Perovskite thin film and preparation method thereof, perovskite battery and power utilization device

Abstract

The invention provides a perovskite thin film and a preparation method thereof, a perovskite battery and a power utilization device. The perovskite thin film comprises a perovskite substrate layer; and a plurality of nano protrusions which are distributed at intervals and are arranged on at least one surface of the perovskite matrix layer. The perovskite thin film provided by the invention can improve the photoelectric conversion efficiency of a perovskite battery.

Description

Technical Field

[0001] The present application relates to the technical field of solar cells, and in particular to a perovskite film and a preparation method thereof, a perovskite cell and an electrical device. Background Art

[0002] The statements herein merely provide background information related to the present application and do not necessarily constitute prior art.

[0003] Perovskite solar cells are devices that use the photoelectric conversion mechanism of perovskite crystal materials to convert solar energy into electrical energy. They are the third generation of solar cells and have many advantages, such as high photoelectric conversion efficiency, simple manufacturing process, and low production cost. They have been extensively studied in recent years. Despite this, there is still a certain distance from the large-scale commercial application of perovskite cells. Among them, how to improve the photoelectric conversion efficiency of perovskite cells is one of the key issues that need to be solved urgently. Summary of the invention

[0004] In view of the above problems, the present application provides a perovskite film and a preparation method thereof, a perovskite cell and an electrical device. The perovskite film can improve the photoelectric conversion efficiency of the perovskite cell.

[0005] In a first aspect, the present application provides a perovskite film, comprising: a perovskite matrix layer; and a plurality of spaced-apart nano-protrusions disposed on at least one surface of the perovskite matrix layer.

[0006] The above-mentioned perovskite film provided in the present application includes a perovskite substrate layer and a plurality of spaced-apart nano-protrusions arranged thereon, wherein the nano-protrusions can enable point contact between the interface of the perovskite film and the charge transport layer arranged adjacent thereto, thereby reducing the contact area between the interface of the perovskite film and the charge transport layer, reducing the contact between the interface of the perovskite film and the charge transport layer, reducing the occurrence of non-radiative recombination caused by interface contact, and improving the open circuit voltage and photoelectric conversion efficiency.

[0007] In some embodiments, the average particle size of the nano-protrusions is 1 nm to 10 nm, and can be optionally 1 nm to 5 nm.

[0008] The average particle size of the nano-protrusions is within the above range, which is conducive to fully realizing the point contact at the interface between the perovskite film and the adjacent charge transfer layer, fully reducing the occurrence of non-radiative recombination caused by interface contact, and improving the open circuit voltage and photoelectric conversion efficiency.

[0009] In some embodiments, the spacing distance between the center points of two adjacent nano-protrusions is 2 nm to 1 μm, and can be optionally 10 nm to 0.5 μm.

[0010] The spacing distance between the center points of two adjacent nano-protrusions is within the above range, which is beneficial to increasing the density of the nano-protrusions on the perovskite film, thereby further reducing the contact area between the two, reducing the occurrence of non-radiative recombination caused by interface contact, and further improving the open circuit voltage and photoelectric conversion efficiency.

[0011] In some embodiments, the nano-protrusions satisfy at least one of the following conditions:

[0012] (1) The nano-protrusions have an irregular columnar morphology;

[0013] (2) The chemical composition of the nano-protrusions includes L m A n-1 B n X 3n+1 , 1≤m≤2, n≥1 and is an integer, where L ion is NH4 + , A ion is a monovalent cation, B ion is a divalent metal cation, C ion and D ion are monovalent and trivalent metal cations respectively, and X ion is a monovalent anion;

[0014] The A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of;

[0015] Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group;

[0016] Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine;

[0017] Optionally, the A ions include organic amine ions and Cs + One or more of;

[0018] The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of;

[0019] Optionally, the B ions include Pb2+ and Sn 2+ One or both of the following:

[0020] The C ions include Cs + 、Ag + , K + And Ru + One or more of;

[0021] The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of;

[0022] The X ions include F - , Cl - Br - and I - One or more of;

[0023] Optionally, the X ions include Cl - Br - and I - One or more of .

[0024] The nano-protrusions have an irregular columnar morphology, which can further promote point contact at the interface between the perovskite film and the adjacent charge transfer layer, further reducing the occurrence of non-radiative recombination caused by interface contact, thereby improving the open circuit voltage and photoelectric conversion efficiency.

[0025] In some embodiments, the perovskite matrix layer satisfies at least one of the following conditions:

[0026] (1) The thickness of the perovskite matrix layer is 100 nm to 1000 nm, and can be optionally 500 nm to 800 nm;

[0027] (2) The chemical composition of the perovskite matrix layer includes a compound ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion;

[0028] The A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of;

[0029] Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group;

[0030] Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine;

[0031] Optionally, the A ions include organic amine ions and Cs + One or more of;

[0032] The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of;

[0033] Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following:

[0034] The C ions include Cs + 、Ag + , K + And Ru + One or more of;

[0035] The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of;

[0036] The X ions include F - , Cl - Br - and I - One or more of;

[0037] Optionally, the X ions include Cl - Br - and I - One or more of;

[0038] Optionally, the chemical composition of the perovskite matrix layer includes an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.1.

[0039] The thickness of the perovskite matrix layer is within the above range, which is beneficial to further promote its light absorption effect.

[0040] In a second aspect, the present application provides a method for a perovskite film, comprising:

[0041] preparing a perovskite matrix layer on the support layer;

[0042] The ammonium salt solution is brought into contact with the surface of the perovskite matrix layer and a first annealing treatment is performed to form a plurality of spaced nano-protrusions on the surface of the perovskite matrix layer, thereby forming a perovskite complex and obtaining the perovskite film.

[0043] The present application provides the above-mentioned method, which can realize the preparation of nano-protrusions only through a simple chemical reaction between the ammonium salt and the perovskite matrix layer and a simple annealing treatment; it does not need to introduce other complex processes (such as mask process), which is beneficial to reduce the process difficulty of device production and manufacturing, and can greatly reduce production costs in large-scale commercial production.

[0044] In some embodiments, the ammonium salt solution satisfies at least one of the following conditions:

[0045] (1) The mass concentration of the ammonium salt solution is 0.05 mg / mL to 1 mg / mL;

[0046] (2) the ammonium salt comprises one or more of ethylenediamine, propylenediamine, butylenediamine and p-phenylenediamine;

[0047] (3) The ammonium salt solution contains a first organic solvent, and the first organic solvent includes one or more of isopropanol, ethanol, ethylene glycol and glycerol.

[0048] The mass concentration of the ammonium salt solution being within the above range is conducive to promoting the reaction between the ammonium salt and the chemical components in the perovskite matrix layer to generate zero-dimensional perovskite, that is, it is conducive to promoting the formation of crystal nuclei.

