Self-repairing sealant for perovskite component and preparation method of self-repairing sealant

Abstract

The invention discloses a self-repairing sealant for a perovskite component and a preparation method of the self-repairing sealant, and belongs to the technical field of sealants, a D-A bond is introduced into a prepolymer A, nano-zinc oxide is loaded on the surface of mesoporous cerium dioxide powder, heptadecafluorodecyl trimethoxysilane and KH-550 are grafted to the surface of composite cerium dioxide for modification, and the self-repairing sealant for the perovskite component is obtained. The preparation method comprises the following steps: compounding cerium dioxide powder, crosslinking with a prepolymer A and a prepolymer B, and combining with other raw materials to obtain the self-repairing sealant for the perovskite component, under the condition of high temperature of 65-90 DEG C, the forward reaction of D-A bonds is facilitated, the effect of self-repairing cracks is achieved, meanwhile, the hydrophobicity is increased by fluorine groups on the compounded cerium dioxide powder, and the self-repairing performance of the sealant is improved. The nano-zinc oxide and the cerium dioxide are added, so that the sealant can keep a good sealing effect in a high-temperature and high-humidity environment, meanwhile, the nano-zinc oxide and the cerium dioxide synergistically play a role in resisting ultraviolet aging, the service life of the self-repairing sealant is further prolonged, and in addition, the flexibility is also improved to a certain extent.

Description

Technical Field

[0001] The present invention belongs to the technical field of sealants, and specifically relates to a self-healing sealant for perovskite components and a preparation method thereof. Background Art

[0002] Perovskite optoelectronic devices (such as solar cells, LEDs, etc.) have become a research hotspot in the fields of new energy and optoelectronics due to their excellent optoelectronic conversion efficiency and low-cost solution processing characteristics. However, the inherent environmental sensitivity of perovskite materials severely restricts their long-term stability and commercialization process. Among them, the encapsulation technology is a key link to protect the perovskite active layer from environmental erosion. With the rapid development of perovskite photovoltaic technology, the performance requirements for encapsulation materials of its components are becoming increasingly stringent.

[0003] The Chinese invention patent application with the publication number CN116023901A discloses a self-healing silicone sealant and its preparation and self-healing methods. The self-healing silicone sealant includes a hydroxyl-terminated organopolysiloxane containing a cyclic branch, dimethyl silicone oil, white oil, fumed silica, methyltributanoneoxime silane, vinyltributanoneoxime silane, a silane coupling agent, and dibutyltin dilaurate. The cyclic branch in the hydroxyl-terminated organopolysiloxane containing a cyclic branch is a cyclosiloxanyl group. When the silicone glue is torn, the cyclosiloxanyl groups between the two cross-sections can be catalytically ring-opened by an alkaline glue catalyst, the two cross-sections are pressed together, and reacted at a certain temperature, and the two cross-sections are re-bonded together, and the cross-section repair can be achieved under the conditions of a catalyst and heating, extending the service life of the silicone sealant.

[0004] However, the sealant used in perovskite components is under the long-term irradiation of ultraviolet light and is prone to aging and cracking. Especially when used in harsh environments such as high temperature and high humidity, it will accelerate the aging speed of the sealant, resulting in a decrease in the adhesion between the sealant and the perovskite component and peeling. Summary of the Invention

[0005] The purpose of the present invention is to provide a self-healing sealant for perovskite components and a preparation method thereof. By polymerizing a D-A compound powder and hexamethylene diisocyanate to obtain prepolymer A, then loading nano-zinc oxide on mesoporous cerium dioxide powder, and then introducing 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and KH-550 for modification, and then obtaining a polyurethane prepolymer through a cross-linking reaction with prepolymer A and prepolymer B, and then mixing with other raw materials for vacuum degassing, the problem of easy peeling under high temperature and high humidity conditions is solved, and the sealant still has good self-healing performance, mechanical properties, and ultraviolet aging resistance in a high temperature and high humidity environment.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of a self-healing sealant for perovskite components, comprising the following steps:

[0008] Step 1: Using sodium oleate as a surfactant and zinc acetate as a precursor, load nano-zinc oxide on mesoporous cerium dioxide powder to obtain composite cerium dioxide powder, and then graft 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and KH-550 onto the surface of the composite cerium dioxide powder to obtain modified composite cerium dioxide powder.

[0009] Step 2: Polymerize D-A compound powder and hexamethylene diisocyanate to obtain prepolymer A, and mix prepolymer A, prepolymer B and modified composite cerium dioxide powder to obtain a polyurethane prepolymer.

