Perovskite batteries, manufacturing methods, and applicable power consumption devices

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 of related applications] This application incorporates Chinese Patent Application No. 202310201482.6, filed on March 6, 2023, entitled "Perovskite Battery, Method of Manufacturing and Applicable Power Consumption Device," which is incorporated into this application in whole by reference.

[0002] This application relates to the field of perovskite batteries, and more particularly to perovskite batteries, manufacturing methods, and applicable power consumption devices. [Background technology]

[0003] With the rapid development of the new energy sector, solar cells are being widely applied in fields such as military, spaceflight, industry, commerce, agriculture, and communications. Perovskite cells are increasingly becoming a hot spot in next-generation solar cell research due to their advantages such as high photoelectric conversion efficiency, simple manufacturing process, and low production and material costs.

[0004] Nickel oxide is the most commonly used inorganic hole transport layer material in trans-type perovskite batteries, making it 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 liquid, further degrading the photoelectric conversion efficiency of the perovskite battery. At the same time, erosion of the perovskite light absorption layer by water and oxygen affects the stability of the perovskite battery to some extent. Therefore, there is still room for improvement in the structure and performance of conventional perovskite batteries. [Overview of the project]

[0005] This application is made in view of the above-mentioned problems, and its purpose is to improve the photoelectric conversion efficiency of the battery by improving the stability of the perovskite layer in order to guarantee the conductivity of the nickel oxide hole transport layer, and to provide a perovskite battery that is less expensive to manufacture and easier to operate.

[0006] To achieve the above objective, this application provides a perovskite battery, a method for manufacturing the same, and a power consumption device.

[0007] A first aspect of this 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 main layer and a surface layer located on the side of the main layer closer to the perovskite layer, wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and the fractional part of an atom of trivalent nickel ions in the surface layer is smaller than the fractional part of an atom of trivalent nickel ions in the main layer.

[0008] The perovskite battery of this application improves the stability of the perovskite layer by reducing the fractional atomic percentage of trivalent nickel ions in the surface layer located on the side of the main body layer closest to the perovskite layer, thereby reducing the reaction between trivalent nickel ions and the perovskite in the perovskite layer, and by 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 this application, the fractions of atoms of trivalent nickel ions in the surface layer decrease in a gradient along the thickness direction of the surface layer, from the side closer to the main layer to the side further away from the main layer. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0010] In any embodiment of this application, the fractions of a hundredth of an atom of trivalent nickel ions are reduced along the thickness direction of the surface layer in a gradient of 0.5 to 4 nm. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer.

[0011] In any embodiment of this application, the difference in atomic fractions of trivalent nickel ions between two adjacent gradients is 2-20%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer.

[0012] In any embodiment of this application, the fractional part per hundred of an atom of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1 to 15%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0013] In any embodiment of this application, the fractional part per hundred of an atom of trivalent nickel ions in the main body layer is 20-65%. This further enhances the photoelectric conversion efficiency of the battery by guaranteeing electrical conductivity and improving the stability of the perovskite layer.

[0014] In any embodiment of this application, the thickness of the surface layer is 2 to 15 nm, and / or the thickness of the main body layer is 10 to 40 nm. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0015] A second aspect of this application provides a method for manufacturing a perovskite cell, the method being: (1) The step of providing a first electrode, (2) The step of manufacturing a hole transport layer on the first electrode, (3) A step of manufacturing a perovskite layer on the hole transport layer, (4) A step of manufacturing an electron transport layer on the perovskite layer; (5) A step of manufacturing a second electrode on the electron transport layer to obtain the perovskite battery, where the hole transport layer includes a main body layer and a surface layer disposed on a side of the main body layer close to the perovskite layer, where the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of trivalent nickel ions in the surface layer is smaller than the atomic percentage of trivalent nickel ions in the main body layer.

[0016] The method of the present application has a lower cost, is easy to operate, and is easy for large-scale industrial applications.

[0017] In any embodiment of the present application, step (2) includes a step of manufacturing a hole transport layer on the first electrode by using a magnetron sputtering method with a nickel oxide target material. Thereby, the perovskite battery of the first aspect of the present application can be manufactured more easily.

