 65 parts by mass of POE, 70 parts by mass, 75 parts by mass, 80 parts by mass, 85 parts by mass, and any value between any two of these; the monomer containing dynamic borate ester bonds may include 8 parts by mass, 10 parts by mass, 12 parts by mass, 14 parts by mass, 16 parts by mass, 18 parts by mass, 20 parts by mass, and any value between any two of these; the free radical crosslinking agent may include 0.3 parts by mass, 0.5 parts by mass, 0.7 parts by mass, 0.9 parts by mass, 1.2 parts by mass, and any value between any two of these; and the first auxiliary agent may include 0.6 parts by mass, 1 part by mass, 1.5 parts by mass, 1.9 parts by mass, and any value between any two of these.

[0031] In some embodiments of the present invention, the raw materials of the core layer, typically but not limitingly, include, for example, hydrophobically modified nano-attapulgite in any mass fraction of 5 parts, 8 parts, 10 parts, 12 parts, and any value between any two of these; hydrophobically modified nano-silica in any mass fraction of 5 parts, 8 parts, 10 parts, and any value between any two of these; functionalized graphene in any mass fraction of 0.5 parts, 1 part, 1.5 parts, 2 parts, and any value between any two of these; pH-responsive microcapsules A in any mass fraction of 5 parts, 8 parts, 10 parts, 12 parts, and any value between any two of these; UV-resistant microcapsules B in any mass fraction of 3 parts, 5 parts, 8 parts, and any value between any two of these; the second auxiliary agent in any mass fraction of 1 part, 1.5 parts, 2 parts, 2.8 parts, and any value between any two of these; and in the blend matrix, the mass ratio of POE to PIB can be 70:30, 75:25, 80:20, 85:15, and any value between any two of these.

[0032] In some embodiments of the present invention, the monomer containing dynamic borate bonds includes resorcinol bis(p-borate phenyl) ether; the monomer containing dynamic borate bonds is a dynamic borate bond self-healing monomer, which is a dynamic borate bond crosslinking agent.

[0033] In some embodiments of the present invention, POE is a polyolefin elastomer with a melt flow index (MFR) of 4.5~5.5 g / 10 min; preferably 5 g / 10 min.

[0034] In some embodiments of the present invention, the free radical crosslinking agent includes dicumyl peroxide (DCP).

[0035] In some embodiments of the present invention, the first adjuvant, by weight, comprises the following components: 0.2 to 0.5 parts of antioxidant, 0.1 to 0.4 parts of light stabilizer, and 0.3 to 1 part of interfacial coupling agent; preferably, the antioxidant comprises a hindered phenolic antioxidant, such as antioxidant 1010; the light stabilizer comprises a hindered amine (HALS) light stabilizer, such as Tinuvin 770; and the interfacial coupling agent comprises vinyltriethoxysilane.

[0036] In some embodiments of the present invention, the raw material of the first surface layer, by mass parts, includes the following components: 65-85 parts of POE, 8-20 parts of monomer containing dynamic borate ester bonds, 0.3-1.2 parts of free radical crosslinking agent, 0.2-0.5 parts of antioxidant, 0.1-0.4 parts of light stabilizer, and 0.3-1 parts of interfacial coupling agent.

[0037] In some preferred embodiments of the present invention, the raw material of the first surface layer, by mass parts, includes the following components: 73-78 parts of POE, 10-15 parts of monomer containing dynamic borate ester bonds, 0.5-1 part of free radical crosslinking agent, 0.2-0.5 parts of antioxidant, 0.1-0.4 parts of light stabilizer, and 0.3-1 part of interfacial coupling agent.

[0038] In some embodiments of the present invention, pH-responsive microcapsule A includes a core material and a first shell layer and a second shell layer sequentially disposed on the surface of the core material; the core material includes an EP polymer and a lead scavenging agent in a mass ratio of 1:(0.3~0.6); the first shell layer includes polyurea and / or polyurethane; and the second shell layer includes a pH-responsive polyelectrolyte composite layer.

[0039] In some embodiments of the invention, typically but not limitingly, for example, the mass ratio of the EP polymer to the lead trapping agent can be 1:0.3, 1:0.4, 1:0.5, 1:0.6, and any value between any two thereof.

[0040] The EP polymer is an alkoxyvinylimidazolium bis(trifluoromethanesulfonyl)imide type self-healing polymer, see Wang, S., Lu, G., Li, X., et al. (2025). A rapid self-healing polymer mediated by ion aggregates achieves effective encapsulation of sustainable perovskite solar cells. Science Advances, 11(47). In some embodiments of the invention, the lead trapping agent comprises citric acid and polyacrylic acid in a mass ratio of 1:(0.3 to 0.6); typically, but not limitingly, for example, the mass ratio of citric acid and polyacrylic acid may be 1:0.3, 1:0.4, 1:0.5, 1:0.6, and any value between any two thereof.

[0041] In some embodiments of the present invention, the pH-responsive polyelectrolyte composite layer comprises sodium alginate and chitosan.

[0042] In some embodiments of the present invention, the pH-responsive microcapsule A has a particle size of 10-30 μm, a first shell thickness of 1.5-2.5 μm, and a second shell thickness of 0.5-1.5 μm; typically, but not limitingly, for example, the particle size of the pH-responsive microcapsule A can be 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and any two of these; the thickness of the first shell can be 1.5 μm, 2 μm, 2.5 μm, and any two of these; and the thickness of the second shell can be 0.5 μm, 1 μm, 1.5 μm, and any two of these.

[0043] Release characteristics of pH-responsive microcapsule A: At pH 7.2, the cumulative release rate is <2% after 72 hours; at pH 5.2, the cumulative release rate reaches 81% after 24 hours.

[0044] The pH-responsive microcapsule A features a double-shell structure: an inner and outer shell. The inner shell (first shell) is a hydrophobic, dense wall material of polyurea or polyurethane, formed through oil / water interface polymerization. This isolates the EP polymer from external water, oxygen, and heat, preventing premature consumption during film preparation and normal encapsulation. The outer shell (second shell) is a pH-responsive polyelectrolyte composite layer, constructed from sodium alginate and chitosan natural polymers through electrostatic layer-by-layer self-assembly or interfacial cross-linking. Under normal encapsulation conditions (pH approximately 7), the negatively charged sodium alginate interacts with the positively charged chitosan to maintain the density of the multilayer film structure. When water vapor permeation leads to lead ion hydrolysis and the formation of a locally weakly acidic environment (pH 5.0~5.5), the protonation degree of chitosan amino groups decreases, resulting in a reduction in charge. Simultaneously, the carboxyl protonation of sodium alginate leads to a decrease in its negative charge. This charge imbalance causes swelling and structural disintegration of the polyelectrolyte network structure, significantly increasing the permeability of the outer shell. Ultimately, this rupture facilitates the active release of the core material.