[0010] Step 3: Use a high-speed disperser to uniformly mix the polyurethane prepolymer, diisononyl phthalate, low molecular weight polyamide, KH-550, dibutyltin dilaurate, titanium dioxide and low molecular weight polyether polyol, and perform vacuum degassing to obtain a self-healing sealant for perovskite components.

[0011] Furthermore, the composite cerium dioxide powder is prepared by the following steps:

[0012] Prepare mesoporous cerium dioxide powder by the template method, add the mesoporous cerium dioxide powder, absolute ethanol and sodium oleate into a reaction kettle, stir at 80-90 °C and dropwise add an aqueous solution of zinc acetate with a concentration of 0.5 mol / L, react for 30-40 min, cool to room temperature, filter, and dry to obtain composite cerium dioxide powder;

[0013] The dosage ratio of the mesoporous cerium dioxide powder, absolute ethanol, sodium oleate and aqueous zinc acetate solution is 10-15 g: 400-500 mL: 3-3.2 g: 10-15 mL.

[0014] Furthermore, the modified composite cerium dioxide powder is prepared by the following steps:

[0015] Add the aqueous ethanol solution and the composite cerium dioxide powder into a reaction kettle, ultrasonically disperse for 30-40 min, then add 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, KH-550 and acetic acid, adjust the pH value to 4-5, and react at 60-70 °C and 300-500 r / min for 6-8 h, cool to room temperature, filter with suction, wash, and dry to obtain the modified composite cerium dioxide powder;

[0016] The dosage ratio of the aqueous ethanol solution, the composite cerium dioxide powder, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and KH-550 is: 1-1.5 L: 10-15 g: 1-3 g: 1-3 g.

[0017] Furthermore, the D-A compound powder is prepared by the following steps:

[0018] Add furfuryl alcohol, bismaleimide and acetone into a reaction kettle, react at 70 - 80 °C and 500 - 800 r / min for 24 - 26 h, cool to room temperature, remove acetone by rotary evaporation to obtain a concentrated solution, then transfer it to ether to precipitate, filter, wash, dry and grind to obtain D-A compound powder;

[0019] The dosage ratio of furfuryl alcohol, bismaleimide and acetone is 50 - 55 g : 70 - 75 g : 1 - 1.1 L.

[0020] Furthermore, prepolymer A is prepared through the following steps:

[0021] Add hexamethylene diisocyanate, D-A compound powder and anhydrous dimethylformamide into a reaction kettle, react at 75 - 80 °C under argon protection for 3 - 5 h to obtain prepolymer A;

[0022] The dosage ratio of hexamethylene diisocyanate, D-A compound powder and anhydrous dimethylformamide is 0.7 - 1 g : 11 - 14 g : 200 - 250 mL.

[0023] Furthermore, prepolymer B is prepared through the following steps:

[0024] Add hexamethylene diisocyanate, anhydrous dimethylformamide, polytetrahydrofuran and dibutyltin dilaurate into a reaction kettle, react at 70 - 75 °C under argon protection for 3 - 5 h to obtain prepolymer B;

[0025] The dosage ratio of hexamethylene diisocyanate, anhydrous dimethylformamide, polytetrahydrofuran and dibutyltin dilaurate is 26 - 28 g : 300 - 350 mL : 160 - 170 g : 0.15 - 0.2 g.

[0026] Furthermore, the dosage ratio of prepolymer A, prepolymer B and modified composite cerium dioxide powder is 200 - 250 mL : 300 - 350 mL : 10 - 15 g.

[0027] Furthermore, the mass ratio of the polyurethane prepolymer, diisononyl phthalate, low molecular weight polyamide, KH-550, dibutyltin dilaurate, titanium dioxide and low molecular weight polyether polyol is 160 - 165 : 15 - 20 : 10 - 12 : 3 - 5 : 0.16 - 0.5 : 10 - 20 : 15 - 20.

[0028] Furthermore, the vacuum degree for vacuum degassing is -0.09 - -0.10 MPa, the rotation speed is 35 - 40 r / min, and the time is 20 - 30 min.

