Modified two-dimensional polyaramid applied to perovskite battery and preparation method thereof

Abstract

The application relates to the technical field of modified two-dimensional polyaramid, and discloses a modified two-dimensional polyaramid applied to a perovskite battery and a preparation method thereof, which comprises the following preparation steps: uniformly mixing melitic acid chloride, melamine, a functionalized diamine monomer, N-methyl-2-pyrrolidone and pyridine to obtain a mixture; performing a polycondensation reaction on the mixture, adding isopropyl alcohol for quenching, adding deionized water to precipitate, collecting the precipitate through filtration, washing and drying the precipitate to obtain the modified two-dimensional polyaramid. The functionalized diamine monomer formed by intermediates 3, terephthalic acid and melamine is reacted with melitic acid chloride and melamine to form the modified two-dimensional polyaramid, which can be dissolved in common solvents, is beneficial to forming a high-quality modified two-dimensional polyaramid nanofilm on the surface of perovskite, and the formed modified two-dimensional polyaramid nanofilm can block the invasion of oxygen and water vapor, thereby prolonging the service life of the perovskite battery.

Description

Technical Field

[0001] This invention relates to the field of modified two-dimensional polyarylamide technology, specifically to a modified two-dimensional polyarylamide for use in perovskite solar cells and its preparation method. Background Technology

[0002] Perovskite solar cells are a new type of photovoltaic cell that relies on perovskite structural materials for photoelectric conversion. They use perovskite-like structural materials that do not contain calcium or titanium elements. The material has a stable structure and is easy to prepare. Its structure consists of: a transparent electrode, an electron transport layer, a mesoporous silica layer, a perovskite light-absorbing layer, a hole transport layer, and a metal electrode.

[0003] Perovskite solar cells have attracted much attention due to their high photoelectric conversion efficiency, low cost, and solution-processability. However, perovskite solar cells are susceptible to the effects of moisture, oxygen, and light, which can cause the perovskite to degrade, turning from a shiny black color into yellow waste and reducing the efficiency of the perovskite solar cells. Therefore, a two-dimensional polyarylamide protective film is coated on the surface of the perovskite, which can maintain its good condition even after being placed in the air.

[0004] Two-dimensional polyarylamide materials are aromatic polyamide polymers in which aromatic rings are directly connected to amide groups in the main chain. Also known as aromatic nylon, they have high strength, high temperature resistance, high melting temperature and excellent chemical resistance, and are widely used in perovskite solar cells. However, polyarylamide is difficult to dissolve in common solvents, making it difficult to form high-quality films. Moreover, its function is limited and it does not have the ability to perform multiple synergistic passivation of perovskite defects. Summary of the Invention

[0005] Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a modified two-dimensional polyarylamide for use in perovskite solar cells and its preparation method, which solves the problems that two-dimensional polyarylamide materials are difficult to dissolve in common solvents, difficult to form high-quality thin films, and have limited functionality.

[0006] Technical solution To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a modified two-dimensional polyarylamide for use in perovskite solar cells includes the following preparation steps: S1. Mix pyromellitic methyl chloride, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone and pyridine evenly to obtain a mixture; S2. The mixture is subjected to a polycondensation reaction, isopropanol is added for quenching, deionized water is added to precipitate the precipitate, the precipitate is collected by filtration, and the precipitate is washed and dried to obtain modified two-dimensional polyarylamide. Among them, the functionalized diamine monomer is formed by reacting intermediate 2 with (3-bromopropyl)trimethylammonium bromide and potassium iodide to form intermediate 3, and intermediate 3 is then reacted with melamine and terephthalic acid. Intermediate 2 is formed by the reaction of 2,6-dimethylaniline and benzaldehyde to form intermediate 1, which is then subjected to an amidation reaction with 10-undecenoyl chloride.

