Perovskite cell, preparation method thereof and photovoltaic module

Abstract

The invention discloses a perovskite cell, a preparation method thereof and a photovoltaic module, and the preparation method of the perovskite cell comprises the following steps: providing a basic cell module which comprises a perovskite layer; and carrying out at least one cold treatment on the basic battery assembly at the temperature of-18 DEG C to 8 DEG C. According to the invention, the basic cell assembly is subjected to cold treatment, so that the perovskite crystal phase can be fixed, the migration and recombination of electron holes can be slowed down, the stability of the structure and performance of the perovskite crystal phase can be maintained, the frozen perovskite film surface is more uniform and compact, the water and oxygen isolation capability of the perovskite layer can be improved, and the stability of the cell device can be improved; and the service life of the battery device is prolonged, so that the battery device can be repeatedly prepared and used for a long period.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic modules, and in particular to a perovskite cell and a preparation method thereof, and a photovoltaic module. Background Art

[0002] Perovskite solar cells have the advantages of high efficiency, long life, high conversion efficiency and low cost, and can be widely used in the field of solar cells, such as perovskite thin-film solar cells, perovskite crystalline silicon solar cells, etc. Compared with traditional solar cells, perovskite solar cells can not only be used for rooftop solar power generation of residential and commercial buildings, but also in public facilities, rural power grids and other fields.

[0003] Although the photoelectric conversion efficiency and production cost of perovskite are obviously superior to those of crystalline silicon, stability is still an urgent problem that researchers in this field around the world are currently trying to solve. The stability issue has become the decisive factor in whether perovskite solar cell technology can be commercialized on a large scale. The instability of perovskite solar cells comes from two aspects: from the perspective of thin-film batteries themselves, the phase structure of the perovskite layer in the battery itself is unstable; from the perspective of the overall device structure, the design and packaging structure of commercial products bring unstable effects. According to current research theories, factors that affect the stability of perovskite solar cells include water, oxygen, light, and temperature in the environment, which cause microscopic damage to the device such as film degradation, which is directly reflected in the attenuation of product efficiency. In particular, photovoltaic products are usually used in open areas with sufficient sunlight. In high-temperature environments, their phase structure is more likely to change, thus affecting stability. Summary of the invention

[0004] Based on this, in order to improve the stability of perovskite cells without adding additional materials, it is necessary to provide a perovskite cell and a preparation method thereof and a photovoltaic module.

[0005] The present invention provides a method for preparing a perovskite battery, comprising the following steps:

[0006] Providing a basic battery component, the basic battery component comprising a perovskite layer;

[0007] The basic battery assembly is subjected to at least one cold treatment at a temperature of -18°C to 8°C.

[0008] In one embodiment, the cold treatment time is 2 hours to 26 hours.

[0009] In one embodiment, the temperature of the cold treatment is -15°C~5°C.

[0010] In one embodiment, the cold treatment is performed in an environment free of water and oxygen.

[0011] In one embodiment, the basic battery component includes a substrate, a first transport layer, and the perovskite layer stacked in sequence.

[0012] In one of the embodiments, the basic battery assembly further includes a second transmission layer disposed on a surface of the perovskite layer away from the first transmission layer.

[0013] In one embodiment, the materials of the first transmission layer and the second transmission layer independently have a structure shown in Formula I:

[0014] Formula I;

[0015] Among them, A represents the electron acceptor, D represents the electron donor, X represents the donor group, and Y represents the acceptor group.

[0016] In one embodiment, the step of preparing the basic battery component includes at least one annealing treatment.

[0017] Furthermore, the present application also provides a perovskite battery prepared according to the above-mentioned preparation method.

[0018] Furthermore, the present application also provides a photovoltaic module, including the perovskite cell as described above.

[0019] The present application can fix the perovskite crystal phase, slow down the migration and recombination of electron holes, and maintain the stability of the perovskite crystal phase structure and performance by cold-treating the basic battery components. After freezing, the surface of the perovskite film is more uniform and dense, which can improve the ability of the perovskite layer to isolate water and oxygen, enhance the electrical performance and stability of the battery device, and extend the service life of the battery device, thereby ensuring that the battery device can be repeatedly prepared and used for a long period of time. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0021] Figure 1 Schematic diagram of the change in photoelectric conversion efficiency of the perovskite solar cell modules of Examples 1 to 3 of the present application and Comparative Examples 1 to 3 under continuous illumination conditions. DETAILED DESCRIPTION

[0022] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present application are given in the drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0024] The term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, wherein the any and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. For example, "A and / or B" includes three parallel solutions: A, B, and "a combination of A and B".

