Perovskite precursor solution, perovskite thin film, perovskite cell and preparation method thereof, and photovoltaic module

Abstract

The invention belongs to the technical field of solar cells. The invention provides a perovskite precursor solution, a perovskite thin film, a perovskite cell and a preparation method thereof, and a photovoltaic module. The perovskite precursor solution comprises a perovskite material, an additive and a first solvent, the perovskite material is of an ABX3 type structure, and A is a monovalent cation; b is a divalent cation; x is a monovalent anion; the additive is an organic matter with an amino functional group and a keto functional group. According to the perovskite thin film provided by the embodiment of the invention, the phenomenon of broadband gap perovskite thin film segregation can be inhibited, so that the stability of a perovskite battery comprising the perovskite thin film is enhanced.

Description

Technical Field

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

[0002] Wide bandgap perovskite solar cells, as the front cell in tandem cells, are the key to achieving efficient and stable tandem solar cells. This adjustable bandgap property enables wide bandgap perovskite solar cells to be optimized for different lighting conditions and application scenarios, thereby improving their adaptability and practicality.

[0003] However, the high halogen bromine content in the wide-bandgap perovskite component causes the halogen migration (phase transition) process to change dramatically during the crystallization process, which easily forms non-radiative recombination centers, thus affecting the quality and performance of the perovskite film. This segregation phenomenon not only reduces the photoelectric conversion efficiency of perovskite solar cells, but also affects the long-term stability of the device.

[0004] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the invention

[0005] The embodiments of the present application provide a perovskite precursor solution, a perovskite film, a perovskite cell and a preparation method thereof, and a photovoltaic module to solve or alleviate the above-mentioned technical problems such as low photoelectric efficiency and low long-term stability caused by segregation.

[0006] According to a first aspect of an embodiment of the present application, a perovskite precursor solution is provided, characterized in that it includes: a perovskite material, an additive and a first solvent, wherein the perovskite material is an ABX3 type structure, wherein A is a monovalent cation; B is a divalent cation; X is a monovalent anion; and the additive is an organic substance having an amino functional group and a keto functional group.

[0007] The perovskite precursor solution of the embodiment of the present application includes a perovskite material and an additive, wherein the additive is an organic substance having an amino group and a keto group. Among them, the amino functional group can combine with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, while the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduce defects and vacancies in the lattice, and thus stabilize the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ions (X) is jointly inhibited and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, thereby suppressing the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film made from the precursor solution.

[0008] According to an embodiment of the present application, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione.

[0009] According to an embodiment of the present application, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ions, methylamine ions, and cesium ions; B is one or more of divalent lead ions and divalent tin ions; and X is selected from halogen ions.

[0010] According to the embodiments of the present application, in the perovskite precursor solution, the concentration of the perovskite material is 1-3 mol / L.

[0011] According to an embodiment of the present application, in the perovskite precursor solution, the concentration of the additive is 1%-10% of the concentration of the perovskite material.

[0012] According to a second aspect of an embodiment of the present application, a perovskite film is provided, wherein the perovskite film is formed by a perovskite precursor solution, wherein the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent, wherein the perovskite material is an ABX3 type structure, wherein A is a monovalent cation; B is a divalent cation; X is a monovalent anion; and the additive is an organic substance having an amino functional group and a keto functional group.

[0013] The perovskite film of the embodiment of the present application includes a perovskite material and an additive, and the additive is an organic substance having an amino group and a keto group. Among them, the amino functional group can be combined with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of the perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, and the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduce defects and vacancies in the lattice, and thus stabilize the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ion (X) is jointly suppressed and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, so as to suppress the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film.

[0014] According to an embodiment of the present application, based on the total mass of the perovskite film, the molar ratio of the perovskite material to the additive is 10:(0.1-1).

[0015] According to an embodiment of the present application, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione.

[0016] According to an embodiment of the present application, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ions, methylamine ions, and cesium ions; B is one or more of divalent lead ions and divalent tin ions; and X is selected from halogen ions.

