Organic silicon packaging adhesive film for space photovoltaic module and preparation method

Abstract

The invention belongs to the field of photovoltaic packaging, and relates to an organic silicon packaging adhesive film for a space photovoltaic module and a preparation method of the organic silicon packaging adhesive film, the organic silicon packaging adhesive film is prepared by coating on a basement film and thermocuring preforming, the organic silicon packaging adhesive film comprises a composite matrix and a composite radiation-resistant agent, the composite matrix comprises phenyl-containing linear silicone oil, and the composite radiation-resistant agent comprises phenyl-containing linear silicone oil. The phenyl-containing body type silicon resin is in chemical combination connection with the linear silicone oil; the composite radiation-resistant agent comprises titanate modified nano cerium oxide and silane modified nano zirconium oxide which have a synergistic effect; the ultraviolet radiation resistance of the adhesive film obtained by compounding the composite matrix and the composite radiation-resistant agent is 11000 ESH, the electron radiation resistance is 1 * 10 < 15 > e / cm < 2 >, and the temperature resistance range of the adhesive film is-196 DEG C to 400 DEG C.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic module encapsulation materials technology, specifically to an organosilicon encapsulation film for space photovoltaic modules and its preparation method. Background Technology

[0002] With the continuous advancement of space exploration technology, photovoltaic modules, as core energy supply components for space equipment, directly determine the success or failure of space missions through their long-term reliability. The space environment is extremely harsh, with a wide range of temperature fluctuations, such as the low temperatures of deep space, intense sunlight in near-Earth orbit, and high temperatures on planetary surfaces. It also experiences strong gamma rays and high-energy ultraviolet radiation, placing far more stringent requirements on the encapsulation films of photovoltaic modules than those for terrestrial applications.

[0003] The EVA and POE films commonly used in existing ground-mounted photovoltaic modules have weak radiation resistance of the C-C bonds in their molecular chains. They are prone to degradation and aging under the strong radiation of space, and their high and low temperature resistance is poor. They are easily brittle and fractured in ultra-low temperature environments, and rapidly decompose and flow at high temperatures, making them completely unsuitable for the extreme temperature environment of space. Conventional silicone films have excellent temperature resistance due to the high bond energy (452kJ / mol) of the Si-O-Si backbone, and can withstand a wide temperature range. However, their molecular structure design is simple, relying only on the basic silicone framework, and cannot simultaneously meet the requirements of radiation resistance and high temperature resistance. Under the combined effects of high temperature and strong radiation, molecular chain breakage and cross-linking deterioration will still occur, leading to a sharp decline in mechanical and optical properties.

[0004] Some existing technologies attempt to improve the radiation resistance of silicone materials by adding radiation-resistant additives. However, these are mostly simple mixtures without optimizing the additive structure, leading to problems such as uneven additive dispersion and poor compatibility with the silicone matrix. This not only reduces the film's transmittance and affects the photovoltaic module's photoelectric conversion efficiency but also fails to provide long-term radiation protection, making it difficult to meet the long-term service requirements of space photovoltaic modules. Furthermore, in the photovoltaic field, silicone materials are mostly in liquid form, encapsulated in photovoltaic modules via potting. This results in uneven film thickness, low production efficiency, and structural defects such as air bubbles. Air bubbles can become the starting point for radiation degradation, further reducing the film's reliability in the space environment. Although there are methods for preparing solid silicone films, such as UV curing, thermosetting, or a combination of both, silicone films prepared using these methods suffer from slow production efficiency, difficulty in achieving lightweight designs, low transmittance, and uneven thickness. Moreover, the radiation and temperature resistance of these silicone films also cannot meet the requirements of space photovoltaic modules. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an organosilicon encapsulating film for space photovoltaic modules and its preparation method. Through a combination of "optimized composite matrix molecular structure + radiation-resistant agent formulation + advanced molding process," the organosilicon encapsulating film can withstand temperature variations of -196℃ to 400℃ in the space environment, and has a UV irradiance resistance of 11000 ESH and an electron irradiance resistance of 1x10⁻¹⁰. 15 e / cm 2 At the same time, it does not affect the light transmittance of the film.

[0006] On the one hand, the present invention provides an organosilicon encapsulating film for space photovoltaic modules, the technical solution of which is as follows:

[0007] The silicone encapsulating film comprises: a composite matrix and a composite radiation-resistant agent dispersed in the composite matrix; the composite matrix comprises a phenyl-containing linear silicone oil and a phenyl-containing bulk silicone resin chemically linked to the linear silicone oil; the composite radiation-resistant agent comprises titanate-modified nano-cerium oxide and silane-modified nano-zirconia with synergistic effects; through the compounding of the phenyl groups in the composite matrix, the linkage between the linear silicone oil and the bulk silicone resin, and the synergistic effect of the titanate-modified nano-cerium oxide and silane-modified nano-zirconia, the silicone encapsulating film achieves a UV radiation resistance of 11000 ESH and an electron radiation resistance of 1x10⁻⁶. 15 e / cm 2 Furthermore, the temperature resistance range of the silicone encapsulation film is -196℃ to 400℃.

[0008] Preferably, the linear silicone oil is a vinyl-terminated methylphenyl silicone oil, wherein the phenyl content is 30.0~40.0 wt%.

[0009] Preferably, the bulk silicone resin is a transparent vinyl methyl phenyl silicone resin, wherein the phenyl content is 10.0~30.0 wt% and the vinyl content is 0.60~12.00 wt%.

[0010] Preferably, the particle size of the titanate-modified nano-zirconia is ≤50.0 nm.

[0011] Preferably, the particle size of the silane-modified nano-zirconia is 10.0~20.0 nm.

[0012] Furthermore, the silicone encapsulating film also includes hydrophobically modified fumed silica, preferably with a particle size of 10.0~20.0 nm.

[0013] Furthermore, the silicone encapsulating film also includes hydrogen-containing silicone oil, transparent platinum catalyst, inhibitor, silane coupling agent, and ultraviolet absorber.

[0014] Preferably, by weight, the composition comprises 35.0-65.0 parts of vinyl-terminated methylphenyl silicone oil, 20.0-40.0 parts of transparent vinyl methylphenyl silicone resin, 1.50-3.50 parts of titanate-modified nano-cerium oxide, 0.50-2.00 parts of silane-modified nano-zirconia, 6.0-16.0 parts of hydrogen-containing silicone oil, 0.02-0.50 parts of transparent platinum catalyst, 0.15-0.50 parts of inhibitor, 1.50-5.00 parts of hydrophobic modified fumed silica, 1.50-5.00 parts of silane coupling agent, and 0.60-2.20 parts of ultraviolet absorber.

[0015] On the other hand, the present invention provides a method for preparing an organosilicon encapsulating film, the technical solution of which is as follows:

[0016] The preparation methods include premix preparation, coating molding, and thermosetting preforming.

[0017] Furthermore, the preparation of premixes includes the preparation of titanate-modified nano-cerium oxide, silane-modified nano-zirconia, composite radiation-resistant agent, matrix mixture, and crosslinking system dispersion.

[0018] Furthermore, coating molding includes the preparation of the adhesive solution and the preparation of the wet film.

