CN115332453A - Preparation method of high-performance perovskite battery - Google Patents

Preparation method of high-performance perovskite battery Download PDF

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CN115332453A
CN115332453A CN202211039169.9A CN202211039169A CN115332453A CN 115332453 A CN115332453 A CN 115332453A CN 202211039169 A CN202211039169 A CN 202211039169A CN 115332453 A CN115332453 A CN 115332453A
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perovskite
methyl
copper sheet
film
transport layer
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张一卫
毛春峰
杨成函
马林
周钰明
朱敏
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Southeast University
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Abstract

The invention discloses a preparation method of a high-performance perovskite battery. Utilizes an electrochemical assisted interface growth method to realize the coordination of lead metal ions and methyl ammonium halide to form perovskite NH with compact surface 2 CH 3 PbX 3 A film. Then, by using a microwave radiation combined electrochemical assisted interface growth method, titanium ore is used as an anode to realize coordination of titanium ions and 2-methyl aromatic dicarboxylic acid, and simultaneously, methyl in the 2-methyl aromatic dicarboxylic acid is coordinated with perovskite halogen to inhibit crystal defects, so that the titanium metal organic framework film uniformly grows on the surface of the perovskite film. The perovskite cell of the invention has the photoelectric conversion efficiency of more than 23 percent, and the initial efficiency of more than 82 percent can be still maintained after the perovskite cell is aged for 30 days under the conditions of 40 percent of relative humidity and 60 ℃, thereby solving the problems of poor stability and photoelectric conversion efficiency of the traditional perovskite cellLow and the like.

Description

Preparation method of high-performance perovskite battery
Technical Field
The invention relates to a preparation method of a solar cell, in particular to a preparation method of a high-performance perovskite cell.
Background
The solar cell is a semiconductor photoelectric device for converting light energy into electric energy, and has important research value in the field of energy conversion. The perovskite cell is a novel all-solid-state thin-film solar cell and has the advantages of high extinction coefficient, low exciton binding energy, long carrier diffusion distance and the like, so that the perovskite cell shows incomparable rapid development speed and huge commercial prospect compared with other types of cells.
However, the practical application of the perovskite solar cell at present has the bottlenecks that the stability is poor and the photoelectric conversion efficiency cannot meet the commercial requirement, and the main reasons are that the perovskite material is easy to have irreversible chemical reaction with a metal electrode, the outdoor environment is complex, and the perovskite material is easy to decompose in humid air, so that the performance is attenuated. In order to overcome the above bottleneck problem, related researchers have studied on the aspect of perovskite thin film modification, for example, in the process of manufacturing a perovskite solar cell, patent CN 114497379A deposits a layer of DHA on the surface of the perovskite thin film to function as a protective layer. The stability of the perovskite battery is obviously improved, but the perovskite battery needs high temperature condition of 500 ℃ in the preparation process, and the operation difficulty and the cost are increased. Patent CN 114171681A uses tris (pentafluorophenyl) boron (TPFPB) material at SnO 2 The perovskite solar cell is remarkably improved in humidity stability and long-term stability by preparing the modification layer film on the electron transmission layer. But the photoelectric conversion efficiency is only 19.4%, and is not obviously improved compared with the current perovskite cell, mainly because the modification layer does not play a role in synergistically promoting the carrier mobility. In patent CN 114284438A, coumarin is added in the perovskite light absorption layer, so that oxygen in a coumarin molecular structure is bonded with elements in perovskite, defects in perovskite are passivated, and photoelectric conversion efficiency and operation stability of the perovskite solar cell are improved. The photoelectric conversion efficiency is improved to 20.19%, and although the photoelectric conversion efficiency is improved to a certain extent, the coumarin molecular structure does not have the function of cooperatively exciting a photon-generated carrier, so that the photoelectric conversion efficiency of the perovskite cell cannot be further improved.
In view of the above, the existing perovskite battery cannot meet the requirements of commercial battery application, and the development of perovskite batteries capable of improving photoelectric conversion efficiency, mild process, strong humidity stability and long-term stability is not slow enough.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a high-performance perovskite battery with strong perovskite stability and strong photoelectric property.
