Colorful anti-aging photovoltaic module packaging adhesive film and preparation method thereof

Abstract

The invention discloses a colorful anti-aging photovoltaic module packaging adhesive film and a preparation method thereof, and belongs to the technical field of packaging adhesive films. The colorful anti-aging packaging adhesive film for the photovoltaic module is prepared by the following steps: performing ion doping on first pretreated perovskite quantum dots and trizinc citrate; meanwhile, pre-mixing the second pre-treated perovskite quantum dots with a toughening agent, then adding a flame retardant for secondary mixing, finally adding a cross-linking agent and an EVA solution into the secondarily mixed material, adding the ion-doped first pre-treated perovskite quantum dots for continuous mixing, and then performing blade coating to obtain the perovskite quantum dot composite material. The prepared colorful anti-aging photovoltaic module packaging adhesive film is good in anti-aging effect, and the working stability and the photoelectric conversion efficiency of a photovoltaic cell can be effectively improved.

Description

Technical Field

[0001] The present invention relates to a colorful anti-aging photovoltaic module encapsulation film and a preparation method thereof. Background Art

[0002] As the core protective material of crystalline silicon solar cells, the photovoltaic module encapsulation film undertakes multiple functions such as sealing the cell module, improving the light energy utilization rate, and extending the device life. Photovoltaic films represented by ethylene-vinyl acetate copolymer (EVA) are widely used due to their low cost and excellent processing performance. However, traditional EVA films lack the ability of light conversion and have insufficient utilization of short-wave ultraviolet light (300 - 400 nm), resulting in limited efficiency of crystalline silicon cells. To improve the light conversion efficiency, in recent years, researchers have compounded down-conversion materials (such as luminescent dyes, colloidal quantum dots) with EVA to expand the spectral response range through wavelength conversion from ultraviolet light to visible light. However, the existing technologies have significant defects: the light absorption bandwidth of the film causes energy loss, the dyes are easily photo-degraded, the quantum dots have poor stability and complex synthesis processes, and long-term exposure to environments such as humidity and ultraviolet radiation easily leads to ion leakage and efficiency decay, making it difficult to meet the commercial requirements.

[0003] All-inorganic perovskite quantum dots (CsPbX 3 ) are considered ideal down-conversion materials due to advantages such as a visible light full-spectrum emission, high quantum yield, and adjustable bandgap. However, their characteristics of many surface defects and susceptibility to environmental humidity and oxygen erosion severely restrict the device life. To address this problem, existing research has improved the stability through methods such as ion doping, core-shell coating, and ligand modification, but these means often come at the cost of sacrificing optical performance or increasing the process complexity. Especially in polymer encapsulation systems, the poor interfacial compatibility between quantum dots and polymers easily leads to aggregation and inactivation, and thermo-oxidative aging accelerates ion migration, resulting in a decrease in the light transmittance and a sharp reduction in the PL intensity of the film after aging, making it difficult to balance efficiency improvement and long-term anti-aging performance.

[0004] Therefore, the applicant has researched and prepared a colorful anti-aging photovoltaic module encapsulation film Summary of the Invention

[0005] The object of the present invention is to provide a colorful anti-aging photovoltaic module encapsulation film and a preparation method thereof to solve the technical problems mentioned in the above background art.

[0006] The technical solution to achieve the object of the present invention is: In a first aspect, the present invention provides a colorful anti-aging photovoltaic module encapsulation film, which is obtained by pre-mixing second pretreated perovskite quantum dots with a toughening agent, adding a flame retardant for mixing, then adding a crosslinking agent and an EVA solution for mixing, and then adding first pretreated perovskite quantum dots after ion doping for mixing and doctor blading.

[0007] Further, the second pre-treated perovskite quantum dots are obtained by ligand exchange of perovskite quantum dots with glycine; the first pre-treated perovskite quantum dots are obtained by ligand exchange of perovskite quantum dots with cysteine.

[0008] Further, the toughening agent is ethylene glycol methacrylate acetoacetate.

[0009] Further, the flame retardant is diethyl benzaldehyde phosphite.

[0010] Further, the ion doping is zinc ion doping, and the zinc ion raw material is tris zinc citrate.

