Strontium titanate nanomicromaterial, method for preparing the same, and its use

Abstract

Strontium titanate nanomicromaterials, methods for preparing the same, and their use. The raw materials for preparing the strontium titanate nanomaterials include a substrate and a dispersant. The mass of the dispersant is 0.05 to 0.2% of the mass of the substrate. The raw materials for preparing the substrates include, in terms of mass fraction, 50 to 90 parts of powdered resin, 10 to 50 parts of curing agent, 0 to 20 parts of antioxidant, 0.05 to 0.2 parts of catalyst, 0 to 10 parts of surface modifier, 0 to 20 parts of light stabilizer, and 0.05 to 5 parts of strontium titanate nanoadditive, which is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate in a mass ratio of 3 to 4:4 to 6:1 to 2. The strontium titanate nanomaterials have excellent weather resistance.

Description

Technical Field

[0001] This application claims the priority of Chinese Patent Application No. CN202310776712.1, titled "Strontium Titanate Nano-Micro Material, Its Preparation Method and Its Use", filed with the China National Intellectual Property Administration on June 29, 2023, the entire content of which is incorporated herein by reference.

[0002] The present invention relates to the technical field of functional materials, and particularly to strontium titanate nano-micro materials, their preparation methods and their uses.

Background Art

[0003] Solar energy is a clean energy source. Photovoltaic power generation converts light energy directly into electrical energy using solar cells. A single solar cell cannot be used directly as a power source. It is necessary to connect a large number of single solar cells in series and parallel and encapsulate them tightly to form a photovoltaic module. The photovoltaic module, also known as a solar panel, is a core component of a solar power generation system. Its operating principle is to convert solar energy into electrical energy based on the photovoltaic effect.

[0004] Conventional photovoltaic applications have been mainly dominated by centralized photovoltaic power generation systems installed on the ground. Due to the continuous progress of photovoltaic technology and the diversification of application scenarios, the proportion of distributed photovoltaic power has been increasing rapidly. Distributed photovoltaic power generation refers to photovoltaic power generation equipment installed near users, which operates characterized by self-generation and self-consumption by users, surplus power supplied to the grid, and balance adjustment in the power distribution system. Distributed photovoltaic power generation maximally utilizes the solar resources in the region to replace and reduce fossil energy consumption, following the principles of location-specific adaptation, clean and efficient operation, distributed layout, and nearby utilization.

[0005] Conventional photovoltaic modules typically use tempered glass as the encapsulation material to seal the solar cells, resulting in problems such as high weight, limited application scenarios, difficult installation, and lack of aesthetic appeal. To address these issues, lightweight photovoltaic modules have emerged, meeting the demands of the distributed photovoltaic market. Lightweight photovoltaic modules typically use encapsulation materials made from acrylic powder coatings. These acrylic powder coatings mainly consist of acrylic resin, a curing agent, and several conventional additives, and have poor weather resistance. [Overview of the Initiative]

[0006] The object of the present invention is to provide strontium titanate nanomicromaterials, methods for preparing the same, and applications thereof. The strontium titanate nanomicromaterials provided by the present invention have excellent weather resistance.

[0007] To achieve the above objectives, the present invention provides the following technical solutions.

[0008] The present invention relates to a strontium titanate nanomicromaterial, wherein the raw materials for preparing the strontium titanate nanomicromaterial include a substrate and a dispersant, and the amount of the dispersant is 0.05% to 0.2% by weight, based on the weight of the substrate. The base material consists of the following raw materials by weight: 50-90 parts of powdered resin, 10-50 parts of hardener, 0-20 parts antioxidant, 0.05 to 0.2 parts of catalyst, 0-10 parts surface conditioning agent, 0-20 parts of light stabilizer, The present invention provides a strontium titanate nanomicromaterial containing 0.05 to 5 parts of strontium titanate nanoadditive, wherein the strontium titanate nanoadditive is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate, and the octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate are present in a weight ratio of 3 to 4:4 to 6:1 to 2.

[0009] Preferably, the strontium titanate nanoadditive has a particle size of 50 to 300 nm.

[0010] Preferably, octahedral strontium titanate has a particle size of 100-200 nm. Hexahedral strontium titanate has a particle size of 100-200 nm. Irregularly shaped strontium titanate has a particle size of 50-100 nm.

[0011] Preferably, the powdered resin comprises one or more selected from the group consisting of acrylic resin, polyurethane resin, and polyester resin.

[0012] Preferably, the acrylic resin is an epoxy acrylic resin.

[0013] Preferably, the curing agent comprises one or more selected from the group consisting of dodecandioic acid, triglycidyl isocyanurate, and isocyanate.

