Optical conversion glass fiber composite board and preparation method and application thereof

Abstract

The present application relates to a kind of light conversion glass fiber composite board and its preparation method and application, the light conversion glass fiber composite board includes photonic crystal layer and fluorescent conversion layer;The photonic crystal layer includes photonic crystal film;The fluorescent conversion layer includes fluorescent conversion glass fiber composite material, and the preparation raw material of the fluorescent conversion glass fiber composite material includes fluorescent conversion material.The light conversion glass fiber composite board provided by the present application can not only block ultraviolet light, but also convert ultraviolet light into visible light, and be used as the front plate of photovoltaic module to improve the stability and output power of photovoltaic module.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic panel technology, and in particular to a light conversion fiberglass composite panel, its preparation method, and its application. Background Technology

[0002] Currently, effectively utilizing solar energy is one of the solutions for achieving sustainable energy use. The stability and output power of photovoltaic modules are particularly important. On the one hand, photovoltaic modules will inevitably be eroded by the environment and age when used outdoors, resulting in insufficient long-term stability. On the other hand, the output power of photovoltaic modules still needs to be improved.

[0003] CN213936204U discloses a photovoltaic encapsulation material and a photovoltaic module with weather-resistant protection. The photovoltaic encapsulation material includes a flexible encapsulation layer, which comprises a thermosetting powder-coated composite fiber cloth. At least one surface of the flexible encapsulation layer is provided with a light-transmitting weather-resistant coating formed by a curing process. This technical solution improves weather resistance by setting a light-transmitting weather-resistant coating; however, under long-term high temperature and humidity or ultraviolet damp heat conditions, various problems such as interlayer delamination and coating yellowing are prone to occur, which will seriously affect the conversion efficiency of perovskite solar cell modules and cannot maintain long-term stability.

[0004] CN114248525A discloses a front panel material for photovoltaic modules, its preparation method, and its application. The front panel material includes a substrate layer, an adhesive layer containing a UV absorber, and a protective layer containing fluorine. This technical solution improves weather resistance by adding a UV absorber to the adhesive layer. However, to ensure the long-term effective adhesion of the adhesive layer, the amount of UV absorber added is limited, resulting in limited weather resistance and minimal improvement in the stability of the photovoltaic module.

[0005] Therefore, there is a need to develop a photovoltaic module encapsulation material that can improve the stability and conversion efficiency of photovoltaic modules. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a light-conversion fiberglass composite board, its preparation method, and its application. The light-conversion fiberglass composite board can both block ultraviolet light and convert ultraviolet light into visible light. When used as the front panel of a photovoltaic module, it can improve the stability and output power of the photovoltaic module.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a light-conversion glass fiber composite plate, the light-conversion glass fiber composite plate comprising a photonic crystal layer and a fluorescence conversion layer; the photonic crystal layer comprising an electrospun photonic crystal thin film; the fluorescence conversion layer comprising a fluorescence conversion glass fiber composite material, the raw materials for preparing the fluorescence conversion glass fiber composite material comprising a fluorescence conversion material.

[0009] In this invention, the photonic crystal layer reflects ultraviolet light, reducing photoaging of the resin matrix of the fluorescence conversion layer, and achieves a localized field enhancement effect, increasing the electromagnetic field intensity at specific wavelengths, thereby improving the excitation efficiency of the fluorescent material in the fluorescence conversion layer (the enhancement factor can reach 5-10 times). The fluorescence conversion layer absorbs unreflected ultraviolet light and converts it into visible light. Using this light-converting fiberglass composite board as the front panel of a photovoltaic module not only improves its UV resistance but also converts ultraviolet light into visible light, increasing the output power of the photovoltaic module.

[0010] Preferably, the photonic crystal film includes an electrospun photonic crystal film and / or a photonic crystal coated film, and more preferably an electrospun photonic crystal film.

[0011] Preferably, the electrospun photonic crystal thin film comprises helical spun fibers.

[0012] In this invention, the helical arrangement of the spiral-spun fibers can disrupt symmetry, achieve wide-angle ultraviolet reflection (incident angle of 0~60°, internal reflectivity fluctuation <5%), reflect more ultraviolet light, and reduce photoaging of the fluorescent conversion layer resin matrix.

[0013] Preferably, the thickness of the electrospun photonic crystal film is 3~20 μm, such as 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, 17 μm or 19 μm.

[0014] Preferably, the raw materials for preparing the photonic crystal thin film include a photonic crystal dispersion, which comprises the following components by mass percentage: 10%~15% photonic crystal material (e.g., 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14% or 14.5%, etc.), 5%~10% polyethylene oxide (PEO) (e.g., 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%, etc.), and 75%~85% solvent (e.g., 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83% or 84%, etc.).

[0015] Preferably, the photonic crystal material includes any one or a combination of at least two of ZrO2@PMMA microspheres, ZnO / SiO2 composite materials, or GeO2-TiO2 heterojunctions.

[0016] Preferably, the ZrO2@PMMA microspheres have a core-shell structure, with a core layer of ZrO2 and a shell layer of PMMA. The thickness of the shell layer is 20~30 nm, such as 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm or 29 nm.

[0017] Preferably, the ZrO2@PMMA microspheres have a particle size of 180~230 nm, such as 185 nm, 190 nm, 195 nm, 200 nm, 205 nm, 215 nm, 220 nm or 225 nm.

[0018] In this invention, "@" in the ZrO2@PMMA microspheres represents a core-shell composite structure, " / " in the ZnO / SiO2 composite material represents a composite formed through simple physical mixing, and "-" in the GeO2-TiO2 heterojunction represents a composite structure forming a heterojunction.