[0049] In some embodiments, the first annealing treatment satisfies at least one of the following conditions:

[0050] (1) The temperature of the first annealing treatment is 90° C. to 120° C.;

[0051] (2) The first annealing treatment time is 5 minutes to 10 minutes.

[0052] The temperature and time of the first annealing treatment are within the above range, which is beneficial to promoting the growth of the nano-protrusions in an island-like growth mode.

[0053] In some embodiments, the method further comprises: performing an impurity removal treatment on the perovskite composite.

[0054] In some embodiments, the step of removing impurities from the perovskite composite comprises:

[0055] bringing a second organic solvent into contact with the surface of the perovskite composite and performing a second annealing treatment;

[0056] Optionally, the second organic solvent includes one or more of isopropanol, ethanol, ethylene glycol and glycerol;

[0057] Optionally, the temperature of the second annealing treatment is 90° C. to 120° C.;

[0058] Optionally, the second annealing treatment lasts for 5 min to 10 min.

[0059] In the above steps, by using the second organic solvent to clean the surface of the perovskite complex, the impurities can be relatively completely dissolved in the second organic solvent; and then the second annealing treatment is performed to relatively completely remove the impurities.

[0060] In some embodiments, the step of preparing a perovskite matrix layer on the support layer comprises:

[0061] contacting a perovskite precursor solution with an anti-solvent on the support layer to form a wet film of the perovskite matrix layer;

[0062] Performing a third annealing treatment on the wet film of the perovskite matrix layer to obtain the perovskite matrix layer;

[0063] Optionally, the temperature of the third annealing treatment is 90° C. to 150° C.;

[0064] Optionally, the third annealing treatment lasts for 10 min to 40 min.

[0065] In the above steps, the perovskite precursor solution is treated with an anti-solvent, which is beneficial to improving the crystallinity of the perovskite matrix layer at room temperature; and then a third annealing treatment is performed, which is beneficial to further promote the crystal growth of the perovskite matrix layer and remove the residual anti-solvent.

[0066] In some embodiments, the method satisfies at least one of the following conditions:

[0067] (1) The perovskite precursor solution contains a compound ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion;

[0068] The A ions include organic cations, Li +、Na + , K + , Rb + and Cs + One or more of;

[0069] Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group;

[0070] Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine;

[0071] Optionally, the A ions include organic amine ions and Cs + One or more of;

[0072] The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of;

[0073] Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following:

[0074] The C ions include Cs + 、Ag + , K + And Ru + One or more of;

[0075] The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of;

[0076] The X ions include F - , Cl - Br - and I - One or more of;

[0077] Optionally, the X ions include Cl - Br - and one or more of I-;

[0078] Optionally, the perovskite precursor solution contains an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.1;

[0079] (2) The molar concentration of the perovskite precursor solution is 1 mol / L to 1.8 mol / L;

[0080] (3) The anti-solvent comprises one or more of chlorobenzene, anisole, ethyl ether and ethyl acetate.

[0081] The molar concentration of the perovskite precursor solution is within the above range, which can provide sufficient organic light-emitting materials for the perovskite matrix layer, thereby providing sufficient photoelectrons to make the luminescence efficiency (photoelectric conversion efficiency) of the perovskite cell at a relatively high level.

[0082] In a third aspect, the present application provides a perovskite cell, comprising the perovskite film described in the first aspect of the present application or the perovskite film prepared by the method described in the second aspect of the present application.

[0083] In some embodiments, the perovskite film includes a first electrode layer, a perovskite layer, a first charge transport layer, and a second electrode layer stacked in sequence, and the perovskite layer includes the perovskite film, wherein the nano-protrusions in the perovskite film face the first charge transport layer along the thickness direction of the perovskite layer.

[0084] The perovskite cell provided in the present application includes the aforementioned perovskite film, and the nano-protrusions in the perovskite film face the first charge transport layer. Thus, the nano-protrusions can enable point contact at the interface between the perovskite layer and the first charge transport layer, thereby reducing the contact area between the perovskite layer and the first charge transport layer, reducing the occurrence of non-radiative recombination caused by the interface contact between the two, and thereby improving the open circuit voltage and photoelectric conversion efficiency of the battery.

[0085] In some embodiments, the first charge transport layer includes a first charge transport matrix layer, and a filler disposed on the surface of the first charge transport matrix layer, wherein the filler extends along the thickness direction of the first charge transport matrix layer and fills the gaps formed by the nano-protrusions;

[0086] Optionally, the first charge transport layer comprises an electron transport layer;

[0087] Optionally, the first charge transport matrix layer has the same chemical composition as the filler.

[0088] In some embodiments, the perovskite cell further comprises a second charge transport layer, wherein the second charge transport layer is disposed between the first electrode layer and the perovskite layer;

[0089] Optionally, the second charge transport layer comprises a hole transport layer.

[0090] The first charge transport layer includes a filler formed by filling in the gaps formed by the nano-protrusions, and the filler can achieve point contact between the first charge transport layer and the perovskite layer. At the same time, by adjusting the spacing between the nano-protrusions, the number of gaps formed by the nano-protrusions on the perovskite layer per unit area can be adjusted, and the density of the filler can be adjusted. By adjusting the density of the filler, the filling amount of the first charge transport layer can be adjusted, thereby achieving the control of the contact surface between the first charge transport layer and the perovskite layer, and fully reducing the occurrence of non-radiative recombination between the two, effectively improving the open circuit voltage and photoelectric conversion efficiency of the battery.

[0091] In a fourth aspect, the present application provides an electrical device comprising the perovskite cell described in the third aspect of the present application.

[0092] The details of one or more embodiments of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0093] In order to better describe and illustrate the embodiments or examples of those applications disclosed herein, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered as limiting the scope of any of the disclosed applications, the embodiments or examples currently described, and the best modes of these applications currently understood. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the accompanying drawings:

[0094] Figure 1 Schematic diagram of the structure of a perovskite film according to one embodiment of the present application.

[0095] Figure 2 This is a schematic diagram of the structure of a perovskite battery according to one embodiment of the present application.

[0096] Figure 3 This is a schematic structural diagram of a perovskite cell according to another embodiment of the present application.

[0097] Figure 4 This is a schematic structural diagram of a perovskite cell according to another embodiment of the present application.

[0098] Figure 5 A schematic diagram of an electrical device using a perovskite battery according to an embodiment of the present application as a power source.

[0099] Figure 6 This is a surface morphology diagram of a perovskite film according to one embodiment of the present application.

[0100] Description of reference numerals:

[0101] 10 first electrode; 20 second charge transport layer; 30 perovskite layer; 40 first charge transport layer; 50 second electrode layer; 310 perovskite matrix layer; 320 nano-protrusions; 410 first charge transport matrix layer; 420 filler. DETAILED DESCRIPTION

[0102] Below, some embodiments of the perovskite film and its preparation method, perovskite battery and electrical device of the present application are described in detail with appropriate reference to the drawings. However, there are cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structure are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following descriptions are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0103] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it 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 example, when a parameter is expressed as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9 and 10.