[0011] In a second aspect, the present invention provides a method for preparing a colorful anti-aging photovoltaic module encapsulation film as described in the first aspect, comprising the following preparation steps: (1) Under nitrogen protection, 0.076 - 0.078 parts by mass of p-toluenesulfonic acid and molecular sieve are put into a reaction kettle, and then 0.37 - 0.39 parts by mass of the second pre-treated perovskite quantum dots uniformly dispersed in 17 - 18 parts by mass of mesitylene are added. Then, 0.31 - 0.33 parts by mass of ethylene glycol methacrylate acetoacetate are added and stirred for 20 - 40 min, and then the temperature is raised to 165 - 175 °C and stirred for reaction for 7 - 9 h to obtain a premix; (2) The premix obtained in step (1) is mixed with 0.43 - 0.46 parts by mass of the flame retardant, and then 0.053 - 0.055 parts by mass of trifluoroacetic acid are added. Then, it is stirred overnight under nitrogen and in the dark, and then 0.53 - 0.54 parts by mass of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are added and stirred at room temperature for 2.5 - 3.5 h. 0.78 - 0.79 parts by mass of triethylamine and 1.1 - 1.2 parts by mass of boron trifluoride diethyl etherate are added, and stirring is continued overnight at room temperature to obtain a remix; (3) Under nitrogen protection, the remix obtained in step (2) is mixed with 10 parts by mass of EVA, and then 5.4 - 5.6 parts by mass of benzoyl peroxide are added. The temperature is raised to 55 - 65 °C and stirred for 15 - 25 min, and then the temperature is raised to 75 - 85 °C and stirred for reaction for 7 - 8 h. Then, 0.06 - 0.08 parts by mass of the first pre-treated perovskite quantum dots after ion doping are added to obtain a colorful anti-aging photovoltaic module encapsulation film liquid; (4) The colorful anti-aging photovoltaic module encapsulation film liquid obtained in step (3) is scrape-coated on a polysilicon solar cell and heated overnight in an oven at 60 °C to obtain a 100-μm-thick colorful anti-aging photovoltaic module encapsulation film.

[0012] Further, the preparation steps of the second pre-treated perovskite quantum dots are as follows: Disperse 1 part by mass of perovskite quantum dots in 2 - 4 parts by mass of toluene, then add 0.6 - 1.3 parts by mass of acetonitrile, then add 0.6 - 0.8 parts by mass of glycine, then centrifuge at 8000 rpm for 5 min to obtain the precipitate, and then disperse it in 2 - 3 parts by mass of n-hexane and centrifuge at 4000 rpm for 5 min to obtain the supernatant; Place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4°C for at least 12 h; Before use, place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the second pre-treated perovskite quantum dots.

[0013] Further, the preparation steps of the first pre-treated perovskite quantum dots after ion doping are as follows: Add 1 part by mass of the first pre-treated perovskite quantum dots to a DMF solution of 7.98 - 13.44 parts by mass of zinc citrate and ultrasonically oscillate for 8 - 12 min. Then, raise the temperature to 130°C for dehydration condensation for 11 - 13 h. Subsequently, place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the first pre-treated perovskite quantum dots after ion doping; The mass ratio of zinc citrate to DMF in the DMF solution of zinc citrate is 1:18 - 20.

[0014] Further, the preparation steps of the first pre-treated perovskite quantum dots are as follows: Disperse 1 part by mass of perovskite quantum dots in 2 - 4 parts by mass of toluene, then add 0.6 - 1.3 parts by mass of acetonitrile, then add 0.97 - 1.29 parts by mass of cysteine, then centrifuge at 8000 rpm for 5 min to obtain the precipitate, and then disperse it in 2 - 3 parts by mass of n-hexane and centrifuge at 4000 rpm for 5 min to obtain the supernatant; Place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4°C for at least 12 h; Subsequently, place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the first pre-treated perovskite quantum dots.

[0015] Further, the preparation method of diethyl benzylphosphonate is as follows: Under nitrogen protection, dissolve 3 parts by mass of tetrakis(triphenylphosphine)palladium and 4.7 - 4.9 parts by mass of p-bromobenzaldehyde in 325 - 335 parts by mass of DMSO under nitrogen protection. Then add 7.7 - 7.8 parts by mass of N,N-diisopropylethylamine and 10.3 - 10.5 parts by mass of ethyl phosphite. Then heat to 85 - 95°C and react for 41 - 43 h. Then add 345 - 355 parts by mass of deionized water to disperse for 5 - 15 min, extract with 400 parts by mass of dichloromethane, and then wash and extract the organic layer with 150 parts by mass of deionized water and 150 parts by mass of saturated sodium bicarbonate solution in sequence, and remove the solvent to obtain diethyl benzylphosphonate.

[0016] By adopting the above technical solutions, the present invention has the following beneficial effects: (1) The colorful anti-aging photovoltaic module encapsulation film of the present invention is prepared by pre-mixing the second pre-treated perovskite quantum dots with a toughening agent, adding a flame retardant for mixing, then adding a cross-linking agent and an EVA solution for mixing, and then adding the first pre-treated perovskite quantum dots after ion doping for mixing and scraping. The prepared colorful anti-aging photovoltaic module encapsulation film has good anti-aging effect and can effectively improve the working stability and photoelectric conversion efficiency of photovoltaic cells.