[0007] Furthermore, the functionalized diamine monomer is prepared by the following steps: A1. After heating 2,6-dimethylaniline, benzaldehyde and concentrated HCl were added and reacted at 155-165℃ for 20-22h. After adding ethanol to form a precipitate, sodium hydroxide solution was added to adjust the pH. After standing, the precipitate was collected by suction filtration, washed, dried, and recrystallized in toluene. The precipitate was removed, dried, and intermediate 1 was obtained. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine and stir at 30-40℃ for 40-50 min. Remove the triethylamine hydrochloride solid by filtration, collect the filtrate, and evaporate the filtrate to obtain intermediate 2. A3. Add intermediate 2 and (3-bromopropyl)trimethylammonium bromide to tetrahydrofuran, stir until homogeneous, add azobisisobutyronitrile, stir and react at 50-60℃ for 1-2 h, add potassium iodide, continue stirring, and then collect the product by rotary evaporation to obtain intermediate 3. A4. Add intermediate 3, melamine, and terephthalic acid to N-methyl-2-pyrrolidone and pyridine, stir until homogeneous, react at 90-110℃ for 30-40 min, place in methanol to form a precipitate, wash the precipitate, dry, and obtain the functionalized diamine monomer.

[0008] Furthermore, in the above A1 reaction process, concentrated HCl acts as a catalyst, enabling 2,6-dimethylaniline to react with the aldehyde group of benzaldehyde to obtain intermediate 1, as shown in the following reaction formula:

[0009] Furthermore, in the above A2 reaction process, an amino group on the molecular chain of intermediate 1 can react with the acyl chloride group of 10-undecenoyl chloride, causing 10-undecenoyl chloride to be grafted onto the molecular chain of intermediate 1, yielding intermediate 2, as shown in the following reaction formula:

[0010] Furthermore, in the above A3 reaction, azobisisobutyronitrile acts as an initiator in the organic solvent tetrahydrofuran, causing (3-bromopropyl)trimethylammonium bromide to lose its bromine atom, forming a free radical. This free radical can attack the double bond carried by 10-undecenoyl chloride in intermediate 2, causing (3-bromopropyl)trimethylammonium bromide to graft onto the molecular chain of intermediate 2, forming intermediate 3, as shown in the following reaction formula:

[0011] Furthermore, in the A4 reaction described above, N-methyl-2-pyrrolidone and pyridine are used as solvents, and terephthalic acid is used as a crosslinking agent, allowing the carboxyl group of terephthalic acid to react with the amino group of intermediate 3 and the amino group of melamine, thereby grafting intermediate 3 onto melamine to obtain a functionalized diamine monomer, as shown in the following reaction formula:

[0012] Further, in step A1, the mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol and toluene is (3.4-3.6)g:(1.2-1.4)g:(0.4-0.5)g:(15-20)g:(10-15)g.

[0013] Further, in step A2, the mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride and triethylamine is (3-3.5)g:(50-60)g:(1-1.5)g:(0.8-1)g.

[0014] Further, in step A3, the mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide is (2.3-2.7)g:(2-2.5)g:(40-50)g:(0.6-0.8)g:(2.2-2.5)g.

[0015] Further, in step A4, the mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol is (2.5-2.7)g:(2.8-3)g:(2-2.3)g:(15-20)g:(10-15)g:(30-35)g.

[0016] Further, in step S1, the mass ratio of pyromellitic methyl chloride, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone and pyridine is (10-12)g:(7-8)g:(1-2)g:(65-70)g:(10-15)g.

[0017] Furthermore, in step S2, during the quenching process of adding isopropanol, the amount of isopropanol added is 60-70% of the mixture.

[0018] Furthermore, in step S2, the polycondensation reaction temperature is 20-30℃, and the polycondensation reaction time is 20-24h.

[0019] Furthermore, in step S2, the drying temperature is 60-80℃ and the drying time is 10-12h.

[0020] Further, in step S2, the washing specifically involves washing the precipitate three times with isopropanol, three times with deionized water, and three times with acetone.

[0021] Beneficial technical effects (1) In the technical solution of the present invention, by introducing the intermediate 1 formed by the reaction of 2,6-dimethylaniline and benzaldehyde into the modified two-dimensional polyarylamide molecular chain, on the one hand, the monomer formed by the reaction of 2,6-dimethylaniline and benzaldehyde has a flexible tetramethyl structure, which can increase the free volume of polyarylamide, reduce the molecular packing density of polyarylamide, and thus increase the distance between polyarylamide molecular chains, so that solvent molecules can easily penetrate into the modified two-dimensional polyarylamide, improve the solubility of the modified two-dimensional polyarylamide, and avoid the polyarylamide being difficult to dissolve in the solvent, resulting in poor film quality on the perovskite surface and affecting the efficiency of the titanium dioxide solar cell. On the other hand, the monomer formed by 2,6-dimethylaniline and benzaldehyde contains two amino groups, which is conducive to grafting hydrophobic long chains and quaternary ammonium salt functional groups, which are introduced into the modified two-dimensional polyarylamide molecular chain, so that the modified two-dimensional polyarylamide can fill the halogen vacancies on the perovskite surface, form a dense hydrophobic barrier on the perovskite surface, effectively block water molecules from penetrating, and improve the efficiency of the perovskite cell.