[0014] Preferably, the antioxidant comprises one or more selected from the group consisting of octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, benzofuranone derivatives, and thioester antioxidants.

[0015] Preferably, the catalyst comprises tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole.

[0016] Preferably, the surface modifier includes benzoin.

[0017] Preferably, the light stabilizer includes a triazine light stabilizer or a hindered amine light stabilizer.

[0018] Preferably, the substrate has a particle size of 30 to 150 μm.

[0019] Preferably, the dispersant comprises one or more selected from the group consisting of alumina, fumed silica, and glass microbeads.

[0020] Preferably, the dispersant has a particle size of 2 to 8 μm.

[0021] The present invention The process involves mixing the raw materials of the base material, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain the base material, and then mixing the base material with a dispersant to obtain strontium titanate nanomicromaterial, or The present invention provides a method for preparing strontium titanate nanomicromaterial according to the above embodiment, comprising the steps of mixing the raw materials of the base material with a dispersant, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain strontium titanate nanomicromaterial.

[0022] Preferably, melt extrusion is carried out at a temperature of 90 to 130°C.

[0023] The present invention provides the use of strontium titanate nanomicromaterials according to the above embodiments or strontium titanate nanomicromaterials prepared by the method according to the above embodiments in photovoltaic module encapsulation materials.

[0024] Beneficial effects In the present invention, by adding a strontium titanate nano-additive obtained by combining strontium titanate having a specific form to the base material of the strontium titanate nano-micro material, the strontium titanate nano-micro material can achieve both excellent weather resistance and improvement in photoelectric conversion efficiency, and is suitable for use in the production of a photovoltaic module encapsulation material. From the results of the examples, it can be seen that the strontium titanate nano-micro material according to the present invention exhibits excellent resistance to ultraviolet aging, neutral salt spray, and high temperature and high humidity, as well as high photoelectric conversion efficiency.

Brief Description of the Drawings

[0025] [Figure 1] SEM image of hexahedral strontium titanate. [Figure 2] SEM image of a mixture of irregular-shaped strontium titanate and octahedral strontium titanate. [Figure 3] Shows the results of the damp heat resistance test of the material prepared in Example 1. [Figure 4] Shows the results of the damp heat resistance test of the material prepared in Comparative Example 1. [Figure 5] Shows the results of the ultraviolet aging test in Test Example 3 for the material prepared in Example 1. [Figure 6] Shows the results of the ultraviolet aging test in Test Example 3 for the material prepared in Comparative Example 1. [Figure 7] Shows the results of the ultraviolet aging test in Test Example 4 for the materials prepared in Example 1, Comparative Example 2, and Comparative Example 3. [Figure 8] Shows the results of the ultraviolet aging test in Test Example 4 for the materials prepared in Comparative Example 4, Comparative Example 5, and Comparative Example 6. [Figure 9] Shows the results of the ultraviolet aging test in Test Example 4 for the materials prepared in Comparative Example 7, Comparative Example 8, and Comparative Example 9. [Figure 10] Shows the results of the neutral salt spray test for the materials prepared in Example 1, Comparative Example 2, and Comparative Example 3. [Figure 11]The results of the neutral salt spray test for the materials prepared in Comparative Examples 4, 5, and 6 are shown. [Figure 12] The results of the neutral salt spray test for the materials prepared in Comparative Examples 7, 8, and 9 are shown. [Modes for carrying out the invention]

[0026] The present invention relates to a strontium titanate nanomicromaterial, wherein the raw materials for preparing the strontium titanate nanomicromaterial include a substrate and a dispersant, and the amount of the dispersant is 0.05% to 0.2% by weight, based on the weight of the substrate. The base material consists of the following raw materials by weight: 50-90 parts of powdered resin, 10-50 parts of hardener, 0-20 parts antioxidant, 0.05 to 0.2 parts of catalyst, 0-10 parts surface conditioning agent, 0-20 parts of light stabilizer, The present invention provides a strontium titanate nanomicromaterial containing 0.05 to 5 parts of strontium titanate nanoadditive, wherein the strontium titanate nanoadditive is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate, and the octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate are present in a weight ratio of 3 to 4:4 to 6:1 to 2.

[0027] The strontium titanate nanomicromaterial of the present invention is a powder coating used as a photovoltaic module encapsulation material and exhibits excellent weather resistance. The nanomicromaterial according to the present invention is defined by the dimensions of the material (i.e., the nanoscale and microscale material) rather than by the amount of strontium titanate nanoadditive used.

[0028] In the present invention, unless otherwise specified, all raw materials used are commercially available products known to those skilled in the art, or are prepared using methods known to those skilled in the art.