[0017] (2) The second pre-treated perovskite quantum dots of the present invention are obtained by ligand exchange of perovskite quantum dots with glycine; the first pre-treated perovskite quantum dots are obtained by ligand exchange of perovskite quantum dots with cysteine; through the exchange of groups such as amino and carboxyl with oleic acid and oleylamine in the perovskite quantum, it is adsorbed on the Pb atom, and the amino group interacts with Br through hydrogen bonds - to passivate the trap state, which can effectively improve the photoluminescence quantum yield and stability of perovskite quantum dots, and further improve the working stability and photoelectric conversion efficiency of photovoltaic modules.

[0018] (3) The toughening agent used in the present invention is ethylene glycol methacrylate acetoacetate, which can effectively toughen the colorful anti-aging photovoltaic module encapsulation film and improve its mechanical properties.

[0019] (4) The flame retardant used in the present invention is diethyl benzaldehyde phosphite, which can endow the colorful anti-aging photovoltaic module encapsulation film with good flame retardancy.

[0020] (5) Ion doping is also carried out on the first pre-treated perovskite quantum dots of the present invention. The ion doping is zinc ion doping, and the zinc ion raw material is tris zinc citrate. On the one hand, zinc ion doping can be introduced. The interaction between Zn2+ and Br- passivates the defect states on the surface and inside of the nanocrystal, inhibits non-radiative recombination. After Zn2+ replaces Pb2+, the interaction of the Pb-Br bond is weakened, and the formation of vacancy defects is reduced. The doping improves the formation energy of the first perovskite quantum dots and enhances the photoluminescence quantum yield and stability of the first perovskite quantum dots; on the other hand, citric acid reacts with cysteine in the first perovskite quantum dots and then dehydrates and condenses to form a pyridone acid-based compound, effectively enhancing the anti-aging performance of the colorful anti-aging photovoltaic module encapsulation film.

[0021] (6) When preparing the colorful anti-aging photovoltaic module encapsulation adhesive film of the present invention, the second pretreated perovskite quantum dots and the toughening agent are pre-mixed, then the flame retardant is added for mixing, and then the cross-linking agent and the EVA solution are added for mixing; wherein, glycine of the second pretreated perovskite quantum dots reacts with ethylene glycol methacrylate acetoacetate to form pyrrole by Knorr reaction, and then pyrrole reacts with benzaldehyde of the flame retardant, and boron trifluoride etherate is introduced during the reaction to form a bispyrrole phosphate compound containing boron fluoride, grafting the toughening agent, the flame retardant, and the second pretreated perovskite quantum dots well together; then after adding the cross-linking agent and the EVA solution for mixing, under the action of the cross-linking agent benzoyl peroxide, ethylene glycol methacrylate acetoacetate reacts with the EVA base material through an olefin bond for grafting toughening, uniformly mixing and grafting the raw materials such as the second pretreated perovskite quantum dots, the flame retardant, and the toughening agent with the EVA base material, avoiding the problems of decreased working stability and photoelectric conversion efficiency of the photovoltaic module caused by problems such as compatibility and dispersibility. Specific embodiments

[0022] In order to better understand the above technical solution, the following will specifically describe the above technical solution in detail in conjunction with specific embodiments.

[0023] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0024] The following embodiments are only used to more clearly illustrate the technical solution of the present invention and cannot be used to limit the protection scope of the present invention.

[0025] Some raw materials of the embodiments and comparative examples of the present invention are as follows: The preparation method of diethyl benzaldehyde phosphite is as follows: Under nitrogen protection, 3 parts by mass of tetrakis(triphenylphosphine)palladium and 4.8 parts by mass of p-bromobenzaldehyde are dissolved in 330 parts by mass of DMSO under nitrogen protection, then 7.75 parts by mass of N,N-diisopropylethylamine and 10.4 parts by mass of ethyl phosphite are added, then heated to 90 °C and reacted for 42 h, then 350 parts by mass of deionized water is added to disperse for 10 min, extracted with 400 parts by mass of dichloromethane, and then the organic layer is washed and extracted successively with 150 parts by mass of deionized water and 150 parts by mass of saturated sodium bicarbonate solution, and the solvent is removed to obtain diethyl benzaldehyde phosphite.

[0026] The perovskite quantum dots use CsPbBr with oleic acid and oleylamine as ligands 3 .

[0027] The VA content in EVA is 32%.