[0022] (2) In the technical solution of the present invention, intermediate 2, which is formed by the reaction of intermediate 1 and 10-undecenoyl chloride, is introduced into the modified two-dimensional polyarylamide molecular chain. On the one hand, 10-undecenoyl chloride contains a long-chain alkane structure and has good waterproof performance. It can form a dense hydrophobic barrier on the surface of perovskite, effectively blocking water molecules from penetrating and avoiding the perovskite battery from being easily affected by moisture and oxygen, which would lead to the degradation of perovskite and affect the efficiency of perovskite battery. On the other hand, 10-undecenoyl chloride contains a long-chain alkane structure and can form a disordered three-dimensional network structure in the modified two-dimensional polyarylamide, which can effectively fix the modified two-dimensional polyarylamide chain, prevent it from peeling off under thermal or mechanical stress, and improve the efficiency of perovskite battery.

[0023] (3) In the technical solution of the present invention, intermediate 3, formed by reacting intermediate 2 with (3-bromopropyl)trimethylammonium bromide and potassium iodide, is introduced into the modified two-dimensional polyarylamide molecular chain. On the one hand, the halogen ions and iodine ions provided by intermediate 3 can fill the positively charged vacancies left by the loss of halogen ions on the perovskite surface due to coordination unsaturation, thermal disturbance or ion migration, eliminate the positively charged defect state of the perovskite battery, and improve the efficiency of the perovskite battery. On the other hand, intermediate 3 contains quaternary ammonium salt cation groups that can form electrostatic interactions with the perovskite surface, improve the stability of the perovskite interface, and the modified two-dimensional polyarylamide forms electrostatic interactions with the perovskite battery through intermediate 3, thereby improving the interfacial bonding force between the modified two-dimensional polyarylamide and the perovskite battery.

[0024] (4) In the technical solution of the present invention, the functionalized diamine monomer formed by intermediate 3, terephthalic acid and melamine reacts with pyromellitic chloride and melamine to form a modified two-dimensional polyarylamide, which can be dissolved in common solvents, which is beneficial to forming a high-quality modified two-dimensional polyarylamide nanofilm on the perovskite surface. The modified two-dimensional polyarylamide nanofilm formed can block the invasion of oxygen and water vapor, extend the service life of perovskite battery, and also eliminate the positively charged defect state of perovskite battery, thereby improving the efficiency of perovskite battery. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0027] Trimethylbenzene chloride, melamine, N-methyl-2-pyrrolidone and pyridine, isopropanol.

[0028] Example 1 A method for preparing a modified two-dimensional polyarylamide for use in perovskite solar cells, specifically including the following steps: S1. Mix pyromellitic methyl methacrylate (PMMC), melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone, and pyridine evenly to obtain a mixture; the mass ratio of PMMC, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone, and pyridine is 10g:7g:1g:65g:10g; S2. The mixture is subjected to a polycondensation reaction at 20°C for 20 hours. Isopropanol is added for quenching, wherein the amount of isopropanol added is 60% of the mixture. Deionized water is added to precipitate the precipitate. The precipitate is collected by filtration and washed three times with isopropanol, three times with deionized water, and three times with acetone. The precipitate is dried at 60°C for 10 hours to obtain modified two-dimensional polyarylamide.

[0029] Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120℃, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 155℃ for 20 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60℃ for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80℃ for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.4 g: 1.2 g: 0.4 g: 15 g: 10 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir the reaction at 30°C for 40 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride and triethylamine is 3 g: 50 g: 1 g: 0.8 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 50°C for 1 hour. Potassium iodide was added, and the mixture was stirred for another 10 minutes. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.3 g: 2 g: 40 g: 0.6 g: 2.2 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 90°C for 30 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90°C, and dried in an oven at 70°C for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.5 g: 2.8 g: 2 g: 15 g: 10 g: 30 g.