[0019] In this invention, the ZrO2@PMMA microspheres, which have a high refractive index (refractive index ≈ 2.2) and a low refractive index (refractive index ≈ 1.49), form a strong refractive index contrast, thus widening the photonic bandgap. ZrO2@PMMA microspheres are helically arranged in helical spun fibers, forming a photonic bandgap covering the 280~400nm wavelength range, reflecting more than 90% of incident ultraviolet light. In the ZnO / SiO2 composite material, ZnO (refractive index ≈2.0, ultraviolet region) and SiO2 (refractive index ≈1.45) form a strong refractive index difference (Δn≈0.55), reflecting ultraviolet light (especially ultraviolet light with wavelengths of 280~400 nm) through Bragg scattering. In the GeO2-TiO2 heterojunction, TiO2 (rutile phase, refractive index ≈2.7, ultraviolet region) and GeO2 (refractive index ≈1.6) form a strong refractive index difference (Δn≈1.1), achieving a wider ultraviolet reflection band (ultraviolet light with wavelengths of 250~400nm), thereby reducing the ultraviolet aging of the resin system in the fluorescent conversion glass fiber composite material. When applied to photovoltaic modules, it can also reduce the impact of ultraviolet light on the solar cells.

[0020] For example, the ZrO2@PMMA microspheres are prepared by the following method:

[0021] (a) ZrO2 nanospheres were dispersed in toluene to form a mixture, a silane coupling agent containing double bonds was added, and then the mixture was reacted under nitrogen protection. After centrifugation and washing, ZrO2 with double bonds on the surface was obtained.

[0022] (b) The ZrO2 with double bonds on the surface obtained in step (a), tetrahydrofuran (THF), 2-bromoisobutyryl bromide (BIBB) and acid binding agent are mixed and reacted to obtain ZrO2 modified with ATRP initiator.

[0023] (c) The ATRP initiator-modified ZrO2, methyl methacrylate and catalyst system obtained in step (b) are mixed and reacted to obtain the ZrO2@PMMA microspheres.

[0024] Preferably, the silane coupling agent containing double bonds in step (a) is 3-(isobutenoyloxy)propyltrimethoxysilane.

[0025] Preferably, the reaction in step (a) is followed by a step of centrifugation and washing with a mixture of ethanol and water.

[0026] Preferably, the acid-binding agent in step (b) comprises triethylamine.

[0027] Preferably, the reaction described in step (b) is followed by a step of centrifugation and washing with tetrahydrofuran (THF).

[0028] Preferably, the methyl methacrylate in step (c) is methyl methacrylate with the polymerization inhibitor removed by an alkaline alumina column.

[0029] Preferably, the catalyst system in step (c) comprises a copper catalyst, N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) and dimethylformamide (DMF).

[0030] Preferably, the copper catalyst comprises cuprous bromide (CuBr).

[0031] Preferably, the reaction in step (c) is carried out under a nitrogen atmosphere.

[0032] Preferably, the reaction temperature in step (c) is 55~65℃ (e.g., 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63% or 64%), and the reaction time is 4~8 h (e.g., 4.5 h, 5 h, 6 h, 6.5 h, 7 h or 7.5 h), more preferably 6~8 h.

[0033] Preferably, the reaction in step (c) is followed by a step of removing the copper catalyst by passing it through a neutral alumina column after dilution with tetrahydrofuran, and then purifying it by methanol precipitation.

[0034] Preferably, the weight-average molecular weight of the polyethylene oxide is 50,000 to 150,000, such as 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000 or 140,000.

[0035] In this invention, the polyethylene oxide has a high weight-average molecular weight, which helps to adjust the viscosity of the photonic crystal dispersion, increase the solution elasticity of the photonic crystal dispersion, and make the relaxation time >0.1s.

[0036] Preferably, the viscosity of the photonic crystal dispersion at 25°C is 800~1200 cP, such as 850 cP, 900 cP, 950 cP, 1000 cP, 1050 cP, 1100 cP or 1150 cP.

[0037] In this invention, the viscosity of the photonic crystal dispersion at 25°C is preferably 800~1200 cP. If the viscosity is too low, it will easily lead to jet instability, and if the viscosity is too high, it will inhibit spiral twisting.

[0038] Preferably, the solvent includes dimethylformamide.

[0039] Preferably, the electrospun photonic crystal thin film is prepared by electrospinning.

[0040] Preferably, the voltage of the electrospinning is 15~18 kV (e.g., 15.5 kV, 16 kV, 16.5 kV, 17 kV or 17.5 kV, etc.).

[0041] In this invention, the voltage for electrospinning is preferably 15~18 kV; high voltage enhances the jet stretching force. If the voltage is too high, it will cause uneven fiber diameter. If it exceeds 20 kV, it will cause a straight jet and will not be able to obtain spiral spun fibers.

[0042] Preferably, the receiving distance of the electrospinning is 10~30 cm (e.g., 12 cm, 14 cm, 16 cm, 18 cm, 20 cm, 22 cm, 24 cm, 26 cm or 28 cm, etc.).

[0043] Preferably, the rotational speed of the receiving roller in the electrospinning is 500~1200 rpm (e.g., 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm or 1100 rpm, etc.), and more preferably 800~1200 rpm.

[0044] In this invention, the rotation speed of the receiving roller in electrospinning is preferably 500~1200 rpm. If the rotation speed of the receiving roller is too low, the spinning fibers will accumulate randomly; if the rotation speed of the receiving roller is too high, the spinning fibers will be over-oriented, which will disrupt the spiral cycle.

[0045] Preferably, the diameter of the receiving roller of the electrospinning is 5 to 8 cm (e.g., 5.5 cm, 6 cm, 6.5 cm, 7 cm or 7.5 cm, etc.).