[0104] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0105] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0106] Unless otherwise specified, the terms "include", "contain" and "comprise" mentioned in this application may be open-ended or closed-ended. For open-ended situations, for example, the terms "include", "contain" and "comprise" may mean that other members, elements or method steps not listed may also be included or comprised, or may only include or comprise the listed members, elements or method steps.

[0107] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". Further, any of the following conditions satisfies the condition "A or B": 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).

[0108] In this application, 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.

[0109] In the present application, "plurality", "multiple" and the like, unless otherwise specified, refer to a number greater than or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0110] In the present application, 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.

[0111] In this application, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3~5h or 3-5h both mean that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0112] In perovskite cells, there are usually serious interface defects at the interface between the perovskite layer and the electron transport layer. This defect can cause serious non-radiative recombination between holes on the perovskite surface and electrons extracted from the electron transport layer, resulting in open circuit voltage loss and affecting device efficiency. Therefore, it is usually necessary to introduce a passivation layer to reduce non-radiative recombination and increase the open circuit voltage of the device. Commonly used passivation layers are basically insulating materials, which will affect charge transfer and reduce the short-circuit current density of the device.

[0113] Based on this, in the first aspect, the present application provides a perovskite film, such as Figure 1 As shown, it includes a perovskite matrix layer 310 and a plurality of spaced-apart nano-protrusions 320 disposed on at least one surface of the perovskite matrix layer 310 .

[0114] The above-mentioned perovskite film provided by the present application includes a perovskite matrix layer and a plurality of spaced nano-protrusions arranged thereon. When the perovskite film is used in a perovskite battery, the perovskite matrix layer serves as the main layer of the perovskite film, plays a major role in light absorption, and realizes the conversion of light energy into electrical energy. The plurality of spaced nano-protrusions arranged on the surface of the perovskite matrix layer can make the perovskite film and the charge transport layer interface arranged adjacent thereto realize point contact, thereby reducing the contact area between the perovskite film and the charge transport layer interface, reducing the contact between the perovskite film and the charge transport layer interface, reducing the occurrence of non-radiative recombination caused by interface contact, and improving the open circuit voltage and photoelectric conversion efficiency.

[0115] At the same time, after the above-mentioned perovskite film is used in perovskite batteries, there is no need to introduce an additional insulating passivation layer to reduce the non-radiative recombination between the interface of the perovskite layer and the charge transfer layer, and the charges can be transmitted through multiple nano-protrusions, which is beneficial to improve the short-circuit current density compared to the introduction of an insulating passivation layer.

[0116] In some embodiments, the nanoprotrusions (with Figure 6 The average particle size of the nano-protrusions (corresponding to the white bright spots in the figure) is 1 nm to 10 nm. For example, the average particle size of the nano-protrusions can be 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm or within a range of any of the above values. Optionally, the average particle size is 1 nm to 5 nm.

[0117] It can be understood that the nano-protrusions of the present application are discontinuous and randomly distributed on the perovskite matrix layer.

[0118] In this application, unless otherwise specified, the average particle size of the nano-protrusions refers to the average particle size of the nano-protrusions contained in the perovskite film per unit area. The particle size of the nano-protrusions can be measured by methods known in the art. For example, an atomic force microscope (Oxford Instruments, model Cypher VRS) can be used for measurement.

[0119] The average particle size of the nano-protrusions is within the above range, which is conducive to fully realizing the point contact at the interface between the perovskite film and the adjacent charge transport layer, fully reducing the contact area between the perovskite film and the charge transport layer, reducing the contact between the perovskite film and the charge transport layer, and fully reducing the occurrence of non-radiative recombination caused by interface contact, thereby improving the open circuit voltage and photoelectric conversion efficiency.

[0120] In some embodiments, the spacing distance between the center points of two adjacent nano-protrusions is 2nm-1μm, for example, the spacing distance between the center points of two adjacent nano-protrusions can be 2nm, 5nm, 10nm, 50nm, 0.1μm, 0.2μm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.7μm, 0.8μm, 0.9μm, 1μm or in the range of any of the above values. Optionally, the spacing distance is 10nm-0.5μm.

[0121] In the present application, the center point of the nano-protrusion refers to the center position of the projection formed by the nano-protrusion on the perovskite film surface, and the spacing distance between the center points of two adjacent nano-protrusions is the distance between the center positions of the projections formed by two adjacent nano-protrusions on the perovskite film surface, which can be measured by a method known in the art. For example, a scanning electron microscope (Hitachi, model HD-2700) can be used for measurement.

[0122] The spacing distance between the center points of two adjacent nano-protrusions is within the above range, which is conducive to increasing the number of nano-protrusions per unit area on the perovskite film, that is, increasing the density of nano-protrusions on the perovskite film. The increase in the density of nanoparticles on the perovskite film is conducive to increasing the number of point contacts at the interface between the perovskite film and the charge transfer layer, thereby further reducing the contact surface between the two, reducing the occurrence of non-radiative recombination caused by interface contact, and further improving the open circuit voltage and photoelectric conversion efficiency.

[0123] In the present application, the contact between the interface between the perovskite film and the charge transport layer is regulated by matching the average particle size of the nano-protrusions with the distance between their center points, so that partial contact is achieved between the charge transport layer and the perovskite film. This fully reduces the interface contact between the two without affecting the charge transfer of the perovskite film, reduces the occurrence of non-radiative recombination caused by the interface contact, and improves the open circuit voltage and photoelectric conversion efficiency.

[0124] In some embodiments, the nano-protrusions have an irregular columnar morphology.

[0125] It can be understood that the “irregular columnar” mentioned in the present application means that the morphology of the nano-protrusion is similar to a columnar shape, but is not a completely regular columnar shape; for example, any cross section along the axial direction may have a cross-sectional area that is not completely consistent.

[0126] The nano-protrusions have an irregular columnar morphology, which can further promote point contact at the interface between the perovskite film and the adjacent charge transfer layer, further reducing the occurrence of non-radiative recombination caused by interface contact, thereby improving the open circuit voltage and photoelectric conversion efficiency.

[0127] In some embodiments, the chemical composition of the nanoprotrusions includes L m A n-1 B n X 3n+1 , 1≤m≤2, n≥1 and is an integer, where L ion is NH4 + , A ion is a monovalent cation, B ion is a divalent metal cation, C ion and D ion are monovalent and trivalent metal cations respectively, and X ion is a monovalent anion.

[0128] In some embodiments, the A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of .

[0129] In some embodiments, the organic cation includes at least one of an organic amine ion, a carbamimidyl group and an imidazolyl group.