The technical scheme is as follows: the preparation method of the high-performance perovskite battery comprises the following steps:
(1) Taking a methyl ammonium halide-hydrogen peroxide solution as an electrolyte, a lead sheet as an anode and a copper sheet as a cathode, and obtaining the copper sheet coated with the perovskite thin film with a compact surface by an electrochemical assisted interface growth method;
(2) 2-methyl aromatic dicarboxylic acid-hydrogen peroxide solution is used as electrolyte, titanium ore is used as anode, copper sheet coated by perovskite film with compact surface is used as cathode, and the perovskite film with titanium metal organic framework regulation and control is prepared by drying by microwave radiation combined with electrochemical assisted interface growth method;
(3) And assembling the perovskite thin film with titanium metal organic framework regulation and control as an absorption layer to form the perovskite battery.
Further, the methyl ammonium halide in the step (1) is one of methyl ammonium bromide, methyl ammonium chloride and methyl ammonium iodide. The mass ratio of the methyl ammonium halide to the hydrogen peroxide solution is 1.
Further, the copper sheet in the step (1) is treated by acid and organic solvent to remove a surface oxidation layer; the acid is one of hydrochloric acid and sulfuric acid; 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. Under the condition, the oxide on the surface of the copper can be easily removed, copper ions are exposed, and the generated perovskite film is tightly wrapped on the copper sheet.
Further, the thickness of the copper sheet in the step (1) is 5 mm-1 cm. Under the condition, the copper sheet is treated by acid and organic solvent, so that a surface oxidation layer can be well removed, and the perovskite thin film can also uniformly grow on the copper sheet.
Further, the reaction conditions of the electrochemical assisted interface growth method in the step (1) comprise current density and reaction time, wherein the current density is 0.25-4 mA/cm 2 The reaction time is 6-48 h. Under the current density and the reaction time, the hydrogen peroxide is facilitated to generate a hydroxyl excited state and the directional movement of lead ions, and the growth of the perovskite film is synergistically promoted.
Further, the 2-methyl aromatic dicarboxylic acid in the step (2) is 2-methyl terephthalic acid and/or 2-methyl naphthalene-1, 4-dicarboxylic acid; the mass ratio of the 2-methyl aromatic dicarboxylic acid to the hydrogen peroxide solution is (1).
Further, the microwave frequency range of the microwave radiation combined electrochemical assisted interface growth method in the step (2) is 300-1000 MHz, and the current density is 0.1-3 mA/cm 2 The reaction time is 6-24 h. Under the microwave frequency range, current density and reaction time, the hydrogen peroxide is favorable for generating a hydroxyl excited state and the directional movement of titanium ions, the coordination of the titanium ions and 2-methyl aromatic dicarboxylic acid is favorable, the coordination of methyl and halogen on perovskite is also favorable, and the stability of the perovskite battery is improved.
Further, the drying temperature in the drying condition in the step (2) is 60-80 ℃, and the drying time is 6-10 h.
Further, in the step (3), the perovskite thin film with titanium metal organic framework regulation and control is used as an absorption layer of the perovskite solar cell, a hole transport layer and an electron transport layer are prepared on the absorption layer through a spin coating method, and a metal electrode and conductive glass are coated on the electron transport layer and the hole transport layer in sequence to form the perovskite solar cell. The material of the spin-coating method is PTAA. The PTAA solvent is one of chloroform and chlorobenzene, the concentration is 0.2-0.5 mol/L, and the thickness is 15-35 nm. The vapor plating metal counter electrode is one of gold and silver, the vapor plating speed is 0.2-0.5A/s, and the thickness is 80-110 nm. The conductive glass is FTO conductive glass.
The invention principle is as follows: the invention adopts an electrochemical auxiliary interface growth method to prepare the perovskite filmThe membrane is used for accelerating the oxidation process of the surface of the anode by using a hydroxyl excited state generated by hydrogen peroxide under the action of current, promoting electron transfer, realizing the rapid dissolution of an anode lead sheet to form lead cations, gathering the lead cations on the surface of a copper sheet, and forming CH by coordinating with methyl ammonium halide around a cathode 3 NH 2 PbX 3 . According to the invention, the generation of anode titanium ions is accelerated by using a microwave radiation combined electrochemical assisted interface growth method, microwaves and current are combined, so that the titanium ions can be accelerated to directionally move to the vicinity of a cathode, the inter-ionic metal coordination of the titanium ions and 2-methyl aromatic dicarboxylic acid is realized, and the formation of a titanium metal organic framework modification layer with a large specific surface area and a porous surface on the surface of a perovskite film is facilitated.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) The invention breaks through the traditional multi-step operations of mixing, separating, membrane making and the like, can form the perovskite thin film with uniform distribution in one step under the synergistic action of current and hydroxyl excited states, and adopts the microwave radiation combined with the electrochemical assisted interface growth method to grow the titanium metal organic framework on the surface of the perovskite thin film, thereby not only synergistically promoting the formation of photon-generated carriers to improve the photoelectric conversion efficiency, but also improving the stability of the perovskite battery. (2) The perovskite cell provided by the invention has the photoelectric conversion efficiency of more than 23%, and the initial efficiency of more than 82% is still maintained after the perovskite cell is aged for 30 days under the conditions of 40% of relative humidity and 60 ℃, so that the problems of poor stability, low photoelectric conversion efficiency and the like of the traditional perovskite cell are solved. (3) The perovskite thin film prepared by the method has the advantages of mild reaction conditions, environmental protection, no need of post-treatment, easy operation and the like.