[0045] The preparation method of pH-responsive microcapsule A includes the following steps: An EP polymer and a lead scavenging agent at a mass ratio of 1:(0.3~0.6) were dissolved in anhydrous chloroform and stirred until homogeneous to form an oil phase; the concentration of the EP polymer in the oil phase was 10wt%~20wt%. Polyvinyl alcohol (PVA) emulsifier is added to deionized water to form an aqueous phase with a concentration of 0.5wt%~2wt%. Under nitrogen protection, the oil phase is slowly dripped into the aqueous phase with a volume ratio of 1:(4~10). The mixture is emulsified at a high speed of 5000~8000 rpm for 15~30 min to form a stable O / W type emulsion. Add polyurea prepolymer (toluene diisocyanate TDI) or multifunctional isocyanate (isocyanate monomers or their prepolymers with a functionality ≥2, such as toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI)) to the O / W type emulsion, adjust the pH to 5.5~7.0, and react at 65~75℃ for 3~5h to allow the wall material to be deposited and cured on the surface of the oil droplets to form the first shell layer; After the first shell layer has completely solidified, the system is cooled to 40~50℃, and sodium alginate solution (concentration of 0.5wt%~2wt%, pH of 5.2~5.8) and chitosan solution (concentration of 0.5wt%~2wt%, pH of 5.2~5.8) are added layer by layer. After each addition, the mixture is stirred for 20~40 min to allow the polyelectrolyte to be adsorbed and composited on the shell surface layer by layer, thus constructing 3~5 layers of LBL-deposited pH polyelectrolyte composite layer. Finally, the mixture is stirred at room temperature (25℃) for 1~2 h to stabilize the shell layer. Then, centrifugation was performed (3000~5000 rpm, 10~15 min), followed by washing with deionized water and anhydrous ethanol 3~5 times in sequence, and drying in a vacuum drying oven at 40~50℃ for 12~24 h to obtain pH-responsive microcapsules A.

[0046] Experimental verification of the pH-responsive release mechanism of pH-responsive microcapsule A: Under pH=7.2 conditions (normal encapsulation environment), the pH-responsive polyelectrolyte composite layer basically does not release the core material, and the cumulative release rate is less than 2% after 72h; when the ambient pH drops to 5.2 (simulating the weakly acidic microenvironment generated by perovskite hydrolysis), the swelling rate of the pH-responsive polyelectrolyte composite layer increases significantly within 12h, and the cumulative release rate climbs to 81% after 24h; the pH-responsive mechanism driven by the weakly acidic environment accurately realizes the on-demand release protection strategy, which is significantly different from conventional non-pH-responsive external repair systems.

[0047] In some embodiments of the present invention, the anti-UV microcapsule B includes a core material and a shell layer disposed on the surface of the core material; the core material includes an ultraviolet absorber and a hindered amine (HALS) light stabilizer in a mass ratio of (1.8~2.2):1; the shell layer includes melamine-formaldehyde resin (MF); preferably, the mass ratio of the ultraviolet absorber and the hindered amine light stabilizer is 2:1; the ultraviolet absorber includes, but is not limited to, UV-9; the hindered amine light stabilizer includes, but is not limited to, Tinuvin 770.

[0048] In some embodiments of the present invention, the particle size of the anti-UV microcapsule B is 5 to 20 μm; typically, but not limitingly, for example, the particle size of the anti-UV microcapsule B can be 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, and any value between any two of these.

[0049] In some embodiments of the present invention, the preparation method of anti-ultraviolet microcapsule B includes the following steps: According to the molar ratio of melamine to formaldehyde of 1:(2~3), melamine, formaldehyde solution and deionized water are added to the reaction flask, the pH is adjusted to 8~9 with triethanolamine, the temperature is raised to 60~70℃ and reacted for 30~60 min to obtain a clear MF prepolymer aqueous solution. A UV absorber and a hindered amine light stabilizer with a mass ratio of (1.8~2.2):1 are mixed and dissolved in an appropriate amount of toluene or ethyl acetate. The mixture is then emulsified at high speed (6000~10000 rpm, 15~30 min) in an aqueous phase containing an emulsifier (such as sodium dodecylbenzenesulfonate, concentration of 1wt%~2wt%) to form an O / W type emulsion. Add the MF prepolymer aqueous solution to the above O / W type, adjust the pH to 3-4 with dilute hydrochloric acid, and react at 55-65℃ for 2-4 hours to allow MF to be deposited and solidified on the surface of the oil droplets. After cooling, centrifuge to separate the contents, wash with deionized water and anhydrous ethanol 3-5 times, and vacuum dry at 40-50℃ to obtain UV-resistant microcapsules B.

[0050] In some embodiments of the present invention, the hydrophobically modified nanoattapulgite includes nanoattapulgite that has been hydrophobically modified with a silane coupling agent.

[0051] In some embodiments of the present invention, the preparation method of hydrophobically modified nano-attapulgite includes: hydrophobically modifying nano-attapulgite with a silane coupling agent (KH570 or octadecyltrimethoxysilane); specifically, it includes the following steps: dispersing nano-attapulgite in a mixed solvent of ethanol and water, adding 1% to 5% of the silane coupling agent by mass of nano-attapulgite, stirring and reacting at 60 to 80°C for 4 to 6 hours, and obtaining hydrophobically modified nano-attapulgite after centrifugation, washing, and drying.

[0052] In some embodiments of the invention, the hydrophobically modified nanoattapulgite is fibrous and has an aspect ratio of 15 to 30; typically, but not limitingly, for example, the aspect ratio of the hydrophobically modified nanoattapulgite may be 15, 20, 25, 30 and any value between any two of these.

[0053] In some embodiments of the present invention, the hydrophobically modified nano-silica includes nano-silica that has been hydrophobically modified with a silane coupling agent.

[0054] In some embodiments of the present invention, the hydrophobically modified nano-silica is spherical particles with a particle size of 20~50nm.

[0055] In some embodiments of the present invention, the preparation method of hydrophobically modified nano-silica includes: hydrophobically modifying nano-silica with a silane coupling agent (KH570 or hexamethyldisilazane); specifically, it includes the following steps: dispersing nano-silica with a particle size of 20-50 nm in anhydrous ethanol, adding 3%-10% of the silane coupling agent by mass of the nano-silica, stirring and reacting at 50-70°C for 4-8 h, centrifuging, washing, and drying to obtain hydrophobically modified nano-silica. The hydrophobically modified nano-silica can be prepared by the above method or using hydrophobic nano-silica purchased from Xuancheng Jingrui New Materials.

[0056] In some embodiments of the present invention, functionalized graphene includes graphene surface-treated with a silane coupling agent.