[0130] In some embodiments, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, and hexylamine.

[0131] Optionally, the A ions include organic amine ions and Cs + One or more of .

[0132] In some embodiments, the B ions include Pb 2+Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of .

[0133] Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following.

[0134] In some embodiments, the C ions include Cs + 、Ag + , K + And Ru + One or more of.

[0135] In some embodiments, the D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of .

[0136] In some embodiments, the X ions include F-, Cl - Br - and one or more of I-.

[0137] Optionally, the X ions include Cl-, Br - and I - One or more of .

[0138] In some embodiments, the thickness of the perovskite matrix layer is 100 nm to 1000 nm, for example, the thickness of the perovskite matrix layer can be 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm or within a range consisting of any of the above values. Optionally, the thickness is 500 nm to 800 nm.

[0139] In the present application, the thickness of the perovskite matrix layer has a well-known meaning in the art and can be measured by methods known in the art, for example, by using a micrometer.

[0140] The thickness of the perovskite matrix layer is within the above range, which is beneficial to further promote its light absorption effect.

[0141] In some embodiments, the chemical composition of the perovskite matrix layer includes compounds ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion.

[0142] In some embodiments, the A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of .

[0143] In some embodiments, the organic cation includes at least one of an organic amine ion, a carbamimidyl group and an imidazolyl group.

[0144] In some embodiments, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, and hexylamine.

[0145] Optionally, the A ions include organic amine ions and Cs + One or more of .

[0146] In some embodiments, the B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of .

[0147] Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following.

[0148] In some embodiments, the C ions include Cs + 、Ag + , K + And Ru + One or more of.

[0149] In some embodiments, the D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of .

[0150] In some embodiments, the X ions include F - , Cl - Br - and I - One or more of .

[0151] Optionally, the X ions include Cl - Br - and I - One or more of .

[0152] In some embodiments, the chemical composition of the perovskite matrix layer includes an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.1.

[0153] In a second aspect, the present application provides a method for preparing the perovskite film according to the first aspect of the present application, which may include the following steps:

[0154] S10, preparing a perovskite matrix layer on the support layer;

[0155] S20, bringing the ammonium salt solution into contact with the surface of the perovskite matrix layer and performing a first annealing treatment to form a plurality of spaced-apart nano-protrusions on the surface of the perovskite matrix layer, forming a perovskite complex, and obtaining a perovskite film.

[0156] Without intending to be bound by any theory, the inventors speculate that after the ammonium salt solution is brought into contact with the surface of the perovskite matrix layer, the ammonium salt can interact with the chemical components in the perovskite matrix layer to generate a zero-dimensional perovskite, which can serve as a growth nucleus for the nano-protrusions. Then, during the first annealing process, the perovskite is used as a nucleus and grows in an island growth mode, thereby forming a plurality of spaced nano-protrusions in situ on the surface of the perovskite matrix layer.

[0157] Therefore, the method provided in the present application can realize the preparation of nano-protrusions only through a simple chemical reaction between the ammonium salt and the perovskite matrix layer and a simple annealing treatment; it does not need to introduce other complex processes (such as mask process), which is beneficial to reduce the process difficulty of device production and manufacturing, and can significantly reduce production costs in large-scale commercial production.

[0158] In some embodiments, the ammonium salt includes a diammonium salt. For example, it may include but is not limited to one or more of ethylenediamine, propylenediamine, butylenediamine, p-phenylenediamine, etc. The diammonium salt can interact with the chemical components (perovskite components) in the perovskite matrix layer to provide growth nuclei for the growth of multiple nano-protrusions.

[0159] In some embodiments, the mass concentration of the ammonium salt solution is 0.05 mg / mL to 1 mg / mL. For example, the mass concentration of the ammonium salt solution can be 0.05 mg / mL, 0.08 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL or within the range of any of the above values.

[0160] The mass concentration of the ammonium salt solution being within the above range is conducive to promoting the reaction between the ammonium salt and the chemical components in the perovskite matrix layer to generate zero-dimensional perovskite, that is, it is conducive to promoting the formation of crystal nuclei.

[0161] In some embodiments, the temperature of the first annealing treatment is 90° C. to 120° C. For example, the temperature of the first annealing treatment can be 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C. or any range thereof.

[0162] In some embodiments, the first annealing treatment time is 5 min to 10 min. For example, the first annealing treatment time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min or any range thereof.

[0163] The temperature and time of the first annealing treatment are within the above range, which is beneficial to promoting the growth of the nano-protrusions in an island-like growth mode.

[0164] In some embodiments, the ammonium salt solution includes a first organic solvent, which can dissolve the ammonium salt without affecting the properties of the perovskite matrix layer. For example, the first organic solvent can include but is not limited to one or more of isopropanol, ethanol, ethylene glycol and glycerol.

[0165] In some implementations, the above method may further include the following step S30:

[0166] S30, performing impurity removal treatment on the perovskite complex to obtain the perovskite film.

[0167] In some embodiments, the impurity removal treatment of the perovskite composite in the above step S30 may further include the following steps:

[0168] S300 , bringing a second organic solvent into contact with the surface of the perovskite complex and performing a second annealing treatment.

[0169] After the nano-protrusions are formed in step S20, unreacted impurities such as ammonium salts will remain on the surface of the perovskite complex. By using a second organic solvent to clean the surface of the perovskite complex, the impurities can be relatively completely dissolved in the second organic solvent. Then, a second annealing treatment is performed to relatively completely remove the impurities.

[0170] In some embodiments, the second solvent may include, but is not limited to, one or more of isopropanol, ethanol, ethylene glycol, and glycerol.

[0171] In some embodiments, the temperature of the second annealing treatment is 90° C. to 120° C. For example, the temperature of the second annealing treatment can be 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C. or any range thereof.

[0172] In some embodiments, the second annealing treatment time is 5 min to 10 min. For example, the first annealing treatment time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min or any range thereof.

[0173] The temperature and time of the second annealing treatment are within the above range, which is conducive to achieving relatively complete removal of impurities.

[0174] In some embodiments, the step S10 of preparing a perovskite matrix layer on the support layer may include the following steps:

[0175] S100, contacting a perovskite precursor solution with an anti-solvent on the support layer to form a wet film of the perovskite matrix layer;

[0176] S110, performing a third annealing treatment on the wet film of the perovskite matrix layer to obtain the perovskite matrix layer.

[0177] In the above preparation steps S100 to S110, the perovskite precursor solution is treated with an anti-solvent, which is beneficial to improving the crystallinity of the perovskite matrix layer at room temperature; and then a third annealing treatment is performed, which is beneficial to further promote the crystal growth of the perovskite matrix layer and remove the residual anti-solvent.

[0178] In some embodiments, the perovskite precursor solution contains a compound ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion.