[0019] Specifically, the preparation of titanate-modified nano-cerium oxide involves dispersing a titanate coupling agent and nano-cerium oxide in an 80% n-butanol aqueous solution and stirring at room temperature for 20-60 minutes to obtain a titanate-modified nano-cerium oxide liquid; wherein the amount of titanate coupling agent added is 8%-10% of the mass of nano-cerium oxide.

[0020] Specifically, the preparation of silane-modified nano-zirconia involves dispersing a silane coupling agent and nano-zirconia in an 80% n-butanol aqueous solution and stirring at room temperature for 20-60 minutes to obtain a silane-modified nano-zirconia liquid; wherein the amount of silane coupling agent added is 8%-10% of the mass of nano-cerium oxide.

[0021] Specifically, the composite radiation-resistant agent is prepared by mixing titanate-modified nano-cerium oxide liquid and silane-modified nano-zirconia liquid at a mass ratio of 2:1, stirring at 60~80℃, magnetically stirring for 1~3 hours, refluxing for 0.5~3 hours, rotary evaporating under reduced pressure for 20~50 minutes, vacuum drying to constant weight, and grinding to obtain the composite radiation-resistant agent.

[0022] Specifically, the matrix mixture is prepared as follows: vinyl-terminated methylphenyl silicone oil and transparent vinyl methylphenyl silicone resin are added to a vacuum kneader, the kneading temperature is set to 160~200℃ and the kneading speed is set to 80~200rpm, and the kneading is carried out for 10~40 minutes. After cooling to room temperature, composite radiation resistant agent, hydrophobic modified fumed silica and ultraviolet absorber are added, and stirring is continued for 20~45 minutes to obtain the matrix mixture.

[0023] Specifically, the crosslinking system dispersion is prepared by mixing hydrogen-containing silicone oil and silane coupling agent, stirring at a speed of 1000~2000 rpm for 30~55 minutes, and vacuum degassing at a pressure of -0.08~-0.11 MPa for 20~45 minutes to obtain the crosslinking system dispersion.

[0024] Specifically, the preparation of the adhesive solution is as follows: the matrix mixture, the crosslinking system dispersion, the transparent platinum catalyst and the inhibitor are mixed, the stirring speed is set to 1500~2000 rpm and stirred for 30~60 minutes, the vacuum degassing pressure is set to -0.09~-0.1 MPa and vacuum degassing is carried out for 30~60 minutes to obtain the adhesive solution;

[0025] Specifically, wet film preparation: using precision doctor blade coating or spraying equipment, the adhesive is uniformly coated onto the substrate film, with the coating thickness set to 0.05~0.20mm and the coating speed set to 0.6~1.2m / min, to obtain a wet film attached to the surface of the substrate film.

[0026] Specifically, thermosetting preforming: The wet film is preformed by heating, with the heating temperature set to 80~120℃ and the holding time to 10~50 minutes, to obtain a preformed silicone film.

[0027] Preferably, the base film is selected from PET, PP or PI film.

[0028] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0029] 1. Excellent high and low temperature resistance: The composite matrix system, which combines linear silicone oil and three-dimensional silicone resin, with the optimized molecular structure of the composite matrix with high phenyl content, enhances the stability of the Si-O-Si main chain. The film can maintain good flexibility (elongation at break ≥350%) and adhesion (peel strength to glass ≥42N) in the range of -196℃ to 400℃, without embrittlement, peeling, decomposition or flow, making it suitable for the extreme high and low temperature fluctuation environment of space.

[0030] 2. Synergistic effect of radiation resistance and high light transmittance: The conjugated π-electron system of the phenyl groups in the composite matrix can disperse radiation energy. Combined with titanate-modified nano-cerium oxide and silane-modified nano-zirconia dual radiation-resistant agents, and synergistic with UV absorbers, a triple radiation protection system is formed, with a cumulative UV radiation dose of 11000 ESH and an electron radiation dose of 1x10⁻¹⁰. 15 e / cm 2 Afterwards, the tensile strength reduction rate is ≤14%, the elongation at break reduction rate is ≤11%, and the visible light transmittance is ≥95%, completely solving the problem that radiation resistance and transmittance cannot be satisfied at the same time;

[0031] 3. Advanced molding process: The thermosetting pre-forming process coated on the base film eliminates the need for UV curing and main curing steps, completing the molding in one step, simplifying the production process and increasing production efficiency by more than 40% compared to traditional curing processes; the film thickness is precisely controlled within the thin range of 0.05~0.20mm, with excellent uniformity (deviation controlled within ±4%), and no structural defects such as bubbles. The base film plays a load-bearing role, which can ensure the stability of the pre-formed shape and meet the requirements of lightweight and thin-film aerospace photovoltaic modules;

[0032] 4. Standard performance meets requirements: Hydrogen-containing silicone oil is used as a crosslinking agent, avoiding metal ion residue, resulting in excellent PID resistance of the film (power attenuation rate ≤1.3% after dual 85V, reverse 1000V, 96h test) and volume resistivity ≥5×10¹ 5 Ω·cm, peel strength from glass ≥45N / cm, shrinkage ≤0.6%, can directly replace EVA and POE films;

[0033] 5. Strong long-term stability: The titanate or silane on the surface of the composite radiation-resistant agent can be chemically bonded to the composite matrix, resulting in uniform dispersion and minimal migration. The high phenyl content molecular chain structure of the composite matrix, combined with the radiation-resistant agent, provides long-term stable radiation resistance. The curing process leaves no small molecule residue, preventing contamination of the solar cells and meeting the long-term service requirements of space photovoltaic modules. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0035] In a first aspect, the present invention provides an organosilicon encapsulating film for space photovoltaic modules, comprising a composite matrix, wherein the composite matrix comprises a phenyl-containing linear silicone oil and a phenyl-containing bulk silicone resin chemically bonded to the linear silicone oil. Preferably, the linear silicone oil is a vinyl-terminated methylphenyl silicone oil, wherein the phenyl content is 30.0~40.0 wt%. The bulk silicone resin is a transparent vinylmethylphenyl silicone resin, wherein the phenyl content is 10.0~30.0 wt% and the vinyl content is 0.60~12.00 wt%. Among them, the high phenyl content of vinyl-terminated methylphenyl silicone oil enables its conjugated π-electron system to disperse irradiation energy. The steric hindrance effect brought about by the high phenyl content enhances the rigidity of the molecular chain and maintains some flexibility of the linear resin, making it suitable for extreme high and low temperature environments without affecting the light transmittance of the film. In transparent vinyl methylphenyl silicone resin, the vinyl content enables further cross-linking of the transparent vinyl methylphenyl silicone resin. The formed three-dimensional network structure can hinder the spread of irradiation degradation and make the light transmittance of the organosilicon encapsulation film ≥95%. The high phenyl content also enables its conjugated π-electron system to disperse irradiation energy. Using vinyl-terminated methylphenyl silicone oil and vinyl methylphenyl silicone resin with high phenyl content as the composite matrix, the radiation resistance of the silicone encapsulation film is enhanced. Furthermore, by utilizing the vinyl groups on the vinyl-terminated methylphenyl silicone oil and vinyl methylphenyl silicone resin molecules, a system of interconnected "linear chains + network structures" is constructed to strengthen the stability of the Si-O-Si main chain. This allows the silicone encapsulation film to maintain good flexibility (elongation at break ≥350%) and adhesion (peel strength to glass ≥42N) within a temperature range of -196℃ to 400℃, without embrittlement, peeling, decomposition, or flow, making it suitable for the extreme high and low temperature fluctuations of space. This achieves a balance between radiation resistance and high and low temperature resistance.