[0057] In some embodiments of the present invention, the preparation method of functionalized graphene includes: surface pretreatment of graphene using KH560 silane coupling agent; specifically including the following steps: adding graphene powder to a water-alcohol solution of KH560 (KH560, methanol and water in a volume ratio of 10:80:10, pH adjusted to 4-5 with acetic acid), stirring and hydrolyzing at room temperature (25°C) for 0.5-1 h; then heating to 60°C and continuing to stir and react for 3-5 h; the reaction product is filtered, washed and vacuum dried to obtain functionalized graphene.

[0058] In some embodiments of the present invention, the second auxiliary agent comprises, by weight parts, the following components: 0.5 to 1.5 parts of irradiation crosslinking agent, 0.2 to 0.5 parts of antioxidant, and 0.3 to 0.8 parts of interface coupling agent; preferably, the irradiation crosslinking agent includes, but is not limited to, TAIC; the antioxidant includes, but is not limited to, antioxidant 1010; and the interface coupling agent includes, but is not limited to, vinyltriethoxysilane.

[0059] In some embodiments of the present invention, the raw materials of the core layer, by mass parts, include the following components: 70-85 parts POE, 15-30 parts PIB, 5-12 parts hydrophobically modified nano-attapulgite, 5-10 parts hydrophobically modified nano-silica, 0.5-2 parts functionalized graphene, 5-12 parts pH-responsive microcapsules A, 3-8 parts UV-resistant microcapsules B, 0.5-1.5 parts irradiation crosslinking agent, 0.2-0.5 parts antioxidant, and 0.3-0.8 parts interfacial coupling agent.

[0060] In some embodiments of the present invention, the low-temperature modified EVA is an EVA material that can be crosslinked at 100~120℃ through grafting modification or blending modification; specifically, it can be prepared according to the method of Example 1 in the patent with publication number CN114891456B, or purchased from Changzhou Baijia Film Technology Co., Ltd. for low-temperature laminated EVA film special resin (model GT-12E).

[0061] In some embodiments of the present invention, the preparation method of maleic anhydride-grafted POE (POE-g-MAH) includes the following steps: mixing maleic anhydride (MAH) and POE resin at a mass ratio of 1:(5~10), adding 0.1~0.5 parts of initiator dicumyl peroxide (DCP), performing a melt grafting reaction in a twin-screw extruder at 160~190°C, and extruding and granulating to obtain POE-g-MAH. Maleic anhydride-grafted POE can be prepared according to the above scheme, or purchased from Kraton FG1901, Nengzhiguang W1A, etc.

[0062] In some embodiments of the present invention, the low-temperature peroxide crosslinking agent includes TBEC.

[0063] In some embodiments of the present invention, the anti-hydrolysis agent includes a carbodiimide anti-hydrolysis agent; preferably, carbodiimide Stabaxol P-100.

[0064] In some embodiments of the present invention, the nano acid absorbent comprises nano CaO and nano MgO in a mass ratio of 1:(1~2); typically, but not limitingly, for example, the mass ratio of nano CaO and nano MgO may be 1:1, 1:1.5, 1:2, and any value between any two thereof.

[0065] In some embodiments of the present invention, the particle size of the nano acid absorber is 30-80 nm; typically, but not limitingly, for example, the particle size of the nano acid absorber can be 30 nm, 50 nm, 70 nm, 80 nm, and any value between any two of these.

[0066] In some embodiments of the present invention, the third auxiliary agent comprises, by weight, the following components: 0.2 to 0.5 parts of antioxidant and 0.5 to 1.5 parts of silane coupling agent.

[0067] In some embodiments of the present invention, the second surface layer comprises, by weight parts, the following components: 80-95 parts of low-temperature modified EVA, 5-20 parts of maleic anhydride-grafted POE, 0.5-1.5 parts of low-temperature peroxide crosslinking agent, 1-3 parts of anti-hydrolysis agent, 2-6 parts of nano acid absorber, 0.2-0.5 parts of antioxidant, and 0.5-1.5 parts of silane coupling agent.

[0068] In some preferred embodiments of the present invention, the second surface layer comprises, by weight parts: 85-90 parts of low-temperature modified EVA, 5-10 parts of maleic anhydride-grafted POE, 0.5-1.5 parts of low-temperature peroxide crosslinking agent, 1-3 parts of anti-hydrolysis agent, 2-6 parts of nano acid absorber, 0.2-0.5 parts of antioxidant, and 0.5-1.5 parts of silane coupling agent.

[0069] A dual self-repairing synergistic system integrates the intrinsic dynamic covalent bond self-repair of the first surface layer with the exogenous active repair of the pH-responsive microcapsules A (including EP polymer and lead scavenging agent) in the core layer. The first surface layer achieves repeated healing under heating conditions of 50-100℃ (zero consumption of repair materials). In the weakly acidic microenvironment (pH 5.0-5.5) generated by perovskite leakage, the core layer releases the EP polymer and lead scavenging agent through the swelling and rupture of the outer shell of sodium alginate and chitosan, completing the dual tasks of chemical repair and lead capture. The two self-repairing systems are complementary in space and function, jointly forming a complete damage management closed loop encompassing repeated mild injuries and skin-level self-healing, penetrating severe injuries and weakly acidic chemical triggering by moisture invasion, and organ-level chemical bonding and lead capture.

[0070] Constructing a barrier core layer synergistically composed of a blended matrix of POE and PIB and a three-mode filler: PIB and POE are blended as the core matrix (POE:PIB = 70:30~85:15, mass ratio), while fibrous hydrophobically modified nano-attapulgite (Aspect ratio 15~30), spherical hydrophobically modified nano-silica, and two-dimensional functionalized graphene filler are introduced to form a three-dimensional labyrinthine diffusion path of fibers, spheres, and sheets, achieving a synergistic barrier effect that reduces WVTR by about 97%.

[0071] pH-responsive microcapsule A is a pH-responsive double-shell microcapsule. It uses a compound of EP polymer and lead scavenging agent as the core material, polyurea and / or polyurethane as the inner shell (protecting the active components), and sodium alginate and chitosan as the pH-responsive outer shell. The self-healing EP polymer and lead scavenging agent are encapsulated within this double-shell microcapsule. It is stable under normal encapsulation conditions (pH 7.2), with a cumulative release of less than 2% over 24 hours. When perovskite leakage creates a weakly acidic microenvironment (pH 5.0–5.5), the outer shell swells and ruptures, and the EP polymer release rate increases to 81% within 24 hours. Lead adsorption and filtration are completed in one step, achieving integrated active protection through on-demand release, chemical bonding repair, and lead adsorption.