[0179] In some embodiments, the A ions include organic cations, Li + 、Na+ , K + , Rb + and Cs + One or more of .

[0180] In some embodiments, the organic cation includes at least one of an organic amine ion, a carbamimidyl group and an imidazolyl group.

[0181] In some embodiments, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, and hexylamine.

[0182] Optionally, the A ions include organic amine ions and Cs + One or more of .

[0183] In some embodiments, the B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of .

[0184] Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following.

[0185] In some embodiments, the C ions include Cs + 、Ag + , K + And Ru + One or more of.

[0186] In some embodiments, the D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of .

[0187] In some embodiments, the X ions include F - , Cl - Br - and one or more of I-.

[0188] Optionally, the X ions include Cl-, Br - and one or more of I-.

[0189] In some embodiments, the perovskite precursor solution contains an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.1.

[0190] In some embodiments, the molar concentration of the perovskite precursor solution is 1 mol / L to 1.8 mol / L. For example, the molar concentration of the perovskite precursor solution can be 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L or within a range consisting of any of the above values.

[0191] The molar concentration of the perovskite precursor solution is within the above range, which can provide sufficient organic light-emitting materials for the perovskite matrix layer, thereby providing sufficient photoelectrons to make the luminescence efficiency (photoelectric conversion efficiency) of the perovskite cell at a relatively high level.

[0192] In some embodiments, the perovskite precursor solution also includes a third organic solvent, which may include but is not limited to one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, 2-mercaptoethanol and 1-methyl-2-pyrrolidone.

[0193] In some embodiments, the anti-solvent promotes the crystal growth of the perovskite matrix layer; it may include but is not limited to one or more of chlorobenzene, anisole, ethyl ether, ethyl acetate, and the like.

[0194] In some embodiments, the temperature of the third annealing treatment is 90° C. to 150° C. For example, the temperature of the third annealing treatment can be 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C. or within a range consisting of any of the above values.

[0195] In some embodiments, the third annealing treatment lasts for 10 min to 40 min. For example, the third annealing treatment lasts for 10 min, 20 min, 30 min, 40 min, or any range thereof.

[0196] The temperature and time of the third annealing treatment are within the above range, which is beneficial to further promote the crystal growth of the perovskite matrix layer and remove the residual anti-solvent.

[0197] In a third aspect, the present application provides a perovskite cell, which includes the perovskite film described in the first aspect of the present application or the perovskite film prepared by the method described in the second aspect of the present application.

[0198] In some embodiments, the present application provides a perovskite cell, comprising a first electrode, a second electrode, and the perovskite film described in the first aspect of the present application, wherein the perovskite film is disposed between the first electrode and the second electrode.

[0199] The perovskite film described in the first aspect of the present application is a light-absorbing layer in a perovskite cell.

[0200] When the perovskite battery is working, after the light-absorbing layer is exposed to light, the internal electrons gain energy and break free from the light-absorbing layer to form negatively charged electron carriers, and at the same time form positively charged hole carriers, thereby obtaining electron-hole pairs. Free electrons and free holes are transmitted in opposite directions through the corresponding transport layer, so that electrons and holes flow, forming external current, and realizing the conversion of light energy into electrical energy. Further, after the light-absorbing layer absorbs photons, it is stimulated to generate electron-hole pairs, which further dissociate to form free carriers with opposite charges, among which free electrons are transmitted to the positive electrode through the electron transport layer, and free holes are transmitted to the negative electrode through the hole transport layer. The two free carriers are collected by the corresponding electrodes respectively, further forming photocurrent in the circuit of the perovskite battery.

[0201] In some embodiments, Figure 3 As shown, the perovskite battery includes a first electrode layer 10, a perovskite layer 30, a first charge transport layer 40 and a second electrode layer 50 which are stacked in sequence, the perovskite layer 30 includes the perovskite film mentioned above in the present application, and the nano-protrusions in the perovskite film face the first charge transport layer 40 along the thickness direction of the perovskite layer 30.

[0202] The perovskite cell provided in the present application includes the aforementioned perovskite film, and the nano-protrusions in the perovskite film face the first charge transport layer. Thus, the nano-protrusions can enable point contact at the interface between the perovskite layer and the first charge transport layer, thereby reducing the contact area between the perovskite layer and the first charge transport layer, reducing the occurrence of non-radiative recombination caused by the interface contact between the two, and thereby improving the open circuit voltage and photoelectric conversion efficiency of the battery.

[0203] In some embodiments, the first charge transport layer 40 includes a first charge transport matrix layer 410 and a filler 420 disposed on the surface of the first charge transport matrix layer, wherein the filler 420 extends along the thickness direction of the first charge transport matrix layer 410 and fills the gaps formed by the nano-protrusions 320 .

[0204] It can be understood that the above-mentioned filling body is automatically filled and formed based on the presence of multiple nano-protrusions on the perovskite layer when the first charge transport layer is prepared on the perovskite layer after the perovskite layer is prepared.

[0205] The first charge transport layer includes a filler formed by filling in the gaps formed by the nano-protrusions, and the filler can achieve point contact between the first charge transport layer and the perovskite layer. At the same time, by adjusting the spacing between the nano-protrusions, the number of gaps formed by the nano-protrusions on the perovskite layer per unit area can be adjusted, and the density of the filler can be adjusted. By adjusting the density of the filler, the filling amount of the first charge transport layer can be adjusted, thereby achieving the control of the contact surface between the first charge transport layer and the perovskite layer, and fully reducing the occurrence of non-radiative recombination between the two, effectively improving the open circuit voltage and photoelectric conversion efficiency of the battery.

[0206] In some embodiments, the first charge transport matrix layer has the same chemical composition as the filler.

[0207] In some embodiments, the first charge transport layer comprises an electron transport layer.

[0208] When the first charge transport layer includes an electron transport layer, the nano-protrusions in the perovskite layer can reduce the contact interface between the perovskite layer and the electron transport layer, reduce the non-radiative recombination of holes on the surface of the perovskite layer and electrons in the electron transport layer caused by interface defects, thereby improving the photoelectric conversion efficiency of the battery.

[0209] In some embodiments, Figure 4 As shown, the perovskite battery may include a first electrode layer 10, a second charge transport layer 20, a perovskite layer 30, a first charge transport layer 40 and a second electrode layer 50 stacked in sequence, and the second charge transport layer 20 is arranged between the first electrode layer 10 and the perovskite layer 30.

[0210] In some embodiments, the second charge transport layer comprises a hole transport layer.

[0211] In some embodiments, the perovskite cell may include a first electrode layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked in sequence.

[0212] In some embodiments, the perovskite cell may include a first electrode layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked in sequence.

[0213] In some embodiments, the perovskite cell may include a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked in sequence.

[0214] The electron transport layer can extract and transport electron carriers and block the passage of free holes.