[0025] In this article, unless otherwise specified, "one or more" means any one of the listed items or any combination of the listed items. Similarly, "one or more" and other expressions that mean "one or more" are also understood in the same way unless otherwise specified.

[0026] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as limiting the previous technical solution, nor can they be understood as limiting the scope of protection of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0027] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0028] In this document, the terms "first", "second", "third", "fourth", etc. in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0029] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0030] Herein, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is considered to be continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval only refers to integers within the numerical interval, including the two endpoint integers of the numerical range, and each integer between the two endpoints, is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0031] Herein, the term "room temperature" or "normal temperature" generally refers to 4°C~35°C, for example, 20°C±5°C. In some embodiments herein, "room temperature" or "normal temperature" refers to 10°C~30°C. In some embodiments herein, "room temperature" or "normal temperature" refers to 20°C~30°C.

[0032] In this article, if there are multiple steps involved in the method flow, unless there is a clear different description in this article, there is no strict order restriction for the execution of these steps, and they can be executed in other orders than described. Moreover, any step can include multiple sub-steps or multiple stages, and these sub-steps or stages are not necessarily executed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be executed in turn, alternating or simultaneously with other steps or parts of sub-steps or stages of other steps.

[0033] The present application provides a method for preparing a perovskite battery, comprising the following steps:

[0034] Providing a basic battery component, the basic battery component including a perovskite layer;

[0035] The basic battery components are subjected to at least one cold treatment at a temperature between -18°C and 8°C.

[0036] The present application can fix the perovskite crystal phase, slow down the migration and recombination of electron holes, and maintain the stability of the perovskite crystal phase structure and performance by cold-treating the basic battery components. After freezing, the surface of the perovskite film is more uniform and dense, which can improve the ability of the perovskite layer to isolate water and oxygen, enhance the electrical performance and stability of the battery device, and extend the service life of the battery device, thereby ensuring that the battery device can be repeatedly prepared and used for a long period of time.

[0037] In a specific example, the cold treatment time is 2 hours to 26 hours.

[0038] Further, the time of cold treatment is 3 hours to 24 hours. Specifically, the time of cold treatment can be but not limited to 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 3 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours or 26 hours.

[0039] Further, the temperature of the cold treatment is -15°C to 5°C. Specifically, the temperature of the cold treatment can be, but is not limited to, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C or 5°C.

[0040] In a specific example, the cold treatment is performed in a water-free and oxygen-free environment. It is understandable that water vapor and oxygen may have an impact on perovskite photoelectric devices. The cold treatment is performed in a water-free and oxygen-free environment to prevent the condensed water during the freezing process from causing degradation and other damage to the device. It should be noted that the vacuum environment described above can be a water-free and oxygen-free environment, or the basic battery components can be sealed to make them water-free and oxygen-free. Preferably, the above-mentioned cold treatment is performed in a vacuum environment.

[0041] In a specific example, the basic battery assembly includes a substrate, a first transmission layer, and a perovskite layer stacked in sequence.

[0042] In a specific example, the basic battery assembly further includes a second transmission layer disposed on a surface of the perovskite layer away from the first transmission layer.

[0043] The materials of the first transmission layer and the second transmission layer independently have the structure shown in Formula I:

[0044] Formula I;

[0045] Among them, A represents the electron acceptor, D represents the electron donor, X represents the donor group, and Y represents the acceptor group.

[0046] It can be understood that the first transport layer is a hole transport layer and the second transport layer is an electron transport layer, or the second transport layer is a hole transport layer and the first transport layer is an electron transport layer.

[0047] In a specific example, the material of the hole transport layer is selected from , , , , , , , , , , , , , , , and Further, the material of the hole transport layer is 2,7-MeO-2PACz or TMPA-CPA .

[0048] The material of the electron transport layer may be, but is not limited to, one or both of fullerene and its derivatives.

[0049] It can be understood that the substrate is a transparent electrode, and the material of the transparent electrode can be but is not limited to one or more of FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide) and IWO (tungsten-doped indium oxide).