[0018] In any embodiment of the present application, the conditions of the magnetron sputtering method include that in the manufacture of the main body layer, the argon-oxygen ratio used is 500:(1 - 200). Thereby, the perovskite battery of the first aspect of the present application can be manufactured more easily.

[0019] In any embodiment of the present application, the conditions of the magnetron sputtering method include that in the manufacture of the surface layer, the argon-oxygen ratio used is higher than the argon-oxygen ratio used in the manufacture of the main body layer. Thereby, the perovskite battery of the first aspect of the present application can be manufactured more easily.

[0020] A third aspect of this application provides a power consumption device, the power consumption device comprising a perovskite cell as described in the first aspect of this application, or a perovskite cell obtained by the method described in the second aspect of this application, the perovskite cell being used to supply power to the power consumption device.

[0021] The perovskite battery of this application improves the photoelectric conversion efficiency of the battery by reducing the fractional atomic percentage of trivalent nickel ions in the surface layer located on the side of the main body layer closest to the perovskite layer, thereby reducing the reaction between trivalent nickel ions and the perovskite in the perovskite layer, and by ensuring the conductivity of the hole transport layer containing nickel oxide. [Brief explanation of the drawing]

[0022] To more clearly illustrate the technical concept of the embodiments of this application, the following is a brief introduction to the drawings that may be used in the embodiments of this application. It is obvious that the drawings described below represent only a few embodiments of this application, and those skilled in the art can obtain other drawings based on these drawings without expending any creative effort. In the drawings, [Figure 1] This is a schematic diagram of the structure of a perovskite battery in one embodiment of the present application. [Modes for carrying out the invention]

[0023] The following description will detail embodiments specifically disclosing the perovskite battery and its manufacturing method, as well as the corresponding power consumption device, with appropriate reference to the drawings. However, unnecessary detailed explanations may be omitted. For example, detailed explanations of well-known matters and redundant explanations of structures that are actually the same may be omitted. This is to avoid making the following explanation unnecessarily long and to make it easily understandable to those skilled in the art. The drawings and the following description are provided to enable those skilled in the art to fully understand this application and do not limit the topics described in the claims.

[0024] The “range” disclosed in this application is limited in the form of a lower limit and an upper limit, and a given range is limited by selecting one lower limit and one upper limit, which define the boundary of a particular range. The range thus limited may or may not include the endpoints, and any combination is possible, that is, any lower limit can be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 can also be assumed. Furthermore, if the minimum range values ​​are listed as 1 and 2, and the maximum range values ​​are listed as 3, 4 and 5, then the ranges 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5 can all be assumed. In this application, unless otherwise specified, the numerical range “a-b” represents an abbreviated expression for any combination of real numbers a-b, where a and b are both real numbers. For example, the numerical range "0 to 5" indicates that all real numbers between "0 to 5" have already been listed in this specification, and "0 to 5" is simply an abbreviated representation of combinations of these numbers. Also, when a parameter is described as an integer ≥ 2, it is equivalent to disclosing that this parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0025] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical inventions.

[0026] Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical concepts.

[0027] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the fact that the method includes steps (a) and (b) means that the method may include steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, the method mentioned may further include step (c), and step (c) may be added to the method in any order, for example the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), and so on.

[0028] Unless otherwise specified, the terms “includes” and “inclusion” as used in this application may be open or closed. For example, “includes” and “inclusion” may mean that other components not listed may be included or inclusion, or that only the listed components may be included or inclusion.

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

[0030] Nickel oxide is the most commonly used inorganic hole transport layer material in trans-type perovskite batteries and is a preferred candidate for the industrialization of perovskite batteries. However, trivalent nickel present on the surface of the hole transport layer reacts with A-site cations and X-site halogens in the perovskite precursor liquid, further degrading the photoelectric conversion efficiency of the perovskite battery. At the same time, 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 this application, the hole transport layer (especially nickel oxide (NiO)) is used. x A passivation layer containing nickel(II) oxide is placed between the hole transport layer and the perovskite layer, resulting in high photoelectric conversion efficiency and good long-term stability, while also being less expensive and easier to manufacture.