[0215] The hole transport layer can extract and transport hole carriers and block the passage of free electrons.

[0216] It can be understood that the perovskite battery includes two electrodes, namely a first electrode and a second electrode, one of which serves as a positive electrode and can collect electron carriers transmitted via an electron transport layer, and the other serves as a negative electrode and can collect hole carriers transmitted via a hole transport layer.

[0217] In some embodiments, the electron transport layer material may include but is not limited to one or more of the following materials and their derivatives: imide compounds, quinone compounds, fullerenes and their derivatives, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), calcium titanate (CaTiO3), lithium fluoride (LiF), calcium fluoride (CaF2), poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), poly 3-hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4 -ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides, silicon oxide (SiO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), etc.; wherein the metal elements 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.

[0218] In some embodiments, the hole transport layer may include, but is not limited to, one or more of the following materials and their derivatives: 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), nickel oxide (NiO x ), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS), WO3 and other materials can transport holes and block electrons.

[0219] In some embodiments, one of the "first charge transport layer" and the "second charge transport layer" is an electron transport layer, and the other is a hole transport layer. In some embodiments, the first charge transport layer is an electron transport layer. In some embodiments, the first charge transport layer is a hole transport layer.

[0220] In some embodiments, one of the "first electrode" and the "second electrode" is a transparent electrode for light incidence. In some embodiments, the first electrode is a transparent electrode.

[0221] In some embodiments, the material of the transparent electrode may be exemplified by, but not limited to, one or more of the following materials: FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), etc.

[0222] In some embodiments, the second electrode comprises a conductive material, and further, the conductive material may be an organic conductive material, an inorganic conductive material, or a combination thereof. Non-limiting examples of inorganic conductive materials include metal conductive materials, and further, the metal conductive material may include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), etc., or any suitable mixture of the aforementioned elements. The conductive material may include a conductive oxide, and further, the conductive material may be a conductive oxide; non-limiting examples of conductive oxides may include one or more of FTO, ITO, IWO, AZO, etc.

[0223] In some embodiments, the perovskite cell may include a transparent electrode, a perovskite layer, an electron transport layer, and a second electrode layer stacked in sequence.

[0224] In some embodiments, the perovskite cell may include a transparent electrode, a perovskite layer, a hole transport layer, and a second electrode layer stacked in sequence.

[0225] In some embodiments, the perovskite cell may include a transparent electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked in sequence.

[0226] In some embodiments, the perovskite cell may include a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked in sequence.

[0227] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0228] The perovskite cells provided in this application may include formal and trans forms.

[0229] Officially, the perovskite cell includes a transparent electrode and an electron transport layer, a perovskite layer, a hole transport layer and a second electrode layer stacked in sequence on the transparent electrode.

[0230] For the trans type, the perovskite cell comprises a transparent electrode and a hole transport layer, a perovskite layer, an electron transport layer and a second electrode layer sequentially stacked on the transparent electrode, wherein the transparent electrode is used for light incidence.

[0231] In some embodiments, the perovskite cell includes the following structures arranged in sequence: a substrate layer (which may be a glass substrate or a flexible substrate), a first electrode, a hole transport layer, a perovskite layer, 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, polyethylene naphthalate, etc. Optionally, the first electrode is a transparent electrode for light incidence.

[0232] In some embodiments, the perovskite cell comprises the following structures arranged in sequence: a substrate layer (glass substrate or flexible substrate), a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. Optionally, the first electrode is a transparent electrode for light incidence. The definition of the flexible substrate can be found in the above text.

[0233] The substrate layer involved in the implementation manner or example of the present application may be, but is not limited to, a glass substrate or a flexible substrate.

[0234] In some embodiments, the substrate layer is a flexible substrate layer. Further, the material of the substrate layer may be, for example (but not limited to), an organic polymer material, and further, may be mixed in different proportions with one or more of the following materials: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0235] In the present application, the specifications of the perovskite cell are not particularly limited and may be, but not limited to, 300 mm×300 mm.

[0236] It can be understood that the structure of the perovskite battery involved in the present application may not be limited to the structural layers listed above. Other functional layers, such as buffer layers, can also be introduced as needed. In some embodiments, the perovskite battery can be provided with a buffer layer with a suitable energy level, which can play a role in reducing energy level barriers, promoting energy level matching, improving carrier extraction efficiency, and at the same time, passivating interface defect states, protecting light absorption layers, inhibiting water molecules, oxygen oxidation and decomposition of batteries, improving photoelectric conversion efficiency, and improving the stability of perovskite batteries. One or more of the above. Depending on the location of the buffer layer, the type of buffer layer may include a buffer layer between the hole transport layer and the anode, a buffer layer between the electron transport layer and the cathode, a buffer layer between the hole transport layer and the absorption layer, and a buffer layer between the electron transport layer and the absorption layer. The materials that can be used for the buffer layer in the perovskite battery may include, but are not limited to: Cu2O, NiO, AZO, TiO2, etc.

[0237] In a fourth aspect, the present application provides an electrical device comprising the perovskite cell described in the third aspect of the present application.

[0238] In some embodiments, the perovskite battery can be used as a power generation device of an electrical device. The type of the power generation device can include but is not limited to integrated power generation. The location of the power generation device can include but is not limited to the roof, back panel, etc. of a car.

[0239] Furthermore, the above-mentioned electrical devices may include mobile devices, such as mobile phones, laptop computers, etc., electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited thereto.

[0240] Figure 5 The electrical device is taken as an example. The electrical device is a car, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0241] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0242] As another example, the power-consuming device may be a wearable device, such as a watch.

[0243] Example

[0244] Below, some embodiments of the present application are described. The embodiments described below are exemplary, are only used to explain the present application, and cannot be construed as limiting the present application. In the embodiments, if the technology or conditions are not indicated, they are carried out according to the description above, or according to the technology or conditions described in the document in this area or according to the product specification. The reagents used or the instruments that do not indicate the manufacturer are conventional products that can be obtained commercially, or can be synthesized in a conventional manner by commercially available products.

[0245] In the following embodiments, "room temperature" refers to 20°C to 30°C, and further, may be 25°C.

[0246] Example 1

[0247] The perovskite cell prepared in Example 1 adopts an inverted pin structure.

[0248] (1) Preparation of the first electrode

[0249] Take a 5cm×5cm FTO conductive glass, leave an insulating area after laser etching, use deionized water, detergent, ethanol, isopropanol, acetone, ethanol, deionized water for 20 minutes, blow dry with N2, and use it as the first electrode.