[0017] According to the third aspect of the embodiment of the present application, a perovskite battery is provided. The battery comprises a transparent conductive glass, a first charge transport layer, a perovskite film, a second charge transport layer and a back electrode which are stacked in sequence. The perovskite film is formed by a perovskite precursor solution; the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent; the perovskite material is an ABX3 type structure, A is a monovalent cation; B is a divalent cation; X is a monovalent anion; the additive is an organic substance having an amino functional group and a keto functional group.

[0018] The perovskite film in the perovskite battery of the embodiment of the present application includes a perovskite material and an additive, wherein the additive is an organic substance having an amino group and a keto group. Among them, the amino functional group can combine with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, while the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduce defects and vacancies in the lattice, and thus stabilize the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ions (X) is jointly inhibited and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, thereby suppressing the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film.

[0019] According to an embodiment of the present application, the thickness of the perovskite film is 400-700 nm.

[0020] According to an embodiment of the present application, the thickness of the first charge transport layer is 1-100 nm.

[0021] According to an embodiment of the present application, the thickness of the second charge transport layer is 1-100 nm.

[0022] In a fourth aspect of the embodiment of the present application, a method for preparing a perovskite cell is provided, comprising the following steps: (1) providing transparent conductive glass; (2) forming a first charge transport layer on one surface of the transparent conductive glass; (3) forming a perovskite film on the side of the first charge transport layer away from the transparent conductive glass; (4) forming a second charge transport layer on the side of the perovskite film away from the first charge transport layer; (5) forming a back electrode on the side of the second charge transport layer away from the perovskite film, wherein the perovskite film is formed by a perovskite precursor solution; the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent, the perovskite material is an ABX3 type structure, A is a monovalent cation; B is a divalent cation; X is a monovalent anion; and the additive is an organic substance having an amino functional group and a keto functional group. The method of the embodiment of the present application is simple to operate and can obtain a perovskite cell with high photoelectric efficiency and good long-term stability.

[0023] A fifth aspect of an embodiment of the present application provides a photovoltaic module, comprising the perovskite cell of the third aspect or the perovskite cell prepared by the method of the fourth aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the multiple drawings represent the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings only depict some embodiments disclosed in the present application and should not be regarded as limiting the scope of the present application.

[0025] Figure 1 is a schematic diagram of the structure of a perovskite battery provided in an embodiment of the present application; Figure 2 The embodiments of the present application provide a graph of the test results of MPPT (maximum power point tracking) of the perovskite solar cells of Example 1 and Comparative Example 1.

[0026] Description of reference numerals: 1: transparent conductive glass; 2: first charge transport layer; 3: perovskite film; 4: second charge transport layer; 5: back electrode. DETAILED DESCRIPTION

[0027] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. In the accompanying drawings, for clarity, the sizes of layers, regions, elements and their relative sizes may be exaggerated. Wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be understood as limitations on the present application. It should be noted that, in the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0028] It should be understood that when an element or layer is referred to as "on ...", "adjacent to ...", "connected to" or "coupled to" other elements or layers, it can be directly on, adjacent to, connected to or coupled to other elements or layers, or there can be intervening elements or layers. On the contrary, when an element is referred to as "directly on ...", "directly adjacent to ...", "directly connected to" or "directly coupled to" other elements or layers, there is no intervening element or layer. It should be understood that although the terms first, second, third, etc. can be used to describe various elements, components, regions, layers and / or parts, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teachings of the present application, the first element, component, region, layer or part discussed below can be represented as the second element, component, region, layer or part. When the second element, component, region, layer or part is discussed, it does not indicate that the present application necessarily has the first element, component, region, layer or part.

[0029] In this application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0030] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein, for example. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0031] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for broadly including quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0032] In a first aspect of an embodiment of the present application, a perovskite precursor solution is provided. The perovskite precursor solution comprises a perovskite material, an additive and a first solvent, wherein the perovskite material is an ABX3 type structure, wherein A is a monovalent cation, B is a divalent cation, X is a monovalent anion, and the additive is an organic substance having an amino functional group and a keto functional group.

[0033] The perovskite precursor solution of the embodiment of the present application includes a perovskite material and an additive, wherein the additive is an organic substance having an amino group and a keto group. Among them, the amino functional group can combine with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, while the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduce defects and vacancies in the lattice, and thus stabilize the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ions (X) is jointly inhibited and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, thereby suppressing the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery prepared by the perovskite precursor.

