Perovskite battery, manufacturing method and corresponding power consuming device

Abstract

The present application relates to a perovskite battery, a method of manufacturing, and a corresponding power consuming device, the perovskite battery comprising, in order, a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, wherein the hole transport layer comprises a body layer and a surface layer disposed on a side of the body layer closer to the perovskite layer, the hole transport layer comprising nickel oxide containing trivalent nickel ions, wherein the atomic percentage of the trivalent nickel ions in the surface layer is smaller than the atomic percentage of the trivalent nickel ions in the body layer, and the corresponding method of manufacturing and power consuming device.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application references Chinese Patent Application No. 202310201482.6, filed on March 6, 2023, entitled "Perovskite Battery, Manufacturing Method and Corresponding Power Consumption Device," which is incorporated herein by reference in its entirety.

[0002] The present application relates to the field of perovskite batteries, and in particular to perovskite batteries, methods of manufacture and corresponding power consuming devices. [Background technology]

[0003] With the rapid development of new energy fields, solar cells are widely used in military, spaceflight, industry, commerce, agriculture, communications, etc. Perovskite cells have gradually become a hotspot in next-generation solar cell research due to their advantages such as high photoelectric conversion efficiency, simple fabrication process, and low production and material costs.

[0004] Nickel oxide, the most commonly used inorganic hole transport layer material in trans-type perovskite batteries, is a favorable candidate for the industrialization of perovskite batteries. However, trivalent nickel present on the surface of the nickel oxide hole transport layer reacts with A-site cations and X-site halogens in the perovskite precursor solution, further degrading the photoelectric conversion efficiency of perovskite batteries. At the same time, corrosion of the perovskite light absorption layer by water and oxygen can affect the stability of perovskite batteries to some extent. Therefore, the structure and performance of conventional perovskite batteries still need improvement. Summary of the Invention

[0005] The present application has been made in view of the above problems, and its objective is to provide a perovskite battery that improves the photoelectric conversion efficiency of the battery by improving the stability of the perovskite layer in ensuring the conductivity of the nickel oxide hole transport layer, and that has a lower manufacturing cost and is simple to operate.

[0006] To achieve the above object, the present application provides a perovskite battery, a manufacturing method thereof, and a power consumption device.

[0007] A first aspect of the present application provides a perovskite battery comprising, in order, a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, wherein the hole transport layer comprises a body layer and a surface layer disposed on a side of the body layer closer to the perovskite layer, and wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and the atomic percentage of the trivalent nickel ions in the surface layer is smaller than the atomic percentage of the trivalent nickel ions in the body layer.

[0008] The perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer located on the side of the main layer closest to the perovskite layer, thereby reducing the reaction between the trivalent nickel ions and the perovskite in the perovskite layer, thereby improving the stability of the perovskite layer and ensuring the conductivity of the hole transport layer containing nickel oxide, thereby improving the photoelectric conversion efficiency of the battery.

[0009] In any embodiment of the present application, the atomic percentage of trivalent nickel ions in the surface layer gradually decreases along the thickness direction of the surface layer from the side closer to the main layer to the side farther from the main layer, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0010] In some embodiments of the present application, the atomic percentage of trivalent nickel ions decreases along the thickness direction of the surface layer in a gradient of 0.5 to 4 nm, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0011] In any embodiment of the present application, the difference in atomic percentage of trivalent nickel ions between two adjacent gradients is 2-20%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0012] In any embodiment of the present application, the atomic percentage of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1-15%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the battery.

[0013] In any embodiment of the present application, the atomic percentage of trivalent nickel ions in the main layer is 20 to 65%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the battery.

[0014] In any embodiment of the present application, the thickness of the surface layer is 2 to 15 nm and / or the thickness of the main layer is 10 to 40 nm, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0015] A second aspect of the present application provides a method of manufacturing a perovskite battery, said method comprising: (1) providing a first electrode; (2) forming a hole transport layer on the first electrode; (3) fabricating a perovskite layer on the hole transport layer; (4) fabricating an electron transport layer on the perovskite layer; (5) fabricating a second electrode on the electron transport layer to obtain the perovskite battery; Here, the hole transport layer includes a main layer and a surface layer disposed on the side of the main layer closer to the perovskite layer, and the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of the trivalent nickel ions in the surface layer is smaller than the atomic percentage of the trivalent nickel ions in the main layer.

[0016] The method of the present application is lower cost, simple to operate, and amenable to large-scale industrial application.

[0017] In any embodiment of the present application, step (2) includes fabricating a hole transport layer on the first electrode using a magnetron sputtering method with a nickel oxide target material, thereby simplifying the fabrication of the perovskite battery of the first aspect of the present application.