[0028] (Example 1) A preparation method of a colorful anti-aging photovoltaic module encapsulation film, comprising the following preparation steps: (1) Under nitrogen protection, 0.076 parts by mass of p-toluenesulfonic acid and molecular sieve are put into a reaction kettle, and then 0.37 parts by mass of second pretreated perovskite quantum dots uniformly dispersed in 17 parts by mass of mesitylene are added. Then, 0.31 parts by mass of ethylene glycol methacrylate acetoacetate is added and stirred for 20 min. Subsequently, the temperature is raised to 165 °C and stirred for reaction for 7 h to obtain a premix; (2) The premix prepared in step (1) is mixed with 0.43 parts by mass of a flame retardant, and then 0.053 parts by mass of trifluoroacetic acid is added. Subsequently, it is stirred overnight under nitrogen and in the dark. Then, 0.53 parts by mass of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is added and stirred at room temperature for 2.5 h. 0.78 parts by mass of triethylamine and 1.1 parts by mass of boron trifluoride diethyl etherate are added, and stirring is continued overnight at room temperature to obtain a remix; (3) Under nitrogen protection, the remix prepared in step (2) is mixed with 10 parts by mass of EVA, and then 5.4 parts by mass of benzoyl peroxide is added. The temperature is raised to 55 °C and stirred for 15 min, and then the temperature is raised to 75 °C and stirred for reaction for 7 h. Subsequently, 0.06 parts by mass of ion-doped first pretreated perovskite quantum dots are added to obtain a colorful anti-aging photovoltaic module encapsulation film liquid; (4) The colorful anti-aging photovoltaic module encapsulation film liquid prepared in step (3) is scrape-coated on a polysilicon solar cell and heated overnight in an oven at 60 °C to obtain a 100-μm-thick colorful anti-aging photovoltaic module encapsulation film liquid. Further, the preparation steps of the second pretreated perovskite quantum dots are as follows: 1 part by mass of perovskite quantum dots is dispersed in 2 parts by mass of toluene, and then 0.6 parts by mass of acetonitrile is added, and then 0.6 parts by mass of glycine is added. Then, it is centrifuged at 8000 rpm for 5 min to take the precipitate, and then redispersed in 2 parts by mass of n-hexane and centrifuged at 4000 rpm for 5 min to take the supernatant; the supernatant is placed in a glass bottle, sealed, and stored in a refrigerator at 4 °C for at least 12 h; before use, it is placed in a centrifuge tube and centrifuged at 4000 rpm for 5 min to obtain the second pretreated perovskite quantum dots.

[0029] The preparation steps of the ion-doped first pretreated perovskite quantum dots are as follows: 1 part by mass of the first pretreated perovskite quantum dots is added to a DMF solution of 7.98 parts by mass of zinc citrate and ultrasonically oscillated for 8 min. Then, the temperature is raised to 130 °C for dehydration condensation for 11 h. Subsequently, it is placed in a centrifuge tube and centrifuged at 4000 rpm for 5 min to obtain the ion-doped first pretreated perovskite quantum dots; the mass ratio of zinc citrate to DMF in the DMF solution of zinc citrate is 1:18.

[0030] The preparation steps of the first pre-treated perovskite quantum dots are as follows: Disperse 1 part by mass of perovskite quantum dots in 2 parts by mass of toluene, then add 0.6 part by mass of acetonitrile, and then add 0.97 part by mass of cysteine. Next, centrifuge at 8000 rpm for 5 min to obtain the precipitate, and then disperse it in 2 parts by mass of n-hexane and centrifuge at 4000 rpm for 5 min to obtain the supernatant. Place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4 °C for at least 12 h. Then place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the first pre-treated perovskite quantum dots.

[0031] (Example 2) A preparation method of a colorful anti-aging photovoltaic module encapsulation film includes the following preparation steps: (1) Under nitrogen protection, put 0.077 part by mass of p-toluenesulfonic acid and molecular sieve into a reaction kettle, then add 0.38 part by mass of the second pre-treated perovskite quantum dots uniformly dispersed in 17.5 parts by mass of mesitylene, and then add 0.32 part by mass of ethylene glycol methyl acrylate acetoacetate and mix and stir for 30 min. Then raise the temperature to 170 °C and stir and react for 8 h to obtain a premix; (2) Mix the premix obtained in step (1) with 0.445 part by mass of a flame retardant, then add 0.054 part by mass of trifluoroacetic acid, and then stir overnight under nitrogen and in the dark. Then add 0.535 part by mass of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and stir at room temperature for 3 h, add 0.785 part by mass of triethylamine and 1.15 part by mass of boron trifluoride diethyl ether, and continue to stir overnight at room temperature to obtain a remix; (3) Under nitrogen protection, mix the remix obtained in step (2) with 10 parts by mass of EVA, then add 5.5 parts by mass of benzoyl peroxide, raise the temperature to 60 °C and stir for 20 min, then raise the temperature to 80 °C and stir and react for 7.5 h. Then add 0.07 part by mass of the first pre-treated perovskite quantum dots after ion doping to obtain a colorful anti-aging photovoltaic module encapsulation film liquid; (4) Coat the colorful anti-aging photovoltaic module encapsulation film liquid obtained in step (3) on a polysilicon solar cell and heat it overnight in an oven at 60 °C to obtain a 100-μm-thick colorful anti-aging photovoltaic module encapsulation film.