[0031] Perovskite cell 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 main layer and a surface layer located on the side of the main layer closer to the perovskite layer, wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and the fractions of atoms of trivalent nickel ions in the surface layer are smaller than the fractions of atoms of trivalent nickel ions in the main layer.

[0032] The perovskite battery of this application improves the stability of the perovskite layer by reducing the fractional atomic percentage of trivalent nickel ions in the surface layer located on the side of the main body layer closest to the perovskite layer, thereby reducing the reaction between trivalent nickel ions and the perovskite in the perovskite layer, and by 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 It can be expressed as such, and it can represent a compound containing oxygen and nickel.

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

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

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

[0037] In some embodiments of this application, the fractions of a hundred atoms of trivalent nickel ions in the surface layer decrease in a gradient along the thickness direction of the surface layer, from the side closer to the main layer to the side further away from the main layer. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0038] The aforementioned "gradient decrease" refers to the fact that while the fractional percentage of trivalent nickel ions remains constant within one gradient, the fractional percentage of trivalent nickel ions located in another gradient directly adjacent to this gradient, away from the main layer of this gradient, decreases relative to the fractional percentage of trivalent nickel ions within this gradient.

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

[0040] In some embodiments of this application, the fractional part of an atom of trivalent nickel ions decreases along the thickness direction of the surface layer in a gradient of 0.5 to 4 nm. This improves the photoelectric conversion efficiency of the battery by further ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer. To make it clear, "0.5 to 4 nm" means 0.5 nm to 4 nm.

[0041] In some embodiments, a gradient of 1.5 to 4 nm in thickness is generally defined 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, a thickness of 1.5 to 2.5 nm is generally defined as a gradient 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 generally 1 to 10. The "number of gradients" refers to the number of fractions of atoms of trivalent nickel ions in the surface layer that change with the thickness of the surface layer. Calculating from the side closest to the main layer, the gradient closest to the main layer in the surface layer is gradient 1, and along the thickness direction of the surface layer to the perovskite layer, the gradients are sequentially called gradient 2, gradient 3, gradient 4... and so on. By analogy, the gradient closest to the perovskite layer is called the outermost gradient.

[0044] In some embodiments, the number of gradients in the surface layer is generally 3 to 6.

[0045] In some embodiments of this application, the difference in atomic fractions of trivalent nickel ions between two adjacent gradients is 2-20%. This improves the photoelectric conversion efficiency of the battery by further ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer. To be clear, "2-20%" means 2%-20%.

[0046] In some embodiments, the difference in atomic fractions of trivalent nickel ions between two adjacent gradients is 2% to 10%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer.

[0047] In some embodiments, the difference in atomic fractions of trivalent nickel ions between two adjacent gradients is 3.5% to 6%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity while simultaneously improving the stability of the perovskite layer.

[0048] In some embodiments of this application, the fractional part per hundred of an atom of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1 to 15%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0049] The aforementioned "outermost gradient" refers to one of the gradients in the hole transport layer that is furthest from the main layer on the surface 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 fractions” refers to the percentage of the number of atoms of the ion in the layer or gradient where it is located, and is calculated based on the total number of atoms in the layer or gradient where it is located. The number of atoms refers to the number of atoms of the ion in the layer or gradient where it is located, and is measured based on X-ray photoelectron spectroscopy (XPS).

[0051] In some embodiments, the fractions of a hundred atoms of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1-12%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0052] In some embodiments, the fractional part per hundred of an atom of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1-10%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0053] In some embodiments, the fractions of a hundred atoms of trivalent nickel ions in the outermost gradient of the surface layer that is in direct contact with the perovskite layer is 1-5%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0054] In some embodiments of this application, the fractional part per hundred of an atom of trivalent nickel ions in the main body layer is 20-65%. This further enhances the photoelectric conversion efficiency of the battery by ensuring electrical conductivity and improving the stability of the perovskite layer.

[0055] In some embodiments, the fractional part per hundred of an atom of trivalent nickel ions in the main body layer is 25-40%. This further enhances the photoelectric conversion efficiency of the battery by guaranteeing electrical conductivity and improving the stability of the perovskite layer.