[0034] In some embodiments, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione. These organic substances contain amino and keto functional groups, which can be used to improve the polybromine problem in the wide band gap perovskite component, reduce the serious segregation phenomenon in the wide band gap, enhance the stability of the perovskite battery, and reduce the defects in the perovskite film and improve the film quality.

[0035] In some embodiments, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ion (FA), methylamine ion (MA), and cesium ion (Cs); B is one or more of divalent lead ion (Pb) and divalent tin ion (Sn); and X is selected from halogen ions.

[0036] Furthermore, X is Cl - Br - ,I - One or more of .

[0037] In some embodiments, the first solvent includes at least one of DMF, DMSO, NMP, and 2-ME.

[0038] Furthermore, the first solvent is DMF and DMSO, and the ratio of DMF:DMSO is (3-6):1.

[0039] In some embodiments, in the first mixed solution, the concentration of the perovskite material is 1-3 mol / L.

[0040] In some embodiments, in the first mixed solution, the concentration of the additive is 1%-10% of the concentration of the perovskite material.

[0041] In a second aspect of the embodiment of the present application, a perovskite film is provided. The perovskite film is formed by a perovskite precursor solution, the perovskite precursor solution comprising: a perovskite material, an additive and a first solvent, the perovskite material is an ABX3 type structure, the A is a monovalent cation; the B is a divalent cation; the X is a monovalent anion; the additive is an organic substance having an amino functional group and a keto functional group.

[0042] The perovskite film of the embodiment of the present application includes a perovskite material and an additive, wherein the additive is an organic substance having an amino group and a keto group. Among them, the amino functional group can be combined with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of the perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, while the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduces defects and vacancies in the lattice, and thus stabilizes the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ion (X) is jointly suppressed and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, so as to suppress the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film.

[0043] In some embodiments, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione. These organic substances contain amino and keto functional groups, which can be used to improve the polybromine problem in the wide band gap perovskite component, reduce the serious segregation phenomenon in the wide band gap, enhance the stability of the perovskite battery, and reduce the defects in the perovskite film and improve the film quality.

[0044] In some embodiments, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ion (FA), methylamine ion (MA), and cesium ion (Cs); B is one or more of divalent lead ion (Pb) and divalent tin ion (Sn); and X is selected from halogen ions.

[0045] Furthermore, X is Cl - Br - ,I - One or more of .

[0046] In some embodiments, in the perovskite film, the molar ratio of the perovskite material to the additive is 10:(0.1-1). This can further improve the quality of the perovskite film and the stability of the perovskite battery.

[0047] In some embodiments, the first solvent includes at least one of DMF, DMSO, NMP, and 2-ME.

[0048] Furthermore, the first solvent is DMF and DMSO, and the volume ratio of DMF:DMSO is (3-6):1.

[0049] According to a third aspect of the embodiments of the present application, a perovskite battery is provided. Figure 1 The battery comprises a transparent conductive glass 1, a first charge transport layer 2, a perovskite film 3, a second charge transport layer 4 and a back electrode 5 which are stacked in sequence. The perovskite film is formed by a perovskite precursor solution, and the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent. The perovskite material is an ABX3 type structure, A is a monovalent cation; B is a divalent cation; X is a monovalent anion; and the additive is an organic substance having an amino functional group and a keto functional group.

[0050] The perovskite film in the perovskite battery of the embodiment of the present application is formed by a perovskite precursor solution, and the perovskite precursor solution includes: a perovskite material, an additive and a first solvent, and the additive is an organic matter having an amino group and a keto group. Among them, the amino functional group can be combined with the coordinated unsaturated divalent cations (such as Pb²⁺) in the perovskite through a coordination bond to form a stable chemical bond, thereby hindering the movement of halogen anions through hydrogen bonds, effectively alleviating the segregation phenomenon of perovskite; the oxygen atom in the keto group can also serve as a ligand to form a coordination compound with the B-site ion. In this case, the oxygen atom provides a lone pair of electrons, and the B-site ion provides an empty orbital to form a coordination bond. This coordination effect further enhances the interaction between the keto group and the perovskite lattice, helps to stabilize the entire structure, reduce defects and vacancies in the lattice, and thus stabilize the perovskite structure. At the same time, through the synergistic effect of the amino functional group and the keto functional group, the movement of the halogen ions (X) is jointly inhibited and restricted by stabilizing the uncoordinated B-site ions and fixing the coordinated B-site ions, thereby suppressing the segregation of the wide-bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film.