[0030] Example 2 A method for preparing a modified two-dimensional polyarylamide for use in perovskite solar cells, specifically including the following steps: S1. Mix pyromellitic methyl methacrylate (PMMC), melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), and pyridine evenly to obtain a mixture; the mass ratio of PMMC, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), and pyridine is 11g:7.5g:1.5g:67g:13g. S2. The mixture was subjected to a polycondensation reaction at 25°C for 22 hours. Isopropanol was added for quenching, wherein the amount of isopropanol added was 65% of the mixture. Deionized water was added to precipitate the precipitate. The precipitate was collected by filtration and washed 3 times with isopropanol, 3 times with deionized water, and 3 times with acetone. The precipitate was dried at 70°C for 11 hours to obtain the modified two-dimensional polyarylamide.

[0031] Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120℃, then benzaldehyde and 37% concentrated HCl were added. The mixture was reacted at 160℃ for 21 h. After adding ethanol to form a precipitate, 10% sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60℃ for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80℃ for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol and toluene was 3.5 g: 1.3 g: 0.45 g: 18 g: 13 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir at 35°C for 45 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.2 g: 55 g: 1.3 g: 0.9 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 55°C for 1.5 h. Potassium iodide was added, and the mixture was stirred for another 10 min. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.5 g:2.3 g:45 g:0.7 g:2.3 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 100℃ for 35 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.6 g: 2.9 g: 2.2 g: 18 g: 13 g: 33 g.

[0032] Example 3 A method for preparing a modified two-dimensional polyarylamide for use in perovskite solar cells, specifically including the following steps: S1. Mix pyromellitic methyl methacrylate (PMMC), melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone, and pyridine evenly to obtain a mixture; the mass ratio of PMMC, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone, and pyridine is 12g:8g:2g:70g:15g; S2. The mixture was subjected to a polycondensation reaction at 30°C for 24 hours. Isopropanol was added to quench the reaction, wherein the amount of isopropanol added was 70% of the mixture. Deionized water was added to precipitate the precipitate. The precipitate was collected by filtration and washed three times with isopropanol, three times with deionized water, and three times with acetone. The precipitate was dried at 80°C for 12 hours to obtain the modified two-dimensional polyarylamide.

[0033] Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120°C, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 165°C for 22 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60°C for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80°C for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.6 g: 1.4 g: 0.5 g: 20 g: 15 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir the reaction at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 60°C for 2 hours. Potassium iodide was added, and the mixture was stirred for another 10 minutes. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.7 g:2.5 g:50 g:0.8 g:2.5 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 110℃ for 40 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.7 g: 3 g: 2.3 g: 20 g: 15 g: 35 g.

[0034] Comparative Example 1 The only difference between this comparative example and Example 3 is the preparation of the functionalized diamine monomer, as detailed below: Functionalized diamine monomers are prepared by the following steps: A1. Add p-phenylenediamine to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of p-phenylenediamine, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 60°C for 2 hours. Potassium iodide was added, and the mixture was stirred for another 10 minutes. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.7 g:2.5 g:50 g:0.8 g:2.5 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 110℃ for 40 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.7 g: 3 g: 2.3 g: 20 g: 15 g: 35 g.

[0035] Comparative Example 2 The only difference between this comparative example and Example 3 is the preparation of the functionalized diamine monomer, as detailed below: Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120°C, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 165°C for 22 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60°C for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80°C for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.6 g: 1.4 g: 0.5 g: 20 g: 15 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add acetyl chloride and triethylamine, and stir at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, acetyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 60°C for 2 hours. Potassium iodide was added, and the mixture was stirred for another 10 minutes. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.7 g:2.5 g:50 g:0.8 g:2.5 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 110℃ for 40 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.7 g: 3 g: 2.3 g: 20 g: 15 g: 35 g.

[0036] Comparative Example 3 The only difference between this comparative example and Example 3 is the preparation of the functionalized diamine monomer, as detailed below: Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120°C, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 165°C for 22 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60°C for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80°C for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.6 g: 1.4 g: 0.5 g: 20 g: 15 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir the reaction at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was then added, and the mixture was stirred at 60°C for 2 hours. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, and azobisisobutyronitrile was 2.7 g:3 g:50 g:0.8 g. A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 110℃ for 40 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.7 g: 3 g: 2.3 g: 20 g: 15 g: 35 g.