[0032] The preparation steps of the second pre-treated perovskite quantum dots are as follows: Disperse 1 part by mass of perovskite quantum dots in 3 parts by mass of toluene, then add 0.95 part by mass of acetonitrile, then add 0.7 part by mass of glycine, then centrifuge at 8000 rpm for 5 min to obtain the precipitate, and then disperse it in 2.5 parts by mass of n-hexane and centrifuge at 4000 rpm for 5 min to obtain the supernatant; Place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4 °C for at least 12 h; Before use, place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the second pre-treated perovskite quantum dots.

[0033] The preparation steps of the first pre-treated perovskite quantum dots after ion doping are as follows: Add 1 part by mass of the first pre-treated perovskite quantum dots to a DMF solution of 10.71 parts by mass of zinc citrate and ultrasonically oscillate for 10 min, then heat up to 130 °C for dehydration condensation for 12 h, and then place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the first pre-treated perovskite quantum dots after ion doping; The mass ratio of zinc citrate to DMF in the DMF solution of zinc citrate is 1:19.

[0034] The preparation steps of the first pre-treated perovskite quantum dots are as follows: Disperse 1 part by mass of perovskite quantum dots in 3 parts by mass of toluene, then add 0.95 part by mass of acetonitrile, then add 1.13 parts by mass of cysteine, then centrifuge at 8000 rpm for 5 min to obtain the precipitate, and then disperse it in 2.5 parts by mass of n-hexane and centrifuge at 4000 rpm for 5 min to obtain the supernatant; Place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4 °C for at least 12 h; Then place it in a centrifuge tube and centrifuge at 4000 rpm for 5 min to obtain the first pre-treated perovskite quantum dots.

[0035] (Example 3) A preparation method of a colorful anti-aging photovoltaic module encapsulation film includes the following preparation steps: (1) Under nitrogen protection, put 0.078 part by mass of p-toluenesulfonic acid and molecular sieve into a reaction kettle, then add 0.39 part by mass of the second pre-treated perovskite quantum dots uniformly dispersed in 18 parts by mass of mesitylene, then add 0.33 part by mass of ethylene glycol methacrylate acetoacetate and mix and stir for 40 min, then heat up to 175 °C and stir and react for 9 h to obtain a premix; (2) Mix the premix prepared in step (1) with 0.46 part by mass of a flame retardant, then add 0.055 part by mass of trifluoroacetic acid, then stir overnight under nitrogen and in the dark, then add 0.54 part by mass of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and stir at room temperature for 3.5 h, add 0.79 part by mass of triethylamine and 1.2 part by mass of boron trifluoride diethyl ether, and continue to stir overnight at room temperature to obtain a remix; (3) Under nitrogen protection, the re-mixed material prepared in step (2) is mixed with 10 parts by mass of EVA, then 5.6 parts by mass of benzoyl peroxide is added, the temperature is raised to 65 °C and stirred for 25 min, then the temperature is raised to 85 °C and stirred and reacted for 8 h. Subsequently, 0.08 part by mass of the first pretreated perovskite quantum dots after ion doping is added to obtain a colorful anti-aging photovoltaic module encapsulation adhesive film liquid; (4) The colorful anti-aging photovoltaic module encapsulation adhesive film liquid prepared in step (3) is scrape-coated on a polysilicon solar cell and heated overnight in an oven at 60 °C to obtain a 100-μm-thick colorful anti-aging photovoltaic module encapsulation adhesive film.

[0036] The preparation steps of the second pretreated perovskite quantum dots are as follows: 1 part by mass of perovskite quantum dots is dispersed in 4 parts by mass of toluene, then 1.3 parts by mass of acetonitrile is added, then 0.8 part by mass of glycine is added, and then centrifuged at 8000 rpm for 5 min to take the precipitate, and then dispersed in 3 parts by mass of n-hexane and centrifuged at 4000 rpm for 5 min to take the supernatant; the supernatant is placed in a glass bottle, sealed, and stored in a refrigerator at 4 °C for at least 12 h; before use, it is placed in a centrifuge tube and centrifuged at 4000 rpm for 5 min to obtain the second pretreated perovskite quantum dots.