[0018] In any embodiment of the present application, the conditions of the magnetron sputtering method include that the argon / oxygen ratio used in producing the main body layer is 500:(1 to 200), thereby making it possible to more easily produce the perovskite battery of the first aspect of the present application.

[0019] In any embodiment of the present application, the conditions of the magnetron sputtering method include using a higher argon-oxygen ratio in the production of the surface layer than in the production of the main body layer, thereby making it easier to produce the perovskite battery of the first aspect of the present application.

[0020] A third aspect of the present application provides a power consuming device comprising a perovskite battery according to the first aspect of the present application or a perovskite battery produced by the method according to the second aspect of the present application, wherein the perovskite battery is used to power the power consuming device.

[0021] The perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer located on the side of the main layer closer to the perovskite layer by several hundred percent, thereby reducing the reaction between trivalent nickel ions and the perovskite in the perovskite layer and ensuring the conductivity of the hole transport layer containing nickel oxide, thereby improving the photoelectric conversion efficiency of the battery. [Brief explanation of the drawings]

[0022] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without any creative efforts. [Figure 1] 1 is a structural schematic diagram of a perovskite battery according to an embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, with appropriate reference to the drawings, embodiments specifically disclosing the perovskite battery and its manufacturing method, and the corresponding power consumption device of the present application will be described in detail. However, unnecessary detailed description may be omitted. For example, detailed description of well-known matters and redundant description of actually identical structures may be omitted. This is to avoid the following description becoming unnecessarily long and to facilitate understanding by those skilled in the art. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application, and do not limit the subject matter described in the claims.

[0024] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of the end values, and any combination is possible; i.e., any lower limit can be combined with any upper limit to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also possible. Furthermore, if 1 and 2 are listed as minimum range values ​​and 3, 4, and 5 are listed as maximum range values, the ranges 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all possible. In this application, unless otherwise specified, a numerical range "a to b" is a shorthand notation for any combination of real numbers a to b, where a and b are both real numbers. For example, the numerical range "0-5" represents that the present specification has already listed all real numbers between "0-5," and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0025] Unless otherwise stated, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0026] Unless otherwise stated, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0027] Unless otherwise specified, all steps in this application may be performed in order or randomly, preferably in order. For example, a reference to a method including steps (a) and (b) means that the method may include steps (a) and (b) performed in order, or steps (b) and (a) performed in order. For example, a reference to a method may further include step (c), and this means that step (c) may be added to the method in any order, e.g., 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.

[0028] Unless otherwise specified, the terms "comprise" and "include" used in this application may be open-ended or closed-ended. For example, the terms "comprise" and "include" may further include or include other components not listed, or may include or include only the listed components.

[0029] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) but B is true (or exists), or when both A and B are true (or exist).

[0030] Nickel oxide, as the most commonly used inorganic hole transport layer material in trans-type perovskite batteries, is a favorable candidate for the industrialization of perovskite batteries. However, trivalent nickel present on the surface of the hole transport layer reacts with the A-site cations and X-site halogens in the perovskite precursor solution, further degrading the photoelectric conversion efficiency of the perovskite battery. At the same time, the erosion of the perovskite light absorption layer by water and oxygen affects the stability of the perovskite battery to some extent. In the perovskite battery of the present application, the hole transport layer (especially nickel oxide (NiO)) is used as the material for the hole transport layer. x An interface passivation layer containing nickel(II) oxide is provided between the hole transport layer and the perovskite layer, resulting in high photoelectric conversion efficiency and good long-term stability, while also enabling a lower manufacturing cost and easier operation.

[0031] Perovskite Battery In some embodiments, a first aspect of the present application provides a perovskite battery comprising, in order, a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, wherein the hole transport layer comprises a body layer and a surface layer disposed on a side of the body layer closer to the perovskite layer, and wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and wherein the atomic percentage of trivalent nickel ions in the surface layer is smaller than the atomic percentage of trivalent nickel ions in the body layer.

[0032] The perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer located on the side of the main layer closest to the perovskite layer, thereby reducing the reaction between the trivalent nickel ions and the perovskite in the perovskite layer, thereby improving the stability of the perovskite layer and ensuring the conductivity of the hole transport layer containing nickel oxide, thereby improving the photoelectric conversion efficiency of the battery.

[0033] In some embodiments, the hole transport layer comprises nickel oxide containing trivalent nickel ions, where nickel oxide is generally NiOx which can represent compounds containing oxygen and nickel.

[0034] In some embodiments, the hole transport layer is a nickel oxide hole transport layer.

[0035] In some embodiments, materials such as NiO, Ni(OH)2, Ni2O3, NiOOH may be present in the hole transport layer.

[0036] In some embodiments, in the hole transport layer, trivalent nickel ions are generally present in the form of Ni2O3, NiOOH, etc., and divalent nickel ions are generally present in the form of NiO, Ni(OH)2, etc.