[0072] Low-corrosion synergistic encapsulation strategy: The second surface layer integrates a three-in-one low-corrosion protection system consisting of low-temperature peroxide crosslinking agent TBEC, carbodiimide anti-hydrolysis agent, and nano acid absorbers (nano CaO and nano MgO); TBEC achieves low-temperature curing at 100~120℃; the carbodiimide anti-hydrolysis agent reduces acetic acid generation from the source by eliminating carboxyl groups; the nano acid absorbers capture residual acetic acid, synergistically solving the problem of acetic acid corrosion in EVA-based encapsulation, while providing a complete technical path for low-temperature encapsulation of components.

[0073] In some embodiments of the present invention, the thickness of the first surface layer is 80 to 120 μm; typically, but not limitingly, for example, the thickness of the first surface layer can be 80 μm, 100 μm, 120 μm, and any value between any two of these.

[0074] In some embodiments of the present invention, the thickness of the core layer is 200 to 320 μm; typically, but not limitingly, for example, the thickness of the core layer can be 200 μm, 250 μm, 300 μm, 320 μm, and any value between any two of these.

[0075] In some embodiments of the present invention, the thickness of the second surface layer is 60 to 100 μm; typically, but not limitingly, for example, the thickness of the second surface layer can be 60 μm, 80 μm, 100 μm, and any value between any two of these.

[0076] In some embodiments of the present invention, the method for preparing a self-healing encapsulating film includes the following steps: S1. The premixed first surface layer material, the premixed core layer material and the premixed second surface layer material are co-extruded and cast to obtain a semi-finished film. S2. Pre-crosslink the semi-finished adhesive film to obtain a self-healing encapsulating adhesive film.

[0077] In some embodiments of the present invention, in step S1, POE, monomers containing dynamic borate ester bonds, free radical crosslinking agents, antioxidants, light stabilizers and interfacial coupling agents are mixed uniformly at 800~1200 rpm for 8~15 min using a high-speed mixer at room temperature (e.g., 25°C) to obtain the premixed first surface layer raw material.

[0078] In some embodiments of the present invention, in step S1, POE and PIB are blended in a two-roll mill or internal mixer at 130-150°C for 8-15 minutes to fully melt and combine, thereby obtaining a blended matrix. pH-responsive microcapsules A and UV-resistant microcapsules B were pre-dispersed with POE at a mass ratio of 1:(0.2~0.5) (e.g., 2~5 parts of POE were added for every 10 parts of pH-responsive microcapsules A). The mixture was stirred at 200~400 rpm for 5~10 min at room temperature (e.g., 25°C) to obtain pH-responsive bilayer shell microcapsules A and UV-resistant microcapsules B with POE adhering to their surfaces. The pH-responsive bilayer shell microcapsules A and UV-resistant microcapsules B were added in a pre-dispersed form. Hydrophobically modified nano-attapulgite, hydrophobically modified nano-silica, and functionalized graphene are respectively premixed with POE accounting for 30%~60% of their own mass in an internal mixer or high-speed mixer at 80~100℃ for 5~10 min to obtain hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, and functionalized graphene masterbatch; hydrophobically modified nano-attapulgite, hydrophobically modified nano-silica, and functionalized graphene are added in a pre-dispersed form. pH-responsive microcapsules A with POE adhering to the surface, UV-resistant microcapsules B with POE adhering to the surface, hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-SiO2 masterbatch, functionalized graphene masterbatch, and blended matrix are mixed, and then irradiation crosslinking agent, antioxidant, and interfacial coupling agent are added. Mixing is continued for 5-10 minutes until each component is uniformly dispersed to obtain the premixed core layer raw material.

[0079] In some embodiments of the present invention, in step S1, low-temperature modified EVA, maleic anhydride-grafted POE, low-temperature peroxide crosslinking agent, anti-hydrolysis agent, nano acid absorber, antioxidant, and silane coupling agent are stirred at 800-1200 rpm for 10-20 min at room temperature (e.g., 25°C) using a high-speed mixer to obtain the premixed second surface layer material.

[0080] In some embodiments of the present invention, in step S1, the three-layer co-extrusion casting process includes: the premixed first surface layer material, the premixed core layer material, and the premixed second surface layer material are respectively added to the corresponding hoppers of the three extruders; The extruder temperature for adding the premixed first surface material is set as follows: feeding section 100~120℃, melting section 130~150℃, and die section 120~140℃. The extruder temperature for adding the premixed core material is set as follows: feeding section 110~130℃, melting section 135~155℃, die section 130~145℃; the upper limit of the temperature should not exceed 160~165℃ to prevent the pH-responsive microcapsule A from thermal deformation or premature rupture, and to ensure the stable existence of the pH-responsive microcapsule A during processing. The extruder temperature for adding the premixed second surface material is set as follows: feeding section 90~110℃, melting section 110~130℃, and die section 100~120℃. Three types of melts are extruded together using a three-layer co-extrusion die to form a three-layer integrated cast film. The cast film is rapidly cooled and shaped by cooling rollers (temperature controlled at 25~40℃); After being pulled, cut, and rolled up, a semi-finished film is obtained.

[0081] In some embodiments of the present invention, step S2 includes the pre-crosslinking treatment comprising: applying ultraviolet light with a wavelength of 320-400 nm at a concentration of 200-500 mJ / cm². 2 The irradiation dose is used to irradiate the semi-finished film, so that the gel content in the semi-finished film is 30%~50%.

[0082] The semi-finished film was subjected to UV-A band (320~400nm) ultraviolet light at a speed of 200~500mJ / cm 2 The film is pre-crosslinked by irradiation dose to obtain a moderate degree of crosslinking (gel content of 30%~50%), ensuring that the film has good mechanical strength and dimensional stability during subsequent winding and use; it is then cut, inspected and packaged according to the predetermined width to obtain the final encapsulated film product.

[0083] In some embodiments of the present invention, a perovskite battery is also provided, comprising the above-described self-healing encapsulating film.

[0084] In some embodiments of the present invention, a method for preparing the above-mentioned perovskite solar cell is also provided, comprising the following steps: The glass cover, self-healing encapsulating film, perovskite battery chip and backplane are stacked and assembled; during the stacking and assembly process, the perovskite battery chip is placed between the glass cover and the backplane; the self-healing encapsulating film is cut into a sheet of the same size as the battery module, with the second surface facing the backplane and the first surface facing the cover, and the cover surface facing upward. After lamination and assembly, the components are placed in a vacuum laminator for lamination. The lamination parameters are set as follows: temperature 100~120℃, vacuum evacuation time 3~6min, lamination pressure 30~60kPa, and total lamination time 10~20min. After lamination, allow it to cool naturally to below 50°C, then remove it to obtain the perovskite solar cell.