[0037] The preparation steps of the first pretreated perovskite quantum dots after ion doping are as follows: 1 part by mass of the first pretreated perovskite quantum dots is added to a DMF solution of 13.44 parts by mass of zinc citrate and ultrasonically oscillated for 12 min. Then, the temperature is raised to 130 °C for dehydration condensation for 13 h, and then placed in a centrifuge tube and centrifuged at 4000 rpm for 5 min to obtain the first pretreated perovskite quantum dots after ion doping; the mass ratio of zinc citrate to DMF in the DMF solution of zinc citrate is 1:20.

[0038] The preparation steps of the first pretreated perovskite quantum dots are as follows: 1 part by mass of perovskite quantum dots is dispersed in 4 parts by mass of toluene, then 1.3 parts by mass of acetonitrile is added, then 1.29 parts by mass of cysteine is added, and then centrifuged at 8000 rpm for 5 min to take the precipitate, and then dispersed in 3 parts by mass of n-hexane and centrifuged at 4000 rpm for 5 min to take the supernatant; the supernatant is placed in a glass bottle, sealed, and stored in a refrigerator at 4 °C for at least 12 h; then placed in a centrifuge tube and centrifuged at 4000 rpm for 5 min to obtain the first pretreated perovskite quantum dots.

[0039] (Comparative Example 1) The difference between Comparative Example 1 and Example 2 is that the colorful anti-aging photovoltaic module encapsulation adhesive film in Comparative Example 1 does not use ethylene glycol dimethacrylate as a toughening agent, but uses conventional CPE as a toughening agent, and the remaining steps and components are the same as those in Example 2.

[0040] (Comparative Example 2) The difference between Comparative Example 2 and Example 2 is that: the colorful anti-aging photovoltaic module encapsulation film of Comparative Example 2 uses triphenyl phosphate as the flame retardant instead of diethyl benzaldehyde phosphite, and the remaining steps and components are the same as those of Example 2.

[0041] (Comparative Example 3) The difference between Comparative Example 3 and Example 2 is that: for the colorful anti-aging photovoltaic module encapsulation film of Comparative Example 3, neither the second pre-treated perovskite quantum dots nor the first pre-treated perovskite quantum dots are subjected to ligand exchange, but CsPbBr is directly used 3 , and the remaining steps and components are the same as those of Example 2.

[0042] (Comparative Example 4) The difference between Comparative Example 4 and Example 2 is that: the first pre-treated perovskite quantum dots of the colorful anti-aging photovoltaic module encapsulation film are not ion-doped, and the remaining steps and components are the same as those of Example 2.

[0043] (Comparative Example 5) The difference between Comparative Example 5 and Example 2 is that: diethyl zinc is used instead of zinc citrate for the ion doping of the first pre-treated perovskite quantum dots of the colorful anti-aging photovoltaic module encapsulation film, and the remaining steps and components are the same as those of Example 2.

[0044] (Comparative Example 6) The difference between Comparative Example 6 and Example 2 is that: when preparing the colorful anti-aging photovoltaic module encapsulation film, the toughening agent, flame retardant, cross-linking agent, EVA solution, and the first pre-treated perovskite quantum dots after ion doping are directly mixed, and the remaining steps and components are the same as those of Example 2.

[0045] (Effect Example) UV resistance: Use a UV-Vis spectrophotometer to measure the change in the transmittance of the film in the 300 - 400 nm wavelength band before and after aging; the transmittance retention rate before and after UV = 100% (transmittance retention rate after UV / transmittance retention rate before UV).

[0046] Working stability: Place the photovoltaic cell encapsulated with the colorful anti-aging photovoltaic module encapsulation film under a solar simulator, and adjust the simulator parameters to simulate standard test conditions (light intensity is 1000 W / m², temperature is 25 °C); use a power tester to measure the initial power P 0 of the photovoltaic cell, and let the photovoltaic cell work continuously for 1000 h while keeping the test conditions stable; after 1000 h, measure the power P 1 of the photovoltaic cell again; calculate the power attenuation rate: power attenuation rate = [(P 0 - P 1 ) / P 0× 100%.

[0047] Photovoltaic conversion efficiency: Place the photovoltaic cell encapsulated with the colorful anti-aging photovoltaic module encapsulation film under a solar simulator, and adjust the simulator parameters to standard test conditions; connect an electronic load and a power tester, and measure the current and voltage of the photovoltaic cell at different operating points by changing the resistance value of the electronic load; according to the measured current-voltage curve, find the maximum power point Pmax; measure the power of the incident light Pin at this time; calculate the photovoltaic conversion efficiency: Photovoltaic conversion efficiency = (Pmax / Pin) × 100%.

[0048] The following Table 1 shows the performance data results of the colorful anti-aging photovoltaic module encapsulation films of Examples 1 to 3 and Comparative Examples 1 to 6: Table 1

[0049] As can be seen from Table 1 above, the colorful anti-aging photovoltaic module encapsulation films prepared in Examples 1 to 3 have good anti-aging effects, and the working stability and photovoltaic conversion efficiency of the photovoltaic cells are good.