[0036] The silicone encapsulating film for space photovoltaic modules provided by this invention further includes a composite radiation-resistant agent dispersed in a composite matrix. This composite radiation-resistant agent comprises titanate-modified nano-cerium oxide and silane-modified nano-zirconia, exhibiting synergistic effects. On one hand, titanate-modified nano-cerium oxide can effectively absorb the energy generated by high-energy radiation (especially ultraviolet light and high-energy particles), thereby greatly mitigating the problem of the silicone encapsulating film darkening due to radiation; Ce³⁺ / Ce 4The redox cycle of ⁺ captures irradiated free radicals, thus preventing yellowing of the silicone encapsulation film. On the other hand, silane-modified nano-zirconia, with its unique lattice structure, can inhibit the cross-linking and degradation of the molecular chains in the composite matrix, synergistically broadening the radiation resistance spectrum with nano-cerium oxide. The refractive index of the composite radiation-resistant agent matches that of the composite matrix, preventing optical interference and ensuring the transmittance of the silicone encapsulation film. The composite radiation-resistant agent effectively resists external radiation and inhibits internal aging of the silicone encapsulation film, enabling it to exhibit excellent radiation resistance without affecting transmittance. Through the combination of phenyl groups in the composite matrix, the connection between the linear silicone oil and the bulk silicone resin, and the synergistic effect of titanate-modified nano-cerium oxide and silane-modified nano-zirconia, the silicone encapsulation film achieves a UV irradiance resistance of 11000 ESH and an electron irradiance resistance of 1x10⁻⁶. 15 e / cm 2 It can be applied to space environments where temperatures vary between -196℃ and 400℃, while maintaining excellent light transmittance.

[0037] Preferably, the particle size of titanate-modified nano-zirconia is ≤50.0 nm, and the particle size of silane-modified nano-zirconia is 10.0~20.0 nm. This avoids light scattering and ensures both the light transmittance of the encapsulant film and the light utilization rate of the photovoltaic module. The low particle size and high compatibility design of the composite radiation-resistant agent ensures light transmittance, with a visible light transmittance ≥95%. This allows the silicone encapsulant film to possess both radiation resistance and high light transmittance, solving the problem of simultaneously failing to meet the requirements of radiation resistance and light transmittance.

[0038] Titanate esters or silanes can improve the compatibility of nano-cerium oxide or nano-zirconia in the composite matrix, thus ensuring their full and uniform distribution within the silicone encapsulation film and preventing agglomeration. Furthermore, the titanate esters or silanes on the surface of the composite radiation-resistant agent can chemically bond with the composite matrix, resulting in uniform dispersion and minimal migration. This ensures the long-term stability of the radiation resistance performance synergistically achieved by the high phenyl content molecular chain structure of the composite matrix and the radiation-resistant agent. The curing process leaves no small molecule residue, preventing contamination of the solar cells and meeting the long-term service requirements of space photovoltaic modules.

[0039] Furthermore, the silicone encapsulating film for space photovoltaic modules provided by this invention may also include a UV absorber, which specifically absorbs high-energy ultraviolet light, preventing UV damage to Si-O bonds. Using vinyl-terminated methylphenyl silicone oil with high phenyl content and transparent vinyl methylphenyl silicone resin as the composite matrix, a system with interconnected "linear chains + network structures" is constructed using vinyl groups. The conjugated π-electron system of the phenyl groups can disperse irradiation energy. Combined with a composite radiation-resistant agent composed of titanate-modified nano-cerium oxide and silane-modified nano-zirconia, it works synergistically with the UV absorber to form triple radiation protection, inhibiting radiation-induced degradation of the composite matrix molecular chains from the source. Even with cumulative UV irradiation reaching 11000 ESH and electron irradiation reaching 1x10⁻¹⁰ ESH, this protection is effective. 15 e / cm 2 Even after that, it can still maintain excellent mechanical properties, such as tensile strength reduction rate ≤14% and elongation at break reduction rate ≤11%.

[0040] Preferably, the ultraviolet absorber is a benzotriazole compound. Specifically, it can be selected from one or more of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-α-cumylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] or 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole.

[0041] Furthermore, the silicone encapsulating film for space photovoltaic modules provided by this invention also includes hydrophobically modified fumed silica. The hydrophobically modified fumed silica fills the gaps between the molecular chains of the composite matrix, enhancing the mechanical strength and shrinkage resistance of the silicone encapsulating film, and can also indirectly inhibit irradiation-accelerated degradation.

[0042] Preferably, the particle size of the hydrophobically modified fumed silica is 10.0~20.0 nm.

[0043] Furthermore, the silicone encapsulating film for space photovoltaic modules provided by this invention also includes hydrogen-containing silicone oil and a transparent platinum catalyst. The hydrogen-containing silicone oil provides ample crosslinking sites, forming a dense Si-C bond crosslinking network with the vinyl groups in the composite matrix, enhancing the stability of the silicone encapsulating film molding, thereby ensuring uniform thickness and low shrinkage of the silicone encapsulating film. The transparent platinum catalyst can efficiently catalyze the hydrosilylation reaction between the hydrogen-containing silicone oil and the vinyl groups in the composite matrix; by controlling the amount added, the light transmittance of the silicone encapsulating film can be maintained.

[0044] Preferably, the hydrogen-containing silicone oil is selected from one or more of linear liquid hydrogen-containing silicone oil or branched / resin-type hydrogen-containing silicone oil. Using hydrogen-containing silicone oil as a crosslinking agent avoids metal ion residue, resulting in excellent PID resistance of the film (power attenuation rate ≤1.3% after dual 85V, reverse 1000V, 96h test) and a volume resistivity ≥5×10¹. 5 Ω·cm, peel strength from glass ≥45N, shrinkage ≤0.6%.

[0045] Preferably, the transparent platinum catalyst is selected from one of Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, cyclohexene-platinum complex, platinum-vinylsiloxane complex, and platinum-divinyltetramethyldisiloxane complex.

[0046] Furthermore, the silicone encapsulating film for space photovoltaic modules provided by this invention also includes inhibitors. Through a reversible coordination mechanism with the platinum catalyst, the inhibitors can temporarily "poison" or "shield" the activity of the platinum catalyst, preventing the reaction from occurring at low / room temperature, while releasing active platinum upon heating, thereby extending the operating time and enabling rapid curing upon heating. Preventing the reaction from occurring at low / room temperature helps improve the storage stability of the silicone encapsulating film.

[0047] Preferably, the inhibitor is selected from one or more of alkynols and vinylcyclosiloxanes. Optionally, the alkynols are selected from one or more of 1-ethynylcyclohexanol, 3-methyl-1-butyn-3-ol, 3,3-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecyn-3-ol, or 3,7,11-trimethyl-1-dodecyn-3-ol. Optionally, the vinylcyclosiloxane is selected from one or more of tetravinyltetramethylcyclotetrasiloxane, dimethyldivinylcyclosiloxane, methyltrivinylcyclosiloxane, or trimethylvinylcyclosiloxane.