[0051] In some embodiments, the transparent conductive glass includes at least one of transparent conductive oxide (ITO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), and aluminum-doped zinc oxide (AZO).

[0052] In some embodiments, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ion (FA), methylamine ion (MA), and cesium ion (Cs); B is one or more of divalent lead ion (Pb) and divalent tin ion (Sn); and X is selected from halogen ions.

[0053] Furthermore, X is Cl - Br - ,I - One or more of .

[0054] In some embodiments, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione. These organic substances contain amino and keto functional groups, which can be used to improve the polybromine problem in the wide band gap perovskite component, reduce the serious segregation phenomenon in the wide band gap, enhance the stability of the perovskite battery, and reduce the defects in the perovskite film and improve the film quality.

[0055] In some embodiments, the thickness of the perovskite film is 400-700 nm.

[0056] In some embodiments, the first charge transport layer has a thickness of 1-100 nm.

[0057] In some embodiments, the second charge transport layer has a thickness of 1-100 nm.

[0058] In some embodiments, the first charge transport layer is a hole transport layer, and the second charge transport layer is an electron transport layer.

[0059] Optionally, the first charge transport layer includes at least one of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline (TAPC), and nickel oxide. Thus, the first charge transport layer extracts and transports the photogenerated holes generated by the perovskite layer and suppresses the backflow of electrons.

[0060] Optionally, the first charge transport layer has a thickness of 1-20 nm.

[0061] Optionally, the second charge transport layer includes fullerene and its derivatives (C 60 , C 70Thus, the second charge transport layer is used to extract photogenerated carriers and improve the carrier recombination rate of the interface. Optionally, the second charge transport layer has a thickness of 10-100 nm.

[0062] In some other embodiments, the first charge transport layer is an electron transport layer, and the second charge transport layer is a hole transport layer.

[0063] Optionally, the second charge transport layer includes at least one of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline (TAPC), and nickel oxide. Thus, the second charge transport layer extracts and transports the photogenerated holes generated by the perovskite layer and suppresses the backflow of electrons.

[0064] Optionally, the second charge transport layer has a thickness of 1-20 nm.

[0065] Optionally, the first charge transport layer includes fullerene and its derivatives (C 60 , C 70 Thus, the first charge transport layer is used to extract photogenerated carriers and improve the carrier recombination rate of the interface. Optionally, the first charge transport layer has a thickness of 10-100 nm.

[0066] In some embodiments, the material of the back electrode includes one or more of gold, silver, chromium, and copper.

[0067] In some embodiments, the back electrode has a thickness of 50-200 nm.

[0068] In some embodiments, the perovskite cell further includes a blocking layer, wherein the blocking layer is located on a side of the back electrode close to the second charge transport layer.

[0069] Optionally, the barrier layer comprises BCP.

[0070] Optionally, the barrier layer has a thickness of 2-15 nm.

[0071] In some embodiments, the first solvent includes at least one of DMF, DMSO, NMP, and 2-ME.

[0072] Furthermore, the first solvent is DMF and DMSO, and the volume ratio of DMF:DMSO is (3-6):1.

[0073] In a fourth aspect of the embodiment of the present application, a method for preparing a perovskite cell is provided, comprising the following steps: (1) providing transparent conductive glass; (2) forming a first charge transport layer on one surface of the transparent conductive glass; (3) forming a perovskite film on the side of the first charge transport layer away from the transparent conductive glass; (4) forming a second charge transport layer on the side of the perovskite film away from the first charge transport layer; (5) forming a back electrode on the side of the second charge transport layer away from the perovskite film, wherein the perovskite film is formed by a perovskite precursor solution; the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent, the perovskite material is an ABX3 type structure, A is a monovalent cation; B is a divalent cation; X is a monovalent anion; the additive is an organic substance having an amino functional group and a keto functional group. The method of the embodiment of the present application is simple to operate and can obtain a perovskite cell with high photoelectric efficiency and good long-term stability.