[0029] In the present invention, the raw materials for preparing the strontium titanate nanomicro material include a base material. The raw materials for preparing the base material include 50 to 90 parts by weight, preferably 55 to 80 parts, more preferably 60 to 78 parts, even more preferably 65 to 75 parts, and even more preferably 70 to 72 parts by weight of powdered resin. In the present invention, the powdered resin preferably includes one or more selected from the group consisting of acrylic resin, polyurethane resin, and polyester resin, and is more preferably acrylic resin. Using acrylic resin as the base material is preferable in the present invention due to the advantages of good weather resistance, high film strength, and excellent impact resistance and flexibility. In the present invention, the acrylic resin is preferably epoxy acrylic resin, and more preferably the epoxy acrylic powder coating resin described in patent application CN115651473A. In particular, the raw materials for the epoxy acrylic powder coating resin include 20 to 70 parts of hard monomer, 10 to 60 parts of soft monomer, 10 to 50 parts of crosslinkable monomer, and 0.5 to 8 parts of initiator. The crosslinkable monomers include epoxy-containing monomers and / or hydroxyl-containing monomers. The rigid monomers include at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, dicyclopentadiene acrylate, dicyclopentadiene ethoxyacrylate, styrene, methylstyrene, and acrylonitrile. The flexible monomers include alkyl acrylate compounds. The epoxy-containing monomers include at least one selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, hydroxybutyl glycidyl acrylate, and glycidyl tert-carbonate. The hydroxyl-containing monomers include at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and N-hydroxymethylacrylamide. The weight ratio of epoxy-containing monomers to hydroxyl-containing monomers in the crosslinkable monomers is (2-15):1.The epoxy acrylic powder coating resin is prepared by adding a mixture of hard monomers, soft monomers, crosslinkable monomers, a predetermined amount of 40-50% initiator, and an optional molecular weight modifier dropwise to a solvent, and after the initial reaction, adding the remaining amount of initiator dropwise and continuing the reaction to obtain the epoxy acrylic powder coating resin, wherein the initial reaction is carried out at a temperature of 80-110°C for 2-4 hours, and the subsequent reaction is carried out for 2-4.5 hours.

[0030] The raw materials for preparing the substrate in the present invention include 10 to 50 parts, preferably 15 to 30 parts, more preferably 18 to 25 parts, and even more preferably 20 to 21 parts of curing agent, based on parts by weight of powdered resin. In the present invention, the curing agent preferably includes one or more selected from the group consisting of dodecandioic acid (DDDA), triglycidyl isocyanurate (TGIC), and isocyanate, and more preferably DDDA, TGIC, or isocyanate. The use of the above-mentioned curing agent is preferable in the present invention because it not only ensures the basic physical properties of the formed film but also enhances the film formation efficiency.

[0031] The raw materials for preparing the base material of the present invention include 0 to 20 parts, preferably 0.3 to 10 parts, more preferably 0.5 to 5 parts, and even more preferably 1 to 2 parts, of antioxidant based on parts by weight of powdered resin. In the present invention, the antioxidant preferably includes one or more selected from the group consisting of octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), benzofuranone derivatives, and thioesters, and more preferably antioxidant 1076. The use of the above-mentioned antioxidant is preferred in the present invention because it contributes to improved weather resistance.

[0032] The raw materials for preparing the substrate of the present invention include 0.05 to 0.2 parts, preferably 0.06 to 0.15 parts, more preferably 0.07 to 0.1 parts, and even more preferably 0.075 to 0.085 parts of catalyst, based on parts by weight of powdered resin. In the present invention, the catalyst preferably contains tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole, and more preferably tetrabutylammonium bromide. The use of the above catalyst is preferable in the present invention because it contributes to improving the film formation efficiency.

[0033] The raw materials for preparing the substrate in the present invention include, based on parts by weight of the powdered resin, 0 to 10 parts, preferably 0.3 to 5 parts, more preferably 0.5 to 2 parts, and even more preferably 0.8 to 1 part of a surface modifier. In the present invention, the surface modifier preferably contains benzoin. The use of the above surface modifier is preferable in the present invention because it contributes to improving the surface flatness and light transmittance of the formed film.

[0034] The raw materials for preparing the substrate of the present invention include, based on parts by weight of the powdered resin, 0 to 20 parts, preferably 0.5 to 15 parts, more preferably 0.8 to 10 parts, even more preferably 1.2 to 7 parts, and even more preferably 1.66 to 3 parts of a light stabilizer. In the present invention, the light stabilizer preferably includes a triazine light stabilizer or a hindered amine light stabilizer, and more preferably a triazine light stabilizer. The triazine light stabilizer is preferably 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (light stabilizer UV-405). The hindered amine light stabilizer is preferably one or more selected from the group consisting of high molecular weight triazine-piperidine condensate (light stabilizer 119), Tinuvin 622, and Tinuvin 770. The use of the above light stabilizers is preferred in the present invention because it contributes to improved weather resistance.