[0085] Low-temperature lamination (100~120℃) completely avoids the risk of thermal decomposition of perovskite materials. During use, if the encapsulation layer is damaged by external forces and environmental aging, the dynamic borate ester bonds of the first surface layer can achieve repeated crack healing through thermally reversible dissociation-reassociation reactions within the operating temperature range of 50~85℃. When the crack further extends to the core layer, a large amount of water vapor invades and triggers local hydrolysis of the perovskite to form a weakly acidic microenvironment, the pH-responsive polyelectrolyte composite layer of the pH-responsive double-shell microcapsule A in the core layer swells and ruptures in a localized pH environment of approximately 5.0~5.5, releasing EP polymer and lead adsorbent, filling the crack for chemical bonding repair, and actively adsorbing leaked lead ions.

[0086] Example 1 The method for preparing the self-healing encapsulating film provided in this embodiment includes the following steps: S1. 75 parts of POE (MFR=5g / 10min), 12 parts of resorcinol bis(p-boronate phenyl) ether, 0.8 parts of dicumyl peroxide, 0.3 parts of antioxidant 1010, 0.2 parts of Tinuvin 770 and 0.8 parts of vinyltriethoxysilane were stirred at 1000 rpm for 10min to obtain the premixed first surface layer material. 77.8 parts of POE and 22.2 parts of PIB were blended in an internal mixer at 140°C for 10 minutes to fully melt and combine, thus obtaining a blend matrix. Eight parts of pH-responsive microcapsule A and five parts of UV-resistant microcapsule B were pre-dispersed with POE at a mass ratio of 1:0.4. The mixture was stirred at 300 rpm for 8 minutes at room temperature (25℃) to obtain pH-responsive microcapsule A with POE adhering to its surface and UV-resistant microcapsule B with POE adhering to its surface. Eight parts of hydrophobically modified nano-attapulgite, six parts of hydrophobically modified nano-silica, and one part of functionalized graphene were premixed with POE accounting for 32% of their own mass in an internal mixer at 90°C for 8 minutes to obtain hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, and functionalized graphene masterbatch. pH-responsive microcapsules A with POE adhering to the surface, UV-resistant microcapsules B with POE adhering to the surface, hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, functionalized graphene masterbatch and blend matrix are mixed, and then 1.0 part of TAIC, 0.3 part of antioxidant 1010 and 0.5 part of vinyltriethoxysilane are added and mixed for 8 minutes until each component is uniformly dispersed to obtain the premixed core layer raw material; 88 parts of low-temperature modified EVA (VA=28%), 8 parts of maleic anhydride grafted POE, 1.0 part of TBEC, 2.0 parts of carbodiimide Stabaxol P-100, 2 parts of nano-CaO with an average particle size of 50nm, 2 parts of nano-MgO with an average particle size of 50nm, 0.3 parts of antioxidant 1010 and 1.0 part of KH560 were stirred at 1000rpm for 15min at room temperature (25℃) using a high-speed mixer to obtain the premixed second surface layer material. S2. The premixed first surface layer material, the premixed core layer material, and the premixed second surface layer material are respectively added to the corresponding hoppers of the three extruders; The extruder temperature for adding the premixed first surface material is set as follows: feeding section 110℃, melting section 140℃, and die section 130℃. The extruder temperature for adding the premixed core material is set as follows: feeding section 120℃, melting section 145℃, and die section 140℃. The extruder temperature for adding the premixed second surface material is set as follows: feeding section 100℃, melting section 120℃, and die section 110℃. Three melts are extruded together through a three-layer co-extrusion die to form a three-layer integrated cast film; the cast film is rapidly cooled and shaped by a cooling roller (temperature 30℃); after traction, cutting and winding, a semi-finished film is obtained; Under ultraviolet light at a wavelength of 365 nm, at a speed of 300 mJ / cm 2 The semi-finished adhesive film is irradiated with a certain irradiation dose to make the gel content in the semi-finished adhesive film 30%~50%; thus obtaining a self-healing encapsulating adhesive film. The total thickness of the self-healing encapsulating film is 460 μm; the thickness of the first surface layer in the self-healing encapsulating film is 100 μm, the thickness of the core layer is 280 μm, and the thickness of the second surface layer is 80 μm.

[0087] The preparation method of pH-responsive microcapsule A includes the following steps: An EP polymer and a lead scavenging agent (citric acid and polyacrylic acid in a mass ratio of 1:0.5) were dissolved in anhydrous chloroform and stirred until homogeneous to form an oil phase; the concentration of EP polymer in the oil phase was 15 wt%. Polyvinyl alcohol (PVA) emulsifier was added to deionized water to form an aqueous phase with a concentration of 1 wt%. Under nitrogen protection, the oil phase was slowly dripped into the aqueous phase at a volume ratio of 1:7. The mixture was emulsified at 7000 rpm for 25 minutes to form a stable O / W emulsion. Add polyurea prepolymer (toluene diisocyanate TDI) to the O / W type emulsion, adjust the pH to 6, and react at 70°C for 4 hours to allow the polyurea wall material to be deposited and cured on the surface of the oil droplets, forming the first shell layer; After the first shell layer has completely solidified, the system is cooled to 45°C. Sodium alginate solution (concentration of 1 wt%, pH of 5.2-5.8) and chitosan solution (concentration of 1%, pH of 5.2-5.8) are added layer by layer. After each addition, the mixture is stirred for 30 min to allow the polyelectrolyte to be adsorbed and composited on the shell surface layer by layer, thus constructing 3-5 layers of LBL-deposited pH polyelectrolyte composite layer. Finally, the mixture is stirred for 1.5 h at room temperature (25°C) to stabilize the shell layer. Then, centrifugation was performed (4000 rpm, 12 min), followed by washing with deionized water and anhydrous ethanol four times in sequence, and drying in a vacuum drying oven at 45℃ for 18 h to obtain pH-responsive microcapsules A. The average particle size of pH-responsive microcapsules A was 20 μm, the thickness of the first shell was 2 μm, and the thickness of the second shell was 1 μm.

[0088] The preparation method of anti-ultraviolet microcapsules B includes the following steps: Melamine and formaldehyde were added to a reaction flask with a molar ratio of 1:2.5. The pH was adjusted to 8.5 with triethanolamine and the mixture was heated to 65°C and reacted for 45 minutes to obtain a clear aqueous solution of MF prepolymer. UV-9, an ultraviolet absorber, and Tinuvin 770, a hindered amine light stabilizer, were mixed in a mass ratio of 2:1, dissolved in toluene, and emulsified at high speed (8000 rpm for 20 min) in an aqueous phase containing an emulsifier (sodium dodecylbenzenesulfonate, concentration 1.5 wt%) to form an O / W type emulsion. The aqueous solution of MF prepolymer was dropped into the above O / W type, the pH was adjusted to 3.5 with dilute hydrochloric acid, and the reaction was carried out at 60°C for 3 hours to allow MF to be deposited and solidified on the surface of the oil droplets. After cooling, the microcapsules were centrifuged, washed 3-5 times with deionized water and anhydrous ethanol, and dried under vacuum at 45°C to obtain UV-resistant microcapsules B with an average particle size of 13 μm.