[0056] In some embodiments, the fractional percentage of trivalent nickel ions in the main body layer is 25-35%. This further enhances the photoelectric conversion efficiency of the battery by guaranteeing electrical conductivity and improving the stability of the perovskite layer.

[0057] In some embodiments, the fractional percentage of trivalent nickel ions in the main body layer is 28-33%. This further enhances the photoelectric conversion efficiency of the battery by guaranteeing electrical conductivity and improving the stability of the perovskite layer.

[0058] In some embodiments of this application, the thickness of the surface layer is 2 to 15 nm, and the thickness of the main body layer is 10 to 40 nm. This further ensures electrical conductivity and improves the stability of the perovskite layer, thereby improving the photoelectric conversion efficiency of the battery.

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

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

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

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

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

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

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

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

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

[0068] In some embodiments, the first electrode is an anode layer, which serves to collect holes and is generally called 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 to 1000 nm, for example, 300 to 800 nm.

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

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

[0072] Therefore, in one embodiment of this application, the perovskite battery of this application includes a transparent substrate layer, a first electrode, a nickel oxide hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, which are stacked in order.

[0073] In some embodiments, the perovskite layer is a light-absorbing layer, i.e., the active layer of the perovskite battery, and is made of a perovskite material, and this layer is in the core position of the entire battery structure.

[0074] In some embodiments, the chemical formula of the perovskite layer material is ABX3 or A2CDX6, where A is an inorganic, organic, or organic-inorganic mixed cation, comprising at least one of an organic amine cation, a Cs cation, a K cation, a Rb cation, and a Li cation, wherein the organic amine cation is (NR1R2R3R4) + (R1R2N=CR3R4) + (R1R2N-C(R5)=NR3R4) + Or (R1R2N-C(NR5R6)=R3R4) +selected from, where 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 at least one of a methylamino group (CH3NH3 + )(MA + ), a carbamimidoyl group (HC(NH2)2 + )(FA + ), a cesium ion (Cs + ) and a rubidium ion (Rb + ). For example, A is a methylamino group (CH3NH3 + ) or a carbamimidoyl group (HC(NH2)2 + ).

[0076] B is an inorganic or organic or organic-inorganic hybrid cation and contains 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 is at least one of the divalent metal ions Pb 2+ and Sn 2+ .

[0077] C is an inorganic or organic or organic-inorganic hybrid cation. For example, C is a monovalent metal ion such as Ag + .

[0078] D is an inorganic or organic or organic-inorganic hybrid cation. For example, D is a trivalent metal ion such as a bismuth cation Bi 3+ , an antimony cation Sb 3+ , an indium cation In 3+ , etc.

[0079] X is an inorganic or organic or organic-inorganic hybrid anion. For example, X is one or more of a halogen anion and a carboxylic acid anion. For example, X is a bromine ion (Br -) or iodide ion (I - )

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

[0081] In some embodiments, the band gap of the perovskite layer is 1.20 eV to 2.30 eV.

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

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

[0084] In some embodiments, the perovskite battery further includes 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, effectively block the passage of free holes, and form 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 71The material is at least one of the following: BM), fullerene C60, fullerene C70, cyano group-containing polyphenylacetylene, boron-containing polymer, bathocuproine, batphenanthroline, hydroxyquinoline aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorine group-containing phthalocyanine, titanium dioxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride, sodium fluoride, magnesium fluoride, and zinc sulfide, as well as their derivatives and materials doped or passivated therefrom.

[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: BM), fullerene C60 (C60), fullerene C70 (C70), tin oxide (SnO2), zinc oxide (ZnO), and their derivatives, as well as materials doped or passivated therefrom.

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

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

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

[0091] Therefore, in one embodiment of this application, the perovskite battery of this application includes a transparent substrate layer, a first electrode, a nickel oxide hole transport layer, a perovskite layer, an electron transport layer, and a second electrode, which are stacked in order.

[0092] In some embodiments, the second electrode is a cathode layer, which has the function of collecting free electrons.

[0093] In some embodiments, the second electrode is generally an organic, inorganic, or organic-inorganic mixed conductive material, and includes 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 their alloys, graphite, graphene, and carbon nanotubes.