[0046] In this invention, the diameter of the receiving roller of the electrospinning is preferably 5 to 8 cm. A smaller diameter roller can generate a higher tangential force, achieving a balance between centrifugal force and electrostatic attraction, which helps to induce the spiral deposition of spun fibers.

[0047] Preferably, the ambient humidity for electrospinning is 30%RH~60%RH (e.g., 35%RH, 40%RH, 45%RH, 50%RH or 55%RH, etc.), and more preferably 40%RH~50%RH.

[0048] In this invention, the ambient humidity for electrospinning is preferably 30%RH~60%RH. If the humidity is too low, the solvent in the photonic crystal dispersion will evaporate too quickly, and the resulting spun fibers will be brittle and break easily. If the humidity is too high, it will easily lead to droplet formation.

[0049] Preferably, the receiving roller of the electrospinning reciprocates along the axial direction of the receiving roller, and the frequency of the reciprocating motion is 1~2 Hz (e.g. 1.1 Hz, 1.2 Hz, 1.3 Hz, 1.4 Hz, 1.5 Hz, 1.6 Hz, 1.7 Hz, 1.8 Hz or 1.9 Hz, etc.), and the amplitude is 1~3 cm (e.g. 1.2 cm, 1.4 cm, 1.6 cm, 1.8 cm, 2.0 cm, 2.2 cm, 2.4 cm, 2.6 cm or 2.8 cm, etc.).

[0050] In this invention, the receiving roller, through rotation and reciprocating motion along the axial direction, forces the spun fibers to deposit in a helical trajectory.

[0051] Preferably, the fluorescent conversion glass fiber composite material comprises glass fiber cloth and a resin system.

[0052] Preferably, the mass percentage of the resin system in the fluorescent conversion glass fiber composite material is 25% to 40%, such as 27%, 29%, 31%, 33%, 35%, 37%, or 39%.

[0053] Preferably, the raw materials for preparing the resin system include the following components by weight: 3-8 parts of fluorescent conversion material (e.g., 4, 5, 6 or 7 parts, etc.), 30 parts of epoxy resin, and 10-15 parts of curing agent (e.g., 11, 12, 13 or 14 parts, etc.).

[0054] Preferably, the fluorescence conversion material includes fluorescent quantum dots and / or materials containing rare earth metals.

[0055] Preferably, the fluorescent conversion material includes fluorescent quantum dots and materials containing rare earth metals.

[0056] In this invention, when the fluorescent conversion material is preferably a fluorescent quantum dot or a rare earth metal-containing material, the fluorescent conversion layer has two ultraviolet light conversion pathways: one is the fluorescent quantum dot conversion pathway, where the projected ultraviolet light is absorbed by the fluorescent quantum dot, and the electrons jump to the conduction band and then radiatively recombine; the other is the rare earth metal conversion pathway, where the projected ultraviolet light is absorbed by rare earth metal ions and then undergoes non-radiative transition.

[0057] Preferably, the mass ratio of the fluorescent quantum dots to the rare earth metal-containing material is 1:(4~10), such as 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9 or 1:9.5, etc.

[0058] In this invention, the preferred mass ratio of fluorescent quantum dots to rare earth metal-containing materials is 1:(4~10). If the mass ratio of fluorescent quantum dots to rare earth metal-containing materials is too high or too low, it will lead to a decrease in ultraviolet light conversion effect and a decrease in weather resistance.

[0059] Preferably, the fluorescent quantum dots comprise InP@ZnS quantum dots.

[0060] In this invention, the InP@ZnS quantum dots have a core-shell structure, with InP as the core layer and ZnS as the shell layer.

[0061] Preferably, the fluorescent quantum dots have a particle size of 3 to 5 nm, such as 3.2 nm, 3.4 nm, 3.6 nm, 3.8 nm, 4.0 nm, 4.2 nm, 4.4 nm, 4.6 nm or 4.8 nm.

[0062] Preferably, the rare earth metal-containing material includes SiO2@Eu 3+ .

[0063] In this invention, the SiO2@Eu 3+ For Eu 3+ Doped silicon dioxide has a core-shell structure, with SiO2 as the core layer and Eu content. 3+ The compound has a shell.

[0064] Preferably, the SiO2@Eu 3+ Including Eu 3+ Compounds and mesoporous silica.

[0065] In this invention, the scattering effect of the mesoporous silica can extend the optical path and improve the conversion efficiency.

[0066] Preferably, the pore size of the mesoporous silica is 2~5 nm, such as 2.5 nm, 3.0 nm, 3.5 nm, 4.0 nm or 4.5 nm.

[0067] For example, the SiO2@Eu 3+ Including SiO2@ZrO2@Y2O3:Eu 3+ Core-shell structured phosphor.

[0068] In this invention, residual ultraviolet light not reflected by the photonic crystal layer can be converted into light by InP@ZnS quantum dots (absorption edge ≈380nm) and SiO2@Eu in the fluorescence conversion layer. 3+ (Excitation peak ≈ 395nm) absorption, and InP@ZnS quantum dots and Eu 3+ The Stokes shift difference (≈120nm) can avoid self-absorption, and the combined emission spectrum covers the visible light region of 500~650 nm, realizing visible light conversion.

[0069] Preferably, the thickness of the light conversion fiberglass composite plate is 0.2~0.5 mm, such as 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm or 0.45 mm.

[0070] In a second aspect, the present invention provides a method for preparing a light-conversion fiberglass composite plate as described in the first aspect, the method comprising the following steps: combining a photonic crystal layer and a fluorescence conversion layer to obtain the light-conversion fiberglass composite plate.