[0048] Furthermore, the silicone encapsulating film for space photovoltaic modules provided by this invention also includes a silane coupling agent. The silane coupling agent forms chemical bonds with the photovoltaic module cover plate, improving the adhesion strength between the silicone encapsulating film and the cover plate, while simultaneously binding with the composite matrix molecular chains to optimize the composite matrix interface structure.

[0049] Preferably, the silane coupling agent is selected from one or more of 3-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, or dimethyldimethoxysilane.

[0050] Optionally, the vinyl-terminated methylphenyl silicone oil can be measured in parts by weight as any number of parts between 35.0 and 65.0, including but not limited to 35.0, 36.5, 38.0, 39.5, 41.0, 42.5, 44.0, 45.5, 47.0, 48.5, 50.0, 51.2, 53.0, 54.7, 56.0, 57.5, 59.0, 60.9, 62.0, 62.5, and 65.0 parts.

[0051] Optionally, the transparent vinyl methyl phenyl silicone resin can be measured in parts by weight as any number of parts between 20.0 and 40.0, including but not limited to 20.0, 21.5, 22.8, 24.0, 25.3, 27.0, 28.1, 30.0, 32.1, 34.5, 36.0, 38.1, and 40.0 parts.

[0052] Optionally, the phenyl content in the vinyl-terminated methylphenyl silicone oil can be any mass fraction between 30.0 and 40.0 wt%, including but not limited to 30.0 wt%, 31 wt%, 32.5 wt%, 34.0 wt%, 34.5 wt%, 36.0 wt%, 37.5 wt%, 39.0 wt%, and 40 wt%.

[0053] Optionally, the phenyl content in the transparent vinyl methyl phenyl silicone resin can be any mass fraction between 10.0 and 30.0 wt%, including but not limited to 10.0 wt%, 12.5 wt%, 14.0 wt%, 16.0 wt%, 17.5 wt%, 19.0 wt%, 20 wt%, 22.5 wt%, 24.0 wt%, 25.0 wt%, 27.0 wt%, 28.5 wt%, and 30 wt%.

[0054] Optionally, the vinyl content in the transparent vinyl methyl phenyl silicone resin can be any mass fraction between 0.60 and 12.00 wt%, including but not limited to 0.60 wt%, 0.80 wt%, 0.90 wt%, 1.10 wt%, 1.35 wt%, 1.65 wt%, 2.00 wt%, 2.80 wt%, 3.30 wt%, 3.90 wt%, 4.10 wt%, 4.65 wt%, 5.00 wt%, 5.30 wt%, 5.80 wt%, 6.05 wt%, 6.55 wt%, 7.00 wt%, 7.65 wt%, 8.00 wt%, 8.45 wt%, 8.80 wt%, 9.00 wt%, 9.55 wt%, 9.90 wt%, 10.20 wt%, 10.75 wt%, 11.10 wt%, 11.60 wt%, and 12.00 wt%.

[0055] Optionally, the particle size of the titanate-modified nano-cerium oxide can be any particle size ≤50.0 nm and >0, including but not limited to 5.0, 9.5, 15.0, 18.0, 21.5, 27.8, 30.5, 36.2, 40.5, 45.5, and 50.0 nm.

[0056] Optionally, the titanate-modified nano-cerium oxide can be present in any number of parts by weight between 1.50 and 3.50, including but not limited to 1.50, 1.70, 1.84, 2.05, 2.25, 2.54, 2.74, 3.00, 3.25, and 3.50 parts.

[0057] Optionally, the particle size of silane-modified nano-zirconia can be any particle size between 10.0 and 20.0 nm, including but not limited to 10.0, 11.6, 12.5, 14.9, 16.0, 17.4, 18.9, and 20.0 nm.

[0058] Optionally, the silane-modified nano-zirconia can be measured in parts by weight of any number of parts between 0.50 and 2.00, including but not limited to 0.50, 0.65, 0.80, 0.92, 1.00, 1.12, 1.24, 1.40, 1.55, 1.71, 1.85, and 2.00 parts.

[0059] Optionally, the ultraviolet absorber can be measured in parts by weight from 0.50 to 2.00 parts, including but not limited to 0.50, 0.67, 0.80, 0.95, 1.00, 1.15, 1.34, 1.45, 1.65, 1.81, 1.95, and 2.00 parts.

[0060] Optionally, the hydrophobically modified fumed silica can be any number of parts by weight between 1.50 and 5.00, including but not limited to 1.50, 1.75, 2.00, 2.24, 2.50, 2.76, 3.00, 3.20, 3.50, 3.76, 4.00, 4.30, 4.65, and 5.00 parts.

[0061] Optionally, the particle size of the hydrophobically modified fumed silica can be any particle size between 10.0 and 20.0 nm, including but not limited to 10.0, 12.1, 13.5, 15.0, 16.6, 17.8, 19.0, and 20.0 nm.

[0062] Optionally, the hydrogen-containing silicone oil can be measured in parts by weight as any number of parts between 6.0 and 16.0, including but not limited to 6.0, 7.3, 8.5, 10.0, 11.2, 13.5, 14.5, and 16.0 parts.

[0063] Optionally, the transparent platinum catalyst can be any number of parts by weight between 0.02 and 0.50, including but not limited to 0.02, 0.03, 0.05, 0.09, 0.10, 0.15, 0.20, 0.22, 0.30, 0.36, 0.40, 0.45, and 0.50.

[0064] Optionally, the inhibitor can be any number of parts by weight between 0.15 and 0.50, including but not limited to 0.15, 0.17, 0.20, 0.23, 0.27, 0.30, 0.34, 0.38, 0.42, 0.45, 0.47, and 0.50.

[0065] Optionally, the silane coupling agent can be any number of parts by weight between 1.50 and 5.00, including but not limited to 1.50, 1.65, 1.80, 1.97, 2.00, 2.23, 2.50, 2.70, 2.90, 3.20, 3.50, 3.76, 4.00, 4.25, 4.60, 4.83, and 5.00 parts.

[0066] Secondly, the method for preparing the silicone encapsulating film provided by the present invention includes premix preparation, coating molding, and thermosetting preforming.

[0067] Furthermore, the preparation of premixes includes the preparation of titanate-modified nano-cerium oxide, silane-modified nano-zirconia, composite radiation-resistant agent, matrix mixture, and crosslinking system dispersion.

[0068] Specifically, the preparation of titanate-modified nano-cerium oxide involves dispersing a titanate coupling agent and nano-cerium oxide in an 80% n-butanol aqueous solution and stirring at room temperature for 20-60 minutes to obtain a titanate-modified nano-cerium oxide liquid; wherein the amount of titanate coupling agent added is 8%-10% of the mass of nano-cerium oxide.

[0069] Preferably, the titanate coupling agent is selected from one of isopropoxytriisostearoyl titanium, isopropoxytris(dioctyl phosphate oxy) titanium, isopropoxytris(dioctyl pyrophosphate oxy) titanium, isopropoxytris(dioctyl pyrophosphate oxy) titanium, di(dioctyl phosphate oxy)hydroxyacetic acid titanium, di(dioctyl pyrophosphate oxy)hydroxyacetic acid titanium, di(dioctyl phosphate oxy)ethylenediene titanium, or di(dioctyl pyrophosphate)oxyacetic acid diisopropyl titanate.