[0029] The beneficial effects of the present invention:

[0030] 1. The self-healing sealant for perovskite components in the present invention first introduces D-A bonds into prepolymer A, then loads nano-zinc oxide on the surface of mesoporous cerium dioxide powder, and then grafts heptadecafluorodecyltrimethoxysilane and KH-550 onto the surface of the composite cerium dioxide for modification. Then, it is cross-linked with prepolymer A and prepolymer B and combined with other raw materials to obtain the self-healing sealant for perovskite components. Under the high-temperature condition of 65-90 °C, it is beneficial to the forward reaction of D-A bonds, achieving the effect of self-healing cracks. At the same time, the fluorine groups on the composite cerium dioxide powder increase the hydrophobicity, which is beneficial for the sealant to maintain good sealing performance in high-temperature and high-humidity environments. Meanwhile, nano-zinc oxide and cerium dioxide synergistically improve the UV aging resistance performance, further extending the service life of the self-healing sealant. In addition, there is also a certain improvement in flexibility.

[0031] 2. The composite cerium dioxide powder in the present invention first prepares mesoporous cerium dioxide powder using cerium nitrate hexahydrate as the cerium source, and then uses zinc acetate as the precursor and sodium oleate as the surfactant to synthesize nano-zinc oxide particles, which are filled into the pores of the mesoporous cerium dioxide powder to obtain the composite cerium dioxide powder. The porous structure of the mesoporous cerium dioxide powder improves the loading rate of nano-zinc oxide. Cerium dioxide and nano-zinc oxide play a synergistic role in UV aging resistance. Then, heptadecafluorodecyltrimethoxysilane and KH-550 are grafted onto the surface of the composite cerium dioxide powder. During the thermosetting molding of the self-healing sealant, the amino group reacts with the isocyanate groups in prepolymer A and prepolymer B, increasing the binding force. At the same time, the long chain of heptadecafluorodecyltrimethoxysilane increases the flexibility of the self-healing sealant.

[0032] 3. The polyurethane prepolymer in the present invention first reacts the carbon-carbon double bond in furfuryl alcohol with the carbon-carbon double bond in bismaleimide to form a cyclohexene skeleton, obtaining a D-A compound powder containing D-A bonds. Then, the hydroxyl group in the D-A compound powder reacts with one of the isocyanate groups in hexamethylene diisocyanate to produce polymerization, obtaining prepolymer A. Then, prepolymer A, prepolymer B, and the modified composite cerium dioxide powder are cross-linked together. The isocyanate groups on prepolymer A and prepolymer B react with the amino group in the modified composite cerium dioxide powder to form urea bonds, enhancing the binding force between the two, thereby improving the flexibility of the self-healing sealant. In addition, D-A bonds are beneficial for the occurrence of the forward reaction under high-temperature conditions, producing a self-healing effect. The modified composite cerium dioxide powder also exhibits good hydrophobicity, enabling the self-healing sealant for perovskite components to still have good sealing performance when used in high-temperature and high-humidity environments. Detailed implementation mode

[0033] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0034] Example 1: This example provides a self-healing sealant for perovskite components, which is prepared through the following steps:

[0035] S1: Add 52.5 g of furfuryl alcohol and 625 mL of acetone into a reaction kettle, stir at 75 °C and 650 r / min, then mix 72.5 g of bismaleimide and 425 mL of acetone evenly to obtain a mixed solution. Add the mixed solution dropwise into the reaction kettle and react for 25 h. The carbon-carbon double bonds in furfuryl alcohol react with the carbon-carbon double bonds in bismaleimide to form a cyclohexene skeleton. Cool to room temperature, rotate and evaporate to remove acetone at 37 °C to obtain a concentrated solution. Transfer the concentrated solution to ether to precipitate, filter under reduced pressure, wash the precipitate with ether 4 times, and vacuum dry to constant weight at 65 °C, then grind to obtain D-A compound powder.

[0036] S2: Add 0.85 g of hexamethylene diisocyanate, 12.5 g of D-A compound powder and 225 mL of anhydrous dimethylformamide into a reaction kettle, react at 77 °C under argon protection for 4 h, and confirm the content of isocyanate groups at the reaction end point by the toluene-dibutylamine titration method. The isocyanate groups in hexamethylene diisocyanate react with the hydroxyl groups in the D-A compound powder to polymerize to obtain prepolymer A;

[0037] Add 27 g of hexamethylene diisocyanate, 325 mL of anhydrous dimethylformamide, 165 g of polytetrahydrofuran (Mn = 2000 g / mol) and 0.17 g of dibutyltin dilaurate as a catalyst into a reaction kettle, react at 72 °C under argon protection for 4 h, and confirm the content of isocyanate groups at the reaction end point by the toluene-dibutylamine titration method. The isocyanate groups in hexamethylene diisocyanate react with the hydroxyl groups in polytetrahydrofuran to polymerize to obtain prepolymer B.

