A method for preparing high-performance perovskite battery

Abstract

The present invention discloses a method for preparing a high-performance perovskite battery. An electrochemically assisted interfacial growth method is used to coordinate lead metal ions with methylammonium halide to form a surface-dense perovskite NH2CH3PbX3 film. Then, microwave radiation is combined with an electrochemically assisted interfacial growth method, with titanium ore as the anode, to coordinate titanium ions with 2-methylaromatic dicarboxylic acid. Simultaneously, the methyl group in 2-methylaromatic dicarboxylic acid coordinates with the perovskite halogen, suppressing crystal defects and achieving uniform growth of a titanium metal organic framework film on the surface of the perovskite film. The perovskite battery of the present invention has a photoelectric conversion efficiency of over 23%. After aging for 30 days under conditions of a relative humidity of 40% and a temperature of 60°C, it still maintains an initial efficiency of over 82%, thereby solving the problems of poor stability and low photoelectric conversion efficiency of traditional perovskite batteries.

Description

Technical Field

[0001] The present invention relates to a method for preparing a solar cell, and in particular to a method for preparing a high-performance perovskite cell. Background Art

[0002] Solar cells are semiconductor optoelectronic devices that convert light into electricity, and they hold significant research value in the field of energy conversion. Perovskite cells are a new type of all-solid-state thin-film solar cell, boasting advantages such as a high extinction coefficient, low exciton binding energy, and long carrier diffusion distance. Consequently, perovskite cells demonstrate rapid development and enormous commercial potential unmatched by other types of cells.

[0003] However, the current practical application of perovskite solar cells faces bottlenecks such as poor stability and insufficient photovoltaic conversion efficiency to meet commercial requirements. This is primarily due to the fact that perovskite materials are susceptible to irreversible chemical reactions with metal electrodes, are susceptible to decomposition in the complex outdoor environment, and are susceptible to humid air, leading to performance degradation. To overcome these bottlenecks, researchers have investigated the modification of perovskite thin films. For example, patent CN 114497379 A deposits a layer of DHA on the surface of the perovskite film during the preparation of perovskite solar cells, acting as a protective layer. This significantly improves the stability of the perovskite cell, but the preparation process requires high temperatures of 500°C, increasing operational complexity and cost. Patent CN114171681 A uses tris(pentafluorophenyl)boron (TPFPB) to form a modified layer on the SnO2 electron transport layer, significantly improving the humidity stability and long-term stability of perovskite solar cells. However, the photovoltaic conversion efficiency is only 19.4%, which is not significantly higher than the current photovoltaic conversion efficiency of perovskite cells. This is primarily because the modified layer does not synergistically promote carrier mobility. Patent CN 114284438 A adds coumarin to the perovskite light-absorbing layer, allowing the oxygen in the coumarin molecular structure to bond with elements in the perovskite, passivating defects in the perovskite and improving the photoelectric conversion efficiency and operational stability of the perovskite solar cell. The photoelectric conversion efficiency is increased to 20.19%. While this improvement is significant, the coumarin molecular structure also lacks the ability to synergistically excite photogenerated carriers, preventing further improvement in the perovskite cell's photoelectric conversion efficiency.

[0004] In view of the above situation, the existing perovskite cells cannot meet the requirements for commercial application of batteries. It is urgent to develop perovskite cells that can improve photoelectric conversion efficiency, have a mild process, strong humidity stability and long-term stability. Summary of the Invention

[0005] Purpose of the invention: The purpose of the present invention is to provide a method for preparing a high-performance perovskite battery with strong perovskite stability and strong photoelectric performance.

[0006] Technical solution: The method for preparing a high-performance perovskite battery according to the present invention comprises the following steps:

[0007] (1) Using a methylammonium halide-hydrogen peroxide solution as an electrolyte, a lead sheet as an anode, and a copper sheet as a cathode, an electrochemically assisted interfacial growth method is used to obtain a copper sheet coated with a dense perovskite film;

[0008] (2) Using a 2-methylaromatic dicarboxylic acid-hydrogen peroxide solution as the electrolyte, titanium ore as the anode, and a copper sheet coated with a dense perovskite film as the cathode, microwave radiation combined with an electrochemically assisted interfacial growth method is used to dry and prepare a perovskite film regulated by a titanium metal organic framework;

[0009] (3) The perovskite film regulated by the titanium metal organic framework is used as the absorption layer to assemble into a perovskite battery.

[0010] Furthermore, the methylammonium halide in step (1) is one of methylammonium bromide, methylammonium chloride, and methylammonium iodide. The mass ratio of the methylammonium halide to the hydrogen peroxide solution is 1:1 to 1:5.