[0037] In some embodiments of the present application, the atomic percentage of trivalent nickel ions in the surface layer gradually decreases along the thickness direction of the surface layer from the side closer to the main layer to the side farther from the main layer, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0038] The term "gradiently decreasing" refers to the fact that the atomic percentage of trivalent nickel ions remains the same within one gradient, but the atomic percentage of trivalent nickel ions located in an immediately adjacent gradient away from the main layer of the gradient decreases relative to the atomic percentage of trivalent nickel ions within the gradient.

[0039] In this application, the unit "nm" refers to nanometers.

[0040] In some embodiments of the present application, the atomic percentage of trivalent nickel ions decreases along the thickness direction of the surface layer in a gradient of 0.5 to 4 nm, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell. As can be understood, "0.5 to 4 nm" means 0.5 nm to 4 nm.

[0041] In some embodiments, the thickness of one gradient is generally 1.5 to 4 nm along the thickness direction of the surface layer, in other words, the thickness of one gradient is 1.5 to 4 nm.

[0042] In some embodiments, the thickness of one gradient is generally 1.5 to 2.5 nm along the thickness direction of the surface layer, in other words, the thickness of one gradient is 1.5 to 2.5 nm.

[0043] In some embodiments, the number of gradients in the surface layer is typically 1 to 10. The "number of gradients" refers to the number of atomic percentages of trivalent nickel ions in the surface layer that changes with the thickness of the surface layer. Calculated from the side closer to the main layer, the gradient in the surface layer closest to the main layer is gradient 1, and the gradients along the thickness of the surface layer to the perovskite layer are sequentially designated gradient 2, gradient 3, gradient 4, etc., and the gradient closest to the perovskite layer is referred to as the outermost gradient.

[0044] In some embodiments, the number of gradients in the surface layer is typically between 3 and 6.

[0045] In some embodiments of the present application, the difference in atomic percentage of trivalent nickel ions between two adjacent gradients is 2 to 20%, thereby further ensuring electrical conductivity while improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell. As can be understood, "2 to 20%" means 2% to 20%.

[0046] In some embodiments, the difference in atomic percentage of trivalent nickel ions between two adjacent gradients is 2% to 10%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0047] In some embodiments, the difference in atomic percentage of trivalent nickel ions between two adjacent gradients is 3.5% to 6%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0048] In some embodiments of the present application, the atomic percentage of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1-15%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the battery.

[0049] The "outermost gradient" refers to one gradient of the surface layer of the hole transport layer that is farthest from the main layer, and this gradient layer is in direct contact with the perovskite layer. The thickness of the outermost gradient may be different from or the same as the thickness of the other gradients.

[0050] In this application, the "atomic percentage" refers to the percentage of the number of atoms of the ion in the layer or gradient in which it is located, calculated based on the total number of atoms in the layer or gradient in which it is located. The atomic number refers to the number of atoms of the ion in the layer or gradient in which it is located, and is measured based on X-ray photoelectron spectroscopy (XPS).

[0051] In some embodiments, the atomic percentage of trivalent nickel ions in the outermost gradient of the surface layer in direct contact with the perovskite layer is 1-12%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0052] In some embodiments, the atomic percentage of trivalent nickel ions in the outermost gradient of the surface layer in direct contact with the perovskite layer is 1-10%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0053] In some embodiments, the atomic percentage of trivalent nickel ions in the outermost gradient of the surface layer in direct contact with the perovskite layer is 1-5%, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0054] In some embodiments of the present application, the atomic percentage of trivalent nickel ions in the main layer is 20 to 65%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the battery.

[0055] In some embodiments, the atomic percentage of trivalent nickel ions in the main layer is 25-40%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0056] In some embodiments, the atomic percentage of trivalent nickel ions in the main layer is 25-35%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0057] In some embodiments, the atomic percentage of trivalent nickel ions in the main layer is 28-33%, which further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0058] In some embodiments of the present application, the thickness of the surface layer is 2 to 15 nm and the thickness of the main layer is 10 to 40 nm, thereby further ensuring electrical conductivity and improving the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the cell.

[0059] In some embodiments, the surface layer has a thickness of 2 to 12 nm.

[0060] In some embodiments, the surface layer has a thickness of 8 to 12 nm.

[0061] In some embodiments, the body layer has a thickness of 10 to 30 nm.

[0062] In some embodiments, the body layer has a thickness of 10 to 15 nm.

[0063] In some embodiments, the atomic ratio of trivalent nickel ions to divalent nickel ions in the body layer is 1:1.

[0064] In some embodiments, the total thickness of the hole transport layer is between 12 and 50 nm.

[0065] In some embodiments, the total thickness of the hole transport layer is between 12 and 25 nm.