[0089] The preparation method of hydrophobically modified nano-attapulgite includes the following steps: Nano-attapulgite was dispersed in a mixed solvent of ethanol and water, and KH570 was added at 3% of the mass of nano-attapulgite. The mixture was stirred at 70°C for 5 hours. After centrifugation, washing and drying, fibrous hydrophobic modified nano-attapulgite (aspect ratio of 20) was obtained.

[0090] The preparation method of hydrophobically modified nano-silica includes the following steps: 30 nm nano-silica was dispersed in anhydrous ethanol, and 5% KH570 (by mass of nano-silica) was added. The mixture was stirred at 60 °C for 6 h. After centrifugation, washing, and drying, hydrophobic modified nano-silica was obtained.

[0091] The preparation method of functionalized graphene includes the following steps: Graphene powder was added to an aqueous alcohol solution of KH560 (KH560, methanol and water in a volume ratio of 10:80:10, with the pH adjusted to 4-5 by acetic acid), and the mixture was stirred and hydrolyzed at room temperature (25°C) for 1 hour. Then the temperature was raised to 60°C and the reaction was stirred for another 4 hours. The reaction product was filtered, washed and dried under vacuum to obtain functionalized graphene.

[0092] Low-temperature modified EVA: Low-temperature laminated EVA film special resin (model GT-12E) from Changzhou Baijia Film Technology Co., Ltd.

[0093] Maleic anhydride grafted with POE: Ningbo Nengzhiguang W1A, grafting rate 0.8%~1.2%.

[0094] Example 2 The preparation method of the self-healing encapsulating film provided in this embodiment is the same as that in embodiment 1, except that in step S1, 85 parts of POE and 15 parts of PIB are mixed in an internal mixer at 140°C for 10 minutes to fully melt and composite, thereby obtaining a blend matrix.

[0095] Example 3 The preparation method of the self-healing encapsulating film provided in this embodiment is the same as that in embodiment 1, except that in step S1, 80 parts of POE and 20 parts of PIB are mixed in an internal mixer at 140°C for 10 minutes to fully melt and composite, thereby obtaining a blend matrix.

[0096] Example 4 The preparation method of the self-healing encapsulating film provided in this embodiment is the same as that in embodiment 1, except that in step S1, 75 parts of POE and 25 parts of PIB are mixed in an internal mixer at 140°C for 10 minutes to fully melt and composite, thereby obtaining a blend matrix.

[0097] Example 5 The preparation method of the self-healing encapsulating film provided in this embodiment is the same as that in embodiment 1, except that in step S1, 65 parts of POE (MFR=5g / 10min), 8 parts of resorcinol bis(p-boronate phenyl) ether, 0.3 parts of dicumyl peroxide, 0.2 parts of antioxidant 1010, 0.1 parts of Tinuvin 770 and 0.3 parts of vinyltriethoxysilane are stirred at 1000 rpm for 10min to obtain the premixed first surface layer raw material; 77.8 parts of POE and 22.2 parts of PIB were blended in an internal mixer at 140°C for 10 minutes to fully melt and combine, thus obtaining a blend matrix. Five parts of pH-responsive microcapsule A and three parts of UV-resistant microcapsule B were pre-dispersed with POE at a mass ratio of 1:0.4. The mixture was stirred at 300 rpm for 8 min at room temperature (25℃) to obtain pH-responsive microcapsule A with POE adhering to its surface and UV-resistant microcapsule B with POE adhering to its surface. Five parts of hydrophobically modified nano-attapulgite, five parts of hydrophobically modified nano-silica, and 0.5 parts of functionalized graphene were premixed with POE accounting for 32% of their own mass in an internal mixer at 90°C for 8 minutes to obtain hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, and functionalized graphene masterbatch. pH-responsive microcapsules A with POE adhering to the surface, UV-resistant microcapsules B with POE adhering to the surface, hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, functionalized graphene masterbatch and blend matrix are mixed, and then 0.5 parts of TAIC, 0.2 parts of antioxidant 1010 and 0.3 parts of vinyltriethoxysilane are added and mixed for 8 minutes until all components are uniformly dispersed to obtain the premixed core layer raw material; 80 parts of low-temperature modified EVA (VA=28%), 5 parts of maleic anhydride-grafted POE, 0.5 parts of TBEC, 1 part of carbodiimide Stabaxol P-100, 1 part of nano-CaO with an average particle size of 50 nm, 1 part of nano-MgO with an average particle size of 50 nm, 0.2 parts of antioxidant 1010 and 0.5 parts of KH560 were stirred at 1000 rpm for 15 min at room temperature (25℃) using a high-speed mixer to obtain the premixed second surface layer material.

[0098] Example 6 The preparation method of the self-healing encapsulating film provided in this embodiment is the same as that in embodiment 1, except that in step S1, 85 parts of POE (MFR=5g / 10min), 20 parts of resorcinol bis(p-boronate phenyl) ether, 1.2 parts of dicumyl peroxide, 0.5 parts of antioxidant 1010, 0.4 parts of Tinuvin 770 and 1 part of vinyltriethoxysilane are stirred at 1000 rpm for 10 min to obtain the premixed first surface layer raw material; 77.8 parts of POE and 22.2 parts of PIB were blended in an internal mixer at 140°C for 10 minutes to fully melt and combine, thus obtaining a blend matrix. 12 parts of pH-responsive microcapsule A and 8 parts of UV-resistant microcapsule B were pre-dispersed with POE at a mass ratio of 1:0.4. The mixture was stirred at 300 rpm for 8 min at room temperature (25℃) to obtain pH-responsive microcapsule A with POE adhering to its surface and UV-resistant microcapsule B with POE adhering to its surface. 12 parts of hydrophobically modified nano-attapulgite, 10 parts of hydrophobically modified nano-silica, and 2 parts of functionalized graphene were premixed with POE accounting for 32% of their own mass in an internal mixer at 90°C for 8 minutes to obtain hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, and functionalized graphene masterbatch. pH-responsive microcapsules A with POE adhering to the surface, UV-resistant microcapsules B with POE adhering to the surface, hydrophobically modified nano-attapulgite masterbatch, hydrophobically modified nano-silica masterbatch, functionalized graphene masterbatch and blend matrix are mixed, and then 1.5 parts of TAIC, 0.5 parts of antioxidant 1010 and 0.8 parts of vinyltriethoxysilane are added and mixed for 8 minutes until all components are uniformly dispersed to obtain the premixed core layer raw material; 95 parts of low-temperature modified EVA (VA=28%), 20 parts of maleic anhydride-grafted POE, 1.5 parts of TBEC, 3 parts of carbodiimide Stabaxol P-100, 3 parts of nano-CaO with an average particle size of 50 nm, 3 parts of nano-MgO with an average particle size of 50 nm, 0.5 parts of antioxidant 1010, and 1.5 parts of KH560 were stirred at 1000 rpm for 15 min at room temperature (25℃) using a high-speed mixer to obtain the premixed second surface layer material.