[0037] Comparative Example 4 The only difference between this comparative example and Example 3 is the preparation of the functionalized diamine monomer, as detailed below: Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120°C, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 165°C for 22 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60°C for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80°C for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.6 g: 1.4 g: 0.5 g: 20 g: 15 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir the reaction at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Add intermediate 2 to tetrahydrofuran, stir until homogeneous, add azobisisobutyronitrile, stir and react at 60°C for 2 hours, add potassium iodide, continue stirring for 10 minutes, remove the organic solvent by rotary evaporation at 40°C, collect the product, and obtain intermediate 3; the mass ratio of intermediate 2, tetrahydrofuran, azobisisobutyronitrile and potassium iodide is 5.2 g: 50 g: 0.8 g: 2.5 g; A4. Intermediate 3, melamine, and terephthalic acid were added to N-methyl-2-pyrrolidone and pyridine, stirred evenly, and reacted at 110℃ for 40 min. The mixture was then placed in methanol to form a precipitate, washed three times with deionized water at 90℃, and dried in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer. The mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol was 2.7 g: 3 g: 2.3 g: 20 g: 15 g: 35 g.

[0038] Comparative Example 5 The only difference between this comparative example and Example 3 is the preparation of the functionalized diamine monomer, as detailed below: Functionalized diamine monomers are prepared by the following steps: A1. 2,6-Dimethylaniline was heated to 120°C, then benzaldehyde and 37% (w / w) concentrated HCl were added. The mixture was reacted at 165°C for 22 h. After adding ethanol to form a precipitate, 10% (w / w) sodium hydroxide solution was added to adjust the pH to 7.5. After standing for 2 h, the precipitate was collected by filtration. The precipitate was washed three times with methanol and dried in an oven at 60°C for 4 h. It was then recrystallized in toluene. The precipitate was removed and dried at 80°C for 6 h to obtain intermediate 1. The mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene was 3.6 g: 1.4 g: 0.5 g: 20 g: 15 g. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine, and stir the reaction at 40°C for 50 min. Filter to remove triethylamine hydrochloride solid, collect the filtrate, and evaporate the filtrate to dryness to obtain intermediate 2. The mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride, and triethylamine is 3.5 g: 60 g: 1.5 g: 1 g. A3. Intermediate 2 and (3-bromopropyl)trimethylammonium bromide were added to tetrahydrofuran and stirred until homogeneous. Azobisisobutyronitrile was added, and the mixture was stirred at 60°C for 2 hours. Potassium iodide was added, and the mixture was stirred for another 10 minutes. The organic solvent was removed by rotary evaporation at 40°C, and the product was collected to obtain intermediate 3. The mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide was 2.7 g:2.5 g:50 g:0.8 g:2.5 g. A4. Add intermediate 3 and melamine to N-methyl-2-pyrrolidone and pyridine, stir evenly, react at 110℃ for 40 min, place in methanol to form a precipitate, wash 3 times with deionized water at 90℃, and dry in an oven at 70℃ for 10 min to obtain the functionalized diamine monomer; the mass ratio of intermediate 3, melamine, N-methyl-2-pyrrolidone, pyridine and methanol is 5g:3g:20g:15g:35g.

[0039] The modified two-dimensional polyarylamides prepared in the examples and comparative examples are now subjected to performance tests. The specific test methods are as follows: The modified two-dimensional polyarylamide prepared above was dissolved in dimethylacetamide and stirred evenly to obtain a modified two-dimensional polyarylamide solution, wherein the mass ratio of the modified two-dimensional polyarylamide prepared above to dimethylacetamide was 1g:10g. A TiO2 electron transport layer and a perovskite layer are sequentially deposited on a transparent conductive film glass to obtain a perovskite layer transparent conductive film glass. A modified two-dimensional polyarylamide solution is spin-coated onto the surface of the perovskite layer transparent conductive film glass to form a hole transport layer (spin-coating is performed at a rate of 3000 rpm, and the spin-coating is performed on the perovskite layer for 30 s). Then, a metal back electrode layer is deposited to obtain a perovskite solar cell.

[0040] Photoelectric testing of perovskite solar cells: Using a Keithley 2400 SMU high-performance testing instrument, under AM 1.5G sunlight (100mW / cm²), 2 The perovskite solar cells were irradiated under standard light intensity to test their photoelectric conversion efficiency, open-circuit voltage, fill factor, and short-circuit current density.

[0041] The specific results of the stability test are shown in Table 1.