[0066] In some embodiments, the total thickness of the hole transport layer is between 18 and 25 nm.

[0067] In some embodiments, the perovskite battery is a cis-perovskite battery or a trans-perovskite battery, for example a trans-perovskite battery.

[0068] In some embodiments, the first electrode is an anode layer, which serves to collect holes and is commonly referred to as a transparent electrode.

[0069] In some embodiments, the first electrode is selected from at least one of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), and the thickness of the first electrode layer is 100-1000 nm, for example, 300-800 nm.

[0070] In this application, the unit "cm" refers to centimeter.

[0071] In some embodiments, the perovskite cell further comprises a transparent substrate layer, the transparent substrate layer being selected from at least one of a transparent glass, a polyethylene terephthalate (PET), and a polyimide substrate, and the transparent substrate layer has a thickness of 0.1 to 3 cm.

[0072] Thus, in one embodiment of the present application, the perovskite battery of the present application comprises, in sequential order, a transparent substrate layer, a first electrode, a nickel oxide hole transport layer, a perovskite layer, an electron transport layer, and a second electrode.

[0073] In some embodiments, the perovskite layer is the light absorbing layer, i.e., the active layer of the perovskite cell, and is made of perovskite material, which is the core position of the entire cell structure.

[0074] In some embodiments, the perovskite layer material has a chemical formula of ABX3 or A2CDX6, where A is an inorganic, organic, or mixed organic-inorganic cation, including at least one of an organic amine cation, a Cs cation, a K cation, a Rb cation, and a Li cation, and the organic amine cation is (NR1R2R3R4) + , (R1R2N=CR3R4) + , (R1R2N-C(R5)=NR3R4) + or (R1R2N-C(NR5R6)=R3R4) +wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, a substituted or unsubstituted C1-20 alkyl group or a substituted or unsubstituted aryl group.

[0075] In some embodiments, A is a methylamino group (CH3NH3 + )(MA + ), carbamimidoyl group (HC(NH2)2 + )(FA + ), cesium ions (Cs + ) and rubidium ion (Rb + ) For example, A is a methylamino group (CH3NH3 + ) or carbamimidoyl group (HC(NH2)2 + )

[0076] B is an inorganic, organic, or mixed organic-inorganic cation, and includes at least one of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium. For example, B may be a divalent metal ion, Pb 2+ and Sn 2+ At least one of the following is true.

[0077] C is an inorganic, organic, or mixed organic-inorganic cation. For example, C is a monovalent metal ion, Ag. + And so on.

[0078] D is an inorganic, organic, or mixed organic-inorganic cation. For example, D is a trivalent metal ion, bismuth cation Bi 3+ , antimony cation Sb 3+ , indium cation In 3+ And so on.

[0079] X is an inorganic, organic, or mixed organic-inorganic anion. For example, X is one or more of a halogen anion and a carboxylate anion. For example, X is a bromide ion (Br -) or iodine ion (I - )

[0080] In this application, the unit "eV" refers to electron volts.

[0081] In some embodiments, the bandgap of the perovskite layer is between 1.20 eV and 2.30 eV.

[0082] In some embodiments, the perovskite layer has a thickness of 200 to 800 nm.

[0083] In some embodiments, the perovskite layer has a thickness of 400 to 600 nm.

[0084] In some embodiments, the perovskite cell further comprises an electron transport layer.

[0085] In some embodiments, the function of the electron transport layer is to efficiently transport free electrons generated in the perovskite layer, to effectively block the passage of free holes, and to form an ohmic contact at the interface with the perovskite active layer.

[0086] In some embodiments, the material of the electron transport layer is [6,6]-phenyl-C 61 -Isomethyl butyrate (PC 61 BM), [6,6]-phenyl-C 71 -Methyl butyrate (PC 71BM), fullerene C60, fullerene C70, cyano group-containing polyphenylacetylene, boron-containing polymer, bathocuproine, bathophenanthroline, hydroxyquinoline aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorine group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride, sodium fluoride, magnesium fluoride, and zinc sulfide, as well as derivatives thereof and doped or passivated materials thereof.

[0087] In some embodiments, the material of the electron transport layer is [6,6]-phenyl-C 61 -Isomethyl butyrate (PC 61 BM), [6,6]-phenyl-C 71 -Methyl butyrate (PC 71 The material is at least one of the following materials: fullerene C60 (C60), fullerene C70 (C70), tin oxide (SnO2), zinc oxide (ZnO), and their derivatives, as well as doped or passivated materials thereof.

[0088] In some embodiments, the electron transport layer has a thickness of 10 to 200 nm.

[0089] In some embodiments, the electron transport layer has a thickness of 30 to 120 nm.

[0090] In some embodiments, the electron transport layer has a thickness of 40 to 60 nm.