[0099] Comparative Example 1 The preparation method of the encapsulating film provided in this comparative example is the preparation method of Example 1 in the patent with publication number CN121268359A.

[0100] Comparative Example 2 The preparation method of the encapsulating film provided in this comparative example is the preparation method of Example 2 in the patent with publication number CN121271465A.

[0101] Comparative Example 3 The encapsulating film provided in this comparative example is an EP coating. The preparation method can be found in Wang, S., Li, X., Lu, G., et al. A rapid self-healing polymer mediated by ion aggregates achieves effective encapsulation of sustainable perovskite solar cells. Science Advances, 2025, 11(47): eadp8973.DOI: 10.1126 / sciadv.adp8973. Test case The performance of the self-healing encapsulating films of Examples 2, 3, and 4 was tested, and the results are as follows: Water vapor transmission rate (WVTR) of the core layer in Examples 2, 3 and 4: The WVTR of the core layer was tested after the first and second surface layers were peeled off; the test was conducted using a MOCON PERMATRAN-W 3 / 61 at a temperature of 38°C and a relative humidity of 90%.

[0102] WVTR decreases with increasing PIB content; the WVTR of the core layer (POE:PIB = 85:15) in Example 2 is 0.15 g / m³. 2 / day, the efficiency of the perovskite solar cell module assembled using the encapsulating film of Example 2 decreased by 3.4% after 1000 hours of damp heat treatment (85℃ / 85%RH environment); the WVTR of the core layer (POE:PIB=80:20) in Example 3 was 0.12 g / m 2 / day; the WVTR of the core layer (POE:PIB=75:25) in Example 4 decreased to 0.07 g / m 2 / day, but the elongation at break of the film decreased from 450% to 380%, and the compatibility of POE and PIB declined.

[0103] The water vapor transmission rate (WVTR) of the self-healing encapsulating film of Example 1, the core layer of the self-healing encapsulating film of Example 3 (the core layer was tested after peeling off the first and second surface layers), the encapsulating films of Comparative Examples 1 to 3, and a POE monolayer with a thickness of 300 μm was tested, and the results are shown in Table 1.

[0104] WVTR: Tested using MOCON PERMATRAN-W 3 / 61 at 38°C and 90% relative humidity.

[0105] Table 1

[0106] As shown in Table 1, compared to Comparative Example 1, Example 1 reduced WVTR from 1.8 g / m³. 2 / day decreased to 0.087g / m 2 / day, the reduction reached 95.2%. Among them, the WVTR reduction brought about by the blend matrix of POE and PIB accounted for about 70%, fiber fillers contributed about 20%, and spherical fillers and sheet fillers contributed about 5%. The effects of the three are non-additively superimposed, which proves that the synergistic barrier effect is significant.

[0107] The self-healing performance of the self-healing encapsulating film of Example 1 was tested.

[0108] A 50μm wide scratch was made on the first surface layer of the self-healing encapsulating film using a blade. After treatment under different heating conditions, the scratch splitting closure rate was 98.3% and the tensile strength recovery rate was 94.8% after heating at 50℃ for 15 min. After heating at 80℃ for 5 min, the scratch splitting closure rate was 99.2% and the tensile strength recovery rate was 96.5%.

[0109] After repeating the scratch-repair process 10 times at the same location (80℃ / 5min), the closure rate on the 10th attempt was still 91.8%, and the tensile strength recovery rate was 89.3%. This indicates that the intrinsic dynamic borate ester bond can initiate repair multiple times without consuming the active material.

[0110] pH-responsive microcapsules A-triggered release: The core layer was prepared separately, and a 100 μm through-crack was created. The sample was then immersed in an acetate-sodium acetate buffer solution at pH 5.2 (simulating a perovskite leakage microenvironment) and incubated at 40°C for 24 h. HPLC-UVD detection showed that the EP polymer release rate was 81.2%.

[0111] Crack filling rate (SEM cross-sectional area method): 94%; 5 mg / L Pb² was added to the buffer solution. + After 24 hours, the residual lead concentration in the wastewater was measured by ICP-MS to be 0.035 mg / L, with an adsorption rate of 99.3%.

[0112] The lead leakage suppression effects of the self-healing encapsulating film of Example 1, the encapsulating films of Comparative Examples 1 to 3, and the POE monolayer were tested, and the results are shown in Table 2.

[0113] Lead leakage suppression effect: Components encapsulated with perovskite flakes were prepared according to ASTM D3985 method, with a 1 cm long pre-crack created in the encapsulation layer for each encapsulation scheme. They were then immersed in a simulated acid rain solution at pH 5.0 for 72 hours, and the lead content of the leachate was measured.

[0114] Table 2

[0115] The damp heat aging performance of the self-healing encapsulating film of Example 1 and the encapsulating films of Comparative Examples 1 to 3 was tested, and the results are shown in Table 3.

[0116] Perovskite solar cell modules were assembled using different films. Each module was aged in an 85℃ / 85%RH environmental chamber for 1000 hours. The photoelectric conversion efficiency of the modules under AM1.5G standard conditions before and after aging was tested.

[0117] Table 3

[0118] As shown in Table 3, the efficiency degradation rate of Example 1 is much lower than that of Comparative Examples 1 to 3, indicating that the multi-level comprehensive protection strategy: WVTR reduction + dual self-healing + active lead capture + ultraviolet anti-aging + low-temperature acid-absorbing EVA significantly improves the long-term stability of the module.

[0119] The UV aging performance of the self-healing encapsulating film of Example 1, the encapsulating films of Comparative Examples 1 and 2, and the EVA film was tested, and the results are shown in Table 4.

[0120] UV aging performance: UV irradiation (UV-A 340nm, irradiation intensity 200kWh / m) 2 Aging was assessed by measuring the yellowing index ΔYI using a colorimeter.

[0121] Table 4

[0122] The peel strength of the self-healing encapsulating film of Example 1 and the encapsulating film of Comparative Example 1 was tested.

[0123] Peel strength test: The adhesive film and glass cover are laminated at 110℃, and the 180° peel strength (N / cm) is tested; GB / T2790-1995 "Adhesives 180° Peel Strength Test Method Flexible Materials to Rigid Materials".