Detailed Description
The present invention is described in further detail below.
Example 1
A preparation method of a high-performance perovskite battery comprises the following steps:
(1) Mixing 10mL of methyl ammonium bromide and 10mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a 5mm thick copper sheet in 1mL of hydrochloric acid and 10mL of ethanol solution for 2 hours to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 0.25mA/cm 2 And reacting for 48 hours. Lead sheets become smaller gradually, aggregate on the surfaces of the copper sheets is increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbBr 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 5mL of 2-methyl terephthalic acid with 25mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 300MHz and a current density of 3mA/cm 2 Reacting for 24h, and drying at 60 ℃ for 10h to obtain the perovskite thin film with titanium metal organic framework regulation and control.
(3) 501g of PTAA is dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer with the thickness of 30nm are prepared on a perovskite thin film with titanium metal organic framework regulation and control as an absorption layer of a perovskite solar cell by a spin coating method. And then evaporating gold on the hole transport layer at 0.2A/s, evaporating a gold electrode with the thickness of 90nm, and covering FTO conductive glass on the electron transport layer to form the perovskite solar cell.
Photoelectric performance tests were performed on the perovskite cell prepared in example 1, and the results show that: the photoelectric conversion efficiency was 23.6%. The initial efficiency of 84.3 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
Comparative example 1
(1) Mixing 10mL of methyl ammonium bromide and 10mL of hydrogen peroxide to form electrolyte, taking a lead sheet as an anode, soaking a 5mm thick copper sheet in 1mL of hydrochloric acid and 10mL of ethanol solution for 2 hours to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 0.25mA/cm 2 And reacting for 48 hours. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbBr 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 5mL of 2-methyl terephthalic acid with 25mL of water to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 300MHz and a current density of 3mA/cm 2 Reacting for 24h, and drying for 10h at 60 ℃ to obtain the perovskite film regulated and controlled by the titanium metal organic framework.
(3) 501g of PTAA is dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer with the thickness of 30nm are prepared on a perovskite thin film with titanium metal organic framework regulation and control as an absorption layer of a perovskite solar cell by a spin coating method. And then evaporating gold on the hole transport layer at 0.2A/s, evaporating a gold electrode with the thickness of 90nm, and covering FTO conductive glass on the electron transport layer to form the perovskite solar cell.
The perovskite cell prepared in comparative example 1 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 15.1%. The aging is carried out for 30 days under the conditions of 40 percent of relative humidity and 60 ℃ of temperature, and only the initial efficiency is kept to be 38.8 percent. Compared with the embodiment 1, the hydrogen peroxide in the step (2) of the embodiment 1 is replaced by water, other conditions are not changed, the photoelectric conversion efficiency and stability are obviously reduced, the generation of a hydroxyl excited state is possibly lacked, the oxidation of an anode is not facilitated, the formation of a titanium metal organic framework is inhibited, and the perovskite absorption layer cannot be passivated, so that the photoelectric conversion efficiency and stability are reduced.
Example 2
(1) Mixing 10mL of methyl ammonium bromide and 15mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a 1 cm-thick copper sheet in 1mL of hydrochloric acid and 15mL of acetone solution for 2 hours to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 1mA/cm 2 And reacting for 36h. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbBr 3 A copper sheet wrapped by a film.
(2) Using a copper sheet coated with a perovskite film with a compact surface as a cathode, using titanium ore as an anode, mixing 10mL of 2-methyl terephthalic acid with 10mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 500MHz and a current density of 2.5mA/cm 2 Reacting for 17h, and drying at 60 ℃ for 6h to obtain the perovskite thin film with titanium metal organic framework regulation and control.