[0070] Specifically, the preparation of silane-modified nano-zirconia involves dispersing a silane coupling agent and nano-zirconia in an 80% n-butanol aqueous solution and stirring at room temperature for 20-60 minutes to obtain a silane-modified nano-zirconia liquid; wherein the amount of silane coupling agent added is 8%-10% of the mass of nano-cerium oxide.

[0071] Optionally, the silane coupling agent is selected from one or more of methyltrimethoxysilane, phenyltrimethoxysilane, or dimethyldimethoxysilane.

[0072] Specifically, the composite radiation-resistant agent is prepared by mixing titanate-modified nano-cerium oxide liquid and silane-modified nano-zirconia liquid at a mass ratio of 2:1, stirring at 60~80℃, magnetically stirring for 1~3 hours, refluxing for 0.5~3 hours, rotary evaporating under reduced pressure for 20~50 minutes, vacuum drying to constant weight, and grinding to obtain the composite radiation-resistant agent.

[0073] Specifically, the matrix mixture is prepared as follows: vinyl-terminated methylphenyl silicone oil and transparent vinyl methylphenyl silicone resin are added to a vacuum kneader, the kneading temperature is set to 160~200℃ and the kneading speed is set to 80~200rpm, and the kneading is carried out for 10~40 minutes. After cooling to room temperature, composite radiation resistant agent, hydrophobic modified fumed silica and ultraviolet absorber are added, and stirring is continued for 20~45 minutes to obtain the matrix mixture.

[0074] Specifically, the crosslinking system dispersion is prepared by mixing hydrogen-containing silicone oil and silane coupling agent, stirring at 1000~2000 rpm for 30~55 minutes, setting the vacuum degassing pressure to -0.08~-0.11 MPa, and degassing under vacuum for 20~45 minutes to obtain the crosslinking system dispersion.

[0075] Furthermore, coating molding includes the preparation of the adhesive solution and the preparation of the wet film.

[0076] Specifically, the preparation of the adhesive solution is as follows: the matrix mixture, the crosslinking system dispersion, the transparent platinum catalyst, and the inhibitor are mixed, the stirring speed is set to 1500~2000 rpm, and the mixture is stirred for 30~60 minutes. The vacuum degassing pressure is set to -0.09~-0.1 MPa, and the mixture is vacuum degassed for 30~60 minutes to obtain the adhesive solution.

[0077] Specifically, wet film preparation: using precision doctor blade coating or spraying equipment, the adhesive is uniformly coated onto the substrate film, with the coating thickness set to 0.05~0.20mm and the coating speed set to 0.6~1.2m / min, to obtain a wet film attached to the surface of the substrate film.

[0078] Specifically, thermosetting preforming: The base film coated with adhesive is pre-formed by heating. The heating temperature is set to 80~120℃, and the holding time is 10~50 minutes. After thermosetting, a pre-formed silicone film is obtained.

[0079] Preferably, the base film is selected from PET, PP or PI film.

[0080] This invention employs a "coating onto a base film + thermosetting preforming" process, eliminating UV curing and traditional main curing steps. In the premixing stage, modification and vacuum dispersion ensure uniform dispersion of the composite radiation-resistant agent and enhance its compatibility with the composite matrix. Precision equipment is used to directly coat the adhesive onto the base film, precisely controlling the thickness and uniformity to 0.05~0.20mm to avoid structural defects. In the thermosetting preforming stage, temperature and time control rapidly and fully cure the adhesive, allowing it to adhere to the base film and form the preform in one step, significantly improving production efficiency while ensuring stable film performance. The base film can be made of PET, PP, or PI material, offering both load-bearing capacity and compatibility, and can be selected according to actual needs. Production efficiency is increased by more than 40% compared to traditional curing processes; the film thickness is precisely controlled within the 0.05~0.2mm range, with excellent uniformity (deviation controlled within ±4%), and no structural defects such as bubbles. The load-bearing capacity of the base film ensures the stability of the preformed shape, meeting the lightweight and thin requirements of space photovoltaic modules.

[0081] Optionally, during the preparation of titanate-modified nano-cerium oxide, the stirring time at room temperature is any time between 20 and 60 minutes, including but not limited to 20, 25.5, 27.5, 30, 33.5, 37.5, 40, 43.5, 47.5, 50, 52.5, 56.5, and 60 minutes.

[0082] Optionally, in the preparation of titanate-modified nano-cerium oxide, the amount of titanate coupling agent added is any percentage between 8% and 10% of the mass of nano-cerium oxide, including but not limited to 8%, 8.3%, 8.5%, 8.7%, 9.0%, 9.25%, 9.5%, 9.74%, and 10%.

[0083] Optionally, during the preparation of silane-modified nano-zirconia, the stirring time at room temperature is any time between 20 and 60 minutes, including but not limited to 20, 25.5, 27.5, 30, 33.5, 37.5, 40, 43.5, 47.5, 50, 52.5, 56.5, and 60 minutes.

[0084] Optionally, in the preparation of silane-modified nano-zirconia, the amount of silane coupling agent added is any percentage between 8% and 10% of the mass of nano-zirconia, including but not limited to 8%, 8.3%, 8.5%, 8.7%, 9.0%, 9.25%, 9.5%, 9.74%, and 10%.

[0085] Optionally, during the preparation of the composite radiation-resistant agent, the stirring temperature is set to any temperature between 60 and 80°C, including but not limited to 60°C, 62.5°C, 65°C, 67.5°C, 70°C, 72.5°C, 75°C, 77.5°C, and 80°C.

[0086] Optionally, during the preparation of the composite radiation-resistant agent, the magnetic stirring time can be any time between 1 and 3 hours, including but not limited to 1, 1.1, 1.3, 1.3, 1.8, 2, 2.2, 2.5, 2.75, and 3 hours.

[0087] Optionally, during the preparation of the composite radiation-resistant agent, the condensation reflux time can be any time between 0.5 and 3 hours, including but not limited to 0.5, 0.6, 0.85, 1, 1.1, 1.3, 1.5, 1.75, 2, 2.3, 2.6, 2.8, and 3 hours.

[0088] Optionally, during the preparation of the composite radiation-resistant agent, the reduced pressure rotary evaporation time is any time between 20 and 50 minutes, including but not limited to 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5, and 50 minutes.

[0089] Optionally, during the preparation of the matrix mixture, the kneading temperature is any temperature between 160 and 200°C, including but not limited to 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, and 200°C.

[0090] Optionally, during the preparation of the matrix mixture, the kneading speed is any speed between 80 and 200 rpm, including but not limited to 80 rpm, 90 rpm, 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, 150 rpm, 160 rpm, 170 rpm, 180 rpm, 190 rpm, and 200 rpm.

[0091] Optionally, during the preparation of the matrix mixture, the kneading time is any time between 10 and 40 minutes, including but not limited to 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, and 40 minutes.

[0092] Optionally, during the preparation of the matrix mixture, after adding the additives, the stirring time is continued for any time between 20 and 45 minutes, including but not limited to 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, and 45 minutes.

[0093] Optionally, during the preparation of the crosslinking system dispersion, the stirring speed is any speed between 1000 and 2000 rpm, including but not limited to 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, and 2000 rpm.