[0050] In a specific example, the material of the perovskite layer includes a perovskite metal halide; the chemical formula of the perovskite metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion. Further, A includes Cs + , K + , Rb + , monovalent amine cations and monovalent amidine cations. Non-limiting examples of monovalent amine cations include CH3NH3 + (Methylamine, MA + ), ammonium (NH4 + ). Non-limiting examples of monovalent amidino cations include NH2CH=NH2 + (Formamidine, can be written as FA+ ). B includes Pb 2+ Sn 2+ , Fe 2+ , Mn 2+ 、Ni 2+ ,Ge 2+ 、Co 2+ and Sb 2+ It is understood that X includes I - Br - and Cl - One or more of .

[0051] In a specific example, the step of preparing the basic battery component includes at least one annealing treatment.

[0052] It is understandable that the method for preparing the first transmission layer may be, but is not limited to, mixing the first transmission layer material with the first organic solvent to prepare a first transmission layer material solution, coating the first transmission layer material solution on the substrate, and then performing a first annealing treatment. Specifically, the coating adopts a slit coating, a doctor blade coating or a printing process.

[0053] Further, the method for preparing the perovskite layer may be, but is not limited to, mixing the perovskite metal halide with the second organic solvent to prepare a perovskite layer material solution, coating the perovskite layer material solution on the hole transport layer, removing the second organic solvent, and then performing a second annealing treatment. Specifically, the coating adopts a slit coating, a doctor blade coating or a printing process. Furthermore, the second organic solvent can be removed by a flash vacuum crystallization or a wind knife crystallization process.

[0054] In a specific example, the first transport layer and the perovskite layer can be prepared together. Optionally, the first transport layer and the perovskite layer can be prepared simultaneously by a coating method. Specifically, the first transport layer material and the perovskite layer material are mixed and dissolved in a third organic solution and then stirred, and then coated on the substrate. Furthermore, the third organic solvent can be removed by a flash vacuum crystallization or wind knife crystallization process.

[0055] The first organic solvent and the second organic solvent are each independently selected from at least one of methanol, N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), acetonitrile (ACN), γ-butyrolactone (GBL), dithiocarbylethanol (2-Me), isopropyl alcohol (IPA), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0056] Preferably, the first organic solvent comprises methanol. The second organic solvent and the third organic solvent each independently comprise N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0057] In a specific example, the conditions of the first annealing treatment and the second annealing treatment each independently include an annealing treatment temperature of 100° C. to 130° C. and an annealing treatment time of 5 min to 40 min.

[0058] Preferably, the conditions of the first annealing treatment include an annealing temperature of 100°C to 130°C and an annealing time of 5 min to 15 min. Specifically, the annealing temperature in the first annealing treatment may be but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C or 130°C, and the annealing time may be but is not limited to 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 15 min.

[0059] Preferably, the conditions of the second annealing treatment include an annealing temperature of 100°C to 130°C and an annealing time of 10 min to 40 min. Specifically, the annealing temperature in the second annealing treatment may be but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C or 130°C, and the annealing time may be but is not limited to 10 min, 15 min, 20 min, 25 min, 30 min, 35 min or 40 min.

[0060] Furthermore, the basic battery assembly also includes a metal electrode arranged on the side of the second transport layer away from the perovskite layer. It can be understood that the material of the metal electrode can be but is not limited to any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt) and magnesium (Mg) or any suitable mixture of the aforementioned elements.

[0061] In a specific example, the basic battery assembly further includes a buffer finishing layer between the second transport layer and the metal electrode.

[0062] It can be understood that the basic battery component can be a substrate, a first transmission layer and a perovskite layer stacked in sequence, the basic battery component can also be a substrate, a first transmission layer, a perovskite layer and a second transmission layer stacked in sequence, the basic battery component can also be a substrate, a first transmission layer, a perovskite layer, a second transmission layer and a metal electrode stacked in sequence, and the basic battery component can also be a substrate, a first transmission layer, a perovskite layer, a second transmission layer, a buffer modification layer and a metal electrode stacked in sequence.

[0063] The perovskite cell prepared by the above-mentioned perovskite cell preparation method can also improve the light conversion efficiency and reduce the problem of the decrease in light conversion efficiency of the cell device caused by the increase in temperature.

[0064] Furthermore, the present application also provides a perovskite battery prepared according to the above-mentioned preparation method.

[0065] Furthermore, the present application also provides a photovoltaic module, comprising the perovskite cell as described above.

[0066] The present application is further described in detail below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance given in the present application, and can also be based on the experimental manuals or conventional conditions in the art, can also be based on the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0067] In the following specific embodiments, the measured parameters of raw material components may have slight deviations within the range of weighing accuracy unless otherwise specified. For temperature and time parameters, acceptable deviations caused by instrument test accuracy or operation accuracy are allowed. "Normal temperature" refers to 25°C; "normal pressure" refers to 100KPa or 101KPa.