[0035] The raw materials for preparing the base material of the present invention include, based on parts by weight of powdered resin, 0.05 to 5 parts, preferably 0.1 to 4.8 parts, more preferably 0.5 to 4.5 parts, even more preferably 1 to 4 parts, even more preferably 1.5 to 3.5 parts, and even more preferably 2 to 3.45 parts of strontium titanate nanoadditive. In the present invention, the strontium titanate nanoadditive is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate, and the octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate are present in a weight ratio of 3 to 4:4 to 6:1 to 2, preferably 3 to 3.5:5 to 6:1 to 1.5, and more preferably 3:6:1. In the present invention, the particle size of the strontium titanate nanoadditive is preferably 50 to 300 nm, and more preferably 50 to 200 nm. In the present invention, the particle size of the octahedral strontium titanate is preferably 100 to 200 nm, the particle size (side length) of the hexahedral strontium titanate is preferably 100 to 200 nm, and the particle size of the irregularly shaped strontium titanate is preferably 50 to 100 nm. In the present invention, the strontium titanate nanoadditive is prepared by combining strontium titanate having a specific form, which enables the strontium titanate nanomicromaterial to exhibit excellent weather resistance. Furthermore, the combined use of strontium titanate having different forms provides different crystal facets that facilitate the efficient separation of photogenerated electrons and holes, thereby increasing the photovoltaic conversion efficiency.

[0036] In the present invention, the raw materials for preparing strontium titanate nanomicromaterials include a dispersant. The dispersant preferably contains one or more selected from the group consisting of alumina, fumed silica, and glass microspheres, and more preferably alumina. In the present invention, the amount of dispersant is 0.05 to 0.2% by weight, preferably 0.1 to 0.15% by weight, based on the weight of the substrate. The use of the above-mentioned dispersant is preferred in the present invention because it contributes to avoiding aggregation and improving the processability of the product.

[0037] In the present invention, the particle size of the base material is preferably 30 to 150 μm. The particle size of the dispersant is preferably 2 to 8 μm, more preferably 2 to 4 μm.

[0038] The present invention The process involves mixing the raw materials of the base material, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain the base material, and mixing the base material with a dispersant to obtain strontium titanate nanomicromaterial, or The present invention provides a method for preparing strontium titanate nanomicromaterial according to the above embodiment, which includes the steps of mixing the raw materials of the base material and a dispersant, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain strontium titanate nanomicromaterial.

[0039] In this invention, strontium titanate nanomicromaterials can be prepared using different methods depending on the timing of the addition of the dispersant, the details of which will be described later.

[0040] Method 1 In the present invention, after mixing the raw materials of the base material, the mixture is subjected to melt extrusion, cooling, grinding, and sieving in sequence to obtain the base material. Next, the base material and a dispersant are mixed to obtain strontium titanate nanomicro material. In the present invention, the method of mixing the raw materials of the base material is preferably mechanical mixing. In the present invention, the conditions for mechanical mixing are not particularly limited as long as uniform mixing of all raw materials is ensured. In the present invention, melt extrusion is preferably carried out at a temperature of 90 to 130°C, more preferably 110 to 120°C. In the present invention, cooling is not particularly limited as long as it is carried out by a cooling method well known to those skilled in the art. In the present invention, grinding preferably includes a first grinding and a second grinding that are carried out in succession. The first grinding is carried out to grind the material to a particle size of preferably 0.2 to 1 cm. The second grinding is carried out to grind the material to a particle size of preferably 30 to 150 μm. In the present invention, sieving is not particularly limited as long as a base material of the desired particle size is obtained. In the present invention, the mixing method of the base material and the dispersant is preferably mechanical mixing. In the present invention, the conditions for mechanical mixing are not particularly limited as long as a uniform formulation of the base material and the dispersant is ensured.

[0041] Method 2 In the present invention, after mixing the raw materials of the base material and a dispersant, the mixture is subjected to melt extrusion, cooling, grinding, and sieving in sequence to obtain strontium titanate nanomicromaterial. In the present invention, the method of mixing the raw materials of the base material and the dispersant is preferably mechanical mixing. In the present invention, the conditions for mechanical mixing are not particularly limited as long as uniform mixing of all raw materials is ensured. In this application, the specific operations of melt extrusion, cooling, grinding, and sieving involved in the second method are preferably the same as the operations of the first method and are not described in detail here.