[0038] S3: Add 37 g of cetyltrimethylammonium bromide and 8.5 L of deionized water into a reaction kettle, stir and dissolve, then add a urea solution, adjust the pH value to 10, stir at 22 °C and 400 r / min for 2.5 h, then dropwise add 20 mL of cerium nitrate hexahydrate at a rate of 1 mL / min, react for 15 h, centrifuge and filter, wash the precipitate with absolute ethanol and deionized water 4 times, and vacuum dry to constant weight to obtain mesoporous cerium dioxide powder.

[0039] S4: Add 12.5 g of mesoporous cerium dioxide powder, 450 mL of absolute ethanol, and 3.1 g of sodium oleate into a reaction kettle, stir and dissolve them under the conditions of 85 °C and 400 r / min, then dropwise add 12 mL of an aqueous solution of zinc acetate with a concentration of 0.5 mol / L, react for 35 min, cool to room temperature, centrifuge and filter, and dry to constant weight at 55 °C to obtain composite cerium dioxide powder.

[0040] S5: Add 1.3 L of an aqueous ethanol solution with a concentration of 60 vol% and 12.5 g of composite cerium dioxide powder into a reaction kettle, ultrasonically disperse for 35 min, then add 2 g of the silane coupling agent heptadecafluorodecyltrimethoxysilane, 2 g of KH-550, and acetic acid, adjust the pH value to 4, react at 65 °C and 400 r / min for 7 h, graft the fluorine-containing heptadecafluorodecyltrimethoxysilane and the amino-containing KH-550 onto the surface of the composite cerium dioxide powder together, cool to room temperature, filter by suction, wash the filter cake 6 times with absolute ethanol and deionized water respectively, and vacuum dry at 105 °C for 8 h to obtain modified composite cerium dioxide powder.

[0041] S6: Then add 225 mL of prepolymer A, 325 mL of prepolymer B, and 12.5 g of modified composite cerium dioxide powder into a reaction kettle, rotary evaporate to remove the solvent to obtain a polyurethane prepolymer, and prepare a crosslinked polyurethane prepolymer with polytetrahydrofuran as the soft segment and hexamethylene diisocyanate and trimethylolpropane as the hard segments.

[0042] S7: By mass fraction, mix 162 parts of polyurethane prepolymer, 17 parts of plasticizer diisononyl phthalate, 11 parts of tackifier low molecular weight polyamide, 4 parts of silane coupling agent KH-550, 0.3 part of catalyst dibutyltin dilaurate, 15 parts of inorganic filler titanium dioxide, and 17 parts of low molecular weight polyether polyol, disperse them with a high-speed disperser at 1000 r / min for 1.5 h, and then stir and defoam with a vacuum defoaming mixer for 25 min. The vacuum degree of the vacuum defoaming mixer is -0.095 MPa, and the rotation speed is 37 r / min to obtain a self-healing sealant for perovskite components.

[0043] Example 2: This example provides a self-healing sealant for perovskite components, which is prepared by the following steps:

[0044] S1: Add 50 g of furfuryl alcohol and 600 mL of acetone into a reaction kettle, stir under the conditions of 70 °C and 500 r / min. Then mix 70 g of bismaleimide and 400 mL of acetone evenly to obtain a mixed solution. Add the mixed solution dropwise into the reaction kettle and react for 24 h. The carbon-carbon double bond in furfuryl alcohol reacts with the carbon-carbon double bond in bismaleimide to form a cyclohexene skeleton. Cool to room temperature, rotate and evaporate to remove acetone under the condition of 35 °C to obtain a concentrated solution. Transfer the concentrated solution to ether to precipitate, filter under reduced pressure, wash the precipitate with ether three times, and vacuum dry to constant weight at 60 °C, then grind to obtain the D-A compound powder.

[0045] S2: Add 0.7 g of hexamethylene diisocyanate, 11 g of D-A compound powder and 200 mL of anhydrous dimethylformamide into a reaction kettle, react under the conditions of 75 °C and argon protection for 3 h, and use the toluene-dibutylamine titration method to confirm the content of isocyanate groups at the reaction end point. The isocyanate groups in hexamethylene diisocyanate react with the hydroxyl groups in the D-A compound powder to polymerize to obtain prepolymer A;

[0046] Add 26 g of hexamethylene diisocyanate, 300 mL of anhydrous dimethylformamide, 160 g of polytetrahydrofuran (Mn = 2000 g / mol) and 0.15 g of dibutyltin dilaurate as a catalyst into a reaction kettle, react under the conditions of 70 °C and argon protection for 3 h, and use the toluene-dibutylamine titration method to confirm the content of isocyanate groups at the reaction end point. The isocyanate groups in hexamethylene diisocyanate react with the hydroxyl groups in polytetrahydrofuran to polymerize to obtain prepolymer B.