[0011] Furthermore, the copper sheet in step (1) is treated with an acid and an organic solvent to remove the surface oxide layer; the acid is one of hydrochloric acid and sulfuric acid; and the organic solvent is one or more of ethanol, acetone, and ethyl acetate. The volume ratio of the acid to the organic solvent is 1:10 to 1:20, and the treatment time is 1 to 3 hours. Under these conditions, the copper surface oxide is easily removed, exposing copper ions, and the resulting perovskite film is tightly wrapped around the copper sheet.

[0012] Furthermore, the copper sheet in step (1) has a thickness of 5 mm to 1 cm. Under these conditions, the surface oxide layer can be well removed by treating the copper sheet with acid and organic solvent, and the perovskite film can also be uniformly grown on the copper sheet.

[0013] Furthermore, the reaction conditions of the electrochemically assisted interface growth method in step (1) include current density and reaction time, wherein the current density is 0.25-4 mA / cm 2 , and the reaction time is 6 to 48 hours. At this current density and reaction time, hydrogen peroxide is conducive to the generation of hydroxyl excited states and the directional migration of lead ions, synergistically promoting the growth of perovskite films.

[0014] Furthermore, the 2-methylaromatic dicarboxylic acid in step (2) is 2-methylterephthalic acid and / or 2-methylnaphthalene-1,4-dicarboxylic acid; and the mass ratio of 2-methylaromatic dicarboxylic acid to hydrogen peroxide solution is 1:5 to 1:20.

[0015] Furthermore, the microwave frequency range of the microwave radiation combined with electrochemical assisted interface growth method described in step (2) is 300-1000 MHz, and the current density is 0.1-3 mA / cm 2 , with a reaction time of 6 to 24 hours. This microwave frequency range, current density, and reaction time favor the generation of hydroxyl excited states in hydrogen peroxide and the directional migration of titanium ions, which not only facilitates the coordination of titanium ions with 2-methylaromatic dicarboxylic acid but also facilitates the coordination of methyl groups with halogens on the perovskite, improving the stability of the perovskite cell.

[0016] Furthermore, in the drying conditions described in step (2), the drying temperature is 60 to 80° C. and the drying time is 6 to 10 hours.

[0017] Furthermore, in step (3), a perovskite film regulated by a titanium metal organic framework is used as the absorption layer of a perovskite solar cell, a hole transport layer and an electron transport layer are prepared on the absorption layer by spin coating, and a metal electrode is evaporated on the hole transport layer and a conductive glass is covered on the electron transport layer in sequence to form a perovskite solar cell. The material of the spin coating method is PTAA. The PTAA solvent is one of chloroform and chlorobenzene, with a concentration of 0.2 to 0.5 mol / L and a thickness of 15 to 35 nm. The evaporated metal counter electrode is one of gold and silver, with an evaporation rate of 0.2 to 0.5 A / s and a thickness of 80 to 110 nm. The conductive glass is FTO conductive glass.

[0018] Principle of the Invention: The present invention utilizes an electrochemically assisted interfacial growth method to produce a perovskite film. Under the action of an electric current, the hydroxyl excited state generated by hydrogen peroxide is used to accelerate the oxidation process on the anode surface, promoting electron transfer and achieving rapid dissolution of the anode lead sheet to form lead cations, which accumulate on the copper sheet surface and coordinate with methylammonium halide around the cathode to form CH3NH2PbX3. The present invention utilizes microwave radiation combined with an electrochemically assisted interfacial growth method to accelerate the generation of anode titanium ions. Combining microwaves and electric current can accelerate the directional migration of titanium ions to the vicinity of the cathode, achieving inter-ionic metal coordination between titanium ions and 2-methylaromatic dicarboxylic acid, which is conducive to the formation of a titanium metal organic framework modified layer with a large specific surface area and a porous surface on the surface of the perovskite film.

[0019] Beneficial effects: Compared with the prior art, the present invention has achieved the following significant effects: (1) Breaking through the traditional multi-step operations of mixing, separation, and film formation, the present invention can form a uniformly distributed perovskite film in one step under the synergistic effect of current and hydroxyl excited state, and adopts microwave radiation combined with electrochemical assisted interface growth method to grow titanium metal organic framework on the surface of the perovskite film, which can not only synergistically promote the formation of photogenerated carriers to improve the photoelectric conversion efficiency, but also improve the stability of the perovskite cell. (2) The photoelectric conversion efficiency of the perovskite cell of the present invention is as high as more than 23%. After aging for 30 days under the conditions of relative humidity of 40% and temperature of 60°C, it still maintains an initial efficiency of more than 82%, solving the problems of poor stability and low photoelectric conversion efficiency of traditional perovskite cells. (3) The perovskite film prepared by the present invention has the advantages of mild reaction conditions, green and environmental protection, and easy operation without post-processing. DETAILED DESCRIPTION

[0020] The present invention is described in further detail below.