[0042] The present invention provides the use of strontium titanate nanomicromaterials according to the embodiments described above, or strontium titanate nanomicromaterials prepared by the methods described above, in photovoltaic module encapsulation materials. In the present invention, the photovoltaic module is preferably a lightweight photovoltaic module, and the encapsulation material is specifically a composite flexible material (CFM) prepared from strontium titanate nanomicromaterials and fiber cloth. Composite flexible materials prepared using the strontium titanate nanomicromaterials of the present invention exhibit good weather resistance, excellent ductility (elongation at break ≥ 16%) and mechanical strength (tensile strength ≥ 150 MPa), and high light transmittance (≥ 90%). Furthermore, the composite flexible material is highly stain-resistant and provides an easy-to-clean surface from which most dirt can usually be removed with rainwater alone.

[0043] Embodiments of the present invention will be described below clearly and completely with reference to examples of the present invention. Clearly, the described examples are only a part of, rather than all, of the embodiments of the present invention. All other embodiments that can be obtained by those skilled in the art based on the embodiments of the present invention without creative effort should fall within the scope of the protection of the present invention.

[0044] The strontium titanate nanoadditives used in the examples and comparative examples of the present invention are products prepared in Preparation Examples 1 to 3.

[0045] Preparation Example 1 The hexahedral strontium titanate nanoparticles were prepared by the following process.

[0046] Palmitic acid, ethylene glycol, 1,2-butanediol, and water were mixed to obtain a synthetic morphological modifier containing 0.2% by weight of palmitic acid, 0.2% by weight of ethylene glycol, and 2% by weight of 1,2-butanediol. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the synthetic morphological modifier. The volume ratio of the synthetic morphological modifier to the aqueous solution of titanium tetrachloride was 1:2. The mixture was stirred for 30 minutes while cooling with ice water to obtain mixed solution I.

[0047] Mixed solution I, a 0.033 g / mL aqueous lithium hydroxide solution, and a 0.01 g / mL aqueous strontium hydroxide solution were mixed in a volume ratio of 3:3:1 and stirred for 15 minutes to obtain mixed solution II with a pH of 13.8.

[0048] Mixed solution II was heated to 180°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 48 hours, after which it was cooled at a cooling rate of 2°C / min. The product obtained after the hydrothermal reaction was centrifuged, the precipitate was washed five times alternately with water and ethanol, and finally dried at 90°C for 4 hours to obtain hexahedral strontium titanate nanoparticles.

[0049] Preparation Example 2 The octahedral strontium titanate nanoparticles were prepared by the following process.

[0050] Palmitic acid, ethylene glycol, 1,2-butanediol, and water were mixed to obtain a synthetic morphological modifier containing 0.2% by weight of palmitic acid, 1% by weight of ethylene glycol, and 0.2% by weight of 1,2-butanediol. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the synthetic morphological modifier. The volume ratio of the synthetic morphological modifier to the aqueous solution of titanium tetrachloride was 1:2. The mixture was stirred for 30 minutes while cooling with ice water to obtain mixed solution I.

[0051] Mixed solution I, a 0.033 g / mL aqueous sodium hydroxide solution, and a 0.01 g / mL aqueous strontium chloride hexahydrate solution were mixed in a volume ratio of 3:3:1 and stirred for 30 minutes to obtain mixed solution II with a pH of 14.2.

[0052] Mixed solution II was heated to 190°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 24 hours, after which it was cooled at a cooling rate of 2°C / min. The product obtained after the hydrothermal reaction was centrifuged, the precipitate was washed three times alternately with water and ethanol, and finally dried at 80°C for 6 hours to obtain octahedral strontium titanate nanoparticles.

[0053] Preparation Example 3 Irregularly shaped strontium titanate nanoparticles were prepared by the following process.

[0054] Palmitic acid, ethylene glycol, 1,2-butanediol, and water were mixed to obtain a synthetic morphological modifier containing 0.2% by weight of palmitic acid, 1.2% by weight of ethylene glycol, and 1.6% by weight of 1,2-butanediol. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the synthetic morphological modifier. The volume ratio of the synthetic morphological modifier to the aqueous solution of titanium tetrachloride was 1:2. The mixture was stirred for 30 minutes while cooling with ice water to obtain mixed solution I.

[0055] Mixed solution I, a 0.033 g / mL aqueous sodium hydroxide solution, and a 0.01 g / mL aqueous strontium chloride hexahydrate solution were mixed in a volume ratio of 3:3:1 and stirred for 30 minutes to obtain mixed solution II with a pH of 14.2.

[0056] Mixed solution II was heated to 180°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 72 hours, after which it was cooled at a cooling rate of 2°C / min. The product obtained after the hydrothermal reaction was centrifuged, the precipitate was washed five times alternately with water and ethanol, and finally dried at 80°C for 6 hours to obtain irregularly shaped strontium titanate nanoparticles.