[0071] Preferably, the preparation method includes the following steps:

[0072] (1) A resin liquid formed by mixing fluorescent conversion material, epoxy resin and curing agent is combined with glass fiber cloth to obtain glass fiber prepreg.

[0073] (2) The glass fiber prepreg obtained in step (1) is combined with the electrospun photonic crystal film and hot-pressed to obtain the light conversion glass fiber composite board.

[0074] In this invention, the composite process in step (1) can be carried out by impregnation or by coating the resin liquid onto the fiberglass cloth.

[0075] Preferably, the hot pressing temperature is 120~130℃, such as 121℃, 122℃, 123℃, 124℃, 125℃, 126℃, 127℃, 128℃ or 129℃.

[0076] Preferably, the pressure of the hot pressing is 0.2~0.6 MPa, for example 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa or 0.55 MPa, etc.

[0077] Preferably, the hot pressing time is 15 to 30 minutes, such as 17 minutes, 19 minutes, 21 minutes, 23 minutes, 25 minutes, 27 minutes, or 29 minutes.

[0078] Thirdly, the present invention provides a photovoltaic module, the photovoltaic module comprising the light conversion fiberglass composite plate as described in the first aspect.

[0079] Preferably, the photovoltaic module comprises a waterproof and weather-resistant layer, a first encapsulating film layer, a first light conversion fiberglass composite board layer, a second encapsulating film layer, a cell layer, a third encapsulating film layer, a second light conversion fiberglass composite board layer, a fourth encapsulating film layer, and a backsheet layer, which are stacked sequentially; the first light conversion fiberglass composite board layer and the second light conversion fiberglass composite board layer are each independently a light conversion fiberglass composite board as described in the first aspect.

[0080] Compared with the prior art, the present invention has at least the following beneficial effects:

[0081] The light-conversion fiberglass composite board of this invention includes a photonic crystal layer and a fluorescence conversion layer. The photonic crystal layer reflects ultraviolet light to reduce the photoaging of the resin matrix of the fluorescence conversion layer and realizes the local field enhancement effect, thereby enhancing the electromagnetic field intensity at a specific wavelength and improving the excitation efficiency of the fluorescent material in the fluorescence conversion layer. The fluorescence conversion layer can absorb unreflected ultraviolet light and convert it into visible light. The photovoltaic module made using the light-conversion fiberglass composite board has the characteristics of high output power, resistance to ultraviolet aging, and good stability. Attached Figure Description

[0082] Figure 1 This is a schematic diagram of the structure of the light conversion fiberglass composite panel provided in Example 1;

[0083] Among them, 1-photonic crystal layer; 2-fluorescence conversion layer. Detailed Implementation

[0084] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0085] The sources of some of the raw materials for the following examples and comparative examples are as follows.

[0086] InP@ZnS quantum dots, purchased from Suzhou Xingshuo Nanotechnology Co., Ltd., model InP / ZnS-625-25.

[0087] Preparation Example 1

[0088] This preparation example provides a ZrO2@PMMA microsphere, which is prepared by the following method:

[0089] (a) ZrO2 nanospheres (D50 particle size of 200 nm) were dispersed in anhydrous toluene to form a mixture with a concentration of 5 wt% of ZrO2 nanospheres. 3-(isobutenoyloxy)propyltrimethoxysilane was added, with a mass ratio of 3-(isobutenoyloxy)propyltrimethoxysilane to ZrO2 nanospheres of 1.31:100. The mixture was then reacted at 80 °C for 12 h under nitrogen protection. The mixture was then centrifuged and washed three times with a mixture of ethanol and water at a mass ratio of 4:1 to obtain ZrO2 with double bonds on its surface.

[0090] (b) The ZrO2 with double bonds on the surface obtained in step (a) was dispersed in tetrahydrofuran, with a mass ratio of ZrO2 with double bonds on the surface to tetrahydrofuran of 1:20; then 2-bromoisobutyryl bromide and triethylamine were added, with a molar mass ratio of 3-(isobutyryloxy)propyltrimethoxysilane, 2-bromoisobutyryl bromide and triethylamine of 1:1:1.5. The reaction was carried out in an ice bath for 2 h, and then the temperature was gradually increased to 25 °C and the reaction was continued for 6 h. The ZrO2 modified with ATRP initiator was obtained by centrifugation and washing three times with tetrahydrofuran.

[0091] (c) The ATRP initiator-modified ZrO2, methyl methacrylate and catalyst system obtained in step (b) were added to a Schlenk flask. The mass ratio of the ATRP initiator-modified ZrO2, methyl methacrylate and catalyst system was 1:15:0.1. Nitrogen gas was purged for 30 min to remove oxygen. The reaction was magnetically stirred in an oil bath at 60 °C for 7 h. The reaction was then terminated by an ice bath. The copper catalyst was removed by dilution with tetrahydrofuran and purified by methanol precipitation three times to obtain the ZrO2@PMMA microspheres. The thickness of the shell of the ZrO2@PMMA microspheres was found to be 25 nm by transmission electron microscopy (Thermo Fisher-Talos F200X).

[0092] The methyl methacrylate mentioned above is methyl methacrylate with the polymerization inhibitor removed by alkaline alumina column;

[0093] The catalyst system was prepared by dissolving 0.1 mmol of copper catalyst (cuprous bromide) and 0.2 mmol of N,N,N',N'',N''-pentamethyldiethylenetriamine in 10 mL of dimethylformamide to obtain the catalyst system.