[0124] Example 1: Initial peel strength was 72 N / cm, and after aging at 85℃ / 85%RH for 500h, the peel strength was 68 N / cm (a decrease of about 5.6%). Comparative Example 1: Initial peel strength was 65 N / cm, and after aging at 85℃ / 85%RH for 500 hours, the peel strength was 42 N / cm (a decrease of about 35%).

[0125] The pH-responsive release performance of pH-responsive microcapsule A from Example 1 was tested, and the results are as follows: In vitro release assays were performed on the release curve of pH-responsive double-shell microcapsule A; in a buffer solution at pH 7.2 (simulating a conventional encapsulation environment): the cumulative EP release rate was 1.8% over 24 hours. A buffer solution with a pH of 5.2 (simulating a weakly acidic environment for perovskite hydrolysis): the cumulative EP release rate was 21% at 2h, 54% at 6h, 69% at 12h, and reached 81% at 24h. Lead ion adsorption kinetics (pH 5.2, initial lead concentration 5 mg / L, core layer of the membrane containing microcapsules A): 1h adsorption rate 72%, 6h adsorption rate 94%, 24h adsorption rate 99.3%.

[0126] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can 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 therein, without departing from the spirit and scope of the present invention; 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; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. A self-healing encapsulating film, characterized in that, It includes a first surface layer, a core layer, and a second surface layer arranged sequentially; The raw material of the first surface layer, by mass parts, includes the following components: 65-85 parts of POE, 8-20 parts of monomer containing dynamic borate ester bonds, 0.3-1.2 parts of free radical crosslinking agent, and 0.6-1.9 parts of first auxiliary agent; The raw materials of the core layer, by mass parts, include the following components: 100 parts of blend matrix, 5-12 parts of hydrophobically modified nano-attapulgite, 5-10 parts of hydrophobically modified nano-silica, 0.5-2 parts of functionalized graphene, 5-12 parts of pH-responsive microcapsules A, 3-8 parts of UV-resistant microcapsules B, and 1-2.8 parts of a second auxiliary agent; the blend matrix includes POE and PIB in a mass ratio of (70-85):(15-30); The raw material for the second surface layer, by mass parts, includes the following components: The mixture consists of 80-95 parts of low-temperature modified EVA, 5-20 parts of maleic anhydride-grafted POE, 0.5-1.5 parts of low-temperature peroxide crosslinking agent, 1-3 parts of anti-hydrolysis agent, 2-6 parts of nano acid absorber, and 0.7-2 parts of third auxiliary agent.

2. The self-healing encapsulating film according to claim 1, characterized in that, Includes at least one of the following features (1) to (3); (1) The monomer containing dynamic borate ester bonds includes resorcinol bis(p-boronate phenyl) ether; (2) The free radical crosslinking agent includes dicumyl peroxide; (3) The first additive, by mass parts, includes the following components: 0.2 to 0.5 parts of antioxidant, 0.1 to 0.4 parts of light stabilizer and 0.3 to 1 part of interfacial coupling agent.

3. The self-healing encapsulating film according to claim 1, characterized in that, The pH-responsive microcapsule A comprises a core material and a first shell layer and a second shell layer sequentially disposed on the surface of the core material; the core material comprises an EP polymer and a lead scavenging agent in a mass ratio of 1:(0.3~0.6); the first shell layer comprises polyurea and / or polyurethane; the second shell layer comprises a pH-responsive polyelectrolyte composite layer; Preferably, the lead-capturing agent comprises citric acid and polyacrylic acid in a mass ratio of 1:(0.3~0.6); Preferably, the pH-responsive polyelectrolyte composite layer comprises sodium alginate and chitosan; Preferably, the pH-responsive microcapsule A has a particle size of 10-30 μm, the thickness of the first shell layer is 1.5-2.5 μm, and the thickness of the second shell layer is 0.5-1.5 μm.

4. The self-healing encapsulating film according to claim 1, characterized in that, The UV-resistant microcapsule B comprises a core material and a shell layer disposed on the surface of the core material; the core material comprises a UV absorber and a hindered amine light stabilizer in a mass ratio of (1.8~2.2):1; the shell layer comprises melamine-formaldehyde resin; Preferably, the particle size of the UV-resistant microcapsule B is 5~20μm.

5. The self-healing encapsulating film according to claim 1, characterized in that, Includes at least one of the following features (1) to (6); (1) The hydrophobically modified nano-attapulgite includes nano-attapulgite that has been hydrophobically modified with a silane coupling agent; (2) The hydrophobically modified nano-attapulgite is fibrous and has an aspect ratio of 15~30; (3) The hydrophobically modified nano-silica includes nano-silica that has been hydrophobically modified with a silane coupling agent; (4) The hydrophobically modified nano-silica is spherical particles with a particle size of 20~50nm; (5) The functionalized graphene includes graphene surface-treated with a silane coupling agent; (6) The second additive, by mass parts, includes the following components: 0.5 to 1.5 parts of irradiation crosslinking agent, 0.2 to 0.5 parts of antioxidant and 0.3 to 0.8 parts of interfacial coupling agent.

6. The self-healing encapsulating film according to claim 1, characterized in that, Includes at least one of the following features (1) to (5); (1) The low-temperature peroxide crosslinking agent includes TBEC; (2) The anti-hydrolysis agent includes a carbodiimide anti-hydrolysis agent; (3) The nano acid absorbent comprises nano CaO and nano MgO in a mass ratio of 1:(1~2); (4) The particle size of the nano acid absorbent is 30~80nm; (5) The third auxiliary agent, by mass parts, includes the following components: 0.2 to 0.5 parts of antioxidant and 0.5 to 1.5 parts of silane coupling agent.

7. The self-healing encapsulating film according to claim 1, characterized in that, Includes at least one of the following features (1) to (3); (1) The thickness of the first surface layer is 80~120μm; (2) The thickness of the core layer is 200~320μm; (3) The thickness of the second surface layer is 60~100μm.

8. The method for preparing the self-healing encapsulating film according to any one of claims 1 to 7, characterized in that, Includes the following steps: S1. The premixed first surface layer material, the premixed core layer material and the premixed second surface layer material are co-extruded and cast to obtain a semi-finished film. S2. The semi-finished adhesive film is pre-crosslinked to obtain the self-healing encapsulating adhesive film.

9. The method for preparing the self-healing encapsulating film according to claim 8, characterized in that, The pre-crosslinking treatment includes: under ultraviolet light with a wavelength of 320~400nm, at a concentration of 200~500mJ / cm². 2 The irradiation dose is used to irradiate the semi-finished film, so that the gel content in the semi-finished film is 30%~50%.

10. A perovskite solar cell, characterized in that, Includes the self-healing encapsulating film according to any one of claims 1 to 7.

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