[0094] Optionally, during the preparation of the crosslinking system dispersion, the stirring time is any time between 30 and 55 minutes, including but not limited to 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5, 50, 52.5, and 55 minutes.

[0095] Optionally, during the preparation of the crosslinking system dispersion, the vacuum degassing pressure is any pressure between -0.08 and -0.11 MPa, including but not limited to -0.08, -0.085, -0.09, -0.095, -0.10, -0.105, and -0.11 MPa.

[0096] Optionally, during the preparation of the crosslinking system dispersion, the vacuum degassing time is any time between 20 and 45 minutes, including but not limited to 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, and 45 minutes.

[0097] Optionally, during the preparation of the adhesive solution, the stirring speed is any speed between 1500 and 2000 rpm, including but not limited to 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, and 2000 rpm.

[0098] Optionally, during the preparation of the adhesive solution, the stirring time can be any time between 30 and 60 minutes, including but not limited to 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5, 50, 52.5, 55, 57.5, and 60 minutes.

[0099] Optionally, during the preparation of the adhesive, the vacuum degassing pressure is any pressure between -0.09 and -0.1 MPa, including but not limited to -0.09, 0.092, -0.095, 0.098, and -0.1 MPa.

[0100] Optionally, during the preparation of the adhesive solution, the vacuum degassing time is any time between 30 and 60 minutes, including but not limited to 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5, 50, 52.5, 55, 57.5, and 60 minutes.

[0101] Optionally, during the wet film preparation process, the coating thickness can be any thickness between 0.05 and 0.20 mm, including but not limited to 0.05, 0.06, 0.08, 0.10, 0.12, 0.14, 0.15, 0.17, 0.19, and 0.20 mm.

[0102] Optionally, during the wet film preparation process, the coating speed is any speed between 0.6 and 1.2 m / min, including but not limited to 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, and 1.2 m / min.

[0103] Optionally, during the thermosetting preforming process, the heating temperature is any temperature between 80 and 120°C, including but not limited to 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, and 120°C.

[0104] Optionally, during the thermosetting preforming process, the heat preservation time is any time between 10 and 50 minutes, including but not limited to 10, 15, 20, 25, 30, 35, 40, 45, and 50 minutes.

[0105] The technical solutions of this application will be further described below through several representative embodiments and comparative examples. It should be noted that the following embodiments are only some implementation methods of this application, and not all implementation methods.

[0106] Example 1

[0107] Formula (by weight):

[0108] Vinyl-terminated methylphenyl silicone oil (viscosity 60000 cst, phenyl content 35.0%) 50.0 parts, transparent vinyl methylphenyl silicone resin (phenyl content 20.0%, vinyl content 1.50 wt%) 32 parts, titanate-modified nano-cerium oxide 2.50 parts, silane-modified nano-zirconia 1.20 parts, hydrogen-containing silicone oil (RH-H86 type) 11.0 parts, transparent platinum catalyst (platinum-divinyltetramethyldisiloxane complex) 0.25 parts, tetravinyltetramethylcyclotetrasiloxane 0.30 parts, hydrophobically modified fumed silica (particle size 15 nm) 3.0 parts, 3-glycidyl etheroxypropyltrimethoxysilane 3.50 parts, benzotriazole UV absorber (2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole) 1.5 parts.

[0109] Preparation method:

[0110] (1) Preparation of premix:

[0111] Preparation of titanate-modified nano-cerium oxide: Titanate coupling agent and nano-cerium oxide were dispersed in an 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain titanate-modified nano-cerium oxide liquid; wherein, the amount of titanate coupling agent added was 8% of the mass of nano-cerium oxide. The titanate coupling agent selected was isopropoxytriisostearoyloxytitanium.

[0112] Preparation of silane-modified nano-zirconia: A silane coupling agent and nano-zirconia were dispersed in an 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain a silane-modified nano-zirconia liquid; wherein, the amount of silane coupling agent added was 8% of the mass of nano-zirconia. Methyltrimethoxysilane was selected as the silane coupling agent.

[0113] Preparation of composite radiation resistant agent: Titanate-modified nano-cerium oxide liquid and silane-modified nano-zirconia liquid were mixed at a mass ratio of 2:1, stirred at 70℃, magnetically stirred for 2 hours, refluxed under reduced pressure for 1 hour, rotary evaporated under reduced pressure for 30 minutes, vacuum dried to constant weight, and ground to obtain composite radiation resistant agent.

[0114] Preparation of matrix mixture: Vinyl-terminated methylphenyl silicone oil and transparent vinyl methylphenyl silicone resin were added to a vacuum kneader. The kneading temperature was 180℃ and the kneading speed was 100 rpm. The mixture was kneaded for 15 minutes. After cooling to room temperature, a composite radiation resistant agent, hydrophobic modified fumed silica, and ultraviolet absorber (2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole) were added. The mixture was stirred for another 25 minutes to obtain the matrix mixture.

[0115] Preparation of crosslinking system dispersion: Hydrogen-containing silicone oil and 3-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred at 1200 rpm for 35 minutes, and vacuum degassing was performed at -0.09 MPa for 25 minutes to obtain the crosslinking system dispersion.

[0116] (2) Coating and molding:

[0117] Preparation of adhesive solution: The matrix mixture, crosslinking system dispersion, transparent platinum catalyst and tetravinyltetramethylcyclotetrasiloxane are mixed and stirred at 1800 rpm for 45 minutes. Vacuum degassing is carried out at -0.095 MPa for 35 minutes to obtain the adhesive solution.

[0118] Wet film preparation: The adhesive solution is uniformly coated onto the PET base film using a precision doctor blade coating device. The coating thickness is 0.10 mm and the coating speed is 0.9 m / min.

[0119] (3) Thermosetting preforming: The wet film is heated to 95°C and kept warm for 20 minutes to complete the thermosetting preforming and obtain the preformed silicone film.

[0120] Example 2

[0121] Formula (by weight):

[0122] Vinyl-terminated methylphenyl silicone oil (viscosity 50000 cst, phenyl content 32%) 55 parts, transparent vinyl methylphenyl silicone resin (phenyl content 30%, vinyl content 0.6 wt%) 30 parts, titanate-modified nano-cerium oxide 2.8 parts, silane-modified nano-zirconia 1.5 parts, hydrogen-containing silicone oil (RH-H536 type) 12 parts, transparent platinum catalyst (platinum-vinylsiloxane complex) 0.3 parts, 3-methyl-1-butyn-3-ol 0.35 parts, hydrophobically modified fumed silica (particle size 15 nm) 3.2 parts, 3-glycidyl etheroxypropyltrimethoxysilane 3.8 parts, ultraviolet absorber (2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole) 1.6 parts.

[0123] Preparation method:

[0124] (1) Preparation of premix:

[0125] Preparation of titanate-modified nano-cerium oxide: Titanate coupling agent and nano-cerium oxide were dispersed in 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain titanate-modified nano-cerium oxide liquid; wherein, the amount of titanate coupling agent added was 10% of the mass of nano-cerium oxide. The titanate coupling agent used was isopropoxytris(dioctylpyrophosphateoxy)titanium.

[0126] Preparation of silane-modified nano-zirconia: Silane coupling agent and nano-zirconia are dispersed in 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain silane-modified nano-zirconia liquid; wherein, the amount of silane coupling agent added is 10% of the mass of nano-cerium oxide, and phenyltrimethoxysilane is selected as the silane coupling agent.