[0047] S3: Add 30 g of cetyltrimethylammonium bromide and 8 L of deionized water into a reaction kettle, stir to dissolve, then add a urea solution, adjust the pH value to 9, stir at 20 °C and 300 r / min for 2 h, then dropwise add 15 mL of cerium nitrate hexahydrate at a rate of 1 mL / min, react for 12 h, centrifuge and filter, wash the precipitate with anhydrous ethanol and deionized water three times, and vacuum dry to constant weight to obtain mesoporous cerium dioxide powder.

[0048] S4: Add 10 g of mesoporous cerium dioxide powder, 400 mL of anhydrous ethanol and 3 g of sodium oleate into a reaction kettle, stir and dissolve under the conditions of 80 °C and 300 r / min, then dropwise add 10 mL of an aqueous zinc acetate solution with a concentration of 0.5 mol / L, react for 30 min, cool to room temperature, centrifuge and filter, and dry to constant weight at 50 °C to obtain composite cerium dioxide powder.

[0049] S5: Add 1 L of an ethanol aqueous solution with a concentration of 60 vol% and 10 g of composite cerium dioxide powder into a reaction kettle, ultrasonically disperse for 30 min, then add 1 g of silane coupling agent heptadecafluorodecyltrimethoxysilane, 1 g of KH-550 and acetic acid, adjust the pH value to 4, react at 60 °C and 300 r / min for 6 h, graft the fluorine-containing heptadecafluorodecyltrimethoxysilane and amino-containing KH-550 onto the surface of the composite cerium dioxide powder together, cool to room temperature, filter by suction, wash the filter cake with absolute ethanol and deionized water 5 times respectively, and vacuum dry at 100 °C for 8 h to obtain modified composite cerium dioxide powder.

[0050] S6: Then add 200 mL of prepolymer A, 300 mL of prepolymer B and 10 g of modified composite cerium dioxide powder into a reaction kettle, rotary evaporate to remove the solvent to obtain a polyurethane prepolymer, and prepare a cross-linked polyurethane prepolymer with polytetrahydrofuran as the soft segment and hexamethylene diisocyanate and trimethylolpropane as the hard segments.

[0051] S7: By mass, mix 160 parts of polyurethane prepolymer, 15 parts of plasticizer diisononyl phthalate, 10 parts of tackifier low molecular weight polyamide, 3 parts of silane coupling agent KH-550, 0.16 part of catalyst dibutyltin dilaurate, 10 parts of inorganic filler titanium dioxide and 15 parts of low molecular weight polyether polyol, disperse with a high-speed disperser at 1000 r / min for 1 h, and then stir and defoam with a vacuum defoaming mixer for 20 min. The vacuum degree of the vacuum defoaming mixer is -0.09 MPa and the rotation speed is 35 r / min to obtain a self-healing sealant for perovskite components.

[0052] Example 3: This example provides a self-healing sealant for perovskite components, which is prepared by the following steps:

[0053] S1: Add 55 g of furfuryl alcohol and 650 mL of acetone into a reaction kettle, stir at 80 °C and 800 r / min, then mix 75 g of bismaleimide and 450 mL of acetone evenly to obtain a mixed solution, add the mixed solution dropwise into the reaction kettle, react for 26 h, and the carbon-carbon double bond in furfuryl alcohol reacts with the carbon-carbon double bond in bismaleimide to form a cyclohexene skeleton. Cool to room temperature, rotary evaporate to remove acetone at 40 °C to obtain a concentrated solution, transfer the concentrated solution to ether to precipitate, filter under reduced pressure, wash the precipitate with ether 5 times, and vacuum dry to constant weight at 70 °C, then grind to obtain D-A compound powder.