[0021] Example 1

[0022] A method for preparing a high-performance perovskite battery comprises the following steps:

[0023] (1) 10 mL of methylammonium bromide and 10 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. A 5 mm thick copper sheet was soaked in 1 mL of hydrochloric acid and 10 mL of ethanol solution for 2 h. The treated copper sheet was then used as the cathode. A current density of 0.25 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbBr3 film on the surface.

[0024] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 5 mL of 2-methylterephthalic acid and 25 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 300 MHz and a current density of 3 mA / cm 2 , react for 24 hours, and dry at 60°C for 10 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0025] (3) 501 g of PTAA was dissolved in 500 mL of chloroform and a 30 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.2 A / s, a 90 nm thick gold electrode was evaporated, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0026] Photoelectric performance testing of the perovskite cell prepared in Example 1 showed that the photoelectric conversion efficiency was 23.6%, and the initial efficiency of 84.3% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0027] Comparative Example 1

[0028] (1) 10 mL of methylammonium bromide and 10 mL of hydrogen peroxide were mixed to form an electrolyte. A lead sheet was used as the anode. A 5 mm thick copper sheet was soaked in 1 mL of hydrochloric acid and 10 mL of ethanol for 2 h. The treated copper sheet was then used as the cathode. A current density of 0.25 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbBr3 film on the surface.

[0029] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 5 mL of 2-methylterephthalic acid and 25 mL of water was prepared as the electrolyte in a microwave reactor at a microwave frequency of 300 MHz and a current density of 3 mA / cm 2 , react for 24 hours, and dry at 60°C for 10 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0030] (3) 501 g of PTAA was dissolved in 500 mL of chloroform and a 30 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.2 A / s, a 90 nm thick gold electrode was evaporated, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0031] The photoelectric performance of the perovskite cell prepared in Comparative Example 1 was tested, and the results showed that the photoelectric conversion efficiency was 15.1%. After aging for 30 days under the conditions of 40% relative humidity and 60°C, only 38.8% of the initial efficiency was maintained. Compared with Example 1, when the hydrogen peroxide in step (2) of Example 1 was replaced with water, and other conditions remained unchanged, the photoelectric conversion efficiency and stability decreased significantly. This may be due to the lack of the generation of hydroxyl excited states, which is not conducive to the oxidation of the anode, inhibiting the formation of the titanium metal organic framework, and thus failing to passivate the perovskite absorption layer, resulting in a decrease in photoelectric conversion efficiency and stability.

[0032] Example 2

[0033] (1) 10 mL of methylammonium bromide and 15 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. A 1 cm thick copper sheet was soaked in 1 mL of hydrochloric acid and 15 mL of acetone solution for 2 h. The treated copper sheet was used as the cathode. A current density of 1 mA / cm was applied.2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbBr3 film on the surface.

[0034] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 10 mL of 2-methylterephthalic acid and 10 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 500 MHz and a current density of 2.5 mA / cm 2 , react for 17 hours, and dry at 60°C for 6 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0035] (3) 1252 g of PTAA was dissolved in 500 mL of chloroform and a 20 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.3 A / s, a gold electrode was evaporated to a thickness of 80 nm, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0036] Photoelectric performance testing of the perovskite cell prepared in Example 2 showed that the photoelectric conversion efficiency was 23.5%, and the initial efficiency of 82.8% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0037] Comparative Example 2

[0038] (1) 10 mL of methylammonium bromide and 15 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode and a 1 cm thick copper sheet was used as the cathode. A current density of 1 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbBr3 film on the surface.

[0039] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 10 mL of 2-methylterephthalic acid and 10 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 500 MHz and a current density of 2.5 mA / cm 2 , react for 17 hours, and dry at 60°C for 6 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0040] (3) 1252 g of PTAA was dissolved in 500 mL of chloroform and a 20 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.3 A / s, a gold electrode was evaporated to a thickness of 80 nm, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0041] The photoelectric performance of the perovskite cell prepared in Comparative Example 2 was tested, and the results showed a photoelectric conversion efficiency of 12.7%. After aging for 30 days at 40% relative humidity and 60°C, only 13.5% of the initial efficiency was retained. Compared with Example 2, the hydrochloric acid and acetone treatment of the copper sheet in Example 2 was eliminated, and the untreated copper sheet was used directly. Other conditions remained unchanged. The photoelectric conversion efficiency and stability decreased significantly. This may be because the dense oxide layer on the surface of the copper sheet is not conducive to the adhesion of lead ions to the surface, and the formed perovskite film is easy to fall off, resulting in a decrease in the photoelectric conversion efficiency and stability of the perovskite cell.

