Perovskite solar cell and preparation method thereof, perovskite thin film, photovoltaic module, power utilization device and power generation device

Abstract

The invention provides a perovskite solar cell and a preparation method thereof, a perovskite thin film, a photovoltaic module, a power utilization device and a power generation device, the perovskite solar cell comprises the perovskite thin film, at least one surface of the perovskite thin film is provided with cracks, the thickness of the perovskite thin film is marked as H1, and the thickness of the perovskite thin film is marked as H2. The average depth of the cracks along the thickness direction of the perovskite thin film is recorded as H2, and the H1 and the H2 meet the condition that H2 / H1 is equal to 1%-55%, so that the stability of the perovskite solar cell can be improved.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to a perovskite solar cell and its preparation method, perovskite thin film, photovoltaic module, electrical device and power generation device. Background Technology

[0002] The statements herein are provided only as background information in connection with this application and do not necessarily constitute prior art.

[0003] Perovskite solar cells are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite crystalline materials. They represent the third generation of solar cells and possess numerous advantages, including high photoelectric conversion efficiency, simple fabrication processes, and low production costs, leading to extensive research in recent years. However, large-scale commercial application of perovskite solar cells remains a considerable distance away, and improving their stability is one of the key issues that urgently needs to be addressed. Summary of the Invention

[0004] This application provides a perovskite solar cell and its preparation method, a perovskite thin film, a photovoltaic module, an electrical device, and a power generation device, aiming to improve the stability of perovskite solar cells.

[0005] In a first aspect, this application provides a perovskite solar cell, the perovskite solar cell comprising a perovskite thin film, at least one surface of the perovskite thin film having a crack, the thickness of the perovskite thin film denoted as H1, the average depth of the crack along the thickness direction of the perovskite thin film denoted as H2, wherein H1 and H2 satisfy: H2 / H1 = 1%~55%.

[0006] By designing the perovskite thin film in the above-mentioned perovskite solar cell to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to meet the above conditions, it is easy to form grain boundaries and concave crystal planes at the cracks. During the coating process, the material of the transport layer can be accumulated, increasing the contact area between the material of the perovskite thin film and the material of the transport layer. At the same time, point contact structures can be formed at the crack concave surface. The amount of transport layer material at this concave surface is greater than or equal to that at other contact surfaces, which can easily promote photon separation. It can also improve the interface filling of the perovskite solar cell and enhance the stability of the device, thereby improving the stability of the perovskite solar cell.

[0007] In some implementations, H2 / H1 = 4%~25%. This can further improve the stability of perovskite solar cells.

[0008] In some embodiments, H1 is 150nm~1200nm.

[0009] In some implementations, the H2 is 5nm~660nm.

[0010] In some embodiments, the average number of cracks per square centimeter of the perovskite thin film is 400 to 32,000. This design allows for a certain increase in the open-circuit voltage of the perovskite solar cell. Furthermore, because photons generated during illumination can be rapidly guided away through the transport layer deposited at the cracks, the stability of the perovskite solar cell can be further enhanced, while also extending its lifespan.

[0011] In some embodiments, the average number of cracks per square centimeter of the perovskite thin film is 1,800 to 16,000. This design can further enhance the stability of the perovskite solar cell and further improve its lifespan.

[0012] In some embodiments, the area of ​​one surface of the perovskite thin film is denoted as A1, and the total area of ​​the cracks on that surface is denoted as A2, wherein A1 and A2 satisfy: A2 / A1 = 0.2%~30%. This design ensures that the contact area between the perovskite thin film material and the transport layer material is within a reasonable range, which can further improve the stability of the perovskite solar cell.

[0013] In some embodiments, the average spacing between the cracks is 5 μm to 48 μm. This design can further enhance the stability of perovskite solar cells and further improve their lifespan.

[0014] In some embodiments, the shape of the crack includes one or both of the following: elongated and pore-shaped.

[0015] In some embodiments, the average difference between the surface potential at the crack on the perovskite thin film and the surface potential at other locations on the same surface is 8mV to 80mV. This is beneficial for further improving the open-circuit voltage of the perovskite solar cell.

[0016] In some embodiments, the perovskite material in the perovskite film includes a perovskite-type metal halide, the chemical formula of which includes one or more of ABX3 and A2CDX6; wherein A is a monovalent cation, B is a divalent cation, C is a monovalent cation, D is a trivalent cation, and X is a monovalent anion.

[0017] In some embodiments, A is one or more of a monovalent inorganic cation and a monovalent organic cation, wherein the monovalent inorganic cation includes Li. + Na + K +、Rb + and Cs + One or more of the following, wherein the monovalent organic cation includes one or more of methylamine cation, ethylamine cation, propylamine cation, butylamine cation, pentamine cation, hexamine cation, formamidin cation and imidazole cation.

[0018] In some embodiments, B includes a divalent cation of one or more elements selected from lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium.

[0019] In some implementations, C includes Cs + Ag + K + and Ru + One or more of them.

[0020] In some implementations, D includes Bi. 3+ Ni 3+ Fe 3+ Sb 3+ and In 3+ One or more of them;

[0021] In some embodiments, X comprises a halide ion or a halide-like ion, said halide ion including F - Cl - ,Br - and I - One or more of the following, wherein the halide-like ions include CN - SCN - OCN - N3 - CF4SO4 - HCOO - C6H5S - CH3COO - CF3COO - BH4 - CH3S - ClO4 - BF4 - and BCl4 - One or more of them.

[0022] In some embodiments, the perovskite solar cell further includes a first electrode, a first transport layer, a second transport layer, and a second electrode, wherein the first electrode, the first transport layer, the perovskite thin film, the second transport layer, and the second electrode are stacked sequentially, the first transport layer is either a hole transport layer or an electron transport layer, and the second transport layer is either a hole transport layer or an electron transport layer; the crack is located on the surface of the perovskite thin film away from the first transport layer.

[0023] In some embodiments, the material of the transport layer corresponding to the crack is embedded in the crack. This promotes contact between the perovskite thin film material and the transport layer material, which is beneficial for further improving the stability of the perovskite solar cell.

[0024] In some embodiments, the perovskite solar cell is an inverted pin-type cell, the first electrode is the light incident surface, the first transport layer is a hole transport layer, and the second transport layer is an electron transport layer.

[0025] A second aspect of this application provides a method for preparing a perovskite solar cell, comprising the step of preparing a perovskite thin film; wherein at least one surface of the perovskite thin film has cracks, the thickness of the perovskite thin film is denoted as H1, the average depth of the cracks along the thickness direction of the perovskite thin film is denoted as H2, and H1 and H2 satisfy: H2 / H1 = 1%~55%.

[0026] By designing the perovskite thin film in the above-mentioned perovskite solar cell to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to meet the above conditions, the stability of the perovskite solar cell can be improved.

[0027] In some embodiments, the step of preparing the perovskite thin film includes:

[0028] A perovskite precursor solution containing perovskite material is coated on the surface of a substrate, and after solvent quenching, a perovskite thin film intermediate is formed.

[0029] The perovskite film intermediate is placed in a sealed environment, and a gas containing amine compounds is introduced into the sealed environment. After annealing, the perovskite film is formed under a relative humidity of 1% to 85%.

[0030] In the above embodiments, annealing is performed by introducing a gas containing amine compounds into a closed environment, and secondary crystallization occurs in the perovskite film intermediate under relative humidity conditions of 1% to 85%, which can form a perovskite film with cracks.