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

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

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

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

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

[0099] In some embodiments, a hole blocking layer may be present between the second electrode and the electron transport layer, which is used to prevent the reaction between the second electrode and the perovskite and to avoid a reduction in device efficiency due to Schottky contact between the electron transport layer and the back electrode, while also having an energy level adjustment control function.

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

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

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

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

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

[0105] In some embodiments, a passivation layer may be present 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 electrodes to improve the performance of the perovskite battery.

[0107] In some embodiments, a perovskite cell 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 order, wherein the hole transport layer includes a main layer and a surface layer located on the side of the main layer closest to the perovskite layer. The first electrode is selected from, for example, FTO. The material of the main layer includes, for example, nickel oxide. The material of the surface layer includes, for example, nickel oxide. The material of the electron transport layer includes, for example, C60. The material of the hole blocking layer includes, for example, BCP. The material of the second electrode includes, for example, Cu.

[0108] In some embodiments, as shown in Figure 1, the perovskite battery 10 includes, in order, an FTO 1, a nickel oxide body layer 2, a nickel oxide surface layer 3, a perovskite layer 4, a C60 5, a BCP 6, and a Cu 7, which are stacked in that order. Here, the FTO is the first electrode, the C60 is the electron transport layer, the BCP is the hole blocking layer, and the Cu is the second electrode.

[0109] A second aspect of this application provides a method for manufacturing a perovskite cell as described in the first aspect of this application, the method being: (1) The step of providing a first electrode, (2) The step of manufacturing a hole transport layer on the first electrode, (3) A step of manufacturing a perovskite layer on the hole transport layer, (4) The step of manufacturing an electron transport layer on the perovskite layer, (5) The step of manufacturing a second electrode on the electron transport layer to obtain the perovskite cell, Here, the hole transport layer includes a main layer and a surface layer located on the side of the main layer closer to the perovskite layer, wherein the hole transport layer contains nickel oxide containing trivalent nickel ions, and the fractional part of an atom of trivalent nickel ions in the surface layer is smaller than the fractional part of an atom of trivalent nickel ions in the main layer.

[0110] The method described in this application is less expensive, easier to operate, and readily applicable to large-scale industrial use.

[0111] In some embodiments of this application, step (2) includes the step of manufacturing a hole transport layer on the first electrode using a magnetron sputtering method with respect to a nickel oxide target material. This makes it easier to manufacture the perovskite battery of the first embodiment of this 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 this application, the conditions for the magnetron sputtering method include using an argon-oxygen ratio of 500:(1-200) in the production of the main layer. This makes it easier to manufacture the perovskite battery of the first embodiment of this application.

[0114] In some embodiments, the conditions of the magnetron sputtering method include using an argon-oxygen ratio of 500:(1-100) in the production of the main layer. This makes it easier to manufacture the perovskite battery of the first embodiment of this application.

[0115] In some embodiments, the conditions of the magnetron sputtering method include using an argon-oxygen ratio of 500:(3-100) in the production of the main layer. This makes it easier to manufacture the perovskite battery of the first embodiment of this application.

[0116] In some embodiments, the conditions of the magnetron sputtering method include using an argon-oxygen ratio of 500:(30-70) in the production of the main layer. This makes it easier to manufacture the perovskite battery of the first embodiment of this application.

[0117] In some embodiments of this application, the conditions of the magnetron sputtering method include a higher argon-oxygen ratio used in the production of the surface layer than the argon-oxygen ratio used in the production of the main body layer. This makes it easier to manufacture the perovskite cell of the first embodiment of this application.

[0118] In some embodiments of this application, the conditions for the magnetron sputtering method include obtaining different fractions of an atom gradient of trivalent nickel ions by using different argon-oxygen ratios in the production of different gradients of the surface layer.

[0119] In some embodiments of this application, the conditions for the magnetron sputtering method include a progressively increasing argon-oxygen ratio used in the process of producing different gradients along the thickness direction of the surface layer, from the main body layer side toward the perovskite layer side.

[0120] In some embodiments of this application, for example, step (2) includes the step of manufacturing a nickel oxide layer using DC magnetron sputtering, wherein 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, ..., and the argon-oxygen ratio for the fifth 2 nm (i.e., the outermost gradient) being 500 / 0, and this is used as an analogy.