[0094] Preparation Example 2

[0095] This preparation example provides a SiO2@Eu 3+ The SiO2@Eu 3+It was prepared using the following method:

[0096] (I) Take 0.5g of mesoporous silica (average particle size of 1.3μm and pore size of 4.4 nm), ultrasonically disperse it in 20g of deionized water, add 0.58g of sodium dodecyl sulfate, stir magnetically at room temperature for 30 minutes, centrifuge at 4000 rpm for 5 minutes, discard the supernatant, and wash the precipitate three times alternately with anhydrous ethanol and distilled water to prepare surface-modified silica microspheres.

[0097] (II) 0.5g of the surface-modified silica microspheres prepared in step (I) were added to 11.5g of a 13% zirconium oxynitrate aqueous solution. The mixture was stirred at room temperature for 3 hours, centrifuged at 4000 rpm for 4 minutes, and the precipitate was washed three times with distilled water. The precipitate was dried in an oven at 120°C and ground into powder using a mortar. The powder was placed in a muffle furnace and heated from room temperature to 560°C at a rate of 1°C / min. The temperature was kept constant for 2 hours and then cooled to room temperature. The calcined product was then added to a 13% zirconium oxynitrate aqueous solution at a mass ratio of 1:23. The coating was repeated 8 times to prepare SiO2@ZrO2 core-shell nanospheres.

[0098] (III) Add 1.8484 g of yttrium oxide and 0.1516 g of europium oxide to 14 g of concentrated nitric acid, heat and stir at 80 °C until the solid is completely dissolved, cool to room temperature to obtain a mixed solution of yttrium nitrate and europium nitrate; weigh 1.2 g of polyethylene glycol with an average molecular weight of 6000 and 0.24 g of citric acid, add to 18.95 g of a mixture of deionized water and anhydrous ethanol with a volume ratio of 3:1, stir at room temperature until the solid is completely dissolved, add 0.5 g of SiO2@ZrO2 core-shell nanospheres obtained in step (II), and ultrasonically disperse at room temperature for 5 minutes using an ultrasonic generator. After 10 minutes, add 16g of a mixed solution of yttrium nitrate and europium nitrate, adjust the pH to 3 with concentrated ammonia (25wt%), stir magnetically at room temperature for 4 hours, centrifuge at 4000 rpm for 5 minutes, discard the supernatant, retain the supernatant, dry the precipitate in an oven at 100℃, grind it into powder using a mortar and pestle, place it in a muffle furnace, and calcine it from room temperature to 1100℃ at a rate of 1℃ / min for 2 hours. Cool to room temperature, add the calcined product to the retained supernatant, and repeat the coating process 4 times to prepare the SiO2@Eu 3+ .

[0099] Example 1

[0100] This embodiment provides a light-conversion glass fiber composite plate and its preparation method, the structural schematic diagram of which is shown below. Figure 1 As shown, the light conversion fiberglass composite plate includes a photonic crystal layer 1 and a fluorescence conversion layer 2;

[0101] The photonic crystal layer 1 is an electrospun photonic crystal film, which includes helical spun fibers. The raw material for preparing the electrospun photonic crystal film is a photonic crystal dispersion, which includes the following components by mass percentage: 12% photonic crystal material (ZrO2@PMMA microspheres provided in Preparation Example 1), 8% polyethylene oxide (weight average molecular weight of 100,000), and 80% dimethylformamide.

[0102] The fluorescent conversion layer 2 includes a fluorescent conversion glass fiber composite material, which includes glass fiber cloth and a resin system. The resin system in the fluorescent conversion glass fiber composite material has a mass percentage of 30%. The raw materials for preparing the resin system include the following components by weight: 5 parts of fluorescent conversion material, 30 parts of epoxy resin (bisphenol A type epoxy resin E-51), and 12 parts of curing agent (polyetheramine D230, manufacturer Huntsman).

[0103] The fluorescence conversion materials described above are InP@ZnS quantum dots with a mass ratio of 1:8 and SiO2@Eu provided in Preparation Example 2. 3+ .

[0104] The preparation method includes the following steps:

[0105] (1) The photonic crystal material is dispersed in dimethylformamide, and then polyethylene oxide is added and mixed to form a photonic crystal dispersion. Then, the photonic crystal dispersion is made into spiral spun fibers by electrospinning. The electrospinning process is as follows: the electrospinning voltage is 16 kV, the receiving distance is 20 cm, the rotation speed of the receiving roller is 1000 rpm, and the roller diameter of the receiving roller is 7 cm; the ambient humidity of the electrospinning environment is 45%RH; the receiving roller of the electrospinning reciprocates along the axial direction of the receiving roller, the reciprocating motion frequency is 1.5 Hz, and the amplitude is 2 cm, forming an electrospinned photonic crystal film on the receiving roller. The side of the electrospinned photonic crystal film that contacts the receiving roller is the lower surface of the electrospinned photonic crystal film, and the side away from the receiving roller is the upper surface of the electrospinned photonic crystal film. The thickness of the electrospinned photonic crystal film is 10 μm.

[0106] (2) The resin liquid formed by mixing fluorescent conversion material, epoxy resin and curing agent is coated onto glass fiber cloth for composite to obtain glass fiber prepreg.

[0107] (3) Wipe the glass fiber prepreg obtained in step (2) with isopropanol to remove the release agent residue on the surface of the glass fiber prepreg. Then, lay the release film (polyimide film), the electrospun photonic crystal film obtained in step (1), the glass fiber prepreg and the vacuum bag film in sequence. The upper surface of the electrospun photonic crystal film is in contact with the glass fiber prepreg. Vacuum is drawn and hot-pressed at 125°C and 0.5 MPa for 20 min. Remove the release film and the vacuum bag film to obtain the light conversion glass fiber composite board. The thickness of the light conversion glass fiber composite board is 0.3 mm.