[0057] Figure 1 is a SEM image of hexahedral strontium titanate. As can be seen from Figure 1, hexahedral strontium titanate has side lengths of approximately 100-200 nm.

[0058] Figure 2 is an SEM image of a mixture of irregularly shaped strontium titanate and octahedral strontium titanate. As can be seen from Figure 2, the irregularly shaped strontium titanate has a particle size of approximately 50-100 nm, while the octahedral strontium titanate has a particle size of approximately 100-200 nm.

[0059] Example 1 The raw materials for preparing the strontium titanate nanomicromaterial in this example included a substrate and a dispersant.

[0060] 72 parts by weight of acrylic resin (i.e., epoxy acrylic powder coating resin prepared in Example 7 of Patent Application CN115651473A), 21 parts by weight of curing agent (i.e., DDDA), 1 part by weight of antioxidant (i.e., antioxidant 1076), 0.085 parts by weight of catalyst (i.e., tetrabutylammonium bromide), 0.8 parts by weight of surface modifier (i.e., benzoin), 1.66 parts by weight of light stabilizer (i.e., light stabilizer UV-405), and 3.45 parts by weight of strontium titanate nanoadditive (i.e., a mixture obtained by mixing octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate in a weight ratio of 3:6:1) were mixed. The mixture was melt-extruded at 120°C, the resulting extruded material was cooled and pulverized to a particle size of 0.2 to 1 cm, then further pulverized and sieved to obtain a substrate with a particle size of 30 to 150 μm.

[0061] The dispersant was alumina with a particle size of 2-4 μm, in an amount of 0.1% by weight of the substrate.

[0062] A substrate and a dispersant were mixed to obtain a strontium titanate nanomicro material.

[0063] Comparative Example 1 Photovoltaic competing powder sample: Acrylic powder coating as described in Example 2 of Chinese Patent No. CN201810420474.X.

[0064] Test Example 1 The materials prepared in the examples and comparative examples were subjected to a neutral salt spray (NSS) test as follows.

[0065] 1. Test method: ISO9227:2017.

[0066] 2. Test conditions: Concentration of precipitated salt solution: (50+5) g / L NaCl; Laboratory temperature: (35±2)℃; Salt spray adhesion rate: (1.5 + 0.5) mL / (80 cm) 2 h); pH of the precipitated salt solution at (25±2)℃: 6.5~7.2.

[0067] 3. Examination period: 1,000 hours.

[0068] 4. Test equipment: Programmable salt spray chamber, model CZ-120C.

[0069] 5. Results: The results are shown in Table 1. Table 1 shows that both the strontium titanate nanomicromaterial prepared in Example 1 and the photovoltaic competing powder sample from Comparative Example 1 passed the 1,000-hour neutral salt spray test.

[0070] [Table 1]

[0071] Test Example 2 The following heat and humidity resistance tests were performed on the materials prepared in the examples and comparative examples.

[0072] 1. Test method: Refer to IEC60068-2-67.

[0073] 2. Test conditions: Temperature: (85±2)℃; Relative humidity: (85±5)%.

[0074] 3. Examination period: 1,480 hours.

[0075] 4. Test equipment: Programmable constant temperature and humidity chamber, model ZH-TH-225D.

[0076] 5. Results: The results are shown in Table 2, Figure 3, and Figure 4. Figure 3 shows the results of the humidity and heat resistance test for the material prepared in Example 1, and Figure 4 shows the results of the humidity and heat resistance test for the material prepared in Comparative Example 1. Table 2, Figure 3, and Figure 4 demonstrate that both the strontium titanate nanomicromaterial prepared in Example 1 and the photovoltaic competing powder sample from Comparative Example 1 passed the 1,480-hour humidity and heat resistance test and met the customer requirements.

[0077] [Table 2]

[0078] Test Example 3 The materials prepared in the examples and comparative examples were subjected to ultraviolet aging tests (QUV-B) as follows.

[0079] 1. Test method: GB / T14522-2008.

[0080] 2. Test conditions: Exposure cycle type 7, as detailed in Table 3.

[0081] [Table 3]

[0082] 3. Examination period: 3,000 hours.

[0083] 4. Test equipment: UV QUV / SPRAY, model 20-36601-93-SPRAY.

[0084] 5. Results: The results are shown in Table 4, Figure 5, and Figure 6. Figure 5 shows the results of the UV aging test of the material prepared in Example 1, and Figure 6 shows the results of the UV aging test of the material prepared in Comparative Example 1. Table 4 and Figures 5 and 6 demonstrate that both the strontium titanate nanomicromaterial prepared in Example 1 and the photovoltaic competing powder sample of Comparative Example 1 passed the 3,000-hour UV aging test (QUV-B). Nevertheless, the strontium titanate nanomicromaterial prepared in Example 1 showed better resistance to yellowing than the photovoltaic competing powder sample of Comparative Example 1.