[0074] According to an embodiment of the present application, in step (1), transparent conductive glass is provided.

[0075] In some embodiments, the transparent conductive glass is cleaned and dried, and then treated with a UV-ozone machine for 5-60 minutes.

[0076] Optionally, the cleaning is performed by first using a solution with a detergent:deionized water volume ratio of 1:(20-30), and then using deionized water and anhydrous ethanol for ultrasonic cleaning in an ultrasonic machine for 20-30 minutes respectively.

[0077] Optionally, drying is performed by blowing nitrogen. Optionally, the transparent conductive glass includes at least one of transparent conductive oxide (ITO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), and aluminum-doped zinc oxide (AZO).

[0078] According to an embodiment of the present application, step (2) forms a first charge transport layer on one surface of the transparent conductive glass.

[0079] In some embodiments, the first charge transport layer is a hole transport layer.

[0080] Optionally, the first electron transport layer material includes at least one of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline (TAPC), and nickel oxide. Thus, the first charge transport layer extracts and transports the photogenerated holes generated by the perovskite layer and suppresses the backflow of electrons.

[0081] Optionally, the first charge transport layer has a thickness of 1-20 nm.

[0082] In some other embodiments, the first charge transport layer is an electron transport layer.

[0083] Optionally, the first charge transport layer includes fullerene and its derivatives (C 60 , C 70 Thus, the first charge transport layer is used to extract photogenerated carriers and improve the carrier recombination rate of the interface. Optionally, the first charge transport layer has a thickness of 10-100 nm.

[0084] In some embodiments, the operation of forming the first charge transport layer includes: mixing the first charge transport layer material and a second solvent to obtain a second mixed solution; covering the second mixed solution on one surface of the transparent conductive glass and performing a second annealing.

[0085] Optionally, the second solvent includes isopropanol, ethanol, or the like.

[0086] Optionally, in the second mixed solution, the concentration of the first charge transport layer material is 0.1-1 g / L.

[0087] Optionally, the mixing time is 10-15 hours.

[0088] Optionally, the second annealing is performed at 90-120° C. for 5-20 min.

[0089] According to an embodiment of the present application, step (3) forms a perovskite film on a side of the first charge transport layer away from the transparent conductive glass.

[0090] In some embodiments, a method for forming a perovskite film on a side of the first charge transport layer away from the transparent conductive glass includes: mixing a perovskite material, an additive, and a first solvent to obtain a perovskite precursor solution; and covering the perovskite precursor solution on a side of the first charge transport layer away from the transparent conductive glass to obtain a perovskite film.

[0091] Optionally, the perovskite material is an ABX3 type structure, A is one or more of formamidinium ion (FA), methylamine ion (MA), and cesium ion (Cs); B is one or more of divalent lead ion (Pb) and divalent tin ion (Sn); and X is selected from halogen ions.

[0092] Furthermore, X is Cl - Br - ,I - One or more of .

[0093] In some embodiments, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione. These organic substances contain amino and keto functional groups, which can be used to improve the polybromine problem in the wide band gap perovskite component, reduce the serious segregation phenomenon in the wide band gap, enhance the stability of the perovskite battery, and reduce the defects in the perovskite film and improve the film quality.

[0094] In some embodiments, the first solvent includes at least one of DMF, DMSO, NMP, and 2-ME.

[0095] Furthermore, the first solvent is DMF and DMSO, and the volume ratio of DMF:DMSO is (3-6):1.

[0096] In some embodiments, the concentration of the perovskite material in the perovskite precursor solution is 1-3 mol / L.

[0097] In some embodiments, in the perovskite precursor solution, the concentration of the additive is 1%-10% of the concentration of the perovskite material.

[0098] In some embodiments, the first annealing treatment is performed at a temperature of 100-160° C. for 10-30 min.

[0099] According to an embodiment of the present application, step (4) forms a second charge transport layer on a side of the perovskite film away from the first charge transport layer.