[0108] Example 2

[0109] This embodiment provides a light conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Example 1 is that the photonic crystal dispersion includes the following components by mass percentage: 15% photonic crystal material (ZrO2@PMMA microspheres provided in Example 1), 10% polyethylene oxide (weight average molecular weight of 100,000), and 75% dimethylformamide.

[0110] The resin system in the fluorescent conversion glass fiber composite material has a mass percentage of 40%. The raw materials for preparing the resin system include the following components by weight: 3 parts of fluorescent conversion material, 30 parts of epoxy resin (bisphenol A type epoxy resin E-51), and 12 parts of curing agent (polyetheramine D230, manufactured by Huntsman).

[0111] The aforementioned fluorescence conversion materials are InP@ZnS quantum dots with a mass ratio of 1:5 and SiO2@Eu provided in Preparation Example 2. 3+ .

[0112] The electrospinning process in step (1) of the preparation method is as follows: the electrospinning voltage is 18 kV, the receiving distance is 13 cm, the rotation speed of the receiving roller is 1200 rpm, and the roller diameter of the receiving roller is 8 cm; the ambient humidity of the electrospinning environment is 45%RH; the receiving roller of the electrospinning reciprocates along the axial direction of the receiving roller, the frequency of the reciprocating motion is 2 Hz, and the amplitude is 1 cm; the thickness of the obtained electrospinned photonic crystal film is 5 μm.

[0113] In step (3) of the preparation method, the hot pressing conditions are 120℃ and 0.6 MPa for 30 min, and the thickness of the light conversion fiberglass composite board is 0.25 mm.

[0114] Example 3

[0115] This embodiment provides a light conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Example 1 is that the photonic crystal dispersion includes the following components by mass percentage: 10% photonic crystal material (ZrO2@PMMA microspheres provided in Example 1), 5% polyethylene oxide (weight average molecular weight of 100,000), and 85% dimethylformamide.

[0116] The resin system in the fluorescent conversion glass fiber composite material has a mass percentage of 25%. The raw materials for preparing the resin system include the following components by weight: 7 parts of fluorescent conversion material, 30 parts of epoxy resin (bisphenol A type epoxy resin E-51), and 12 parts of curing agent (polyetheramine D230, manufactured by Huntsman).

[0117] The aforementioned fluorescence conversion materials are InP@ZnS quantum dots with a mass ratio of 1:10 and SiO2@Eu provided in Preparation Example 2. 3+ .

[0118] The electrospinning process in step (1) of the preparation method is as follows: the electrospinning voltage is 15 kV, the receiving distance is 28 cm, the rotation speed of the receiving roller is 800 rpm, and the roller diameter of the receiving roller is 5 cm; the ambient humidity of the electrospinning environment is 45%RH; the receiving roller of the electrospinning reciprocates along the axial direction of the receiving roller, the frequency of the reciprocating motion is 1 Hz, and the amplitude is 3 cm; the thickness of the obtained electrospinned photonic crystal film is 12 μm.

[0119] In step (3) of the preparation method, the hot pressing conditions are 130℃ and 0.3 MPa for 15 min, and the thickness of the light conversion fiberglass composite board is 0.45 mm.

[0120] Example 4

[0121] This embodiment provides a light conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Example 1 is that the photonic crystal dispersion includes the following components by mass percentage: 6% photonic crystal material (ZrO2@PMMA microspheres provided in Example 1), 8% polyethylene oxide (weight average molecular weight of 100,000), and 86% dimethylformamide. Other conditions are the same as in Example 1.

[0122] Example 5

[0123] This embodiment provides a light conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Example 1 is that the photonic crystal dispersion includes the following components by mass percentage: 18% photonic crystal material (ZrO2@PMMA microspheres provided in Example 1), 8% polyethylene oxide (weight average molecular weight of 100,000), and 74% dimethylformamide. Other conditions are the same as in Example 1.

[0124] Example 6

[0125] This embodiment provides a light-conversion fiberglass composite plate and its preparation method. The difference between this embodiment and Embodiment 1 is that the weight of the fluorescent conversion material in the raw materials for preparing the resin system is adjusted to 12 parts, while other conditions are the same as in Embodiment 1.

[0126] Example 7

[0127] This embodiment provides a light-conversion fiberglass composite plate and its preparation method. The difference between this embodiment and Embodiment 1 is that the weight of the fluorescent conversion material in the raw materials for preparing the resin system is adjusted to 1 part, while other conditions are the same as in Embodiment 1.

[0128] Example 8

[0129] This embodiment provides a light-conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Embodiment 1 is that the fluorescence conversion material is InP@ZnS quantum dots, while the other conditions are the same as in Embodiment 1.

[0130] Example 9

[0131] This embodiment provides a light-conversion glass fiber composite plate and its preparation method. The difference between this embodiment and Example 1 is that the fluorescence conversion material is SiO2@Eu provided in Example 2. 3+ Other conditions are the same as in Example 1.

[0132] Example 10

[0133] This embodiment provides a light conversion glass fiber composite board and its preparation method. The difference between this embodiment and Embodiment 1 is that the voltage of electrospinning in step (1) of the preparation method is adjusted to 20 kV, while other conditions are the same as in Embodiment 1.

[0134] Example 11

[0135] This embodiment provides a fiberglass composite plate and its preparation method, which differs from Embodiment 1 in that the photonic crystal layer is a photonic crystal coated thin film;

[0136] In the preparation method, step (1) is adjusted to disperse the photonic crystal material in dimethylformamide, then add polyethylene oxide (weight average molecular weight of 100,000) for mixing, coat it on a release film (polyimide film), dry it, and form a photonic crystal coated film. The basis weight of the photonic crystal coated film is the same as that of the electrospun photonic crystal film prepared in Example 1, and other conditions are the same as in Example 1.