[0031] In some embodiments, the relative humidity is 1% to 50%. This further improves the stability of perovskite solar cells, and controlling the relative humidity range can create crack morphologies that are beneficial to cell stability.

[0032] In some embodiments, the molar mass of the amine compound is 17 g / mol to 210 g / mol.

[0033] In some embodiments, the amine compounds include one or more of aliphatic amines, alkanolamines, amides, alicyclic amines, aromatic amines, and ammonia.

[0034] In some embodiments, the aliphatic amine compound includes one or more of methylamine, dimethylamine, trimethylamine, ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, and n-butylamine.

[0035] In some embodiments, the alkanolamine compound includes one or more of ethanolamine and aminomethanol.

[0036] In some embodiments, the amide compound includes one or more of formamide, acetamide, and butyramide.

[0037] In some embodiments, the alicyclic amine compound includes one or more of cyclohexylamine and piperazine.

[0038] In some embodiments, the aromatic amine compound includes one or more of aniline and o-phenylenediamine.

[0039] In some embodiments, the annealing process conditions include: an annealing temperature of 100°C to 180°C, an annealing time of 6 min to 25 min, and a gap between the perovskite film intermediate and the heating source.

[0040] In some embodiments, the crack forms on the surface of the perovskite film away from the substrate, and the surface of the perovskite film away from the substrate is in contact with the electron transport layer.

[0041] A third aspect of this application provides a perovskite thin film, wherein at least one surface of the perovskite thin film has a crack, the thickness of the perovskite thin film is denoted as H1, the average depth of the crack along the thickness direction of the perovskite thin film is denoted as H2, and H1 and H2 satisfy: H2 / H1=1%~55%.

[0042] By designing the perovskite thin film to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to meet the above conditions, the stability of perovskite solar cells can be improved.

[0043] In some embodiments, the perovskite thin film is the perovskite thin film in the perovskite solar cell described in the first aspect of this application.

[0044] A fourth aspect of this application provides a photovoltaic module comprising at least one of the perovskite solar cells described in the first aspect of this application, the perovskite solar cells prepared by the preparation method described in the second aspect of this application, and the perovskite thin films described in the third aspect of this application.

[0045] The aforementioned photovoltaic module includes at least one of the perovskite solar cell provided in this application, the perovskite solar cell prepared by the preparation method provided in this application, and the perovskite thin film provided in this application, and therefore has at least the same advantages as at least one of the perovskite solar cell, the perovskite solar cell prepared by the preparation method, and the perovskite thin film.

[0046] A fifth aspect of this application provides an electrical device comprising at least one of the perovskite solar cell described in the first aspect of this application, a perovskite solar cell prepared by the preparation method described in the second aspect of this application, a perovskite thin film described in the third aspect of this application, and a photovoltaic module described in the fourth aspect of this application.

[0047] The aforementioned electrical devices include at least one of the perovskite solar cells provided in this application, perovskite solar cells prepared by the preparation method provided in this application, perovskite thin films provided in this application, and photovoltaic modules provided in this application, and therefore have at least the same advantages as at least one of the perovskite solar cells, perovskite solar cells prepared by the preparation method, perovskite thin films, and photovoltaic modules.

[0048] A sixth aspect of this application provides a power generation device, comprising at least one of the perovskite solar cell described in the first aspect of this application, a perovskite solar cell prepared by the preparation method described in the second aspect of this application, a perovskite thin film described in the third aspect of this application, and a photovoltaic module described in the fourth aspect of this application.

[0049] The aforementioned power generation device includes at least one of the perovskite solar cell provided in this application, the perovskite solar cell prepared by the preparation method provided in this application, the perovskite thin film provided in this application, and the photovoltaic module provided in this application, and therefore has at least the same advantages as at least one of the perovskite solar cell, the perovskite solar cell prepared by the preparation method, the perovskite thin film, and the photovoltaic module.

[0050] Details of one or more embodiments of this application are set forth in the following drawings and description. Other features, objects, and advantages of this application will become apparent from the specification, drawings, and claims. Attached Figure Description

[0051] To better describe and illustrate embodiments or examples of the applications disclosed herein, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the embodiments or examples currently described, or the best mode of conduct of these applications as currently understood. Furthermore, throughout the drawings, the same reference numerals denote the same parts. In the drawings:

[0052] Figure 1 This is a schematic diagram of a perovskite solar cell according to an embodiment of this application; it includes a first electrode, a first transport layer, a perovskite layer, a second transport layer, and a second electrode.

[0053] Figure 2 This is a schematic diagram of another embodiment of the perovskite solar cell of this application; it includes a substrate layer, a first electrode, a first transport layer, a perovskite layer, a second transport layer, and a second electrode.

[0054] Figure 3 This is a schematic diagram of a perovskite solar cell according to another embodiment of this application.

[0055] Figure 4 This is a schematic diagram of an electrical device using a perovskite solar cell as a power source according to one embodiment of this application.

[0056] Figure 5 SEM images of the perovskite thin film prepared in Example 1 of this application at different magnifications and at different locations.

[0057] Figure 6 SEM images of the perovskite thin film prepared in Example 1 of this application at different magnifications and at different locations.

[0058] Figure 7 This is a SEM image of the electron transport layer prepared in Example 1 of this application.

[0059] Explanation of reference numerals in the attached figures: 100 is a perovskite solar cell; 110 is a substrate layer; 120 is a first electrode; 130 is a first transport layer; 140 is a perovskite layer; 150 is a second transport layer; 160 is a second electrode; P1 is a first notched area; P2 is a second notched area; P3 is a third notched area; 20 is an electrical device. Detailed Implementation

[0060] The following detailed description, with appropriate reference to the accompanying drawings, discloses some embodiments of the perovskite solar cell and its fabrication method, perovskite thin film, photovoltaic module, power supply device, and power generation device of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0061] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this document; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, stating that a parameter is an integer ≥2 is equivalent to disclosing that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, stating that a parameter is an integer selected from "2-10" is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0062] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0063] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0064] Unless otherwise specified, the terms "comprising," "containing," and "including" as used in this application can be open-ended or closed-ended. In open-ended cases, for example, "comprising," "containing," and "including" can mean that other members, elements, or method steps not listed can also be included, or that only the listed members, elements, or method steps can be included.

[0065] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". Further, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0066] In this application, unless otherwise specified, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0067] In this application, the terms "multiple" or "various" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" means one or more types.

[0068] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0069] In this application, if the unit of a data range is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 3~5 h or 3-5 h both indicate that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0070] In the fabrication of large-area perovskite solar cells, the large roughness fluctuations of the perovskite film make it difficult for subsequent film layers, such as electron transport layers, to completely cover it, resulting in the inefficient extraction of the generated excitons and thus limiting the stability of perovskite solar cells.

[0071] Based on this, one embodiment of this application provides a perovskite solar cell, which includes a perovskite thin film, at least one surface of the perovskite thin film having a crack, the thickness of the perovskite thin film is denoted as H1, the average depth of the crack along the thickness direction of the perovskite thin film is denoted as H2, and H1 and H2 satisfy: H2 / H1=1%~55%.