[0091] Thus, in one embodiment of the present application, the perovskite battery of the present application comprises, in sequential order, a transparent substrate layer, a first electrode, a nickel oxide hole transport layer, a perovskite layer, an electron transport layer, and a second electrode.

[0092] In some embodiments, the second electrode is a cathode layer, which acts to collect free electrons.

[0093] In some embodiments, the second electrode is generally an organic, inorganic, or mixed organic-inorganic conductive material, including at least one of indium tin oxide (ITO), lanthanide metal-doped indium oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and alloys thereof, graphite, graphene, and carbon nanotubes.

[0094] In some embodiments, the second electrode is generally an organic, inorganic, or mixed organic-inorganic conductive material, including Ag, Cu, C, Au, Al, ITO, AZO, BZO, or IZO.

[0095] In some embodiments, the second electrode is generally an organic, inorganic, or mixed organic-inorganic conductive material, including Cu, Ag, Au, or combinations thereof.

[0096] In some embodiments, the second electrode has a thickness of 20 to 200 nm.

[0097] In some embodiments, the second electrode has a thickness of 60 to 100 nm.

[0098] In some embodiments, the second electrode has a thickness of 70 to 90 nm.

[0099] In some embodiments, a hole-blocking layer may be present between the second electrode and the electron transport layer to prevent reaction between the second electrode and the perovskite and to avoid a Schottky contact between the electron transport layer and the back electrode, which would reduce device efficiency, while also providing energy level adjustment control.

[0100] In some embodiments, the hole blocking layer material comprises 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, also known as bathocuproine), calcium acetylacetonate, LiF, 8-hydroxyquinoline aluminum, 1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene, or a combination thereof.

[0101] In some embodiments, the hole blocking layer material comprises BCP.

[0102] In some embodiments, the hole blocking layer has a thickness of 0.1 to 30 nm.

[0103] In some embodiments, the hole blocking layer has a thickness of 3 to 10 nm.

[0104] In some embodiments, the hole blocking layer has a thickness of 4 to 6 nm.

[0105] In some embodiments, there may be a passivation layer between the perovskite layer and the electron transport layer to passivate defects at the interface between them.

[0106] In some embodiments, a passivation layer may be present between the electron transport layer and the electrode to improve the performance of the perovskite cell.

[0107] In some embodiments, the perovskite battery includes a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, a hole blocking layer, and a second electrode, which are stacked in this order, where the hole transport layer includes a body layer and a surface layer disposed on the side of the body layer closer to the perovskite layer. The first electrode is, for example, selected from FTO. The body layer is, for example, made of nickel oxide. The surface layer is, for example, made of nickel oxide. The electron transport layer is, for example, made of C60. The hole blocking layer is, for example, made of BCP. The second electrode is, for example, made of Cu.

[0108] In some embodiments, and with reference to Figure 1, a perovskite cell 10 includes, in sequential order, FTO 1, a nickel oxide body layer 2, a nickel oxide surface layer 3, a perovskite layer 4, C60 5, BCP 6, and Cu 7, where FTO is the first electrode, C60 is the electron transport layer, BCP is the hole blocking layer, and Cu is the second electrode.

[0109] A second aspect of the present application provides a method of manufacturing a perovskite battery according to the first aspect of the present application, said method comprising: (1) providing a first electrode; (2) forming a hole transport layer on the first electrode; (3) fabricating a perovskite layer on the hole transport layer; (4) fabricating an electron transport layer on the perovskite layer; (5) fabricating a second electrode on the electron transport layer to obtain the perovskite battery; Here, the hole transport layer includes a main layer and a surface layer disposed on the side of the main layer closer to the perovskite layer, and the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of the trivalent nickel ions in the surface layer is smaller than the atomic percentage of the trivalent nickel ions in the main layer.

[0110] The method of the present application is lower cost, simple to operate, and amenable to large-scale industrial application.

[0111] In some embodiments of the present application, step (2) includes fabricating a hole transport layer on the first electrode using a magnetron sputtering method using a nickel oxide target material, thereby simplifying the fabrication of the perovskite battery of the first aspect of the present application.

[0112] In some embodiments, in step (2), the nickel-oxygen ratio of the nickel oxide target material is 0.9 to 1.1.

[0113] In some embodiments of the present application, the conditions of the magnetron sputtering method include an argon to oxygen ratio of 500:(1 to 200) used in producing the main body layer, which makes it easier to produce the perovskite battery of the first aspect of the present application.

[0114] In some embodiments, the conditions of the magnetron sputtering method include that the argon to oxygen ratio used in producing the main body layer is 500:(1 to 100), which makes it easier to produce the perovskite battery of the first aspect of the present application.