[0068] Example 1

[0069] (1) Preparation of perovskite precursor solution: Dissolve the perovskite material CsPbI3 and the transport functional material TMPA-CPA in a DMF:DMSO = 4:1 (volume ratio) solvent under stirring at 25°C overnight, wherein the concentration of the perovskite material is 1.5 M, and the concentration of the transport functional material TMPA-CPA is 0.5 mg / mL.

[0070] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0071] (3) The hole transport material solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film, which is then annealed at 120° C. for 10 minutes to grow a hole transport layer film and bond it to ITO.

[0072] (4) The perovskite precursor solution prepared in step (1) is injected into a slit coater, coated on the surface of the hole transport layer to prepare a wet film, the organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals to obtain a perovskite layer.

[0073] (5) The film obtained in step (4) is naturally cooled to room temperature and then vacuum dried and frozen at a temperature of -15°C for 3 hours.

[0074] (6) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0075] (7) The device obtained in step (6) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0076] Example 2

[0077] (1) Preparation of perovskite precursor solution and hole transport material solution: Dissolve the perovskite material CsPbI3 in a DMF:DMSO = 4:1 (volume ratio) solvent at 25°C with stirring overnight to prepare a perovskite precursor solution with a concentration of 1.5 M. Dissolve the transport functional material TMPA-CPA in a methanol solvent to prepare a hole transport material solution with a concentration of 0.5 mg / mL.

[0078] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0079] (3) The hole transport material solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film, which is then annealed at 120° C. for 10 minutes to grow a hole transport layer film and bond it to ITO.

[0080] (4) The perovskite precursor solution prepared in step (1) is injected into a slit coater, coated on the surface of the hole transport layer to prepare a wet film, the organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals to obtain a perovskite layer.

[0081] (5) The film obtained in step (4) is naturally cooled to room temperature and then vacuum dried and frozen at a temperature of 0°C for 3 hours;

[0082] (6) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0083] (7) The device obtained in step (6) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0084] Example 3

[0085] (1) Preparation of perovskite precursor solution and hole transport material solution: Dissolve the perovskite material CsPbI3 in a DMF:DMSO = 4:1 (volume ratio) solvent at 25°C with stirring overnight to prepare a perovskite precursor solution with a concentration of 1.5 M. Dissolve the transport functional material TMPA-CPA in a methanol solvent to prepare a hole transport material solution with a concentration of 0.5 mg / mL.

[0086] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0087] (3) The hole transport material solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film, which is then annealed at 120° C. for 10 minutes to grow a hole transport layer film and bond it to ITO.

[0088] (4) The perovskite precursor solution prepared in step (1) is injected into a slit coater, coated on the surface of the hole transport layer to prepare a wet film, the organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals to obtain a perovskite layer.

[0089] (5) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0090] (6) The device obtained in step (5) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0091] (7) The device obtained in step (6) is vacuum dried and frozen at a temperature of -5°C for 24 hours.

[0092] Comparative Example 1

[0093] (1) Preparation of perovskite precursor solution: Dissolve the perovskite material CsPbI3 and the transport functional material TMPA-CPA in a DMF:DMSO = 4:1 (volume ratio) solvent under stirring at 25°C overnight, wherein the concentration of the perovskite material is 1.5 M, and the concentration of the transport functional material TMPA-CPA is 0.5 mg / mL.

[0094] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0095] (3) The perovskite precursor solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film. The organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals and the first transport layer, thereby obtaining the first transport layer and the perovskite layer.

[0096] (4) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0097] (5) The device obtained in step (4) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0098] Comparative Example 2

[0099] (1) Preparation of perovskite precursor solution: Dissolve the perovskite material CsPbI3 and the transport functional material TMPA-CPA in a DMF:DMSO = 4:1 (volume ratio) solvent under stirring at 25°C overnight, wherein the concentration of the perovskite material is 1.5 M, and the concentration of the transport functional material TMPA-CPA is 0.5 mg / mL.

[0100] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0101] (3) The perovskite precursor solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film. The organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals and the first transport layer, thereby obtaining the first transport layer and the perovskite layer.

[0102] (5) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0103] (6) The device obtained in step (5) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0104] (7) The device obtained in step (6) is vacuum dried and frozen at a temperature of -30°C for 24 hours.