(3) 1252g of PTAA is dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer with the thickness of 20nm are prepared on a perovskite thin film with titanium metal organic framework regulation and control as an absorption layer of a perovskite solar cell by a spin coating method. And then performing gold evaporation plating on the hole transport layer at the rate of 0.3A/s, performing gold evaporation plating on an electrode with the thickness of 80nm, and covering the electron transport layer with FTO conductive glass to form the perovskite solar cell.
Photoelectric performance tests were performed on the perovskite cell prepared in example 2, and the results show that: the photoelectric conversion efficiency was 23.5%. The initial efficiency of 82.8 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
Comparative example 2
(1) Mixing 10mL of methyl ammonium bromide and 15mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode and a 1 cm-thick copper sheet as a cathode, and introducing current with the density of 1mA/cm 2 And reacting for 36h. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbBr 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated by a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 10mL of 2-methyl terephthalic acid with 10mL of hydrogen peroxide to prepare a solution as an electrolyte, and in a microwave reactor, the microwave frequency is 500MHz, and the current density is 2.5mA/cm 2 Reacting at 17h, and drying at 60 ℃ for 6h to obtain the perovskite film regulated and controlled by the titanium metal organic framework.
(3) 1252g of PTAA was dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer with a thickness of 20nm were prepared by spin coating on a perovskite thin film with titanium metal organic framework modulation as the absorption layer of a perovskite solar cell. And then performing gold evaporation plating on the hole transport layer at the rate of 0.3A/s, performing gold evaporation plating on an electrode with the thickness of 80nm, and covering the electron transport layer with FTO conductive glass to form the perovskite solar cell.
The perovskite cell prepared by the comparative example 2 is subjected to a photoelectric property test, and the result shows that: the photoelectric conversion efficiency was 12.7%. The aging is carried out for 30 days under the conditions of 40 percent of relative humidity and 60 ℃ of temperature, and only 13.5 percent of initial efficiency is kept. Compared with the embodiment 2, the copper sheet in the embodiment 2 is not treated by hydrochloric acid and acetone, and the untreated copper sheet is directly used, so that other conditions are not changed, and the photoelectric conversion efficiency and stability are obviously reduced, which is probably because the surface of the copper sheet has a compact oxide layer which is not beneficial to lead ions to be attached to the surface, and the formed perovskite thin film is easy to fall off, so that the photoelectric conversion efficiency and stability of the perovskite battery are reduced.
Example 3
(1) Mixing 10mL of methyl ammonium chloride and 20mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a copper sheet with the thickness of 8mm in 1mL of hydrochloric acid and 20mL of ethyl acetate solution for 1h to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 2mA/cm 2 And reacting for 24 hours. Lead sheets become smaller gradually, aggregate on the surfaces of the copper sheets is increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbCl 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 10mL of 2-methyl terephthalic acid and 20mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 700MHz and a current density of 2mA/cm 2 Reacting for 13h, drying for 10h at 70 ℃ to obtain the perovskite film regulated and controlled by the titanium metal organic framework.
(3) 751g of PTAA was dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer having a thickness of 15nm were prepared by spin coating on a perovskite thin film having a titanium metal organic framework modulation as an absorption layer of a perovskite solar cell. And then evaporating gold on the hole transport layer at 0.4A/s, evaporating a gold electrode with the thickness of 110nm, and covering FTO conductive glass on the electron transport layer to form the perovskite solar cell.
The perovskite cell prepared in example 3 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 24.2%. The initial efficiency is still maintained at 83.1 percent after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
Comparative example 3
(1) Mixing 10mL of methyl ammonium chloride and 20mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a copper sheet with the thickness of 8mm in 1mL of hydrochloric acid and 20mL of ethyl acetate solution for 1 hour to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 2mA/cm 2 And reacting for 24 hours. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets increase, and calcium with compact surfaces is obtainedTitanium mine NH 2 CH 3 PbCl 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 10mL of terephthalic acid and 20mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 700MHz and a current density of 2mA/cm 2 Reacting for 13h, drying for 10h at 70 ℃ to obtain the perovskite film with titanium metal organic framework regulation and control.
(3) 751g of PTAA was dissolved in 500mL of chloroform, and a hole transport layer and an electron transport layer having a thickness of 15nm were prepared by spin coating on a perovskite thin film having a titanium metal organic framework modulation as an absorption layer of a perovskite solar cell. And then evaporating gold on the hole transport layer at 0.4A/s, evaporating a gold electrode with the thickness of 110nm, and covering FTO conductive glass on the electron transport layer to form the perovskite solar cell.