[0115] In some embodiments, the conditions of the magnetron sputtering method include that the argon to oxygen ratio used in producing the main body layer is 500:(3 to 100), which makes it easier to produce the perovskite battery of the first aspect of the present application.

[0116] In some embodiments, the conditions of the magnetron sputtering method include an argon to oxygen ratio of 500:(30-70) used in producing the main body layer, which makes it easier to produce the perovskite battery of the first aspect of the present application.

[0117] In some embodiments of the present application, the conditions of the magnetron sputtering method include using a higher argon-oxygen ratio in the production of the surface layer than in the production of the main body layer, thereby making it easier to produce the perovskite battery of the first aspect of the present application.

[0118] In some embodiments of the present application, the conditions of the magnetron sputtering method include obtaining different atomic percent gradients of trivalent nickel ions in the production of the surface layer by using different argon-oxygen ratios in the production of different gradients.

[0119] In some embodiments of the present application, the conditions of the magnetron sputtering method include using a gradually increasing argon-oxygen ratio in the process of producing a different gradient along the thickness direction of the surface layer from the body layer side to the perovskite layer side.

[0120] In some embodiments of the present application, for example, step (2) includes producing a nickel oxide layer using DC magnetron sputtering, in which the argon / oxygen ratio when sputtering the main layer is 500 / 5, and when sputtering the surface layer, the argon / oxygen ratio is changed every 2 nm, with the argon / oxygen ratio for the first 2 nm being 500 / 4, the argon / oxygen ratio for the second 2 nm being 500 / 3, ..., the argon / oxygen ratio for the fifth 2 nm (i.e., the outermost gradient) being 500 / 0, and so on.

[0121] In some embodiments, step (1) includes depositing a transparent conductive oxide layer on a transparent substrate layer to provide a first electrode deposited on the transparent substrate layer, or the first electrode deposited on the transparent substrate layer may be a commercially available product.

[0122] In some embodiments, in step (1), the transparent substrate layer, e.g., conductive glass, may be further cleaned, e.g., ultrasonically cleaned in water, acetone, and isopropanol, successively, e.g., for 1-30 minutes, blow-dried, and then placed in an ultraviolet ozone device for further cleaning, e.g., for 1-20 minutes.

[0123] In some embodiments, step (3) comprises coating a perovskite precursor solution onto the hole transport layer, pre-drying using a vacuum method, followed by annealing, for example, at a temperature of 80-120°C for 20-40 minutes, and cooling to obtain the perovskite layer, where the coating method may be spin coating, blade coating, slit coating, spray coating, etc.

[0124] In some embodiments, the perovskite precursor solution used in step (3) is prepared by dissolving a perovskite precursor material (e.g., at least one of iodoformamidine, lead iodide, bromomethylamine, iodomethylamine, cesium iodide, lead bromide, etc.) in a solvent (e.g., dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), etc.), stirring uniformly, and filtering to obtain a perovskite precursor solution.

[0125] In some embodiments, in step (5), a second electrode is fabricated. Fabrication of the second electrode may be performed by a method conventional in the art. For example, the electrode may be fabricated using a vapor deposition method.

[0126] In some embodiments, an electron transport layer may be formed prior to step (5). The electron transport layer may be formed by a conventional technique known in the art. For example, the electron transport layer may be formed by spin coating, vapor deposition, or the like.

[0127] A third aspect of the present application provides a power consuming device comprising a perovskite battery according to the first aspect of the present application or a perovskite battery produced by the method according to the second aspect of the present application, wherein the perovskite battery is used to power the power consuming device.

[0128] In some embodiments, the power consuming device is a common device comprising the perovskite battery of the present application, such as in the communications field, transportation field, industrial and agricultural field, lighting field, etc. The power consuming device may include, for example, satellites, communications equipment, traffic lights, lighthouses, radio telephone booths, monitoring equipment in the oil drilling field, power supply systems, camper lights, electric vehicles, electronic device chargers, etc.

[0129] Example The following examples of the present application are described. The examples described below are illustrative and are intended only to interpret the present application and should not be understood as limitations on the present application. If specific techniques or conditions are not specified in the examples, they will be carried out according to the techniques or conditions described in literature in this field or according to the product instructions. If the manufacturers of the reagents or equipment used are not specified, they are all common products that are commercially available.

[0130] 1. Perovskite battery Example 1 1) Twenty pieces of 2.0 x 2.0 cm FTO conductive glass were taken, and 0.35 cm of FTO was removed from each end by laser etching to expose the glass substrate. The FTO conductive glass was then ultrasonically cleaned in 500 mL of water, acetone, and isopropanol, each for 10 minutes (min), and then the solvent was blown off from the cleaned FTO conductive glass using a nitrogen gas gun. The glass was then placed in an ultraviolet ozone device for another 5 minutes of cleaning to obtain a first electrode.