[0085] [Table 4]

[0086] Comparative Example 2 Strontium titanate nanomicromaterials were prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was octahedral strontium titanate.

[0087] Comparative Example 3 Strontium titanate nanomicromaterials were prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was hexahedral strontium titanate.

[0088] Comparative Example 4 Strontium titanate nanomicromaterials were prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was irregularly shaped strontium titanate.

[0089] Comparative Example 5 The strontium titanate nanomaterial was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was obtained by mixing octahedral strontium titanate and hexahedral strontium titanate in a weight ratio of 1:1.

[0090] Comparative Example 6 The strontium titanate nanomicromaterial was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was obtained by mixing octahedral strontium titanate and irregularly shaped strontium titanate in a weight ratio of 1:1.

[0091] Comparative Example 7 The strontium titanate nanomicromaterial was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was obtained by mixing hexahedral strontium titanate and irregularly shaped strontium titanate in a 1:1 weight ratio.

[0092] Comparative Example 8 The strontium titanate nanomicromaterial was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was obtained by mixing octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate in a weight ratio of 1:1:1.

[0093] Comparative Example 9 The strontium titanate nanomaterial was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive used here was obtained by mixing octahedral strontium titanate and hexahedral strontium titanate in a weight ratio of 3:6.

[0094] Test Example 4 The materials prepared in the examples and comparative examples were subjected to ultraviolet aging tests according to the method described in Test Example 3. In this test example, the test period was 2,000 hours. The specific results are shown in Table 5 and Figures 7-9. Figure 7 shows the results of the ultraviolet aging tests for the materials prepared in Example 1, Comparative Example 2, and Comparative Example 3 (from left to right: Example 1, Comparative Example 2, Comparative Example 3). Figure 8 shows the results of the ultraviolet aging tests for the materials prepared in Comparative Example 4, Comparative Example 5, and Comparative Example 6 (from left to right: Comparative Example 4, Comparative Example 5, Comparative Example 6). Figure 9 shows the results of the ultraviolet aging tests for the materials prepared in Comparative Example 7, Comparative Example 8, and Comparative Example 9 (from left to right: Comparative Example 7, Comparative Example 8, Comparative Example 9). As shown in Table 5 and Figures 7-9, the strontium titanate nanomicromaterial prepared in Example 1 of the present invention showed the highest gloss retention rate and lowest yellowing value compared to the comparative example, by using a strontium titanate nanoadditive obtained by mixing octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate in appropriate ratios.

[0095] [Table 5]

[0096] Test Example 5 The materials prepared in the examples and comparative examples were subjected to a neutral salt spray test according to the method described in Test Example 1. In this test example, the test period was 1,000 hours. The specific results are shown in Table 6 and Figures 10-12. Figure 10 shows the results of the neutral salt spray test for the materials prepared in Example 1, Comparative Example 2, and Comparative Example 3 (from left to right: Example 1, Comparative Example 2, Comparative Example 3). Figure 11 shows the results of the neutral salt spray test for the materials prepared in Comparative Example 4, Comparative Example 5, and Comparative Example 6 (from left to right: Comparative Example 4, Comparative Example 5, Comparative Example 6). Figure 12 shows the results of the neutral salt spray test for the materials prepared in Comparative Example 7, Comparative Example 8, and Comparative Example 9 (from left to right: Comparative Example 7, Comparative Example 8, Comparative Example 9). As shown in Table 6 and Figures 10-12, the coating film of the nanomicro material containing only irregularly shaped strontium titanate as the strontium titanate nano-additive in Comparative Example 4 showed significant rusting and relatively poor resistance to neutral salt spray.

[0097] [Table 6]

[0098] Test Example 6 The materials prepared in the examples and comparative examples were subjected to a heat and humidity resistance test (temperature 85°C, relative humidity 85% RH) according to the method described in Test Example 2. In this test example, the test period was 1,480 hours. The specific results are shown in Table 7. As shown in Table 7, the strontium titanate nanomicromaterial prepared in Example 1 of the present invention showed the highest gloss retention rate, lowest color difference value, and lowest yellowing value compared to the comparative example, by using a strontium titanate nanoadditive obtained by mixing octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate in appropriate ratios.

[0099] [Table 7]

[0100] Comparative Example 10 The coating was prepared in the same manner as in Example 1, except that the strontium titanate nanoadditive was not added.