[0072] By designing the perovskite thin film in the aforementioned perovskite solar cell to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to satisfy the above conditions, it is possible to form grain boundaries and concave crystal planes at the cracks. During the coating process, the material of the transport layer can be accumulated, increasing the contact area between the material of the perovskite thin film and the material of the transport layer. At the same time, point contact structures can be formed at the concave cracks, where the amount of transport layer material is greater than or equal to that of other contact surfaces, which facilitates photon separation. This also improves the interface filling of the perovskite solar cell, enhancing device stability and thus improving the stability of the perovskite solar cell while maintaining a high photoelectric conversion efficiency. Specifically, H2 / H1 includes, but is not limited to, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or any range between the foregoing.

[0073] Non-limitingly, the thickness H1 of the perovskite thin film can be determined using SEM (Scanning Electron Microscopy) or a profilometer. For example, a complete perovskite solar cell device can be cut in the middle to obtain a cross-section containing the thickness of the complete device. After preparing the sample, an SEM image can be taken, and then the thickness of the perovskite thin film can be measured. Alternatively, the perovskite solar cell module can be fractured to obtain a trapezoidal fractured surface sample. This sample can be ablated with a laser, first ablated to the surface of the perovskite thin film, and then ablated to the bottom of the perovskite thin film in adjacent areas until the light-receiving layer is reached. Then, the thickness of the perovskite thin film can be measured using a profilometer. Non-limitingly, the average depth H2 of the crack along the thickness direction of the perovskite thin film can be determined using AFM (Atomic Force Microscopy) or a profilometer. For example, a perovskite thin film surface with cracks can be obtained by fractured perovskite solar cell module. Then, the depth of 20 cracks along the thickness direction of the perovskite thin film can be randomly measured using AFM or a profilometer, and the average value can be taken to obtain the average depth H2. Calculate the ratio of H2 to H1, i.e., H2 / H1, from the measured H1 and H2.

[0074] In some implementations, H2 / H1 = 4%~25%. This can further improve the stability of perovskite solar cells.

[0075] In some implementations, H1 is 150nm to 1200nm. Specifically, H1 includes, but is not limited to: 150nm, 300nm, 500nm, 700nm, 900nm, 1000nm, 1200nm, or any range between the two mentioned above.

[0076] In some implementations, H2 is 5nm to 660nm. Specifically, H2 includes, but is not limited to: 5nm, 10nm, 30nm, 50nm, 80nm, 100nm, 130nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 301nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 630nm, 660nm, or any range between the foregoing.

[0077] Non-limiting, for example: when the thickness H1 of the perovskite film is 1200 nm, the average depth H2 of the crack along the thickness direction of the perovskite film can be 660 nm.

[0078] In some embodiments, the average number of cracks per square centimeter of the perovskite thin film is between 400 and 32,000. This design allows for a certain increase in the open-circuit voltage of the perovskite solar cell. Furthermore, because photons generated during illumination can be rapidly conducted away through the transport layer deposited at the cracks, the stability of the perovskite solar cell can be further enhanced, while also extending its lifespan. Specifically, the average number of cracks includes, but is not limited to: 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 4000, 6000, 8000, 10000, 12000, 14000, 16000, 18000, 20000, 24000, 28000, 32000, or any range between the foregoing.

[0079] Without limitation, SEM can be used to determine the average number of cracks per square centimeter of surface area of ​​a perovskite film; for example, an SEM image of a surface of a perovskite film can be taken using an SEM, 20 locations can be randomly selected, each location having an area of ​​1 square centimeter, the number of cracks at these locations can be tested, and the average number of cracks can be obtained by taking the average value.

[0080] In some embodiments, the average number of cracks per square centimeter of the perovskite thin film is 1,800 to 16,000. This design allows for a certain increase in the open-circuit voltage of the perovskite solar cell. Furthermore, because photons generated during illumination can be rapidly conducted away through the transport layer deposited at the cracks, the stability of the perovskite solar cell can be further enhanced, while also extending its lifespan.

[0081] In some embodiments, the area of ​​one surface of the perovskite thin film is denoted as A1, and the total area of ​​cracks on that surface is denoted as A2. A1 and A2 satisfy the condition: A2 / A1 = 0.2%~30%. This design ensures that the contact area between the perovskite thin film material and the transport layer material is within a reasonable range, which can further improve the stability of the perovskite solar cell. Specifically, A2 / A1 includes, but is not limited to: 0.2%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 27%, and 30%.

[0082] Non-limiting, the area A1 of a surface of a perovskite thin film and the total area A2 of cracks on that surface can be determined by SEM; for example, an SEM image of a surface of a perovskite thin film can be taken using SEM, and the total area A2 of cracks on that surface and the area A1 of the perovskite thin film surface can be obtained by image recognition technology, and the ratio of the two can be calculated to obtain A2 / A1.

[0083] It should be noted that the area of ​​one surface of the perovskite thin film can be selected according to actual conditions and requirements. It is not limited to this; a perovskite thin film with an area of ​​several square centimeters or square meters can be selected, such as 0.07 cm². 2 1cm 2 1m 2 2m 2 2.4*1.2m 2 wait.

[0084] In some embodiments, the average spacing between cracks is 5 μm to 48 μm. This design allows for a certain increase in the open-circuit voltage of the perovskite solar cell. Furthermore, because photons generated during illumination can be rapidly guided away through the transport layer deposited at the cracks, the stability of the perovskite solar cell can be further enhanced, and the cell's lifespan can be extended. Specifically, the average spacing between cracks includes, but is not limited to: 5 μm, 5.6 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 43 μm, 45 μm, 48 μm, or any range between the foregoing.

[0085] In a non-limiting manner, SEM can be used to determine the average spacing between cracks; for example, an SEM image of a surface of a perovskite film can be taken, 20 cracks can be randomly selected, and the distance between the center point of each crack and the center point of the nearest crack can be measured using the image scale. The average spacing between cracks can be obtained by taking the average value.

[0086] In some implementations, the crack shape includes one or both of the following: elongated and pore-shaped.

[0087] As a non-limiting example, the aspect ratio of the elongated crack is 3 to 20. It is understood that the above aspect ratios include, but are not limited to: 3, 5, 7, 10, 12, 14, 16, 18, 20 or any range between the foregoing.

[0088] As a non-limiting example, the pore size of the porous crack is 0.2 μm to 1 μm. It is understood that the above pore size includes, but is not limited to: 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm or any range between the foregoing.

[0089] In some embodiments, the average difference between the surface potential at cracks and the surface potential at non-cracked areas on the perovskite thin film is 8mV to 80mV. That is, the average surface potential at cracks on the perovskite thin film relative to the surface potential at non-cracked areas is 8mV to 80mV. The higher surface potential at cracks makes the cracks more suitable as electron extraction channels, which is beneficial for increasing the open-circuit voltage of the perovskite solar cell. Specifically, the aforementioned average difference includes, but is not limited to: 8mV, 10mV, 15mV, 20mV, 25mV, 30mV, 35mV, 40mV, 45mV, 50mV, 55mV, 60mV, 65mV, 70mV, 75mV, and 80mV.

[0090] Non-limiting, AFM can be used to determine the surface potential at cracked and non-cracked locations on a perovskite thin film. For example, AFM can be used to randomly test the surface potential at 20 cracked locations and 20 non-cracked locations on a perovskite thin film, and the average value can be taken. Then, the difference between the two average values ​​is taken to obtain the average difference between the surface potential at cracked locations and the surface potential at non-cracked locations on the perovskite thin film.