[0050] The difference between Comparative Example 1 and Example 2 is that the colorful anti-aging photovoltaic module encapsulation film of Comparative Example 1 does not use ethylene glycol diacrylate acetoacetate as a toughening agent, but uses conventional CPE as a toughening agent, and the compatibility of each raw material component with EVA is poor, which affects the anti-aging effect of the colorful anti-aging photovoltaic module encapsulation film and the working stability and photovoltaic conversion efficiency of the photovoltaic cell prepared with the colorful anti-aging photovoltaic module encapsulation film.

[0051] The difference between Comparative Example 2 and Example 2 is that the colorful anti-aging photovoltaic module encapsulation film of Comparative Example 2 does not use diethyl benzaldehyde phosphite as a flame retardant, but uses triphenyl phosphate as a flame retardant. The compatibility of the flame retardant with EVA is poor, which affects the anti-aging effect of the colorful anti-aging photovoltaic module encapsulation film and the working stability and photovoltaic conversion efficiency of the photovoltaic cell prepared with the colorful anti-aging photovoltaic module encapsulation film. At the same time, the bispyrrole phosphate compound containing boron fluoride generated during the use of diethyl benzaldehyde phosphite in Example 2 effectively enhances the working stability and photovoltaic conversion efficiency of the photovoltaic cell.

[0052] The difference between Comparative Example 3 and Example 2 is that the colorful anti-aging photovoltaic module encapsulation film of Comparative Example 3 does not perform ligand exchange on the second pre-treated perovskite quantum dots and the first pre-treated perovskite quantum dots, and is not passivated with glycine and cysteine. Ion migration causes a significant decrease in the PL intensity and transmittance of the quantum dots, thereby affecting the working stability and photovoltaic conversion efficiency of the photovoltaic cell, and no pyridone acid-based compound is formed, and the anti-aging effect is not ideal.

[0053] The difference between Comparative Example 4 and Example 2 is as follows: The first pre-treated perovskite quantum dots of the colorful anti-aging photovoltaic module encapsulation film are not ion-doped, making it impossible to achieve zinc ion passivation of defects, resulting in a decrease in the luminescence efficiency of the quantum dots, an accelerated decline in performance after aging, affecting the working stability and photoelectric conversion efficiency of the photovoltaic cell, and no pyridone carboxylic acid-based compound is formed, so the anti-aging effect is not ideal.

[0054] The difference between Comparative Example 5 and Example 2 is as follows: Diethylzinc is used instead of zinc citrate for the ion doping of the first pre-treated perovskite quantum dots of the colorful anti-aging photovoltaic module encapsulation film. Diethylzinc has high reactivity and is prone to agglomeration, affecting the film transmittance and stability.

[0055] The difference between Comparative Example 6 and Example 2 is as follows: When preparing the colorful anti-aging photovoltaic module encapsulation film, the toughening agent, flame retardant, cross-linking agent, EVA solution, and the first pre-treated perovskite quantum dots after ion doping are directly mixed without being dispersed and compatibilized through a graft reaction, resulting in serious efficiency decay caused by light scattering and energy loss.

[0056] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A colorful anti-aging photovoltaic module encapsulation film, characterized in that: The colorful anti-aging photovoltaic module encapsulation film is prepared by pre-mixing the second pre-treated perovskite quantum dots with a toughening agent, adding a flame retardant to mix, then adding a cross-linking agent and an EVA solution to mix, and then adding the ion-doped first pre-treated perovskite quantum dots to mix and scrape.

2. The colorful anti-aging photovoltaic module encapsulation film according to claim 1, characterized in that: The second pretreated perovskite quantum dots are obtained by exchanging ligands of the perovskite quantum dots with glycine; and the first pretreated perovskite quantum dots are obtained by exchanging ligands of the perovskite quantum dots with cysteine.

3. The colorful anti-aging photovoltaic module encapsulation film according to claim 1, characterized in that: The toughening agent is ethylene glycol acetoacetate.

4. The colorful anti-aging photovoltaic module encapsulation film according to claim 1, characterized in that: The flame retardant is diethyl benzaldehyde phosphite.

5. The colorful anti-aging photovoltaic module encapsulation film according to claim 1, characterized in that: The ion doping is zinc ion doping, and the zinc ion raw material is trizinc citrate.