[0042] Table 1

[0043] As shown in Table 1, the modified two-dimensional polyarylamides of all embodiments outperform the reference product. They are soluble in common solvents, which is beneficial for forming high-quality modified two-dimensional polyarylamide nanofilms on the perovskite surface. Furthermore, they can block the intrusion of oxygen and moisture, extend the lifespan of the perovskite solar cell, eliminate positively charged defect states, and improve the efficiency of the perovskite solar cell. This fully demonstrates the effectiveness of the modified two-dimensional polyarylamides for perovskite solar cells provided by this invention.

[0044] In Comparative Example 1, intermediate 1 was replaced with a functionalized diamine monomer prepared by p-phenylenediamine to prepare a modified two-dimensional polyarylamide. When spin-coated onto a perovskite solar cell, its photoelectric performance decreased. This demonstrates that the monomer formed by the reaction of 2,6-dimethylaniline and benzaldehyde has a flexible tetramethyl structure, which can improve the solubility of the modified two-dimensional polyarylamide and thus form a high-quality thin film on the perovskite surface, thereby improving the photoelectric performance of the titanium dioxide solar cell.

[0045] Comparative Example 2 used a functionalized diamine monomer prepared by replacing 10-undecenoyl chloride with acetyl chloride to prepare a modified two-dimensional polyarylamide. When spin-coated onto a perovskite solar cell, its photoelectric performance decreased. This demonstrates that by introducing intermediate 2, formed by the reaction of intermediate 1 and 10-undecenoyl chloride, into the modified two-dimensional polyarylamide molecular chain, on the one hand, 10-undecenoyl chloride contains a long-chain alkane structure, which has good water-repellent properties and can form a dense hydrophobic barrier on the perovskite surface, effectively blocking water molecule penetration and preventing the perovskite solar cell from being easily affected by moisture and oxygen, leading to perovskite degradation and affecting the efficiency of the perovskite solar cell. On the other hand, the long-chain alkane structure of 10-undecenoyl chloride can form a randomly distributed three-dimensional network structure in the modified two-dimensional polyarylamide, effectively fixing the modified two-dimensional polyarylamide chain, preventing it from peeling off under thermal or mechanical stress, and improving the efficiency of the perovskite solar cell.

[0046] Comparative Example 3 replaced potassium iodide with (3-bromopropyl)trimethylammonium bromide by mass, and Comparative Example 4 replaced (3-bromopropyl)trimethylammonium bromide by mass. The functionalized diamine monomer prepared by intermediate 2 was used to prepare modified two-dimensional polyarylamide. When spin-coated onto perovskite solar cells, its photoelectric performance decreased. This demonstrates that by introducing intermediate 3, formed by the reaction of intermediate 2 with (3-bromopropyl)trimethylammonium bromide and potassium iodide, into the modified two-dimensional polyarylamide molecular chain, on the one hand, the halide ions and iodide ions provided by intermediate 3 can... It can fill the positively charged vacancies left by the loss of halide ions on the perovskite surface due to coordination unsaturation, thermal disturbance or ion migration, eliminate the positively charged defect state of the perovskite cell and improve the efficiency of the perovskite cell. On the other hand, intermediate 3 contains quaternary ammonium salt cationic groups that can form electrostatic interactions with the perovskite surface, improve the stability of the perovskite interface, and the modified two-dimensional polyarylamide forms electrostatic interactions with the perovskite cell through intermediate 3, thereby improving the interfacial bonding force between the modified two-dimensional polyarylamide and the perovskite cell.

[0047] Comparative Example 5 used a functionalized diamine monomer prepared by replacing terephthalic acid by mass with intermediate 3 to prepare a modified two-dimensional polyarylamide. When spin-coated onto a perovskite solar cell, its photoelectric performance decreased. This demonstrates that the functionalized diamine monomer formed by intermediate 3, terephthalic acid, and melamine reacts with trimesoyl chloride and melamine to form a modified two-dimensional polyarylamide. This modified polyarylamide is soluble in common solvents, which is beneficial for forming a high-quality modified two-dimensional polyarylamide nanofilm on the perovskite surface. Furthermore, the formed modified two-dimensional polyarylamide nanofilm can block the intrusion of oxygen and water vapor, extending the lifespan of the perovskite solar cell. In addition, it can also eliminate positively charged defect states in the perovskite solar cell, thereby improving the efficiency of the perovskite solar cell.