[0127] Preparation of composite radiation resistant agent: Titanate-modified nano-cerium oxide liquid and silane-modified nano-zirconia liquid were mixed at a mass ratio of 2:1, stirred at 70℃, magnetically stirred for 2 hours, refluxed under reduced pressure for 1 hour, rotary evaporated under reduced pressure for 30 minutes, vacuum dried to constant weight, and ground to obtain composite radiation resistant agent.

[0128] Preparation of matrix mixture: Vinyl-terminated methylphenyl silicone oil and transparent vinyl methylphenyl silicone resin are added to a vacuum kneader. The kneading temperature is 180℃ and the kneading speed is 100rpm. Knead for 15 minutes. After cooling to room temperature, add composite radiation resistant agent, hydrophobic modified fumed silica and ultraviolet absorber. Continue stirring for 25 minutes to obtain matrix mixture.

[0129] Preparation of crosslinking system dispersion: Hydrogen-containing silicone oil and 3-glycidyl ether oxypropyltrimethoxysilane were mixed and stirred at 1200 rpm for 35 minutes. Vacuum degassing was carried out at a pressure of -0.09 MPa for 25 minutes to obtain the crosslinking system dispersion.

[0130] (2) Coating and molding:

[0131] Preparation of adhesive solution: The matrix mixture, crosslinking system dispersion, transparent platinum catalyst and 3-methyl-1-butyn-3-ol were mixed and stirred at 1800 rpm for 45 minutes. Vacuum degassing was carried out at -0.095 MPa for 35 minutes to obtain the adhesive solution.

[0132] Wet film preparation: The adhesive solution was uniformly coated onto the PI substrate film using a spraying device. The coating thickness was 0.15 mm and the coating speed was 0.8 m / min.

[0133] (3) Thermosetting preforming: The wet film is heated to 110°C and kept warm for 15 minutes to complete the thermosetting preforming and obtain the preformed silicone encapsulation film.

[0134] Example 3

[0135] Formula (by weight):

[0136] Vinyl-terminated methylphenyl silicone oil (viscosity 70000 cst, phenyl content 38%) 55 parts, transparent vinyl methylphenyl silicone resin (phenyl content 10%, vinyl content 12 wt%) 35 parts, titanate-modified nano-cerium oxide 2.0 parts, silane-modified nano-zirconium oxide 1.0 part, hydrogen-containing silicone oil (RH-H86 type) 9 parts, transparent platinum catalyst (Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) 0.15 parts, tetravinyltetramethylcyclotetrasiloxane 0.25 parts, hydrophobically modified fumed silica (particle size 15 nm) 2.5 parts, 3-methacryloyloxypropyltrimethoxysilane 2.5 parts, ultraviolet absorber (2-(2'-hydroxy-5'-methylphenyl)benzotriazole) 1.2 parts.

[0137] Preparation method:

[0138] (1) Preparation of premix:

[0139] Preparation of titanate-modified nano-cerium oxide: Titanate coupling agent and nano-cerium oxide were dispersed in 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain titanate-modified nano-cerium oxide liquid; wherein, the amount of titanate coupling agent added was 8% of the mass of nano-cerium oxide. The titanate coupling agent used was isopropoxytris(dioctylpyrophosphateoxy)titanium.

[0140] Preparation of silane-modified nano-zirconia: Silane coupling agent and nano-zirconia are dispersed in 80% n-butanol aqueous solution and stirred at room temperature for 40 minutes to obtain silane-modified nano-zirconia liquid; wherein, the amount of silane coupling agent added is 8% of the mass of nano-cerium oxide, and the silane coupling agent is dimethyldimethoxysilane.

[0141] Preparation of composite radiation resistant agent: Titanate-modified nano-cerium oxide liquid and silane-modified nano-zirconia liquid were mixed at a mass ratio of 2:1, stirred at 70℃, magnetically stirred for 2 hours, refluxed under reduced pressure for 1 hour, rotary evaporated under reduced pressure for 30 minutes, vacuum dried to constant weight, and ground to obtain composite radiation resistant agent.

[0142] Preparation of matrix mixture: Vinyl-terminated methylphenyl silicone oil and transparent vinyl methylphenyl silicone resin are added to a vacuum kneader. The kneading temperature is 180℃ and the kneading speed is 200rpm. Knead for 10 minutes. After cooling to room temperature, add composite radiation resistant agent, hydrophobic modified fumed silica and ultraviolet absorber. Continue stirring for 25 minutes to obtain matrix mixture.

[0143] Preparation of crosslinking system dispersion: Hydrogen-containing silicone oil and 3-methacryloyloxypropyltrimethoxysilane were stirred at 1200 rpm for 35 minutes, and then vacuum degassed at -0.08 MPa for 45 minutes to obtain the crosslinking system dispersion.

[0144] (2) Coating and molding:

[0145] Preparation of adhesive solution: The matrix mixture, crosslinking system dispersion, transparent platinum catalyst (PT1003 type) and tetravinyltetramethylcyclotetrasiloxane are mixed and stirred at 1800 rpm for 45 minutes. The vacuum degassing pressure is -0.1 MPa and the vacuum degassing is carried out for 45 minutes to obtain the adhesive solution.

[0146] Wet film preparation: The adhesive is uniformly coated onto the PP base film using a precision doctor blade coating device. The coating thickness is 0.08 mm and the coating speed is 1.2 m / min.

[0147] (3) Thermosetting preforming: The PP base film coated with adhesive is heated to 100°C and kept at that temperature for 20 minutes to complete the thermosetting preforming and obtain the preformed silicone encapsulation film.

[0148] Comparative Example 1

[0149] Formula (by weight):

[0150] 55 parts of ordinary vinyl silicone oil (phenyl-free), 30 parts of ordinary vinyl silicone resin (phenyl-free), 11 parts of hydrogen-containing silicone oil, 0.25 parts of platinum catalyst (platinum-divinyltetramethyldisiloxane complex), 0.3 parts of tetravinyltetramethylcyclotetrasiloxane, and 3 parts of unmodified fumed silica.

[0151] Preparation method:

[0152] Ordinary vinyl silicone oil and ordinary vinyl silicone resin are added to a vacuum kneader. The kneading temperature is 180℃ and the kneading speed is 100rpm. Kneading is carried out for 15 minutes. After cooling to room temperature, unmodified fumed silica is added to obtain a matrix mixture.

[0153] The matrix mixture, platinum catalyst, and tetravinyltetramethylcyclotetrasiloxane were mixed and stirred at 1800 rpm for 45 minutes. The vacuum degassing pressure was -0.095 MPa and the vacuum degassing was carried out for 35 minutes to obtain the adhesive solution.

[0154] A precision doctor blade coating device is used to uniformly coat the adhesive onto the PET base film, with a coating thickness of 0.10 mm and a coating speed of 0.9 m / min.

[0155] The wet film is heated to 95°C and held for 20 minutes to complete the thermosetting pre-forming process and obtain a pre-formed silicone film.