[0091] In some embodiments, the perovskite material in the perovskite film includes a perovskite-type metal halide, the chemical formula of which includes one or more of ABX3 and A2CDX6; wherein A is a monovalent cation, B is a divalent cation, C is a monovalent cation, D is a trivalent cation, and X is a monovalent anion.

[0092] In some embodiments, A is one or more of a monovalent inorganic cation and a monovalent organic cation, including Li. + Na + K + 、Rb + and Cs + One or more of the following, the monovalent organic cations include one or more of the following: methylamine cation, ethylamine cation, propylamine cation, butylamine cation, pentamine cation, hexamine cation, formamidin cation, and imidazole cation. Optionally, A includes organic amine ions and Cs. + One or more of them.

[0093] In some embodiments, B includes a divalent cation of one or more elements selected from lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium.

[0094] In some implementations, C includes Cs + Ag + K + and Ru + One or more of them.

[0095] In some implementations, D includes Bi. 3+ Ni 3+ Fe 3+ Sb 3+ and In 3+ One or more of them. Optionally, D includes In. 3+ Bi 3+ and Sb 3+ One or more of them.

[0096] In some embodiments, X comprises a halide ion or a halide-like ion, the halide ion including F - Cl - ,Br - and I - One or more of the following, halide ions including CN - SCN - OCN - N3 - CF4SO4 - HCOO - C6H5S - CH3COO - CF3COO - BH4 - CH3S - ClO4 - BF4 - and BCl4 -One or more of them. Optionally, X includes Cl. - ,Br - and I - One or more of them.

[0097] In some embodiments, the perovskite solar cell further includes a first electrode, a first transport layer, a second transport layer, and a second electrode, wherein the first electrode, the first transport layer, the perovskite thin film, the second transport layer, and the second electrode are stacked sequentially, the first transport layer is one of a hole transport layer or an electron transport layer, and the second transport layer is another of a hole transport layer or an electron transport layer; the crack is located on the surface of the perovskite thin film away from the first transport layer.

[0098] In some embodiments, the material of the transport layer corresponding to the crack surface is embedded in the crack. This promotes contact between the perovskite thin film material and the transport layer material, which is beneficial for further improving the stability of the perovskite solar cell. It can be understood that either the electron transport layer material or the hole transport layer material is embedded in the crack.

[0099] In some embodiments, the first transport layer is a hole transport layer and the second transport layer is an electron transport layer.

[0100] In some other embodiments, the first transport layer is an electron transport layer and the second transport layer is a hole transport layer.

[0101] The aforementioned perovskite thin film, also known as the perovskite layer, is the light-absorbing layer in a perovskite solar cell. This perovskite solar cell can be either a reverse-pin cell or a conventional nip cell. When the perovskite solar cell operates, after the light-absorbing layer is exposed to light, the internal electrons gain energy and break free from the layer's binding force to form negatively charged electron carriers and positively charged hole carriers, thus creating electron-hole pairs. These free electrons and holes travel in opposite directions through corresponding transport layers, causing electrons and holes to flow and forming an external current, thus converting light energy into electrical energy. Furthermore, after absorbing photons, the perovskite layer is stimulated to generate electron-hole pairs. These pairs further dissociate to form free carriers with opposite charges. The free electrons travel through the electron transport layer to the positive electrode, and the free holes travel through the hole transport layer to the negative electrode. Both types of free carriers are collected by their respective electrodes, further forming a photocurrent in the circuit of the perovskite solar cell.

[0102] The electron transport layer can extract and transport electron carriers and block free holes from passing through.

[0103] The hole transport layer can extract and transport hole carriers and block free electrons from passing through.

[0104] It is understood that in a perovskite solar cell, one of the first and second electrodes serves as the positive electrode, collecting electron carriers transported via the electron transport layer, while the other serves as the negative electrode, collecting hole carriers transported via the hole transport layer. In some embodiments, the perovskite solar cell 100 includes... Figure 1 The structure shown includes a first electrode 120, a first transport layer 130, a perovskite layer 140, a second transport layer 150, and a second electrode 160 arranged sequentially. Further, the structural layers are stacked sequentially as shown.

[0105] In other embodiments, the perovskite solar cell 100 includes... Figure 2 The structure shown includes a substrate layer 110, a first electrode 120, a first transport layer 130, a perovskite layer 140, a second transport layer 150, and a second electrode 160, which are arranged sequentially. Further, the structural layers are stacked sequentially as shown.

[0106] In some embodiments, perovskite solar cells include Figure 3 The structure shown (a vertical cross-sectional view of the device) includes a substrate layer 110, a first electrode 120, a first transport layer 130, a perovskite layer 140, a second transport layer 150, and a second electrode 160, stacked sequentially. P1, P2, and P3 are cross-layer etched regions used to divide the large-area film into different components, forming a series cell structure. P1, P2, and P3 connect spaced-apart structural layers, creating a circuit between the first and second electrodes, thus forming a perovskite solar cell module. P1, P2, and P3 can each be an independent linear etched region, also called an etch line. P1, P2, and P3 can each be an independent laser etched region. The number of P1, P2, and P3 can be one or more. Figure 3 In the first electrode, P1 extends from the surface of the first transport layer through the first transport layer and the bottom of the first electrode to the substrate layer, so that the left and right sides of the P1 are not connected to each other (to achieve insulation). The material in the P1 etching area is the same as that in the perovskite layer. P2 extends from the surface of the second transport layer through the second transport layer, the perovskite layer, and the first transport layer to the surface of the first electrode. The material in the P2 etching area is the same as that of the second electrode. P3 extends from the surface of the second electrode through the second electrode, the second transport layer, the perovskite layer, and the first transport layer to the surface of the first electrode. The P3 etching area is not filled with material.

[0107] In some implementations, the width of P1 is 10~50μm, for example 30μm.

[0108] In some implementations, the width of P2 is 10~200μm, for example 150μm. Further, the interval between P2 and P1 can be 20~80μm, for example 20μm.

[0109] In some implementations, the width of P3 is 10~50μm, for example 15μm. Further, the interval between P3 and P2 can be 20~40μm, for example 20μm.

[0110] In some embodiments, P1 in the perovskite solar cell can extend from the surface of the first transport layer to the bottom of the first electrode, and the filling material of P1 is consistent with the perovskite layer (e.g., Figure 3 (As shown). In other embodiments, P1 in the perovskite solar cell can extend from the surface of the first electrode to the bottom, and the filling material in P1 is consistent with the first transport layer.

[0111] In some implementations, the P3 etched region in a perovskite solar cell may only have the second electrode severed, reducing short circuits between adjacent solar cells. The P3 etched region may also be filled with insulating material.

[0112] In some embodiments, the perovskite solar cell is an inverted pin-type cell, with the first electrode being the light incident surface, the first transport layer being a hole transport layer, and the second transport layer being an electron transport layer.

[0113] In some embodiments, one of the "first electrode" and the "second electrode" is a transparent electrode for light incident. In some embodiments, the first electrode is a transparent electrode.

[0114] In some embodiments, the substrate material is one or more of glass and transparent organic polymers. When the first electrode is a transparent electrode, it is generally selected from non-transparent materials such as indium tin oxide (ITO), lanthanide-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, boron-doped zinc oxide (BZO), zinc aluminum oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), and metallic materials.