[0042] Example 3

[0043] (1) 10 mL of methylammonium chloride and 20 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. An 8 mm thick copper sheet was soaked in 1 mL of hydrochloric acid and 20 mL of ethyl acetate solution for 1 hour to obtain the treated copper sheet, which was used as the cathode. A current density of 2 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbCl3 film on the surface.

[0044] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 10 mL of 2-methylterephthalic acid and 20 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 700 MHz and a current density of 2 mA / cm 2 , react for 13 hours, and dry at 70℃ for 10 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0045] (3) 751 g of PTAA was dissolved in 500 mL of chloroform and a 15 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.4 A / s, a 110 nm thick gold electrode was evaporated, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0046] Photoelectric performance testing of the perovskite cell prepared in Example 3 showed that the photoelectric conversion efficiency was 24.2%, and the initial efficiency of 83.1% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0047] Comparative Example 3

[0048] (1) 10 mL of methylammonium chloride and 20 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. An 8 mm thick copper sheet was soaked in 1 mL of hydrochloric acid and 20 mL of ethyl acetate solution for 1 hour to obtain the treated copper sheet, which was used as the cathode. A current density of 2 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbCl3 film on the surface.

[0049] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 10 mL of terephthalic acid and 20 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 700 MHz and a current density of 2 mA / cm 2 , react for 13 hours, and dry at 70℃ for 10 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0050] (3) 751 g of PTAA was dissolved in 500 mL of chloroform and a 15 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, gold was evaporated on the hole transport layer at 0.4 A / s, a 110 nm thick gold electrode was evaporated, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0051] The photoelectric performance test of the perovskite cell prepared in Comparative Example 3 showed that the photoelectric conversion efficiency was 17.9%. After aging for 30 days under the conditions of relative humidity of 40% and temperature of 60°C, the initial efficiency of 43.2% was still maintained. Compared with Example 3, the photoelectric conversion efficiency and stability were significantly reduced by replacing the 2-methylterephthalic acid in step (2) of Example 3 with terephthalic acid, while other conditions remained unchanged. This may be because terephthalic acid lacks a methyl group compared to 2-methylterephthalic acid, and the methyl group cannot coordinate with the halogen on the perovskite, resulting in the halogen on the perovskite being easily coordinated with the electrode, causing defects in the crystal, a decrease in the rate of photogenerated carriers, and structural instability.

[0052] Example 4

[0053] (1) 5 mL of methylammonium iodide and 25 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. A 7 mm thick copper sheet was soaked in 1 mL of sulfuric acid and 20 mL of ethanol for 3 h. The treated copper sheet was then used as the cathode. A current density of 3 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbI3 film on the surface.

[0054] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 5 mL of 2-methylnaphthalene-1,4-dicarboxylic acid and 18 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 800 MHz and a current density of 1 mA / cm 2 , react for 10 hours, and dry at 70℃ for 8 hours to obtain a perovskite film regulated by a titanium metal organic framework.

[0055] (3) 1002 g of PTAA was dissolved in 500 mL of chlorobenzene, and a 15 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, silver was evaporated on the hole transport layer at 0.5 A / s, a 100 nm thick silver electrode was evaporated, and the electron transport layer was covered with FTO conductive glass to form a perovskite solar cell.

[0056] Photoelectric performance testing of the perovskite cell prepared in Example 4 showed that the photoelectric conversion efficiency was 24.2%, and the initial efficiency of 82.7% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0057] Example 5

[0058] (1) 5 mL of methylammonium bromide and 25 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. A 5 mm thick copper sheet was soaked in 1 mL of sulfuric acid and 18 mL of acetone solution for 1.5 h. The treated copper sheet was then used as the cathode. A current density of 4 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbBr3 film on the surface.

[0059] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 8 mL of 2-methylnaphthalene-1,4-dicarboxylic acid and 23 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 900 MHz and a current density of 0.5 mA / cm 2 After reacting for 6 hours and drying at 80°C for 6 hours, a perovskite film regulated by a titanium metal organic framework can be obtained.

[0060] (3) 501 g of PTAA was dissolved in 500 mL of chlorobenzene, and a 35 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, silver was evaporated at 0.3 A / s on the hole transport layer, an 80 nm thick silver electrode was evaporated, and FTO conductive glass was covered on the electron transport layer to form a perovskite solar cell.