[0137] Comparative Example 1

[0138] This comparative example provides a fiberglass composite board and its preparation method. The difference between this example and Example 1 is that no photonic crystal layer is provided; the preparation method does not include step (1), and no electrospun photonic crystal film is added in step (3); other conditions are the same as in Example 1.

[0139] Comparative Example 2

[0140] This comparative example provides a glass fiber composite board and its preparation method. The difference between this example and Example 1 is that the fluorescent conversion layer is replaced with a glass fiber composite material layer, and the fluorescent conversion material is not added to the raw materials for the preparation of the resin system. In step (2) of the preparation method, no fluorescent conversion material is added, and other conditions are the same as in Example 1.

[0141] Comparative Example 3

[0142] This comparative example provides a fiberglass composite board and its preparation method. The difference between this example and Example 1 is that no photonic crystal layer is provided; the fluorescence conversion layer is replaced with a fiberglass composite material layer; and no fluorescence conversion material is added to the raw materials for the resin system.

[0143] The preparation method does not include step (1), the preparation method does not add fluorescent conversion material in step (2), and does not add electrospun photonic crystal film in step (3).

[0144] Other conditions are the same as in Example 1.

[0145] Application Example 1

[0146] This application example provides a photovoltaic module, which includes a waterproof and weather-resistant layer, a first encapsulating film layer, a first light conversion fiberglass composite board layer, a second encapsulating film layer, a solar cell layer, a third encapsulating film layer, a second light conversion fiberglass composite board layer, a fourth encapsulating film layer, and a backsheet layer stacked sequentially.

[0147] The waterproof and weather-resistant layer comprises a polyvinylidene fluoride film with a thickness of 25 μm.

[0148] The first, second, third, and fourth adhesive film layers are all POE films with a thickness of 0.55 mm.

[0149] Both the first light conversion fiberglass composite plate layer and the second light conversion fiberglass composite plate layer are light conversion fiberglass composite plates provided in Example 1.

[0150] The battery cell layer is a TOPCon battery.

[0151] The encapsulation backsheet layer is a PET film with a thickness of 0.3 mm.

[0152] Application Examples 2-11

[0153] Application Examples 2-11 each provide a photovoltaic module, which differs from Application Example 1 only in that the light conversion fiberglass composite board provided in Example 1 is replaced with the light conversion fiberglass composite board provided in Examples 2-11, while other conditions are the same as in Application Example 1.

[0154] Compare and contrast examples 1-3

[0155] Comparative Application Examples 1-3 each provide a photovoltaic module, the only difference from Application Example 1 is that the light conversion fiberglass composite board provided in Example 1 is replaced with the composite fiberglass board provided in Comparative Examples 1-3, and the other conditions are the same as in Application Example 1.

[0156] Performance testing

[0157] The photovoltaic modules provided in corresponding use cases 1 to application examples 11 and comparative application examples 1 to comparative application examples 3 are subjected to IV testing to obtain the initial output power of the photovoltaic modules; then the output power after UV aging is tested, and the rate of change of the output power after UV aging compared with the initial output power is calculated.

[0158] The above UV aging conditions were as follows: using a UVA-340 lamp at 0.76W / m². 2 nm -1 The cycle of 8 hours of ultraviolet light irradiation followed by 4 hours of condensation under the irradiance was repeated for a total duration of 500 hours.

[0159] The test results are shown in Table 1.

[0160] Table 1

[0161]

[0162] As shown in Table 1, the photovoltaic modules made using the light conversion fiberglass composite panels provided in Examples 1-11 have high output power, and the output power change rate after ultraviolet aging is ≤2.7%. The photovoltaic modules made using the light conversion fiberglass composite panels provided in Examples 1-3 have an initial output power ≥104.97W, and the output power change rate after ultraviolet aging is ≤1%. They are resistant to ultraviolet aging and have good stability.

[0163] Compared with Comparative Application Example 3, the photovoltaic modules made from the light conversion fiberglass composite panels provided in Examples 1-3 have an initial output power that is increased by about 5%.

[0164] Compared to Example 1, if the mass percentage of photonic crystal material in the photonic crystal dispersion is too low (Example 4), the arrangement of photonic crystal material in the fiber structure is incomplete, ultraviolet light reflection is reduced, and the fluorescence conversion efficiency of the fluorescence conversion layer decreases, resulting in deterioration of mechanical properties. This leads to a decrease in the initial output power and stability of the photovoltaic module. If the mass percentage of photonic crystal material in the photonic crystal dispersion is too high (Example 5), the viscosity of the photonic crystal dispersion increases dramatically, the photonic crystal material agglomerates, and the light transmittance decreases. This also leads to a decrease in the initial output power and stability of the photovoltaic module. Therefore, it can be seen that when the mass percentage of photonic crystal material in the photonic crystal dispersion is controlled within a certain range, the light conversion fiberglass composite board produced has better performance.

[0165] Compared with Example 1, if the mass percentage of fluorescent conversion material in the raw materials for preparing the resin system is too high (Example 6), the resin curing will be poor and the light transmittance will decrease, resulting in a decrease in the initial output power and stability of the photovoltaic module. If the mass percentage of fluorescent conversion material in the raw materials for preparing the resin system is too low (Example 7), the ultraviolet conversion will be insufficient and the fluorescence signal will be weak, resulting in a decrease in the initial output power and stability of the photovoltaic module. Therefore, it can be seen that when the content of fluorescent conversion material in the raw materials for preparing the resin system is controlled within a certain range, the light conversion fiberglass composite board will have better performance.