[0105] Comparative Example 3

[0106] (1) Preparation of perovskite precursor solution: Dissolve the perovskite material CsPbI3 and the transport functional material TMPA-CPA in a DMF:DMSO = 4:1 (volume ratio) solvent under stirring at 25°C overnight, wherein the concentration of the perovskite material is 1.5 M, and the concentration of the transport functional material TMPA-CPA is 0.5 mg / mL.

[0107] (2) Take a material with a resistance of about 20 Ω / m 2 Sheet resistance ITO coated 1.1mm thick 10*10cm 2 Glass was used as the substrate. The substrate was ultrasonically cleaned with surfactant, deionized water, acetone and isopropanol for 20 min respectively, and then immersed in isopropanol for later use. The washed substrate was treated with a plasma cleaner for 20 min.

[0108] (3) The perovskite precursor solution prepared in step (1) is injected into a slit coater and coated on the surface of the substrate to prepare a wet film. The organic solvent is removed by air knife crystallization, and then annealed at 120° C. for 30 minutes to grow perovskite crystals and the first transport layer, thereby obtaining the first transport layer and the perovskite layer.

[0109] (5) In 1×10 -4 Under a vacuum level of 1.5 Pa, a C60 layer (25 nm) was deposited as an electron transport layer and a BCP layer (6 nm) was deposited as a buffer modification layer, and then 100 nm of Ag was deposited as the top metal electrode.

[0110] (6) The device obtained in step (5) is packaged with butyl rubber to obtain the perovskite solar cell of this embodiment.

[0111] (7) The device obtained in step (6) is vacuum dried and frozen at a temperature of -15°C for 32 hours.

[0112] Test method: Using a solar simulator (Xenon lamp with AM1.5G filter) in air at room temperature at AM1.5G (100DmWDcm -2 ) The device JV characteristics were measured under . A standard Si diode with a KG5 filter was purchased from and calibrated by the Fujian Photovoltaic Test and Metrology Institute. The light intensity was calibrated using a Si cell as a reference cell to make the spectrum mismatch consistent. The JV characteristics were recorded using a Keithley 2400 source meter unit.

[0113] The performance of the perovskite cells prepared in the above-mentioned embodiments and comparative examples is summarized in the following Table 1.

[0114] Table 1

[0115]

[0116] like Figure 1 The figure shows the change of the photoelectric conversion efficiency of the perovskite solar cell modules obtained in Examples 1, 2, 3 and Comparative Examples 1, 2, 3 under continuous illumination. It can be seen that the perovskite solar cell modules subjected to the freezing treatment of the present application still have good photoelectric conversion efficiency under long-term continuous illumination, reflecting its good stability.

[0117] According to the above comparison, it can be seen that the performance conversion rate of the perovskite battery of the embodiment after freezing treatment is better than that of the perovskite battery of the comparison example. However, the coordination of different freezing treatment objects and freezing conditions in the battery preparation process also has a great influence on other performances of the battery. The freezing conditions need to be within the scope of this application to improve the performance conversion rate of the perovskite battery. Further optimization of the freezing conditions can enable the perovskite battery to improve other battery performance while ensuring a good conversion rate.

[0118] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0119] The above-described embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in detail, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A method for preparing a perovskite battery, characterized in that: The following steps are involved: Providing a basic battery component, the basic battery component comprising a perovskite layer; The basic battery assembly is subjected to at least one cold treatment at a temperature of -18°C to 8°C.

2. The preparation method according to claim 1, characterized in that The cold treatment time is 2 hours to 26 hours.

3. The preparation method according to claim 1, characterized in that: The temperature of the cold treatment is -15°C to 5°C.

4. The preparation method according to claim 1, characterized in that: The basic battery assembly includes a substrate, a first transmission layer and the perovskite layer which are stacked in sequence.

5. The preparation method according to claim 4, characterized in that: The basic battery assembly also includes a second transmission layer disposed on a surface of the perovskite layer away from the first transmission layer.

6. The preparation method according to claim 5, characterized in that: The materials of the first transmission layer and the second transmission layer each independently have a structure shown in Formula I: Formula I; Among them, A represents the electron acceptor, D represents the electron donor, X represents the donor group, and Y represents the acceptor group.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The steps of preparing the basic battery assembly include at least one annealing treatment.

8. The preparation method according to any one of claims 1 to 6, characterized in that: The cold treatment is performed in an environment free of water and oxygen.

9. A perovskite battery, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

10. A photovoltaic module, characterized in that: Comprising the perovskite cell as claimed in claim 9.

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