[0131] 2) On the first electrode, a 12 nm thick main layer was magnetron sputtered using a nickel oxide target material with a nickel-oxygen ratio of 1:1 at a sputtering power of 2000 W with an argon-oxygen ratio of 500:50, and a surface layer was magnetron sputtered at an argon-oxygen ratio of 500:3.

[0132] 3) A perovskite precursor solution with a molar concentration of 1.1 moles / liter (mol / L) was prepared by dissolving 1,362 milligrams (mg) of formamidine hydroiodide (FAI), 228.6 mg of cesium iodide (CsI), and 4,056.9 mg of lead iodide (PbI) in 8 mL of solvent, which was a mixture of N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP) in a volume ratio of 7:1.

[0133] The precursor solution was coated onto the nickel oxide layer, and the sample was then transferred to a vacuum chamber and left to stand for 120 seconds at a vacuum of 100 Pascals (Pa) or less to harden the precursor solution and form a film. The hardened sample was then placed on a hot stage and annealed at 150 degrees Celsius (°C) for 30 minutes, resulting in a 500 nm thick perovskite layer.

[0134] 4) On the perovskite layer obtained in step (3), PC was applied at 1500 revolutions per second (rpm / s). 61 The BM was spin-coated and annealed at 100°C for 10 min to obtain a 50 nm thick electron transport layer, and immediately thereafter, a 0.5 milligram / milliliter (mg / mL) solution of BCP in isopropanol was spin-coated on the electron transport layer at 5000 rpm / s to obtain a 5 nm thick hole blocking layer.

[0135] 5) The device obtained in step (4) was placed in a deposition machine (Model LN-F300), and 10 -5 A metal electrode, Cu, was evaporated under vacuum conditions of 0.05 Pa to form a second electrode layer with a thickness of 80 nm, thereby obtaining the perovskite battery.

[0136] Example 2 The steps of Example 1 were repeated except that in step 2) a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:30 and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0137] Example 3 The steps of Example 1 were repeated except that in step 2) a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:39, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:25, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0138] Example 4 The steps of Example 1 were repeated, with the difference being that in step 2) a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:41, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:30, a 2 nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:16, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0139] Example 5 The steps of Example 1 were repeated, with the difference being that in step 2), a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:43, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:35, a 2 nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:25, a 2 nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:16, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0140] Example 6 The steps of Example 1 were repeated, with the difference being that in step 2), a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:45, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:39, a 2 nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:32, a 2 nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:25, a 2 nm gradient 5 surface layer was sputtered with an argon-oxygen ratio of 500:16, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0141] Example 7 The steps of Example 6 were repeated, with the difference that in step 2) the thickness of the body layer was 10 nm.

[0142] Example 8 The steps of Example 6 were repeated, except that in step 2) the thickness of the body layer was 30 nm.

[0143] Example 9 The steps of Example 1 were repeated, except that in step 2), a 12 nm body layer was sputtered with an argon-oxygen ratio of 500:30, a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:25, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:20, a 2 nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:14, a 2 nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:10, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0144] Example 10 The steps of Example 1 were repeated, except that in step 2), a 12 nm body layer was sputtered with an argon-oxygen ratio of 500:60, a 2 nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:50, a 2 nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:41, a 2 nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:30, a 2 nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:16, and a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0145] Examples 11-12 The steps of Example 10 were repeated, with the difference being that the thickness of the body layer and the atomic percentage of trivalent nickel ions were varied.

[0146] Example 13 The steps of Example 2 were repeated, except that in step 2) a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:0.

[0147] Example 14 The steps of Example 2 were repeated, except that in step 2) a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:1.

[0148] Example 15 The steps of Example 2 were repeated, except that in step 2) a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:16.

[0149] Examples 16 to 19 The steps of Example 2 were repeated, except that the thickness of the first gradient layer and the thickness of the outermost layer were changed.

[0150] Comparative Example 1: The hole transport layer does not include a surface layer The steps of Example 1 were repeated, with the difference being that the surface layer was not produced in step 2).

[0151] Comparative Example 2 The steps of Example 1 were repeated except that a 2 nm outermost layer was sputtered with an argon-oxygen ratio of 500:30.

[0152] The product parameters of the perovskite batteries obtained in the above examples and comparative examples are as shown in Table 1.

[0153] Parameter Test Testing the atomic numbers of divalent and trivalent nickel ions in hole transport and interfacial passivation layers The number of divalent and trivalent nickel ions in the bulk and surface layers of the hole transport layer was measured by X-ray photoelectron spectroscopy (XPS), which was performed using a spectrometer model K-Alpha (manufactured by Thermo Fisher Scientific). Percentage of divalent or trivalent nickel ion atoms = number of divalent or trivalent nickel ion atoms / total number of nickel ion atoms in the layer or gradient in which it is located.