[0061] Photoelectric performance testing of the perovskite cell prepared in Example 5 showed that the photoelectric conversion efficiency was 23.8%, and the initial efficiency of 82.8% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0062] Example 6

[0063] (1) 5 mL of methylammonium iodide and 5 mL of hydrogen peroxide solution were mixed to form an electrolyte. A lead sheet was used as the anode. An 8 mm thick copper sheet was soaked in 1 mL of sulfuric acid and 13 mL of ethyl acetate solution for 2.5 h. The treated copper sheet was then used as the cathode. A current density of 1.5 mA / cm was applied. 2 The lead flakes gradually became smaller, and the aggregates on the surface of the copper flakes increased, resulting in a copper flake coated with a dense perovskite NH2CH3PbI3 film on the surface.

[0064] (2) A copper sheet coated with a dense perovskite film was used as the cathode, titanium ore was used as the anode, and a solution of 12 mL of 2-methylnaphthalene-1,4-dicarboxylic acid and 21 mL of hydrogen peroxide was prepared as the electrolyte in a microwave reactor at a microwave frequency of 1000 MHz and a current density of 0.1 mA / cm 2 After reacting for 10 hours and drying at 80°C for 7 hours, a perovskite film regulated by a titanium metal organic framework can be obtained.

[0065] (3) 751 g of PTAA was dissolved in 500 mL of chlorobenzene, and a 15 nm thick hole transport layer and electron transport layer were prepared by spin coating on a titanium metal organic framework-controlled perovskite film as the perovskite solar cell absorber layer. Then, silver was evaporated at 0.4 A / s on the hole transport layer, a 90 nm thick silver electrode was evaporated, and FTO conductive glass was covered on the electron transport layer to form a perovskite solar cell.

[0066] Photoelectric performance testing of the perovskite cell prepared in Example 6 showed that the photoelectric conversion efficiency was 25.1%, and the initial efficiency of 85.1% was maintained after aging for 30 days at a relative humidity of 40% and a temperature of 60°C.

[0067] It can be seen from the above examples that the perovskite battery prepared by the present invention has high photoelectric conversion efficiency and strong stability, which solves the problem of low stability of the perovskite battery.

Claims

1. A method for preparing a high-performance perovskite battery, characterized in that: The steps include: (1) Using a methylammonium halide-hydrogen peroxide solution as the electrolyte, a lead sheet as the anode, and a copper sheet with the surface oxide layer removed as the cathode, an electrochemically assisted interfacial growth method was used to obtain a copper sheet coated with a dense perovskite film; (2) A 2-methylaromatic dicarboxylic acid-hydrogen peroxide solution was used as the electrolyte, titanium ore was used as the anode, and a copper sheet coated with a dense perovskite film on the surface was used as the cathode. The perovskite film with titanium metal organic framework regulation was obtained by drying using microwave radiation combined with electrochemical assisted interfacial growth method. (3) The perovskite film regulated by the titanium metal organic framework is used as the absorption layer to assemble into a perovskite battery.

2. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (1), the methylammonium halide is at least one of methylammonium bromide, methylammonium chloride or methylammonium iodide.

3. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (1), the mass ratio of methylammonium halide to hydrogen peroxide solution is 1:1 to 1:

5.

4. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (1), the copper sheet is treated with acid and organic solvent to remove the surface oxide layer.

5. The method for preparing a high-performance perovskite battery according to claim 4, wherein: In step (1), the volume ratio of the acid to the organic solvent is 1:10-1:20, and the treatment time is 1-3 h.

6. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (1), the reaction conditions of the electrochemically assisted interface growth method include current density and reaction time, wherein the current density is 0.25~4mA / cm 2 ; The reaction time is 6~48 h.

7. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (2), the 2-methylaromatic dicarboxylic acid is 2-methylterephthalic acid and / or 2-methylnaphthalene-1,4-dicarboxylic acid.

8. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (2), the mass ratio of 2-methylaromatic dicarboxylic acid to hydrogen peroxide solution is 1:5 to 1:

20.

9. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (2), the microwave frequency range of the microwave radiation is 300~1000 MHz, and the current density is 0.1~3 mA / cm 2 , the reaction time is 6~24h.

10. The method for preparing a high-performance perovskite battery according to claim 1, wherein: In step (3), the perovskite film regulated by the titanium metal organic framework is used as the absorption layer of the perovskite solar cell, and the hole transport layer and the electron transport layer are prepared on the absorption layer by spin coating. The metal electrode is evaporated on the hole transport layer and the conductive glass is covered on the electron transport layer in turn to form a perovskite solar cell.