[0250] (2) Preparation of hole transport layer

[0251] NiOx (wherein Ni can be Ni 2+ or Ni 3+) nanoparticle solution (mass concentration of 5 mg / mL) was spin-coated on the above-mentioned transparent conductive glass at a speed of 3000 rpm for 40 s, followed by annealing at 150°C for 15 min; then phosphate carbazole (AEMD) solution (mass concentration of 0.3 mg / mL) was continued to be spin-coated on NiOx at a speed of 5000 rpm for 30 s, followed by annealing at 100°C for 10 min, and naturally cooled to obtain a hole transport layer with a thickness of about 15 nm, which was used as the second charge transport layer.

[0252] (3) Preparation of perovskite layer

[0253] ① Preparation of perovskite precursor layer

[0254] The perovskite precursor solution (the perovskite precursor component is Cs 0.05 FA 0.85 MA 0.1 PbI3, molar concentration of 1.5 mg / mL) was first spin-coated on the hole transport layer at a speed of 1000 rpm for 10 s; then a second spin coating was performed at a speed of 5000 rpm for 30 s; during the second spin coating process, 200 uL of chlorobenzene antisolvent was added at 20 s.

[0255] Afterwards, the film was annealed at 100°C and cooled to room temperature to obtain a perovskite matrix layer with a thickness of about 800 nm.

[0256] ② Preparation of nano-protrusions

[0257] On the perovskite substrate layer, continue to spin-coat the ammonium salt solution (the ammonium salt solution is ethylenediamine salt dissolved in isopropanol solvent to make its mass concentration 0.1 mg / mL) at a spin-coating speed of 5000 rpm and a spin-coating time of 30 seconds, followed by annealing at 100° C. for 10 minutes.

[0258] After cooling, pure isopropanol solvent is used for spin coating at a spin coating speed of 5000 rpm for 30 seconds; then annealing is performed at 100°C for 5 minutes to obtain multiple nano-protrusions, obtain a perovskite film, and form a perovskite layer.

[0259] (4) Preparation of component electron transport layer

[0260] The prepared perovskite layer was placed in a vacuum thermal evaporation device and evacuated to 4×10 -4 Pa, deposit 30nmC 60 , 7nm BCP (bathocuproine) is used to obtain an electron transport layer, which is used as the first charge transport layer.

[0261] (5) Preparation of the Second Electrode

[0262] A Cu counter electrode is deposited on the electron transport layer using a thermal evaporation method using a mask with a specific pattern to form a second electrode with a thickness of about 100 nm to obtain a perovskite cell.

[0263] Embodiments 2 to 24

[0264] The preparation method of the perovskite film and the perovskite battery is similar to that of Example 1, except that the relevant parameters of the perovskite film and the preparation process thereof are adjusted, and the specific parameters are shown in the following Table 1. Wherein, " / " indicates that the corresponding parameter does not exist.

[0265] Comparative Example 1

[0266] The preparation method of the perovskite film and the perovskite battery is similar to that of Example 1, except that in the above step ②, a pure isopropanol solvent of the same mass concentration is used instead of the ammonium salt solution.

[0267] Comparative Example 2

[0268] The method for preparing the perovskite film and the perovskite battery is similar to that in Example 1, except that step ② in the above step (3) is omitted.

[0269] Table 1

[0270]

[0271]

[0272] In addition, relevant performance tests were performed on the perovskite films and perovskite cells in Examples 1 to 24 and Comparative Examples 1 to 2, and the structures are shown in Table 2 below.

[0273] Test Method

[0274] (1) Surface morphology test

[0275] The surface morphology of the perovskite film was tested using a scanning electron microscope (model: Hitachi, HD-2700).

[0276] (2) Photoelectric conversion efficiency test

[0277] At room temperature and pressure, under standard simulated sunlight (AM 1.5G, 100mW / cm 2 ) to test the battery performance and obtain the IV curve (volt-ampere characteristic curve). According to the IV curve and the data fed back by the test equipment (four-channel digital source meter, Keithley2440), the short-circuit current density Jsc (unit: mA / cm 2 ), open circuit voltage Voc (unit V), maximum light output current Jmpp (unit mA) and maximum light output voltage Vmpp (unit V).

[0278] The fill factor FF of the battery can be calculated by the formula FF = Jsc × Voc / (Jmpp × Vmpp), unit %. The photoelectric conversion efficiency PCE of the battery can be calculated by the formula PCE = Jsc × Voc × FF / Pw, unit %; Pw represents the input power, unit mW.

[0279] “Normal temperature and pressure” refers to normal pressure: the pressure is one atmosphere when the temperature is 25°C; normal temperature refers to 20°C to 30°C, and further, it can be 25°C.

[0280] Table 2

[0281] Open circuit voltage(V) Photoelectric conversion efficiency (%) Example 1 1.162 24.3 Example 2 1.143 23.9 Example 3 1.155 24.2 Example 4 1.133 23.7 Example 5 1.146 24.0 Example 6 1.139 23.5 Example 7 1.161 24.5 Example 8 1.123 23.1 Example 9 1.145 23.9 Example 10 1.147 23.7 Embodiment 11 1.128 22.8 Example 12 1.132 23.2 Example 13 1.151 23.6 Embodiment 14 1.140 23.3 Embodiment 15 1.136 23.7 Example 16 1.129 22.9 Embodiment 17 1.155 24.0 Embodiment 18 1.138 23.6 Embodiment 19 1.146 24.3 Embodiment 20 1.130 23.5 Embodiment 21 1.128 22.8 Embodiment 22 1.127 22.5 Embodiment 23 1.129 22.6 Embodiment 24 1.115 22.1 Comparative Example 1 1.112 22.0 Comparative Example 2 1.093 21.4

[0282] In Table 2 above, by comparing the embodiment with comparative example 1, it can be seen that the open circuit voltage and photoelectric conversion efficiency of the embodiment are higher than those of comparative example 1, indicating that the simple isopropanol solvent cannot form nano-protrusions. By comparing the embodiment with comparative example 2, it can be seen that the open circuit voltage and photoelectric conversion efficiency of the embodiment are higher than those of comparative example 2, indicating that the nano-protrusions provided on the perovskite layer of the present application can improve the open circuit voltage and photoelectric conversion efficiency of the battery.

[0283] 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.

[0284] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples. Within the scope of the technical solution of the present application, the embodiments that have the same structure as the technical idea and play the same effect are all included in the technical scope of the present application. The above-mentioned embodiments only express several embodiments of the present application, and the description is relatively detailed, but it cannot be understood as a limitation on the scope of the patent. In addition, without departing from the scope of the subject matter of the present application, various deformations that can be thought of by those skilled in the art and other methods of combining and constructing some of the constituent elements in the embodiments are also included in the scope of the present application. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several deformations and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the attached claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A perovskite film, characterized in that: include: Perovskite matrix layer; and A plurality of spaced-apart nano-protrusions are disposed on at least one surface of the perovskite matrix layer.