[0154] A represents the percentage of trivalent nickel ions in the layer or gradient.

[0155] [Table 1] JPEG2026508354000003.jpg134170

[0156] 2. Performance measurement of perovskite batteries 1. Measurement of photoelectric conversion efficiency Testing was conducted in accordance with the national standard IEC 61215, where the test was conducted under light illumination using a Keithley 2400 digital source meter. The light source was a solar simulator using a 450W xenon lamp with a UV filter, and the light emitted from the light source conformed to the AM 1.5G standard solar spectrum. The cell was connected to the digital source meter and its photoelectric conversion efficiency was measured under light illumination.

[0157] The perovskite batteries obtained in the above examples and comparative examples were tested according to the above process, and the specific values ​​are shown in Table 2.

[0158] [Table 2]

[0159] As can be seen from Tables 1 and 2, the efficiencies of the perovskite batteries of the present application all achieved excellent technical effects, and the efficiencies of the perovskite batteries of Examples 1 to 16 reached 12.9% or more, and the efficiencies of the perovskite batteries of Examples 1 to 7, Examples 10 to 11, Examples 13 to 14 and Example 16 could reach 15% or more.

[0160] The technical features of the embodiments described above can be combined in any manner. For the sake of brevity, not all possible combinations of the technical features in the above embodiments will be described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope of the description in the specification.

[0161] The above-described examples only illustrate some embodiments of the present application, and although the descriptions are relatively specific and detailed, they should not be construed as limiting the patent scope of the present application. It should be noted that those skilled in the art can make multiple modifications and improvements without departing from the concept of the present application, all of which fall within the scope of protection of the present application. Therefore, the scope of protection of the patent of the present application should be determined based on the appended claims, and the specification and drawings can be used to explain the content of the claims. [Explanation of symbols]

[0162] 1-FTO, 2-nickel oxide body layer, 3-nickel oxide surface layer, 4-perovskite layer, 5-C60, 6-BCP, 7-Cu, 10-perovskite cell.

Claims

1. 1. A perovskite battery comprising, in order, a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, wherein the hole transport layer comprises a main layer and a surface layer disposed on a side of the main layer closer to the perovskite layer, wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and wherein the atomic percentage of trivalent nickel ions in the surface layer is smaller than the atomic percentage of trivalent nickel ions in the main layer.

2. 2. The perovskite battery according to claim 1, wherein the atomic percentage by hundreds of percent of trivalent nickel ions in the surface layer decreases gradually along the thickness direction of the surface layer from a side closer to the main body layer to a side farther from the main body layer.

3. 3. The perovskite battery of claim 2, wherein the atomic percentage of trivalent nickel ions decreases in a gradient over a thickness of 0.5 to 4 nm along the thickness direction of the surface layer.

4. 4. The perovskite battery according to claim 2 or 3, wherein the difference in atomic percentage of trivalent nickel ions between two adjacent gradients is 2 to 20%.

5. 5. The perovskite battery according to claim 2, wherein the atomic percentage of trivalent nickel ions in the outermost gradient in the surface layer that is in direct contact with the perovskite layer is 1 to 15%.

6. The perovskite battery according to any one of claims 1 to 5, wherein the atomic percentage of trivalent nickel ions in the main body layer is 20 to 65%.

7. The perovskite battery comprises: (1) the thickness of the surface layer is 2 to 15 nm; (2) The perovskite battery according to any one of claims 1 to 6, having one or more of the following characteristics: (1) the thickness of the main body layer is 10 to 40 nm;

8. 1. A method of manufacturing a perovskite battery, comprising: (1) providing a first electrode; (2) forming a hole transport layer on the first electrode; (3) fabricating a perovskite layer on the hole transport layer; (4) fabricating an electron transport layer on the perovskite layer; (5) fabricating a second electrode on the electron transport layer to obtain the perovskite battery; wherein the hole transport layer includes a main layer and a surface layer disposed on a side of the main layer closer to the perovskite layer, the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of the trivalent nickel ions in the surface layer is smaller than the atomic percentage of the trivalent nickel ions in the main layer.

9. 9. The method of claim 8, wherein step (2) comprises fabricating a hole transport layer on the first electrode using a magnetron sputtering method.

10. 10. The method of claim 9, wherein the magnetron sputtering conditions include an argon to oxygen ratio of 500:(1-200) used in producing the main layer.

11. 11. The method according to claim 9 or 10, wherein the magnetron sputtering conditions include a higher argon-oxygen ratio used in producing the surface layer than in producing the main layer.

12. 12. A power consuming device comprising the perovskite battery according to any one of claims 1 to 7, or a perovskite battery obtained by the method according to any one of claims 8 to 11, wherein the perovskite battery is used to power the power consuming device.

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