[0115] In some embodiments, the material of the first electrode includes one or more of organic conductive materials, inorganic conductive materials, and organic-inorganic mixed conductive materials. Examples of materials for the first electrode include, but are not limited to, one or more of transparent conductive metal oxides, carbon, metals, and their alloys.

[0116] In some embodiments, the material of the first electrode includes one or more of indium tin oxide (ITO), lanthanide-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, boron-doped zinc oxide (BZO), zinc aluminum oxide (AZO), indium zinc oxide (IZO), zinc gallium oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and their alloys, graphite, graphene, and carbon nanotubes. Optionally, the material of the first electrode includes one or more of Ag, Cu, C, Au, Al, ITO, AZO, BZO, and IZO. More preferably, the material of the first electrode includes one or more of Cu, Ag, and Au.

[0117] In some embodiments, the hole transport layer serves to transport holes and block electrons, and may include, but is not limited to, one or more of the following materials or a mixture thereof: 2,2',7,7'-tetratetra(N,N-p-methoxyaniline)-9,9'-spirodifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidinium (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirodifluorene (CzPAF-SBF), p-PY, PPY2, Me-4PA Cz, MeO-2PACz, poly(3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), poly3-hexylthiophene (P3HT), triphenylamine with triphenylene core, polythiophene, phosphate monomer, carbazole monomer, sulfonic acid monomer, triphenylamine monomer, aromatic monomer, imide compound, quinone compound, WO3, thiophene, phthalocyanine, porphyrin, metal oxides (can be written as first metal oxides, such as molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide), molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, cuprous thiocyanate, copper iodide, fluorine-containing phosphonic acid, carbonyl-containing phosphonic acid, carbon nanotubes, graphene.

[0118] In some embodiments, the electron transport layer performs the function of extracting electrons and blocking holes, and may include, but is not limited to, one or more of the following materials: fullerenes and their derivatives (such as isomethyl [6,6]-phenyl-C61-butyrate (PC61BM), methyl [6,6]-phenyl-C71-butyrate (PC71BM), fullerene C60, fullerene C70), cyano-containing polyphenylacetylene, boron-containing polymers, copper bath (BCP), phenanthroline, aluminum hydroxyquinoline, oxadiazole compounds, imide compounds, quinone compounds, methoxytriphenylamine-fluoroformamidinium (OMeTPA-FA), benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, Phosphorus oxides, phosphorus sulfides, fluorine-containing phthalocyanines, calcium titanate (CaTiO3), strontium titanate (SrTiO3), tin sulfide, indium sulfide, lithium fluoride (LiF), sodium fluoride, magnesium fluoride (MgF2), calcium fluoride (CaF2), zinc sulfide, poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), triphenylamine with a triphenylene core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobisfluorene (CzPAF-SBF), polythiophene, cuprous thiocyanate (CuSCN), and metal oxides. As a non-limiting example, the metal element in the metal oxide may include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr. For example, the metal oxide includes, but is not limited to, one or more of titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, and silicon oxide (SiO2).

[0119] In some implementations, the second electrode is also referred to as the back electrode.

[0120] In some embodiments, the second electrode comprises a conductive material. Optionally, the conductive material may be an organic conductive material, an inorganic conductive material, or a combination thereof. Examples of conductive materials include, but are not limited to, one or more of transparent conductive oxides and metallic conductive materials. Further, transparent conductive oxides include one or more of indium tin oxide (ITO), lanthanide-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, boron-doped zinc oxide (BZO), zinc aluminum oxide (AZO), indium zinc oxide (IZO), zinc gallium oxide (GZO), and indium tungsten oxide (IWO). Metallic conductive materials may include 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 foregoing elements.

[0121] In some implementations, the perovskite solar cell is either an inverted pin cell or a conventional nip cell.

[0122] The perovskite solar cells provided in this application can include both conventional and inverted types. For the conventional type, the perovskite solar cell includes a transparent electrode and, sequentially stacked on the transparent electrode, an electron transport layer, a perovskite thin film, a hole transport layer, and a second electrode. For the inverted type, the perovskite solar cell includes a transparent electrode and, sequentially stacked on the transparent electrode, a hole transport layer, a perovskite thin film, an electron transport layer, and a second electrode. The transparent electrode is used for light incident.

[0123] In some embodiments, a perovskite solar cell includes the following structure arranged sequentially: a substrate layer (which may be a glass substrate or a flexible substrate), a first electrode, a hole transport layer, a perovskite thin film, an electron transport layer, and a second electrode. The flexible substrate may include one or more materials selected from polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, and polyethylene terephthalate. Optionally, the first electrode is a transparent electrode for light incident.

[0124] In some embodiments, a perovskite solar cell includes the following structure arranged in sequence: a substrate layer (glass substrate or flexible substrate), a first electrode, an electron transport layer, a perovskite thin film, a hole transport layer, and a second electrode. Optionally, the first electrode is a transparent electrode for light incident. The definition of a flexible substrate can be found above.

[0125] The substrate layer involved in the embodiments or examples of this application can be, but is not limited to, a glass substrate or a flexible substrate.

[0126] In some embodiments, the base layer is a flexible base layer. Further, the material of the base layer may be, for example (but not limited to), an organic polymer material, and may be a mixture of one or more of the following materials in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0127] In some implementations... Figure 3 The substrate 110 in the structure shown is a light-incident glass substrate.

[0128] There are no particular restrictions on the size of perovskite solar cells; they can be, but are not limited to, 300mm × 300mm.

[0129] In some embodiments, perovskite solar cells include single-junction cells and tandem cells. Tandem cells include double-junction cells, triple-junction cells, quadruple-junction cells, etc., which contain perovskite solar cells. Examples include perovskite-perovskite tandem cells and perovskite-crystalline silicon tandem cells.

[0130] Another embodiment of this application provides a method for preparing a perovskite solar cell, including the step of preparing a perovskite thin film; at least one surface of the perovskite thin film has cracks, the thickness of the perovskite thin film is denoted as H1, the average depth of the cracks along the thickness direction of the perovskite thin film is denoted as H2, and H1 and H2 satisfy: H2 / H1=1%~55%.

[0131] By designing the perovskite thin film in the above-mentioned perovskite solar cell to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to meet the above conditions, it is easy to form grain boundaries and concave crystal planes at the cracks. During the coating process, the material of the transport layer can be accumulated, increasing the contact area between the material of the perovskite thin film and the material of the transport layer. At the same time, point contact structures can be formed at the crack concave surface. The amount of transport layer material at this concave surface is greater than or equal to that at other contact surfaces, which can easily promote photon separation. It can also improve the interface filling of the perovskite solar cell, enhance the stability of the device, thereby improving the stability of the perovskite solar cell and keeping the photoelectric conversion efficiency of the perovskite solar cell at a high level.

[0132] In some embodiments, the steps for preparing perovskite thin films include:

[0133] A perovskite precursor solution containing perovskite material is coated on the surface of a substrate, and after solvent quenching, a perovskite thin film intermediate is formed.

[0134] The perovskite film intermediate is placed in a closed environment, and a gas containing amine compounds is introduced into the closed environment. After annealing, it is treated under a relative humidity of 1% to 85% to form a perovskite film.