[0101] Test Example 7 The strontium titanate nanomicromaterials prepared in Example 1 and Comparative Examples 2-4, as well as the coating prepared in Comparative Example 10, were subjected to transient photocurrent response tests under xenon lamp illumination using an electrochemical workstation. Specifically, the photocurrent intensity was measured. The results are shown in Table 8. As can be seen from Table 8, the coating samples without strontium titanate showed no photocurrent, while the strontium titanate nanomicromaterials obtained by adding different forms of strontium titanate showed different photocurrent intensities. Among them, the strontium titanate nanomicromaterial prepared in Comparative Example 2 (with octahedral strontium titanate addition) showed the strongest photocurrent, while the strontium titanate nanomicromaterial prepared in Comparative Example 4 (with irregularly shaped strontium titanate addition) showed the weakest photocurrent. The photocurrent of the strontium titanate nanomicromaterial prepared in Example 1 was 0.279 μA.

[0102] [Table 8]

[0103] From the above test examples, it can be seen that the strontium titanate nanomicromaterial of the present invention exhibits excellent resistance to UV aging, neutral salt spray, and humid heat. Furthermore, the addition of strontium titanate nanoadditives enhances the photoelectric conversion efficiency of the strontium titanate nanomicromaterial, making it suitable for use in the manufacture of photovoltaic module encapsulation materials.

[0104] The above description represents only preferred embodiments of the present invention. Those skilled in the art should note that various improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A strontium titanate nanomicromaterial, wherein the raw materials for preparing the strontium titanate nanomicromaterial include a base material and a dispersant, and the amount of the dispersant is 0.05% to 0.2% by weight, based on the weight of the base material. The aforementioned substrate contains the following raw materials in parts by weight: 50 to 90 parts of powdered resin, 10 to 50 parts of hardener, 0-20 parts antioxidant, 0.05 to 0.2 parts of catalyst, 0 to 10 parts surface modifier, 0 to 20 parts of light stabilizer, and A strontium titanate nanomicromaterial comprising 0.05 to 5 parts of strontium titanate nanoadditive, wherein the strontium titanate nanoadditive is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate, and the octahedral strontium titanate, hexahedral strontium titanate, and irregularly shaped strontium titanate are present in a weight ratio of 3 to 4:4 to 6:1 to 2.

2. The strontium titanate nanomicromaterial according to claim 1, characterized in that the strontium titanate nanoadditive has a particle size of 50 to 300 nm.

3. The strontium titanate nanomicromaterial according to claim 2, characterized in that the octahedral strontium titanate has a particle size of 100 to 200 nm, the hexahedral strontium titanate has a particle size of 100 to 200 nm, and the irregularly shaped strontium titanate has a particle size of 50 to 100 nm.

4. The strontium titanate nanomicromaterial according to claim 1, characterized in that the powder resin comprises one or more selected from the group consisting of acrylic resin, polyurethane resin, and polyester resin.

5. The strontium titanate nanomicro material according to claim 4, characterized in that the acrylic resin is an epoxy acrylic resin.

6. The strontium titanate nanomicromaterial according to claim 1, characterized in that the curing agent comprises one or more selected from the group consisting of dodecanediic acid, triglycidyl isocyanurate, and isocyanate.

7. The strontium titanate nanomicromaterial according to claim 1, characterized in that the antioxidant comprises one or more selected from the group consisting of octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, benzofuranone derivatives, and thioester antioxidants.

8. The strontium titanate nanomicromaterial according to claim 1, characterized in that the catalyst comprises tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole.

9. The strontium titanate nanomicromaterial according to claim 1, characterized in that the surface modifier contains benzoin.

10. The strontium titanate nanomicromaterial according to claim 1, characterized in that the light stabilizer comprises a triazine light stabilizer or a hindered amine light stabilizer.

11. The strontium titanate nanomicro material according to any one of claims 1 to 10, characterized in that the substrate has a particle size of 30 to 150 μm.

12. The strontium titanate nanomicromaterial according to claim 1, characterized in that the dispersant comprises one or more selected from the group consisting of alumina, fumed silica, and glass microbeads.

13. The strontium titanate nanomicromaterial according to claim 1 or 12, characterized in that the dispersant has a particle size of 2 to 8 μm.

14. The process involves mixing the raw materials of the base material, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain the base material, and mixing the base material with a dispersant to obtain strontium titanate nanomicromaterial, or A method for preparing a strontium titanate nanomicromaterial according to any one of claims 1 to 13, comprising the steps of mixing the raw materials of the base material with a dispersant, followed by sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain a strontium titanate nanomicromaterial.

15. The method according to claim 14, characterized in that the melt extrusion is carried out at a temperature of 90 to 130°C.

16. Use of a strontium titanate nanomicromaterial according to any one of claims 1 to 13 or a strontium titanate nanomicromaterial prepared by the method described in claim 14 or 15 in a photovoltaic module encapsulation material.

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