[0100] In some embodiments, the second charge transport layer is an electron transport layer.

[0101] Optionally, the second charge transport layer includes fullerene and its derivatives (C 60, C 70 , PCBM) at least one of them.

[0102] Optionally, the second charge transport layer has a thickness of 10-100 nm.

[0103] In some other embodiments, the second charge transport layer is a hole transport layer.

[0104] Optionally, the second charge transport layer includes at least one of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline (TAPC), and nickel oxide. Thus, the second charge transport layer extracts and transports the photogenerated holes generated by the perovskite layer and suppresses the backflow of electrons.

[0105] Optionally, the second charge transport layer has a thickness of 1-20 nm.

[0106] It can be understood that one of the first charge transport layer and the second charge transport layer is a hole transport layer, and the other is an electron transport layer.

[0107] In some embodiments, the second charge transport layer is formed by thermal evaporation.

[0108] In some embodiments, a blocking layer is formed on a side of the second charge transport layer away from the perovskite film. The blocking layer includes BCP.

[0109] Optionally, the barrier layer has a thickness of 2-15 nm.

[0110] According to an embodiment of the present application, step (5) forms a back electrode on a side of the second charge transport layer away from the perovskite film.

[0111] In some embodiments, the material of the back electrode includes one or more of gold, silver, chromium, and copper.

[0112] In some embodiments, the back electrode is formed by thermal evaporation.

[0113] A fifth aspect of an embodiment of the present application provides a photovoltaic module, comprising the perovskite cell of the third aspect or the perovskite cell prepared by the method of the fourth aspect.

[0114] Hereinafter, exemplary embodiments according to the present application will be described in more detail with reference to the accompanying drawings. It should be noted that these exemplary embodiments can be implemented in many different forms and should not be construed as being limited to the embodiments described herein.

[0115] Example 1 Step 1: Place the ITO glass of 2.5×2.5 cm in size into the cleaning rack, and use a solution of detergent: deionized water volume ratio = 1:20, deionized water and anhydrous ethanol to ultrasonically clean it in an ultrasonic machine for 20 minutes, and then blow dry it with nitrogen for later use.

[0116] Step 2: Weigh 0.5 mg of Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid) and add 1 ml of anhydrous isopropyl alcohol (IPA) solvent in a glove box. After fully dissolving for 12 hours, a precursor solution (second mixed solution) of the hole transport layer (first charge transport layer) is obtained.

[0117] Step 3: Perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3. Aminoacetone and the first solvent (DMF:DMSO volume ratio of 4:1) are mixed to obtain a first mixed solution (wide bandgap perovskite precursor solution), in which the perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3 concentration is 1.4 mol / L, and the concentration of aminoacetone is 5% of the concentration of the perovskite material.

[0118] Step 4: The ITO glass cleaned in step 1 was treated with UV ozone for 15 minutes, and the Me-4PACz solution (second mixed solution) prepared in step 2 was used to prepare a hole transport layer (first charge transport layer) by spin coating, and annealed at 100°C for 10 minutes to obtain a hole transport layer (first charge transport layer) with a thickness of 1 nm. The above operations were all carried out in a glove box with a nitrogen atmosphere.

[0119] Step 5: On the surface of the SAM layer obtained in step 4, the wide bandgap precursor solution (first mixed solution) prepared in step 3 is used to prepare a wide bandgap perovskite film by an anti-solvent method, and then annealed at 130° C. for 20 minutes to obtain a wide bandgap perovskite functional layer film (500 nm thick perovskite film), and the molar ratio of the perovskite material to the added in the perovskite film is 10:0.5.

[0120] Step 6: Place the wide bandgap perovskite functional layer film obtained in step 5 into a sealed box, and use thermal evaporation to obtain a 30nm thick electron transport layer C60 and a 6nm thick barrier layer BCP. Then, a mask of a suitable shape is used as a baffle, and thermal evaporation equipment is used again to deposit a 110nm thick Ag electrode to obtain an effective area of ​​0.1cm 2 Perovskite battery.