[0054] S2: Add 1 g of hexamethylene diisocyanate, 14 g of D-A compound powder, and 250 mL of anhydrous dimethylformamide into a reaction kettle, react for 5 h under the conditions of 80 °C and argon protection, and use the toluene-dibutylamine titration method to confirm the content of isocyanate groups at the reaction end point. The isocyanate groups in hexamethylene diisocyanate react and polymerize with the hydroxyl groups in the D-A compound powder to obtain prepolymer A;

[0055] Add 28 g of hexamethylene diisocyanate, 350 mL of anhydrous dimethylformamide, 170 g of polytetrahydrofuran (Mn = 2000 g / mol), and 0.2 g of dibutyltin dilaurate as a catalyst into a reaction kettle, react for 5 h under the conditions of 75 °C and argon protection, and use the toluene-dibutylamine titration method to confirm the content of isocyanate groups at the reaction end point. The isocyanate groups in hexamethylene diisocyanate react and polymerize with the hydroxyl groups in polytetrahydrofuran to obtain prepolymer B.

[0056] S3: Add 40 g of cetyltrimethylammonium bromide and 9 L of deionized water into a reaction kettle, stir to dissolve, then add a urea solution, adjust the pH value to 10, stir for 3 h under the conditions of 25 °C and 500 r / min, then dropwise add 25 mL of cerium nitrate hexahydrate at a rate of 1 mL / min, react for 18 h, centrifuge and filter, wash the precipitate 5 times with anhydrous ethanol and deionized water, and vacuum dry to constant weight to obtain mesoporous cerium dioxide powder.

[0057] S4: Add 15 g of mesoporous cerium dioxide powder, 500 mL of anhydrous ethanol, and 3.2 g of sodium oleate into a reaction kettle, stir to dissolve under the conditions of 90 °C and 500 r / min, then gradually dropwise add 15 mL of an aqueous zinc acetate solution with a concentration of 0.5 mol / L, react for 40 min, cool to room temperature, centrifuge and filter, and dry to constant weight at 60 °C to obtain composite cerium dioxide powder.

[0058] S5: Add 1.5 L of an ethanol aqueous solution with a concentration of 60 vol% and 15 g of composite cerium dioxide powder into a reaction kettle, ultrasonically disperse for 40 min, then add 3 g of the silane coupling agent 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 3 g of KH-550, and acetic acid, adjust the pH value to 5, react for 8 h under the conditions of 70 °C and 500 r / min, graft the fluorine-containing 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and the amino-containing KH-550 onto the surface of the composite cerium dioxide powder together, cool to room temperature, filter by suction, wash the filter cake 8 times with anhydrous ethanol and deionized water respectively, and vacuum dry at 110 °C for 9 h to obtain modified composite cerium dioxide powder.

[0059] S6: Then, 250 mL of prepolymer A, 350 mL of prepolymer B, and 15 g of modified composite cerium dioxide powder were added to a reaction kettle, and the solvent was removed by rotary evaporation to obtain a polyurethane prepolymer. A polyurethane prepolymer with a crosslinked structure was prepared using polytetrahydrofuran as the soft segment, and hexamethylene diisocyanate and trimethylolpropane as the hard segments.

[0060] S7: By mass, 165 parts of the polyurethane prepolymer, 20 parts of the plasticizer diisononyl phthalate, 12 parts of the tackifier low molecular weight polyamide, 5 parts of the silane coupling agent KH-550, 0.5 part of the catalyst dibutyltin dilaurate, 20 parts of the inorganic filler titanium dioxide, and 20 parts of the low molecular weight polyether polyol were mixed, and dispersed using a high-speed disperser at 1000 r / min for 2 h, and then stirred and degassed using a vacuum degassing mixer for 30 min. The vacuum degree of the vacuum degassing mixer was -0.10 MPa, and the rotation speed was 40 r / min to obtain a self-healing sealant for perovskite components.

[0061] Comparative Example 1: On the basis of Example 1, in step S6, the composite cerium dioxide powder prepared in step S4 was used to replace the modified composite cerium dioxide powder, and the remaining steps remained unchanged to obtain a self-healing sealant for perovskite components.

[0062] Comparative Example 2: On the basis of Example 1, in step S6, the modified composite cerium dioxide powder was removed, and the remaining steps remained unchanged to obtain a self-healing sealant for perovskite components.

[0063] Comparative Example 3: On the basis of Example 1, in step S6, prepolymer A was removed, and the remaining steps remained unchanged to obtain a self-healing sealant for perovskite components.

[0064] The self-healing sealants for perovskite components prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests: The samples were extruded onto a glass plate coated with a release agent using a glue gun to a thickness of about 1 mm, and after drying completely, they were placed in an oven at 70 °C and cured for 24 h, and then tested after standing at room temperature for 7 d.