[0166] Compared with Example 1, if fluorescent quantum dots are not added (Example 8), short-wave ultraviolet conversion is lacking, the spectrum is unbalanced, and the stability of the photovoltaic module decreases. If materials containing rare earth metals are not added (Example 9), long-wave ultraviolet conversion is insufficient, which also leads to a decrease in the stability of the photovoltaic module. It can be seen that the combination of fluorescent quantum dots and materials containing rare earth metals as fluorescent conversion materials produces a light conversion fiberglass composite board with better performance.

[0167] Compared with Example 1, if the voltage of electrospinning is too high (Example 10), the diameter of the spun fibers will be uneven, the interfacial bonding force will be weakened, the ultraviolet reflectivity will be reduced, and the stability of the photovoltaic module will decrease.

[0168] Compared with Example 1, if the photonic crystal layer is a photonic crystal coated thin film (Example 11), the sensitivity of the incident angle of ultraviolet light is enhanced, the ultraviolet reflectivity is reduced, and the initial output power and stability of the photovoltaic module are reduced.

[0169] Compared with Example 1, if the photonic crystal layer is not provided (Comparative Example 1), the ability to reflect ultraviolet light is greatly reduced. Moreover, in the absence of the photonic crystal layer, the ultraviolet sensitivity of the fluorescent conversion material will accelerate degradation or trigger local photocatalytic reactions in the resin, accelerate the breakage of the molecular weight chain of the resin matrix, and the resin system is prone to aging. The resulting photovoltaic module has low initial output power and poor stability.

[0170] Compared with Example 1, if the fluorescence conversion layer is replaced with a glass fiber composite material layer (Comparative Example 2), ultraviolet light cannot be converted into visible light, the ultraviolet light transmittance is high, and the resulting photovoltaic module has low initial output power and poor stability.

[0171] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A light-conversion fiberglass composite board, characterized in that, The light-conversion fiberglass composite panel includes a photonic crystal layer and a fluorescence conversion layer; the photonic crystal layer includes a photonic crystal thin film; The fluorescence conversion layer includes a fluorescence conversion glass fiber composite material, and the raw materials for preparing the fluorescence conversion glass fiber composite material include fluorescence conversion materials; The photonic crystal film includes an electrospun photonic crystal film, which includes helical spun fibers; The electrospun photonic crystal thin film is prepared by electrospinning, wherein the voltage of electrospinning is 15~18kV; the receiving distance of electrospinning is 10~30 cm; the rotation speed of the receiving roller of electrospinning is 500~1200 rpm; the roller diameter of the receiving roller of electrospinning is 5~8 cm; the ambient humidity of electrospinning is 30%RH~60%RH; and the receiving roller of electrospinning reciprocates along the axial direction of the receiving roller, with a reciprocating motion frequency of 1~2 Hz and an amplitude of 1~3 cm.

2. The light conversion fiberglass composite board according to claim 1, characterized in that, The thickness of the electrospun photonic crystal film is 3~20 μm.

3. The light conversion fiberglass composite board according to claim 1, characterized in that, The raw materials for preparing the photonic crystal thin film include a photonic crystal dispersion, which comprises the following components by mass percentage: 10%~15% photonic crystal material, 5%~10% polyethylene oxide, and 75%~85% solvent; The photonic crystal material includes any one or a combination of at least two of ZrO2@PMMA microspheres, ZnO / SiO2 composite materials, or GeO2-TiO2 heterojunctions. The ZrO2@PMMA microspheres have a core-shell structure, with a core of ZrO2 and a shell of PMMA, and the shell thickness is 20~30 nm. The ZrO2@PMMA microspheres have a particle size of 180~230 nm; The weight-average molecular weight of the polyethylene oxide is 50,000 to 150,000. The viscosity of the photonic crystal dispersion at 25°C is 800~1200 cP; The solvent includes dimethylformamide.

4. The light conversion fiberglass composite board according to claim 1, characterized in that, The fluorescent conversion glass fiber composite material comprises glass fiber cloth and a resin system; The resin system in the fluorescent conversion glass fiber composite material has a mass percentage of 25% to 40%.

5. The light conversion fiberglass composite board according to claim 4, characterized in that, The raw materials for preparing the resin system include the following components by weight: 3-8 parts of fluorescent conversion material, 30 parts of epoxy resin, and 10-15 parts of curing agent; The fluorescence conversion material includes fluorescent quantum dots and / or materials containing rare earth metals; The fluorescent quantum dots include InP@ZnS quantum dots; The rare earth metal-containing material includes SiO2@Eu 3+ .

6. The light conversion fiberglass composite board according to claim 1, characterized in that, The thickness of the light conversion fiberglass composite board is 0.2~0.5 mm.

7. A method for preparing a light-conversion glass fiber composite plate as described in any one of claims 1 to 6, characterized in that, The preparation method includes the following steps: combining a photonic crystal layer and a fluorescence conversion layer to obtain the light conversion fiberglass composite plate.

8. The preparation method according to claim 7, characterized in that, The preparation method includes the following steps: (1) A resin liquid formed by mixing fluorescent conversion material, epoxy resin and curing agent is combined with glass fiber cloth to obtain glass fiber prepreg; (2) The glass fiber prepreg obtained in step (1) is combined with the electrospun photonic crystal film and hot-pressed to obtain the light conversion glass fiber composite board; The hot pressing temperature is 120~130℃; The pressure of the hot pressing is 0.2~0.6 MPa; The hot pressing time is 15~30 min.

9. A photovoltaic module, characterized in that, The photovoltaic module includes the light conversion fiberglass composite board as described in any one of claims 1 to 6.

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