The perovskite cell prepared in comparative example 3 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 17.9%. The initial efficiency of 43.2 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature. Compared with the example 3, the 2-methyl terephthalic acid in the step (2) of the example 3 is replaced by the terephthalic acid, other conditions are not changed, the photoelectric conversion efficiency and the stability are obviously reduced, which is probably because the terephthalic acid lacks methyl compared with the 2-methyl terephthalic acid, the methyl can not coordinate with the halogen on the perovskite, the halogen on the perovskite is easy to coordinate with an electrode, the crystal is defective, the rate of a photon-generated carrier is reduced, and the structure is unstable.
Example 4
(1) Mixing 5mL of methyl ammonium iodide and 25mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a 7mm thick copper sheet in 1mL of sulfuric acid and 20mL of ethanol for 3 hours to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 3mA/cm 2 And reacting for 12 hours. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbI 3 A copper sheet wrapped by a film.
(2) The copper sheet coated with the perovskite film with compact surface is used asCathode, titanium ore as anode, mixing 5mL of 2-methylnaphthalene-1, 4-dicarboxylic acid and 18mL of hydrogen peroxide to prepare solution as electrolyte, and placing the solution in a microwave reactor with microwave frequency of 800MHz and current density of 1mA/cm 2 Reacting for 10h, and drying at 70 ℃ for 8h to obtain the perovskite thin film with titanium metal organic framework regulation and control.
(3) 1002g of PTAA is dissolved in 500mL of chlorobenzene, and a hole transport layer and an electron transport layer with the thickness of 15nm are prepared on a perovskite thin film with titanium metal organic framework regulation and control as an absorption layer of a perovskite solar cell by a spin coating method. Then silver is evaporated on the hole transport layer at the rate of 0.5A/s, a silver electrode is evaporated on the hole transport layer at the thickness of 100nm, and the electron transport layer is covered with FTO conductive glass to form the perovskite solar cell.
The perovskite cell prepared in example 4 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 24.2%. The initial efficiency of 82.7 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
Example 5
(1) Mixing 5mL of methyl ammonium bromide and 25mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a 5mm thick copper sheet in 1mL of sulfuric acid and 18mL of acetone solution for 1.5h to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 4mA/cm 2 And reacting for 6 hours. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbBr 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 8mL of 2-methylnaphthalene-1, 4-dicarboxylic acid and 23mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at the microwave frequency of 900MHz and the current density of 0.5mA/cm 2 And after reacting for 6 hours, drying for 6 hours at 80 ℃ to obtain the perovskite thin film with titanium metal organic framework regulation and control.
(3) 501g of PTAA is dissolved in 500mL of chlorobenzene, and a hole transport layer and an electron transport layer with the thickness of 35nm are prepared on a perovskite thin film with a titanium metal organic framework regulation and control as a perovskite solar cell absorption layer by a spin coating method. And then silver is evaporated on the hole transport layer at the rate of 0.3A/s, a silver electrode is evaporated on the hole transport layer at the thickness of 80nm, and the electron transport layer is covered with FTO conductive glass to form the perovskite solar cell.
The perovskite cell prepared in example 5 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 23.8%. The initial efficiency of 82.8 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
Example 6
(1) Mixing 5mL of methyl ammonium iodide and 5mL of hydrogen peroxide solution to form electrolyte, taking a lead sheet as an anode, soaking a copper sheet with the thickness of 8mm in 1mL of sulfuric acid and 13mL of ethyl acetate solution for 2.5 hours to obtain a treated copper sheet, taking the treated copper sheet as a cathode, and introducing a current with the density of 1.5mA/cm 2 And reacting for 24 hours. Lead sheets become smaller gradually, aggregates on the surfaces of the copper sheets are increased, and perovskite NH with compact surfaces is obtained 2 CH 3 PbI 3 A copper sheet wrapped by a film.
(2) Taking a copper sheet coated with a perovskite film with a compact surface as a cathode, taking titanium ore as an anode, mixing 12mL of 2-methylnaphthalene-1, 4-dicarboxylic acid and 21mL of hydrogen peroxide to prepare a solution as an electrolyte, and performing microwave reaction in a microwave reactor at a microwave frequency of 1000MHz and a current density of 0.1mA/cm 2 And after reacting for 10 hours, drying at 80 ℃ for 7 hours to obtain the perovskite thin film with titanium metal organic framework regulation and control.