[0121] Example 2 A perovskite cell was prepared in the manner of Example 1, except that the additive was 1-(2-amino-5-hydroxyphenyl)propan-1-one.

[0122] Example 3 A perovskite cell was prepared in the manner of Example 1, except that the additive was 2-methylamino-5-acetyl-1,3-propanedione.

[0123] Example 4 The perovskite cell was prepared in the same manner as in Example 1, except that: Step 3: Perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3. Aminoacetone and the first solvent (DMF:DMSO=4:1) are mixed to obtain a first mixed solution (wide bandgap perovskite precursor solution), in which the perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3 concentration is 1.4 mol / L, and the concentration of aminoacetone is 1% of the concentration of the perovskite material.

[0124] Step 5: On the surface of the SAM layer obtained in step 4, the wide bandgap precursor solution (first mixed solution) prepared in step 3 is used to prepare a wide bandgap perovskite film by an anti-solvent method, and then annealed at 130° C. for 20 minutes to obtain a wide bandgap perovskite functional layer film (500 nm thick perovskite film), and the molar ratio of the perovskite material to the added in the perovskite film is 10:0.1.

[0125] Example 5 The perovskite cell was prepared in the same manner as in Example 1, except that: Step 3: Perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25)3. Aminoacetone and the first solvent (DMF:DMSO=4:1) are mixed to obtain a first mixed solution (wide bandgap perovskite precursor solution), in which the perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3 concentration is 1.4 mol / L, and the concentration of aminoacetone is 10% of the concentration of the perovskite material.

[0126] Step 5: On the surface of the SAM layer obtained in step 4, the wide bandgap precursor solution (first mixed solution) prepared in step 3 is used to prepare a wide bandgap perovskite film by an anti-solvent method, and then annealed at 130°C for 20 minutes to obtain a wide bandgap perovskite functional layer film (500 angstrom thick perovskite film), and the molar ratio of the perovskite material to the added in the perovskite film is 10:1.

[0127] Example 6 and Example 7 The perovskite cell was prepared in the manner of Example 1, except that the annealing temperatures in step 5 were 100° C. and 160° C., respectively.

[0128] Comparative Example 1 A perovskite cell was prepared in the manner of Example 1, except that no additive was added.

[0129] Comparative Example 2 The perovskite cell was prepared in the same manner as in Example 1, except that Step 3: Perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3. Methylamine and the first solvent (DMF:DMSO=4:1) are mixed to obtain a first mixed solution (wide bandgap perovskite precursor solution), in which the perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3 concentration is 1.4 mol / L, and the concentration of methylamine is 5% of the concentration of the perovskite material.

[0130] Comparative Example 3 The perovskite cell was prepared in the same manner as in Example 1, except that Step 3: Perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25)3. Acetone and the first solvent (DMF:DMSO=4:1) are mixed to obtain a first mixed solution (wide bandgap perovskite precursor solution), in which the perovskite material Cs 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3 concentration is 1.4 mol / L, and the concentration of acetone is 5% of the concentration of the perovskite material.

[0131] The above-mentioned perovskite cell was tested for photoelectric efficiency and maximum power point tracking. The test data are shown in Table 1.

[0132] Photoelectric efficiency test method: test spectrum AM 1.5G, test light intensity 1000W / m 2 , the test temperature is room temperature 25℃.

[0133] Maximum power point tracking: Under steady-state light source, the MPPT controller is used to achieve maximum power point tracking and record the power output at different time points. By comparing the power output at different time points, the performance stability of the perovskite solar cell near the maximum power point can be evaluated.

[0134] Table 1

[0135] As shown in Table 1, by comparing Examples 1-7 and Comparative Examples 1-3, the performance of the perovskite battery of Examples 1-7 is better than that of the perovskite battery of Comparative Examples 1-3. This indicates that the synergistic effect of the amino functional group and the keto functional group can be used to stabilize the uncoordinated B-site ions and fix the coordinated B-site ions, thereby jointly inhibiting and limiting the movement of the halogen ions (X), thereby suppressing the segregation of the wide bandgap perovskite film, thereby enhancing the stability of the perovskite battery containing the perovskite film.