2. The perovskite film according to claim 1, characterized in that The average particle size of the nano-protrusions is 1 nm to 10 nm, and can be optionally 1 nm to 5 nm.

3. The perovskite thin film according to claim 1 or 2, characterized in that: The spacing distance between the center points of two adjacent nano-protrusions is 2 nm to 1 μm, and can be optionally 10 nm to 0.5 μm.

4. The perovskite film according to claim 1 or 2, characterized in that: The nano-protrusions satisfy at least one of the following conditions: (1) The nano-protrusions have an irregular columnar morphology; (2) The chemical composition of the nano-protrusions includes L m A n-1 B n X 3n+1 , 1≤m≤2, n≥1 and is an integer, where L ion is NH4 + , A ion is a monovalent cation, B ion is a divalent metal cation, C ion and D ion are monovalent and trivalent metal cations respectively, and X ion is a monovalent anion; The A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of; Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group; Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine; Optionally, the A ions include organic amine ions and Cs + One or more of; The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of; Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following: The C ions include Cs + 、Ag + , K + And Ru + One or more of; The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of; The X ions include F-, Cl-, Br - and one or more of I-; Optionally, the X ions include Cl-, Br - and I - One or more of .

5. The perovskite thin film according to claim 1 or 2, characterized in that: The perovskite matrix layer satisfies at least one of the following conditions: (1) The thickness of the perovskite matrix layer is 100 nm to 1000 nm, and can be optionally 500 nm to 800 nm; (2) The chemical composition of the perovskite matrix layer includes a compound ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion; The A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of; Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group; Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine; Optionally, the A ions include organic amine ions and Cs + One or more of; The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of; Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following: The C ions include Cs + 、Ag + , K + And Ru + One or more of; The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of; The X ions include F - , Cl - Br - and I - One or more of; Optionally, the X ions include Cl - Br - and I - One or more of; Optionally, the chemical composition of the perovskite matrix layer includes an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.

1.

6. A method for preparing a perovskite film, characterized in that: include: preparing a perovskite matrix layer on the support layer; The ammonium salt solution is brought into contact with the surface of the perovskite matrix layer and a first annealing treatment is performed to form a plurality of spaced nano-protrusions on the surface of the perovskite matrix layer, thereby forming a perovskite complex and obtaining the perovskite film.

7. The method according to claim 6, characterized in that The ammonium salt solution satisfies at least one of the following conditions: (1) The mass concentration of the ammonium salt solution is 0.05 mg / mL to 1 mg / mL; (2) the ammonium salt comprises one or more of ethylenediamine, propylenediamine, butylenediamine and p-phenylenediamine; (3) The ammonium salt solution contains a first organic solvent, and the first organic solvent includes one or more of isopropanol, ethanol, ethylene glycol and glycerol.

8. The method according to claim 6 or 7, characterized in that: The first annealing treatment satisfies at least one of the following conditions: (1) The temperature of the first annealing treatment is 90° C. to 120° C.; (2) The first annealing treatment time is 5 minutes to 10 minutes.

9. The method according to claim 6 or 7, characterized in that: Also includes: The perovskite composite is subjected to an impurity removal treatment.

10. The method according to claim 9, characterized in that The step of removing impurities from the perovskite complex comprises: bringing a second organic solvent into contact with the surface of the perovskite complex and performing a second annealing treatment, Optionally, the second organic solvent includes one or more of isopropanol, ethanol, ethylene glycol and glycerol; Optionally, the temperature of the second annealing treatment is 90° C. to 120° C.; Optionally, the second annealing treatment lasts for 5 min to 10 min.

11. The method according to claim 6 or 7, characterized in that: The step of preparing the perovskite matrix layer on the supporting layer comprises: contacting a perovskite precursor solution with an anti-solvent on the support layer to form a wet film of the perovskite matrix layer; Performing a third annealing treatment on the wet film of the perovskite matrix layer to obtain the perovskite matrix layer; Optionally, the temperature of the third annealing treatment is 90° C. to 150° C.; Optionally, the third annealing treatment lasts for 10 min to 40 min.

12. The method according to claim 11, characterized in that Satisfy at least one of the following conditions: (1) The perovskite precursor solution contains a compound ABX3 or A2CDX6, wherein the A ion is a monovalent cation, the B ion is a divalent metal cation, the C ion and the D ion are monovalent and trivalent metal cations, respectively, and the X ion is a monovalent anion; The A ions include organic cations, Li + 、Na + , K + , Rb + and Cs + One or more of; Optionally, the organic cation includes at least one of an organic amine ion, a carboxamidine group, and an imidazole group; Further optionally, the organic amine ion includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine and hexylamine; Optionally, the A ions include organic amine ions and Cs + One or more of; The B ions include Pb 2+ Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ ,Ge 2+ , Fe 2+ 、Co 2+ , Cu 2+ and Ni 2+ One or more of; Optionally, the B ions include Pb 2+ and Sn 2+ One or both of the following: The C ions include Cs + 、Ag + , K + And Ru + One or more of; The D ions include Bi 3+ 、Ni 3+ , Fe 3+ and Cu 3+ One or more of; The X ions include F - , Cl - Br - and I - One or more of; Optionally, the X ions include Cl - Br - and I - One or more of; Optionally, the perovskite precursor solution contains an organic halide Cs x FA y MA z PbI3, x+y+z=1, 0≤x≤0.05, 0.8≤y≤0.95, 0≤z≤0.1; (2) The molar concentration of the perovskite precursor solution is 1 mol / L to 1.8 mol / L; (3) The anti-solvent comprises one or more of chlorobenzene, anisole, ethyl ether and ethyl acetate.

13. A perovskite battery, characterized in that: The perovskite film comprises the perovskite film according to any one of claims 1 to 5 or the perovskite film prepared by the method according to any one of claims 6 to 12.

14. The perovskite battery according to claim 13, characterized in that: It includes a first electrode layer, a perovskite layer, a first charge transport layer and a second electrode layer which are stacked in sequence, wherein the perovskite layer includes the perovskite film, wherein the nano-protrusions in the perovskite film face the first charge transport layer along the thickness direction of the perovskite layer.

15. The perovskite cell according to claim 14, characterized in that: The first charge transport layer comprises a first charge transport matrix layer, and a filler disposed on the surface of the first charge transport matrix layer, wherein the filler extends along the thickness direction of the first charge transport matrix layer and fills the gaps formed by the nano protrusions; Optionally, the first charge transport layer comprises an electron transport layer; Optionally, the first charge transport matrix layer has the same chemical composition as the filler.

16. The perovskite cell according to claim 14 or 15, characterized in that: Also included is a second charge transport layer, the second charge transport layer being disposed between the first electrode layer and the perovskite layer; Optionally, the second charge transport layer comprises a hole transport layer.

17. An electrical device, characterized in that: A perovskite battery comprising any one of claims 13-16.

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