[0135] In the above-described steps for preparing perovskite thin films, annealing is performed by introducing a gas containing amine compounds into a sealed environment, and secondary crystallization occurs in the perovskite thin film intermediate under relative humidity conditions of 1% to 85%, which can form a perovskite thin film with cracks. Solvent quenching refers to removing more than 90% of the solvent from the perovskite precursor solution, that is, removing more than 90% of the total solvent mass in the perovskite precursor solution by mass, or removing more than 90% of the total solvent volume in the perovskite precursor solution by volume. Specifically, it can be 90%, 92%, 94%, 96%, 98%, 100%, or any range between the two. Solvent quenching can be performed, for example, by treating the perovskite precursor solution containing perovskite material coated on the substrate surface using at least one of vacuum drying and air knife. The vacuum drying includes, but is not limited to, transferring the perovskite thin film intermediate to a vacuum pump and evacuating it for a period of time. The sealed environment is used to confine the gas containing amine compounds to the area where the perovskite thin film intermediate is located. Specifically, humidity includes, but is not limited to: 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or any range between the two mentioned above.

[0136] In some embodiments, the relative humidity is 1% to 50%. This allows the saturated vapor pressure of the perovskite thin film intermediate to be kept within a certain range, which is beneficial for the growth of perovskite seed crystals, promotes directional orientation, and further improves the stability of perovskite solar cells; and controlling the relative humidity range can form crack morphologies that are beneficial to the stability of the cell.

[0137] In some embodiments, the molar mass of the amine compound is 17 g / mol to 210 g / mol. Specifically, the molar mass of the amine compound includes, but is not limited to: 17 g / mol, 20 g / mol, 30 g / mol, 50 g / mol, 70 g / mol, 100 g / mol, 120 g / mol, 140 g / mol, 160 g / mol, 180 g / mol, 200 g / mol, 210 g / mol, or any range between the foregoing.

[0138] In some embodiments, the amine compounds include one or more of aliphatic amines, alkanolamines, amides, alicyclic amines, aromatic amines, and ammonia.

[0139] In some embodiments, the aliphatic amine compound includes one or more of methylamine, dimethylamine, trimethylamine, ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, and n-butylamine.

[0140] In some embodiments, the alkanolamine compound includes one or more of ethanolamine and aminomethanol.

[0141] In some embodiments, the amide compound includes one or more of formamide, acetamide, and butyramide.

[0142] In some embodiments, the alicyclic amine compounds include one or more of cyclohexylamine and piperazine.

[0143] In some embodiments, the aromatic amine compounds include one or more of aniline and o-phenylenediamine.

[0144] In some embodiments, the annealing process conditions include: an annealing temperature of 100°C to 180°C, an annealing time of 6 min to 25 min, and a gap between the perovskite film intermediate and the heating source.

[0145] In a non-limiting sense, the existence of a gap between the perovskite film intermediate and the heating source means that air or other gases are used as the heat transfer medium, and the active area of ​​the perovskite film intermediate does not directly contact the heating source, but is suspended in a sealed box through the dead area of ​​the substrate and a few support points.

[0146] In some embodiments, the heating source is a metal heating source.

[0147] In some implementations, the process includes a settling process.

[0148] In some embodiments, cracks form on the surface of the perovskite film away from the substrate, where the surface of the perovskite film away from the substrate is in contact with the electron transport layer.

[0149] In some embodiments, the substrate is a first transport layer, which is either a hole transport layer or an electron transport layer. Optionally, the first transport layer is a hole transport layer.

[0150] It should be noted that the perovskite solar cell provided in one embodiment of this application can be obtained by controlling the process conditions of the above-described preparation method. Non-limitingly, by controlling the material type, type of amine compound, molar mass, annealing treatment, and relative humidity of the perovskite thin film, the crack morphology on the surface of the perovskite thin film can be controlled, such as the average depth of cracks along the thickness direction of the perovskite thin film; the average number of cracks per square centimeter of the perovskite thin film surface; the total area of ​​cracks on the surface of the perovskite thin film; the average spacing between cracks; the shape of the cracks; and the surface potential at the cracks.

[0151] Another embodiment of this application provides a perovskite thin film, wherein at least one surface of the perovskite thin film has cracks, the thickness of the perovskite thin film is denoted as H1, the average depth of the crack along the thickness direction of the perovskite thin film is denoted as H2, and H1 and H2 satisfy: H2 / H1=1%~55%.

[0152] By designing the perovskite thin film to have cracks on at least one surface, and controlling the thickness H1 of the perovskite thin film and the average depth H2 of the crack along the thickness direction of the perovskite thin film to meet the above conditions, it is easy to form grain boundaries and concave crystal planes at the cracks. During the coating process, the material of the transport layer can be accumulated, increasing the contact area between the material of the perovskite thin film and the material of the transport layer. At the same time, point contact structures can be formed at the concave cracks. The amount of transport layer material at this concave surface is greater than or equal to that at other contact surfaces, which can easily promote photon separation. It can also improve the interface filling of the perovskite solar cell, enhance the stability of the device, thereby improving the stability of the perovskite solar cell and keeping the photoelectric conversion efficiency of the perovskite solar cell at a high level.

[0153] In some embodiments, the perovskite thin film is the perovskite thin film in the perovskite solar cell described above in this application.

[0154] Another embodiment of this application provides a photovoltaic module, including at least one of the perovskite solar cells described above, the perovskite solar cells prepared by the preparation method described above, and the perovskite thin films described above.

[0155] Another embodiment of this application provides an electrical device, including at least one of the perovskite solar cell described above, the perovskite solar cell prepared by the preparation method described above, the perovskite thin film described above, and the photovoltaic module described above.

[0156] In some embodiments, the perovskite solar cells described above can be used as power generation devices for electrical devices. The type of power generation device may include, but is not limited to, integrated power generation. The location of the power generation device may include, but is not limited to, the roof of a vehicle, the back panel, etc.

[0157] Furthermore, the aforementioned electrical devices may include mobile devices, such as mobile phones and laptops, electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited to these.

[0158] Figure 4 This is an example of an electrical device. The electrical device 20 is a car, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.

[0159] Another example of an electrical device could be a mobile phone, tablet, laptop, calculator, etc.

[0160] Another example of an electrical device could be a wearable device, such as a watch.

[0161] Another embodiment of this application provides a power generation device, including at least one of the perovskite solar cell described above, the perovskite solar cell prepared by the preparation method described above, the perovskite thin film described above, and the photovoltaic module described above.

[0162] The following describes some embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where the technology or conditions are not specified in the embodiments, they are performed according to the description above, or according to the technology or conditions described in the literature in this field, or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially, or can be synthesized from commercially available products using conventional methods.

[0163] Example 1: Preparation of perovskite thin films and perovskite solar cells

[0164] (1) Preparation of the first electrode

[0165] A set of FTO conductive glass with a specification of 30cm*30cm is used to etch P1 with infrared laser. P1 is about 30μm wide. The entire glass is divided into 35 sub-cells along the long side. The series resistance of different sub-cells is greater than 10MΩ. The top and bottom 10mm are used as the component welding area.

[0166] The etched conductive glass surface was cleaned twice with acetone and isopropanol, then immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced-air drying oven, and placed in a drying room (humidity below 2%) to serve as the first electrode.

[0167] (2) Preparation of hole transport layer

[0168] The cleaned conductive glass is placed in a magnetron sputtering apparatus to deposit a layer of nickel oxide (NiO), which forms a hole transport layer. x Ni can be Ni 2+ or Ni 3+ The nickel oxide film is approximately 15 nm thick.