[0136] Figure 2 It is a test result graph of MPPT (maximum power point tracking) of the perovskite solar cells of Example 1 and Comparative Example 1 (curve 1 is the result of Example 1, and curve 2 is the result of Comparative Example 1). The MPPT results show that the perovskite film with the addition of aminoacetone significantly improves the photostability of the device.

[0137] It should also be noted that the "some embodiments", "other embodiments", "embodiments", etc. mentioned in this application refer to the specific features, structures or characteristics described in conjunction with the embodiment included in at least one embodiment generally described in this application. The same expression appearing in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure or characteristic is described in conjunction with any embodiment, it is claimed that the realization of such feature, structure or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0138] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0139] It should also be noted that the above are only preferred embodiments of the present application, and the patent protection scope of the present application is not limited thereto. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A perovskite precursor solution, characterized in that: include: Perovskite material, additive and first solvent, The perovskite material is of ABX3 type structure, wherein A is a monovalent cation; B is a divalent cation; and X is a monovalent anion; The additive is an organic substance having an amino functional group and a keto functional group.

2. The perovskite precursor solution according to claim 1, characterized in that The additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione.

3. The perovskite precursor solution according to claim 1, characterized in that The perovskite material is of ABX3 type structure, A is one or more of formamidinium ion, methylamine ion, and cesium ion; B is one or more of divalent lead ion and divalent tin ion; and X is selected from halogen ion.

4. The perovskite precursor solution according to claim 1, characterized in that In the perovskite precursor solution, the concentration of the perovskite material is 1-3 mol / L; And / or, in the perovskite precursor solution, the concentration of the additive is 1%-10% of the concentration of the perovskite material.

5. A perovskite film, characterized in that: The perovskite film is formed from a perovskite precursor solution, wherein the perovskite precursor solution comprises: a perovskite material, an additive and a first solvent. The perovskite material is of ABX3 type structure, wherein A is a monovalent cation; B is a divalent cation; and X is a monovalent anion; The additive is an organic substance having an amino functional group and a keto functional group.

6. The perovskite film according to claim 5, characterized in that: In the perovskite film, the molar ratio of the perovskite material to the additive is 10:(0.1-1); And / or, the additive includes at least one of aminoacetone, 1-(2-amino-5-hydroxyphenyl)propan-1-one, and 2-methylamino-5-acetyl-1,3-propanedione; And / or, the perovskite material is of ABX3 type structure, A is one or more of formamidinium ion, methylamine ion, and cesium ion; B is one or more of divalent lead ion and divalent tin ion; and X is selected from halogen ion.

7. A perovskite battery, characterized in that: The perovskite cell comprises a transparent conductive glass, a first charge transport layer, a perovskite film, a second charge transport layer and a back electrode which are stacked in sequence; wherein the perovskite film is formed from a perovskite precursor solution; The perovskite precursor solution comprises: a perovskite material, an additive and a first solvent; The perovskite material is of ABX3 type structure, wherein A is a monovalent cation, B is a divalent cation, X is a monovalent anion, and the additive is an organic substance having an amino functional group and a keto functional group.

8. The perovskite cell according to claim 7, characterized in that: The thickness of the perovskite film is 400-700nm; and / or, the thickness of the first charge transport layer is 1-100 nm; And / or, the thickness of the second charge transport layer is 1-100 nm.

9. A method for preparing a perovskite battery, characterized in that: The following steps are involved: Providing transparent conductive glass; forming a first charge transport layer on one side surface of the transparent conductive glass; forming a perovskite film on a side of the first charge transport layer away from the transparent conductive glass; forming a second charge transport layer on a side of the perovskite film away from the first charge transport layer; forming a back electrode on a side of the second charge transport layer away from the perovskite film; Wherein, the perovskite film is formed from a perovskite precursor solution; The perovskite precursor solution comprises: a perovskite material, an additive and a first solvent; the perovskite material is an ABX3 type structure, wherein A is a monovalent cation; B is a divalent cation; X is a monovalent anion; and the additive is an organic substance having an amino functional group and a keto functional group.

10. A photovoltaic module, characterized in that: The invention comprises the perovskite battery as described in claim 7 or 8 or the perovskite battery prepared by the method as described in claim 9.

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