[0065] Mechanical properties: Place the sample under ultraviolet light for 24 h, and then test the tensile strength and elongation at break of the sample according to GB / T 528-2009. The cutting knife and cutting machine used in the test meet the requirements of GB / T 2941. The cutting knife used to prepare the dumbbell-shaped specimen is a Type II cutting knife, with a total length of 75 mm, a narrow part length of 25 mm, a narrow part width of 4 mm, a test length of 20 mm, and a speed of 100 mm / min; the temperature during the test is room temperature of 25 °C. After the cut specimen is fixed with a holder, the extensometer is clamped on the specimen, and the distance between the extensometers is the test length of 20 mm. If the specimen breaks within the test length range, it is a valid sample and the data results are retained; if the test breaks at the shoulder or other positions, it is an invalid sample, the data results are discarded, and the test is repeated. The same sample is subjected to at least 5 valid tests, and the final test result is the median.

[0066] Self-healing performance: A scratch repair experiment was carried out using a DM2500P polarizing microscope (POM, Leica, Germany). The steps are as follows: Use a single-sided blade to cut a cross-shaped scratch on the surface of the sample, and then place it on a hot stage (stand still at 75 °C for 12 h), and record the repair situation of the scratch in real time with the help of a polarizing microscope.

[0067] Hydrolysis resistance: Test according to the standard of GB / T 1034-2008. First, cut the sample into 20 mm×20 mm×1 mm, place it in an oven for drying until the mass is constant and record the mass m1 at this time. Immerse the sample in distilled water at 23 °C, take it out once every 24 h of standing, wipe off the water on the surface of the sample with a paper towel and then weigh it, record the mass m2 at this time. After soaking for 7 d, calculate the water absorption rate.

[0068] Table 1 Summary of performance test results

[0069]

[0070] As can be seen from Table 1, the tensile strength and elongation at break before ultraviolet irradiation in Examples 1-3 are higher than those in Comparative Example 1 and Comparative Example 2. In Comparative Example 1, composite cerium dioxide powder is used instead of modified composite cerium dioxide powder, and in Comparative Example 2, modified composite cerium dioxide powder is removed. This shows that the combined use of modified composite cerium dioxide powder, prepolymer A, and prepolymer B improves the flexibility of the self-healing sealant for perovskite components and enhances the overall mechanical properties. The tensile strength and elongation at break after ultraviolet irradiation in Examples 1-3 are slightly lower than those before ultraviolet irradiation, while the tensile strength and elongation at break after ultraviolet irradiation in Comparative Examples 1 and 2 are significantly reduced. In Comparative Example 1, composite cerium dioxide powder is used instead of modified composite cerium dioxide powder, and in Comparative Example 2, modified composite cerium dioxide powder is removed. This indicates that modified composite cerium dioxide powder and nano-zinc oxide have a synergistic effect in improving the ultraviolet aging resistance of the self-healing sealant.

[0071] The repair efficiency in Examples 1-3 is greater than that in Comparative Example 3. In Comparative Example 3, prepolymer A is removed, indicating that the D-A bond in prepolymer A has a self-healing effect at high temperatures. The repair efficiency in Comparative Example 2 is slightly lower than that in Examples 1-3. In Comparative Example 2, modified composite cerium dioxide powder is removed, indicating that the combined use of modified composite cerium dioxide powder and prepolymer A improves the self-healing efficiency of the self-healing sealant.

[0072] The water absorption rate in Examples 1-3 is less than that in Comparative Example 1, and the water absorption rate in Comparative Example 2 is greater than that in Comparative Example 1. In Comparative Example 1, composite cerium dioxide is used instead of modified composite cerium dioxide powder, and in Comparative Example 2, modified composite cerium dioxide powder is removed. This shows that the fluorine-containing modified composite cerium dioxide powder has good hydrophobic properties, which is beneficial for the self-healing sealant to maintain good sealing performance under high humidity conditions.

[0073] It should be noted that in this article, terms such as "including", "comprising", or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device including a series of elements not only includes those elements but also includes other elements not explicitly listed, or further includes elements inherent to such a process, method, article, or device.