[0169] (3) Preparation of perovskite thin films

[0170] A perovskite precursor solution containing FAPbI3 (perovskite material) was coated onto the nickel oxide prepared above using a slit coating method. Then, the solution was transferred to a vacuum device and evacuated for 50 seconds at a vacuum level of 10 Pa to remove more than 90% of the total solvent mass in the perovskite precursor solution (solvent quenching) to form a perovskite thin film intermediate.

[0171] The perovskite film intermediate was placed in a sealed space (oven chamber) and methylamine (amine compound) gas was introduced. It was annealed at 150°C for 10 min. During the annealing process, there was a gap between the perovskite film intermediate and the heating source (i.e., the perovskite film intermediate did not directly contact the heating source). After cooling to room temperature, it was then left to stand for 10 h at a relative humidity of 2% and a temperature of 25°C to obtain a perovskite film with a thickness of 550 nm.

[0172] (4) Fabrication of electron transport layer

[0173] The substrate with the prepared perovskite thin film was placed in a vacuum thermal evaporation equipment and evacuated to a vacuum level of 4*10. -4 Pa, deposition 30nm C 60 The component's electron transport layer uses an 8nm BCP (Bath Copper Particle) layer as a hole blocking layer.

[0174] (5) Preparation of the second electrode

[0175] After depositing the electron transport layer in a vacuum thermal evaporation equipment, a 10nm Ag layer was deposited on its surface, and then the vacuum was broken and the substrate removed. P2 was then laser-etched, with a width of 150μm and a depth reaching the FTO layer surface. The spacing between P2 and P1 was 20μm. The substrate was then placed back into the evaporation equipment and evacuated to a vacuum level of 4*10. -4 After Pa, another Ag layer was deposited, with a thickness of approximately 80 nm.

[0176] After cooling, the vacuum was broken and P3 was etched by a P-second green laser. P3 has a width of 15 μm and a depth of etched to the surface of the first electrode. The interval between P3 and P2 is 20 μm (the positions of the etching lines are P1 / P2 / P3 in sequence).

[0177] Then infrared edge clearing is used on the component, that is, 10 mm is etched on each side of the component.

[0178] The perovskite solar cell prepared in Example 1 adopts an inverted pin structure.

[0179] Examples 2-5

[0180] The preparation process of Examples 2-5 is basically the same as that of Example 1, except that the annealing temperature in step (3) or the type of amine compound gas introduced during annealing is changed, which changes the average depth of the prepared crack. The detailed corresponding parameters and results are shown in Table 1.

[0181] Examples 6-8

[0182] The preparation process of Examples 6-8 is basically the same as that of Example 1, except that the thickness of the perovskite film prepared in step (3) and / or the type of perovskite material are changed. The detailed corresponding parameters and results are shown in Table 1.

[0183] Examples 9-13

[0184] The preparation process of Examples 9-13 is basically the same as that of Example 1, except that the annealing time in step (3) is changed, so that the average number of cracks per square centimeter of the perovskite film surface changes. The detailed corresponding parameters and results are shown in Table 1.

[0185] Examples 14-15

[0186] The preparation process of Examples 14-15 is basically the same as that of Example 1, except that the annealing temperature in step (3) is changed. The detailed corresponding parameters and results are shown in Table 1.

[0187] Examples 16-20

[0188] The preparation process of Examples 16-20 is basically the same as that of Example 1, except that the relative humidity in step (3) is changed. The detailed corresponding parameters and results are shown in Table 1.

[0189] Examples 21-26

[0190] The preparation process of Examples 21-26 is basically the same as that of Example 1, except that the type of perovskite material used in step (3) is changed. The detailed corresponding parameters and results are shown in Table 1.

[0191] Examples 27-34

[0192] The preparation process of Examples 27-34 is basically the same as that of Example 1, except that the type of amine compound gas introduced during the annealing treatment in step (3) is changed. The detailed corresponding parameters and results are shown in Table 1.

[0193] Comparative Examples 1-2

[0194] The preparation process of Comparative Examples 1 and 2 is basically the same as that of Example 1, except that: after the perovskite film intermediate is prepared in step (3), the perovskite film intermediate is directly contacted with the hot plate (heating source) (that is, there is no gap between the perovskite film intermediate and the heating source), and annealed at 150°C for 10 min without subsequent static treatment to obtain perovskite film. In Comparative Example 2, the type of perovskite material is changed at the same time. The detailed corresponding parameters and results are shown in Table 1.

[0195] Comparative Example 3

[0196] The preparation process of Comparative Example 3 is basically the same as that of Example 1, except that the relative humidity, annealing temperature and annealing time in step (3) are changed. The detailed corresponding parameters and results are shown in Table 1.

[0197] Figure 5 and Figure 6 All images are SEM images (scanning electron microscope images) of the perovskite thin films prepared in Example 1 at different magnifications and locations. Figure 7 This is a SEM image of the electron transport layer prepared in Example 1 of this application. Figure 5 and Figure 6 It can be seen that the perovskite film prepared in Example 1 has cracks, and the cracks are elongated and pore-shaped. The cracks are located on the surface of the perovskite film away from the hole transport layer. Figure 7 It can be seen that the electron transport layer covers the surface of the cracked perovskite film, and the material of the electron transport layer is embedded in the crack.

[0198] Test case

[0199] 1. Photoelectric conversion efficiency test

[0200] At 1000 W / m 2 The energy conversion efficiency of the components was tested using a solar simulator.

[0201] Under normal temperature and pressure, a standard light source with an AM1.5G solar light source was used for testing, conforming to the national standard IEC61215. The light intensity was corrected using crystalline silicon solar cells to achieve a solar intensity. The current-voltage characteristic curve of the solar cells under the illumination of the light source was measured using a four-channel digital source meter (Keithley 2440), and the open-circuit voltage Voc, short-circuit current density Jsc, fill factor FF, and photoelectric conversion efficiency PCE of the solar cells were obtained.

[0202] "Normal temperature and pressure" refers to normal pressure: the pressure is one atmosphere at a temperature of 25℃; normal temperature refers to 20℃~30℃, and further, it can be 25℃.

[0203] 2. Battery stability test

[0204] After the test, the battery was placed in an atmospheric environment (relative humidity 65%-85%, ambient temperature approximately 15℃-40℃, specifically 25℃) and left in the dark for 500 hours. The energy conversion efficiency was then tested again (each test continued until there was no hysteresis in both forward and reverse scans, and the energy conversion efficiency was recorded). The ratio of the solar cell efficiency after 500 hours of atmospheric placement (retested efficiency) to the initial efficiency was calculated as the normalized efficiency retention rate of the solar cell after 500 hours of placement.

[0205] Normalized efficiency retention rate = Retest efficiency / Initial efficiency * 100%.

[0206] The test results for each embodiment and each comparative example are detailed in Table 2.

[0207] In Tables 1 and 2, " / " indicates that the substance or parameter does not exist.

[0208] Table 1

[0209]

[0210]

[0211]

[0212]

[0213] Table 2

[0214]

[0215]

[0216]

[0217] As shown in Tables 1 and 2, compared with Comparative Examples 1 to 3, Examples 1 to 34 can effectively improve the stability of perovskite solar cells by controlling H2 / H1 = 1% to 55%, while also maintaining a high level of photoelectric conversion efficiency.