6. A method for preparing a colorful anti-aging photovoltaic module encapsulation film according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: (1) Under nitrogen protection, 0.076-0.078 parts by weight of p-toluenesulfonic acid and molecular sieves are placed in a reactor, followed by adding 0.37-0.39 parts by weight of the second pretreated perovskite quantum dots uniformly dispersed in 17-18 parts by weight of mesitylene, and then adding 0.31-0.33 parts by weight of ethylene glycol acetoacetate and stirring for 20-40 minutes, and then heating to 165-175° C. and stirring for 7-9 hours to obtain a premix; (2) the premix prepared in step (1) is mixed with 0.43-0.46 parts by mass of a flame retardant, and then 0.053-0.055 parts by mass of trifluoroacetic acid is added, followed by stirring overnight under nitrogen and in the dark, and then 0.53-0.54 parts by mass of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is added and stirred at room temperature for 2.5-3.5 hours, and 0.78-0.79 parts by mass of triethylamine and 1.1-1.2 parts by mass of boron trifluoride ether are added, and stirring is continued at room temperature overnight to obtain a remix; (3) Under nitrogen protection, the remix obtained in step (2) was mixed with 10 parts by weight of EVA, and then 5.4-5.6 parts by weight of benzoyl peroxide was added. The mixture was heated to 55-65° C. and stirred for 15-25 min, then heated to 75-85° C. and stirred for 7-8 h. Subsequently, 0.06-0.08 parts by weight of the first pretreated perovskite quantum dots after ion doping were added to obtain a colorful anti-aging photovoltaic module encapsulation film liquid. (4) The colorful anti-aging photovoltaic module encapsulation adhesive film prepared in step (3) is coated on the polycrystalline silicon solar cell and heated in a 60° C. oven overnight to obtain a 100 μm thick colorful anti-aging photovoltaic module encapsulation adhesive film.

7. The method for preparing the colorful anti-aging photovoltaic module encapsulation film according to claim 6, characterized in that: The preparation steps of the second pretreated perovskite quantum dots are as follows: disperse 1 mass part of perovskite quantum dots in 2-4 mass parts of toluene, then add 0.6-1.3 mass parts of acetonitrile, then add 0.6-0.8 mass parts of glycine, then centrifuge at 8000 rpm for 5 minutes to obtain a precipitate, then disperse it in 2-3 mass parts of n-hexane, centrifuge at 4000 rpm for 5 minutes to obtain a supernatant; place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4°C for at least 12 hours; before use, place it in a centrifuge tube and centrifuge it at 4000 rpm for 5 minutes to obtain the second pretreated perovskite quantum dots.

8. The method for preparing the colorful anti-aging photovoltaic module encapsulation film according to claim 6, characterized in that: The steps for preparing the first pre-treated perovskite quantum dots after ion doping are as follows: 1 part by mass of the first pretreated perovskite quantum dots is added to a DMF solution of 7.98 to 13.44 parts by mass of zinc citrate and ultrasonically oscillated for 8 to 12 minutes, then heated to 130°C for dehydration condensation for 11 to 13 hours, and then placed in a centrifuge tube and centrifuged at 4000 rpm for 5 minutes to obtain the first pretreated perovskite quantum dots after ion doping; the mass ratio of zinc citrate to DMF in the DMF solution of zinc citrate is 1:18 to 20.

9. The method for preparing the colorful anti-aging photovoltaic module encapsulation film according to claim 8, characterized in that: The preparation steps of the first pretreated perovskite quantum dots are as follows: disperse 1 part by mass of perovskite quantum dots in 2-4 parts by mass of toluene, then add 0.6-1.3 parts by mass of acetonitrile, and then add 0.97-1.29 parts by mass of cysteine, then centrifuge at 8000 rpm for 5 minutes to obtain a precipitate, and then disperse it in 2-3 parts by mass of n-hexane, and centrifuge at 4000 rpm for 5 minutes to obtain a supernatant; place the supernatant in a glass bottle, seal it, and store it in a refrigerator at 4°C for at least 12 hours; then place it in a centrifuge tube and centrifuge it at 4000 rpm for 5 minutes to obtain the first pretreated perovskite quantum dots.

10. The method for preparing the colorful anti-aging photovoltaic module encapsulation film according to claim 6, characterized in that: The preparation method of the benzaldehyde diethyl phosphite is as follows: Under nitrogen protection, 3 parts by mass of tetrakis(triphenylphosphine)palladium and 4.7-4.9 parts by mass of p-bromobenzaldehyde are dissolved in 325-335 parts by mass of DMSO, followed by adding 7.7-7.8 parts by mass of N,N-diisopropylethylamine and 10.3-10.5 parts by mass of ethyl phosphite, followed by heating to 85-95°C for reaction for 41-43 hours, and then adding 345-355 parts by mass of deionized water for dispersion for 5-15 minutes, extracting with 400 parts by mass of dichloromethane, and then washing and extracting the organic layer with 150 parts by mass of deionized water and 150 parts by mass of saturated sodium bicarbonate solution in sequence, and removing the solvent to obtain benzaldehyde diethyl phosphite.

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