[0074] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

Claims

1. A preparation method of a self-healing sealant for perovskite components, characterized in that, It includes the following steps: Step 1: Using sodium oleate as a surfactant and zinc acetate as a precursor, load nano-zinc oxide on mesoporous cerium dioxide powder to obtain composite cerium dioxide powder, and then graft 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and KH-550 onto the surface of the composite cerium dioxide powder to obtain modified composite cerium dioxide powder; Step 2: Polymerize D-A compound powder and hexamethylene diisocyanate to obtain prepolymer A, and mix prepolymer A, prepolymer B and modified composite cerium dioxide powder to obtain a polyurethane prepolymer; Step 3: Use a high-speed disperser to mix the polyurethane prepolymer, diisononyl phthalate, low molecular weight polyamide, KH-550, dibutyltin dilaurate, titanium dioxide and low molecular weight polyether polyol evenly, and carry out vacuum degassing to obtain a self-healing sealant for perovskite components.

2. The preparation method of a self-healing sealant for perovskite components according to claim 1, characterized in that The composite cerium dioxide powder described in Step 1 is prepared through the following steps: Prepare mesoporous cerium dioxide powder by the template method. Add the mesoporous cerium dioxide powder, absolute ethanol and sodium oleate into a reaction kettle, stir at 80-90 °C and dropwise add an aqueous zinc acetate solution with a concentration of 0.5 mol / L, react for 30-40 min, cool to room temperature, filter and dry to obtain composite cerium dioxide powder; The dosage ratio of the mesoporous cerium dioxide powder, absolute ethanol, sodium oleate and aqueous zinc acetate solution is 10-15 g: 400-500 mL: 3-3.2 g: 10-15 mL.

3. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that, The modified composite cerium dioxide powder described in Step 1 is prepared through the following steps: Add the ethanol aqueous solution and the composite cerium dioxide powder into a reaction kettle, ultrasonically disperse for 30-40 min, then add 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, KH-550 and acetic acid, adjust the pH value to 4-5, react at 60-70 °C and 300-500 r / min for 6-8 h, cool to room temperature, carry out suction filtration, washing and drying to obtain modified composite cerium dioxide powder; The dosage ratio of the ethanol aqueous solution, the composite cerium dioxide powder, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and KH-550 is: 1-1.5 L: 10-15 g: 1-3 g: 1-3 g.

4. The preparation method of a self-healing sealant for perovskite components according to claim 1, characterized in that, The D-A compound powder described in Step 2 is prepared through the following steps: Add furfuryl alcohol, bismaleimide and acetone into a reaction kettle, react at 70-80 °C and 500-800 r / min for 24-26 h, cool to room temperature, rotary evaporate to remove acetone to obtain a concentrated solution, then transfer it to ether to precipitate, filter, wash and dry, and grind to obtain D-A compound powder; The dosage ratio of furfuryl alcohol, bismaleimide and acetone is 50-55 g: 70-75 g: 1-1.1 L.

5. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that, The prepolymer A described in Step 2 is prepared through the following steps: Add hexamethylene diisocyanate, D-A compound powder and anhydrous dimethylformamide into a reaction kettle, react at 75-80 °C under argon protection for 3-5 h to obtain prepolymer A; The dosage ratio of hexamethylene diisocyanate, D-A compound powder and anhydrous dimethylformamide is 0.7-1 g: 11-14 g: 200-250 mL.

6. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that, The prepolymer B described in Step 2 is prepared by the following steps: Add hexamethylene diisocyanate, anhydrous dimethylformamide, polytetrahydrofuran, and dibutyltin dilaurate into a reaction kettle, and react for 3-5 h under the conditions of 70-75 °C and argon protection to obtain prepolymer B; The dosage ratio of the hexamethylene diisocyanate, anhydrous dimethylformamide, polytetrahydrofuran, and dibutyltin dilaurate is 26-28 g: 300-350 mL: 160-170 g: 0.15-0.2 g.

7. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that The dosage ratio of the prepolymer A, prepolymer B, and modified composite cerium dioxide powder described in Step 2 is 200-250 mL: 300-350 mL: 10-15 g.

8. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that, The polyurethane prepolymer, diisononyl phthalate, low molecular weight polyamide, KH-550, dibutyltin dilaurate, titanium dioxide, and low molecular weight polyether polyol described in Step 3 are in a mass ratio of 160-165: 15-20: 10-12: 3-5: 0.16-0.5: 10-20: 15-20.

9. The preparation method of a self-healing sealant for a perovskite component according to claim 1, characterized in that, The vacuum degree of the vacuum defoaming is -0.09--0.10 MPa, the rotation speed is 35-40 r / min, and the time is 20-30 min.

10. A self-healing sealant for perovskite components, characterized in that, It is prepared by the preparation method of a self-healing sealant for perovskite components according to any one of claims 1-9.

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