(3) 751g of PTAA is dissolved in 500mL of chlorobenzene, and a hole transport layer and an electron transport layer with the thickness of 15nm are prepared on a perovskite thin film with titanium metal organic framework regulation and control as a perovskite solar cell absorption layer by a spin coating method. And then silver is evaporated on the hole transport layer at the rate of 0.4A/s, a silver electrode is evaporated on the hole transport layer at the thickness of 90nm, and the electron transport layer is covered with FTO conductive glass to form the perovskite solar cell.
The perovskite cell prepared in example 6 was subjected to a photoelectric property test, and the results showed that: the photoelectric conversion efficiency was 25.1%. The initial efficiency of 85.1 percent is still kept after 30 days of aging under the conditions of 40 percent of relative humidity and 60 ℃ of temperature.
The perovskite battery prepared by the invention has high photoelectric conversion efficiency and strong stability, and solves the problem of weak stability of the perovskite battery.

Claims (10)

1. A preparation method of a high-performance perovskite battery is characterized by comprising the following steps:
(1) Taking methyl ammonium halide-hydrogen peroxide solution as electrolyte, taking a lead sheet as an anode, taking the copper sheet with the surface oxide layer removed as a cathode, and obtaining the copper sheet with the compact surface coated with the perovskite film by an electrochemical assisted interface growth method;
(2) 2-methyl aromatic dicarboxylic acid-hydrogen peroxide solution is used as electrolyte, titanium ore is used as anode, copper sheet coated by perovskite film with compact surface is used as cathode, and the perovskite film with titanium metal organic framework regulation and control is prepared by drying by microwave radiation combined with electrochemical assisted interface growth method;
(3) And assembling the perovskite thin film with titanium metal organic framework regulation and control as an absorption layer to form the perovskite battery.
2. The method for preparing a high-performance perovskite battery according to claim 1, wherein in the step (1), the methyl ammonium halide is at least one of methyl ammonium bromide, methyl ammonium chloride or methyl ammonium iodide.
3. The method for preparing a high-performance perovskite battery according to claim 1, wherein in the step (1), the mass ratio of the methyl ammonium halide to the hydrogen peroxide solution is 1.
4. The method for preparing a high-performance perovskite battery according to claim 1, wherein in the step (1), the copper sheet is treated by acid and organic solvent to remove a surface oxidation layer.
5. The method for preparing a high-performance perovskite battery according to claim 4, wherein in the step (1), the volume ratio of the acid to the organic solvent is 1.
6. According to the rightThe method for preparing a high-performance perovskite battery as defined in claim 1, wherein in the step (1), the reaction conditions of the electrochemical assisted interfacial growth method include current density and reaction time, wherein the current density is 0.25-4 mA/cm 2 (ii) a The reaction time is 6-48 h.
7. The method for preparing a high performance perovskite battery as claimed in claim 1, wherein in the step (2), the 2-methyl aromatic dicarboxylic acid is 2-methyl terephthalic acid and/or 2-methyl naphthalene-1, 4-dicarboxylic acid.
8. The preparation method of the high-performance perovskite battery according to claim 1, wherein in the step (2), the mass ratio of the 2-methyl aromatic dicarboxylic acid to the hydrogen peroxide solution is 1.
9. The process according to claim 1, wherein in step (2), the microwave radiation has a microwave frequency in the range of 300 to 1000MHz and a current density in the range of 0.1 to 3mA/cm 2 The reaction time is 6-24 h.
10. The preparation method of the high-performance perovskite battery as claimed in claim 1, wherein in the step (3), the perovskite thin film with titanium metal organic framework regulation is used as an absorption layer of the perovskite solar battery, a hole transport layer and an electron transport layer are prepared on the absorption layer by a spin coating method, and a metal electrode is sequentially evaporated on the hole transport layer and conductive glass is sequentially coated on the electron transport layer to form the perovskite solar battery.
CN202211039169.9A 2022-08-29 2022-08-29 Preparation method of high-performance perovskite battery Pending CN115332453A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113862712A (en) * 2021-09-15 2021-12-31 中山大学 Preparation method of lead-containing or bismuth-containing perovskite nanocrystal

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113862712A (en) * 2021-09-15 2021-12-31 中山大学 Preparation method of lead-containing or bismuth-containing perovskite nanocrystal
CN113862712B (en) * 2021-09-15 2023-12-01 中山大学 Preparation method of lead-containing or bismuth-containing perovskite nanocrystals

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