[0218] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0219] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. The above-described embodiments only illustrate several embodiments of this application, and their descriptions are relatively detailed, but they should not be construed as limiting the scope of the patent. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, are also included in the scope of this application without departing from the spirit of this application. It should be pointed out that for those skilled in the art, several modifications and improvements can be made without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this application should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A perovskite solar cell, characterized by, The perovskite solar cell comprises a perovskite thin film, at least one surface of the perovskite thin film has cracks, the thickness of the perovskite thin film is denoted as H1, the average depth of the cracks along the thickness direction of the perovskite thin film is denoted as H2, and the H1 and the H2 satisfy: H2 / H1 = 1%~55%.

2. The perovskite solar cell according to claim 1, characterized in that, H2 / H1 = 4%~25%.

3. The perovskite solar cell according to any one of claims 1-2, characterized in that, The H1 is 150nm~1200nm.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, The H2 is 5nm~660nm.

5. The perovskite solar cell according to any one of claims 1 to 4, characterized in that, The average number of the cracks per square centimeter of the surface of the perovskite thin film is 400~32000.

6. The perovskite solar cell according to claim 5, characterized in that, The average number of the cracks per square centimeter of the surface of the perovskite thin film is 1800~16000.

7. The perovskite solar cell according to any one of claims 1 to 6, characterized in that, The area of one surface of the perovskite thin film is denoted as A1, the total area of the cracks on the surface is denoted as A2, and the A1 and the A2 satisfy: A2 / A1 = 0.2%~30%.

8. The perovskite solar cell according to any one of claims 1 to 7, characterized in that, The average distance between the cracks is 5um~48um.

9. The perovskite solar cell according to any one of claims 1 to 8, characterized in that, The shape of the cracks comprises one or both of long strip and hole.

10. The perovskite solar cell according to any one of claims 1 to 9, characterized in that, The average difference between the surface potential at the cracks on the perovskite thin film and the surface potential at the non-crack positions on the surface is 8mV~80mV.

11. The perovskite solar cell according to any one of claims 1 to 10, characterized in that, The perovskite material in the perovskite thin film comprises perovskite type metal halide, the chemical formula of the perovskite type metal halide comprises one or several of ABX3 and A2CDX6; wherein, A is monovalent cation, B is divalent cation, C is monovalent cation, D is trivalent cation, and X is monovalent anion.

12. The perovskite solar cell according to claim 11, characterized in that, The perovskite solar cell has one or several of the following characteristics (1)~(5): (1) A is one or more of monovalent inorganic cations including one or more of Li + , Na + , K + , Rb + , and Cs + , and monovalent organic cations including one or more of methylamine cation, ethylamine cation, propylamine cation, butylamine cation, pentylamine cation, hexylamine cation, formamidine cation, and imidazole cation; (2) B comprises divalent cations of one or several of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; (3) C comprises one or more of Cs + , Ag + , K + , and Ru + . (4) D comprises one or more of Bi 3+ , Ni 3+ , Fe 3+ , Sb 3+ , and In 3+ ; (5) X comprises one or more of a halogen ion including F - , Cl - , Br - , and I - , or a pseudohalogen ion including one or more of CN - , SCN - , OCN - , N3 - , CF4SO4 - , HCOO - , C6H5S - , CH3COO - , CF3COO - , BH4 - , CH3S - , ClO4 - , BF4 - , and BCl4 - .

13. The perovskite solar cell according to any one of claims 1-12, characterized in that, The perovskite solar cell further comprises a first electrode, a first transport layer, a second transport layer and a second electrode, the first electrode, the first transport layer, the perovskite thin film, the second transport layer and the second electrode are sequentially stacked, the first transport layer is one of hole transport layer or electron transport layer, the second transport layer is the other of hole transport layer or electron transport layer; the cracks are located on the surface of the perovskite thin film away from the first transport layer.

14. The perovskite solar cell according to claim 13, characterized in that, The material of the corresponding transport layer of the surface where the cracks are located is embedded in the cracks.

15. The perovskite solar cell according to claim 13 or 14, characterized in that, The perovskite solar cell is a reverse p-i-n type cell, the first electrode is a light incident surface, the first transport layer is a hole transport layer, and the second transport layer is an electron transport layer.

16. A method of manufacturing a perovskite solar cell, characterized by, The method comprises the step of preparing a perovskite thin film; at least one surface of the perovskite thin film has cracks, the thickness of the perovskite thin film is denoted as H1, the average depth of the cracks along the thickness direction of the perovskite thin film is denoted as H2, and the H1 and the H2 satisfy: H2 / H1 = 1%~55%.

17. The preparation method according to claim 16, characterized in that, The step of preparing a perovskite thin film comprises: coating a perovskite precursor solution containing perovskite material on the surface of a substrate, and forming a perovskite thin film intermediate through solvent quenching; The perovskite thin film intermediate is placed in a closed environment, a gas containing an amine compound is introduced into the closed environment, and after annealing treatment, the perovskite thin film is formed under the condition of 1% to 85% relative humidity.

18. The method of claim 17, wherein, The relative humidity is 1% to 50%.

19. The method of any one of claims 17-18, wherein, The molar mass of the amine compound is 17 g / mol to 210 g / mol.

20. The method of any one of claims 17-19, wherein, The amine compound includes one or more of aliphatic amine, alcohol amine, amide, alicyclic amine, aromatic amine, and ammonia.

21. The method of claim 20, wherein, The preparation method satisfies one or more of the following conditions (1) to (5): (1) The aliphatic amine includes one or more of methylamine, dimethylamine, trimethylamine, ethylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, and n-butylamine; (2) The alcohol amine includes one or more of ethanolamine and aminomethanol; (3) The amide includes one or more of formamide, acetamide, and butyramide; (4) The alicyclic amine includes one or more of cyclohexylamine and piperazine; (5) The aromatic amine includes one or more of aniline and o-phenylenediamine.

22. The method of any one of claims 17-21, wherein, The process conditions of the annealing treatment include: the temperature of the annealing treatment is 100°C to 180°C, the time of the annealing treatment is 6 min to 25 min, and there is a gap between the perovskite thin film intermediate and the heating source.

23. The method of any one of claims 17-22, wherein, The crack is formed on the surface of the perovskite thin film away from the substrate, and the surface of the perovskite thin film away from the substrate is in contact with the electron transport layer.

24. A perovskite thin film, characterized in that, The perovskite thin film has at least one surface with a crack, the thickness of the perovskite thin film is denoted as H1, the average depth of the crack along the thickness direction of the perovskite thin film is denoted as H2, and the H1 and the H2 satisfy: H2 / H1 = 1% to 55%.

25. The perovskite thin film of claim 24, wherein, The perovskite thin film in the perovskite solar cell of any one of claims 2 to 15.

26. A photovoltaic module, characterized by At least one of the perovskite solar cell of any one of claims 1 to 15, the perovskite solar cell prepared by the preparation method of any one of claims 16 to 23, and the perovskite thin film of any one of claims 24 to 25.

27. An electrical device, comprising: At least one of the perovskite solar cell of any one of claims 1 to 15, the perovskite solar cell prepared by the preparation method of any one of claims 16 to 23, the perovskite thin film of any one of claims 24 to 25, and the photovoltaic module of claim 26.

28. A power generation device, comprising: At least one of the perovskite solar cell of any one of claims 1 to 15, the perovskite solar cell prepared by the preparation method of any one of claims 16 to 23, the perovskite thin film of any one of claims 24 to 25, and the photovoltaic module of claim 26.

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