[0156] Comparative Example 2

[0157] Formula (by weight):

[0158] Vinyl-terminated methylphenyl silicone oil (viscosity 60000 cst, phenyl content 35.0%) 50.0 parts, transparent vinyl methylphenyl silicone resin (phenyl content 20.0%, vinyl content 1.50 wt%) 32 parts, titanate-modified nano-cerium oxide 2.50 parts, silane-modified nano-zirconia 1.20 parts, hydrogen-containing silicone oil (RH-H86 type) 11.0 parts, transparent platinum catalyst (platinum-divinyltetramethyldisiloxane complex) 0.25 parts, tetravinyltetramethylcyclotetrasiloxane 0.30 parts, hydrophobically modified fumed silica (particle size 15 nm) 3.0 parts, 3-glycidyl etheroxypropyltrimethoxysilane 3.50 parts, benzotriazole UV absorber (2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole) 1.5 parts.

[0159] Preparation method:

[0160] Using a traditional hot-press curing process, without using a base film, the components are mixed evenly and then directly coated onto a carrier plate. After hot-press curing at 150°C for 40 minutes, the adhesive film is obtained by peeling off the carrier plate after cooling. There is no pre-formed design.

[0161] Test method:

[0162] 1. High and low temperature resistance test: The silicone encapsulating film was laminated with glass and cooled. The samples were then placed at -196℃ and 400℃ for 24 hours respectively. The appearance was then observed and the adhesion strength with the glass was tested.

[0163] 2. Radiation resistance test:

[0164] (1) Ultraviolet radiation test: After crosslinking the silicone encapsulating film, the sample was placed in a vacuum or inert gas environment and continuously or cyclically irradiated with a strong ultraviolet light source. By controlling the light source intensity and irradiation time, the dose was accurately accumulated to 11000 ESH. Then, the tensile strength, elongation at break, and visible light transmittance of the silicone encapsulating film before and after irradiation were tested, and the rate of change of tensile strength and elongation at break before and after irradiation were calculated.

[0165] (2) Electron Irradiation Test: After crosslinking the silicone encapsulating film, the sample is placed in a vacuum chamber. An electron gun generates a beam of monoenergetic electrons (e.g., 1 MeV). The electron beam is guided and uniformly irradiates the sample surface. By precisely controlling the beam current intensity (current, unit: ampere) and irradiation time, the cumulative flux can be calculated: Flux = (beam current x time) / (electron charge x area). Then, the tensile strength, elongation at break, and visible light transmittance of the silicone encapsulating film before and after irradiation are tested, and the rate of change of tensile strength and elongation at break before and after irradiation is calculated.

[0166] 3. Other routine performance tests:

[0167] (1) Anti-PID test: Refer to IEC TS 62804, apply a voltage of -1000V in an environment with a temperature of 85℃ and a humidity of 85% for 96 hours, record the power of the module before and after the test, and calculate the power change rate of the module.

[0168] (2) Volume resistivity: Refer to GB / T 29848-2018.

[0169] (3) Shrinkage rate: Refer to GB / T 29848-2018.

[0170] High and low temperature resistance test results

[0171]

[0172] UV radiation resistance test results

[0173]

[0174] Electron radiation resistance test results

[0175]

[0176] Other performance test results

[0177]

[0178] The performance test results above show that this invention, through the design of a high-phenyl molecular structure in the composite matrix, optimization of the triple radiation protection system, and improvement of the "coating onto a base film + thermosetting preforming" process, controls the film thickness to 0.05-0.20 mm and expands the temperature resistance range to -196℃ to 400℃. The silicone film prepared using the technical solution of this invention maintains excellent light transmittance, adhesion to glass, and mechanical properties even in extreme high-temperature, low-temperature, and high-energy radiation environments, and these properties far exceed those of films prepared using traditional curing processes. The conventional properties of the silicone film prepared using the technical solution of this invention, such as initial light transmittance, PID resistance, shrinkage rate, and volume resistivity, also far exceed those of films prepared using traditional curing processes. The preparation method provided by this invention is simpler, has stronger morphological stability, and better adaptability to thinner profiles, effectively adapting to the extreme high-temperature, low-temperature, and high-energy radiation environments of space.

[0179] Based on the above-described preferred embodiments according to this application, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. An organosilicon encapsulating film for space photovoltaic modules, characterized in that: include: A composite matrix comprising a phenyl-containing linear silicone oil and a phenyl-containing three-dimensional silicone resin chemically bonded to the linear silicone oil; as well as, A composite radiation-resistant agent distributed in the composite matrix, the composite radiation-resistant agent comprising titanate-modified nano-cerium oxide and silane-modified nano-zirconia with synergistic effects; Through the combination of phenyl groups in the composite matrix, the connection between the linear silicone oil and the bulk silicone resin, and the synergistic effect of titanate-modified nano-cerium oxide and silane-modified nano-zirconia, the organosilicon encapsulating film achieves a UV irradiance resistance of 11000 ESH and an electron irradiance resistance of 1x10⁻⁶. 15 e / cm 2 Furthermore, the temperature resistance range of the silicone encapsulation film is -196℃ to 400℃.

2. The silicone encapsulating film for space photovoltaic modules according to claim 1, characterized in that: The linear silicone oil is a vinyl-terminated methylphenyl silicone oil, wherein the phenyl content is 30.0~40.0 wt%.

3. The silicone encapsulating film for space photovoltaic modules according to claim 1 or 2, characterized in that: The three-dimensional silicone resin is a transparent vinyl methyl phenyl silicone resin, wherein the phenyl content is 10.0~30.0 wt% and the vinyl content is 0.60~12.00 wt%.

4. The silicone encapsulating film for space photovoltaic modules according to claim 3, characterized in that: The particle size of titanate-modified nano-zirconia is ≤50.0 nm.

5. The silicone encapsulating film for space photovoltaic modules according to claim 3, characterized in that: The particle size of silane-modified nano-zirconia is 10.0~20.0 nm.

6. The silicone encapsulating film for space photovoltaic modules according to claim 3, characterized in that: It also includes hydrophobically modified fumed silica, wherein the particle size of the hydrophobically modified fumed silica is 10.0~20.0 nm.

7. The silicone encapsulating film for space photovoltaic modules according to claim 6, characterized in that: It also includes hydrogen-containing silicone oil, transparent platinum catalyst, inhibitor, silane coupling agent, and ultraviolet absorber.

8. A method for preparing an organosilicon encapsulating film, characterized in that: This includes premix preparation, coating molding, and thermosetting preforming.

9. The method for preparing the organosilicon encapsulating film according to claim 8, characterized in that: The preparation of the premix includes the preparation of titanate-modified nano-cerium oxide, silane-modified nano-zirconia, composite radiation-resistant agent, matrix mixture, and crosslinking system dispersion.

10. The method for preparing the organosilicon encapsulating film according to claim 8, characterized in that: The coating process includes the preparation of the adhesive solution and the preparation of the wet film.

11. The method for preparing the organosilicon encapsulating film according to claim 10, characterized in that: The wet film preparation involves using a precision doctor blade coating or spraying device to uniformly coat the adhesive onto the base film. The coating thickness is set to 0.05~0.20 mm, and the coating speed is set to 0.6~1.2 m / min, thereby obtaining a wet film attached to the surface of the base film.

12. The method for preparing the organosilicon encapsulating film according to claim 11, characterized in that: The thermosetting preforming process involves heating the wet film to preform it at a temperature of 80-120°C for 10-50 minutes to obtain a preformed silicone film.

Images