[0048] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0049] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0050] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments.

Claims

1. A method for preparing modified two-dimensional polyarylamide for use in perovskite solar cells, characterized in that, The preparation steps include the following: S1. Mix pyromellitic methyl chloride, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone and pyridine evenly to obtain a mixture; S2. The mixture is subjected to a polycondensation reaction, isopropanol is added for quenching, deionized water is added to precipitate the precipitate, the precipitate is collected by filtration, and the precipitate is washed and dried to obtain modified two-dimensional polyarylamide. Among them, the functionalized diamine monomer is formed by reacting intermediate 2 with (3-bromopropyl)trimethylammonium bromide and potassium iodide to form intermediate 3, and intermediate 3 is then reacted with melamine and terephthalic acid. Intermediate 2 is formed by the reaction of 2,6-dimethylaniline and benzaldehyde to form intermediate 1, which is then subjected to an amidation reaction with 10-undecenoyl chloride.

2. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 1, characterized in that, The functionalized diamine monomer is prepared by the following steps: A1. After heating 2,6-dimethylaniline, benzaldehyde and concentrated HCl were added and reacted at 155-165℃ for 20-22h. After adding ethanol to form a precipitate, sodium hydroxide solution was added to adjust the pH. After standing, the precipitate was collected by suction filtration, washed, dried, and recrystallized in toluene. The precipitate was removed, dried, and intermediate 1 was obtained. A2. Add intermediate 1 to tetrahydrofuran and stir until dissolved. Add 10-undecenoyl chloride and triethylamine and stir at 30-40℃ for 40-50 min. Remove the triethylamine hydrochloride solid by filtration, collect the filtrate, and evaporate the filtrate to obtain intermediate 2. A3. Add intermediate 2 and (3-bromopropyl)trimethylammonium bromide to tetrahydrofuran, stir until homogeneous, add azobisisobutyronitrile, stir and react at 50-60℃ for 1-2 h, add potassium iodide, continue stirring, and then collect the product by rotary evaporation to obtain intermediate 3. A4. Add intermediate 3, melamine, and terephthalic acid to N-methyl-2-pyrrolidone and pyridine, stir until homogeneous, react at 90-110℃ for 30-40 min, place in methanol to form a precipitate, wash the precipitate, dry, and obtain the functionalized diamine monomer.

3. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 2, characterized in that, In step A1, the mass ratio of 2,6-dimethylaniline, benzaldehyde, concentrated HCl, ethanol, and toluene is (3.4-3.6)g:(1.2-1.4)g:(0.4-0.5)g:(15-20)g:(10-15)g.

4. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 2, characterized in that, In step A2, the mass ratio of intermediate 1, tetrahydrofuran, 10-undecenoyl chloride and triethylamine is (3-3.5)g:(50-60)g:(1-1.5)g:(0.8-1)g.

5. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 2, characterized in that, In step A3, the mass ratio of intermediate 2, (3-bromopropyl)trimethylammonium bromide, tetrahydrofuran, azobisisobutyronitrile, and potassium iodide is (2.3-2.7)g:(2-2.5)g:(40-50)g:(0.6-0.8)g:(2.2-2.5)g.

6. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 2, characterized in that, In step A4, the mass ratio of intermediate 3, melamine, terephthalic acid, N-methyl-2-pyrrolidone, pyridine, and methanol is (2.5-2.7)g:(2.8-3)g:(2-2.3)g:(15-20)g:(10-15)g:(30-35)g.

7. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 1, characterized in that, In step S1, the mass ratio of pyromellitic methyl chloride, melamine, functionalized diamine monomer, N-methyl-2-pyrrolidone and pyridine is (10-12)g:(7-8)g:(1-2)g:(65-70)g:(10-15)g.

8. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 1, characterized in that, In step S2, during the quenching process of adding isopropanol, the amount of isopropanol added is 60-70% of the mixture.

9. The method for preparing a modified two-dimensional polyarylamide for perovskite solar cells according to claim 1, characterized in that, In step S2, the polycondensation reaction temperature is 20-30℃, and the polycondensation reaction time is 20-24h; In step S2, the drying temperature is 60-80℃ and the drying time is 10-12h.

10. The modified two-dimensional polyarylamide prepared by the method for preparing a modified two-dimensional polyarylamide for use in perovskite solar cells according to any one of claims 1-9.

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