[0121] In some embodiments, step (1) includes placing a transparent conductive oxide layer on a transparent substrate layer to obtain a first electrode that adheres to the transparent substrate layer. Alternatively, the first electrode that adheres to the transparent substrate layer may be a commercially available product.

[0122] In some embodiments, in step (1), the transparent substrate layer, for example, conductive glass, may be further cleaned by ultrasonic cleaning with water, acetone, and isopropanol in sequence for, for example, 1 to 30 minutes, then blow-dried, and further cleaned by placing it in an ultraviolet ozone device for, for example, 1 to 20 minutes.

[0123] In some embodiments, step (3) includes coating the 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 obtaining the perovskite layer after cooling. Here, 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), or N-methylpyrrolidone (NMP), etc.), stirring uniformly, filtering, and obtaining a perovskite precursor solution.

[0125] In some embodiments, a second electrode is manufactured in step (5). The second electrode may be manufactured by a method common in the art. For example, the electrode may be manufactured using a vapor deposition method.

[0126] In some embodiments, the electron transport layer may be manufactured before step (5). The electron transport layer is manufactured by conventional means of the art. For example, the electron transport layer may be manufactured using spin coating, vapor deposition, or the like.

[0127] A third aspect of this application provides a power consumption device, the power consumption device comprising a perovskite cell as described in the first aspect of this application, or a perovskite cell obtained by the method described in the second aspect of this application, the perovskite cell being used to supply power to the power consumption device.

[0128] In some embodiments, the power consumption device is a common device including the perovskite battery of this application, for example, in the fields of communications, transportation, industrial agriculture, lighting, etc. The power consumption device may also include, for example, satellites, communication equipment, traffic signals, lighthouses, radio telephone booths, monitoring equipment in the field of oil drilling, power systems, camping lights, electric vehicles, electronic device chargers, etc.

[0129] Examples Examples of the present application are described below. The examples described below are illustrative and are for interpretive purposes only, and should not be considered as limitations thereon. Unless specific techniques or conditions are specified in the examples, they shall be carried out in accordance with the techniques or conditions described in the literature in the art or in accordance with the product instructions. Unless the manufacturer is specified, the reagents or equipment used are all common products available on the market.

[0130] 1. Perovskite Cells Example 1 1) Twenty pieces of 2.0*2.0cm FTO conductive glass were taken, and 0.35cm of FTO was removed from both ends by laser etching to expose the glass substrate. The FTO conductive glass was then ultrasonically cleaned with 500ml (mL) of water, acetone, and isopropanol for 10 minutes each, in that order. After cleaning, the solvent was blown dry over the FTO conductive glass using a nitrogen gas gun, and it was further cleaned in an ultraviolet ozone apparatus for 5 minutes to obtain the first electrode.

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

[0132] 3) 1362 milligrams (mg) of formamidine hydroiodide (FAI), 228.6 mg of cesium iodide (CsI), and 4056.9 mg of lead iodide (PbI2) were dissolved in 8 mL of solvent to prepare a perovskite precursor solution with a molar concentration of 1.1 mol / L (mol / L). The solvent was a mixture of DMF (N,N-dimethylformamide) and NMP (N-methylpyrrolidone) in a volume ratio of 7:1.

[0133] The precursor solution was coated onto a nickel oxide layer, and the sample was then transferred to a vacuum chamber and left to stand for 120 seconds (s) under a vacuum of 100 Pascals (Pa) or less to cure the precursor solution and form a film. After curing, the sample was placed on a hot stage and annealed at a temperature of 150 degrees Celsius (°C) for a duration of 30 minutes. After annealing, a perovskite layer with a thickness of 500 nm was obtained.

[0134] 4) On the perovskite layer obtained in step (3), perform PC at 1500 revolutions per second (rpm / s). 61 BM was spin-coated and annealed at 100°C for 10 minutes to obtain an electron transport layer with a thickness of 50 nm. Immediately thereafter, a solution of BCP in isopropanol with a concentration of 0.5 mg / ml (mg / mL) was spin-coated on the electron transport layer at 5000 rpm / s to obtain a hole blocking layer with a thickness of 5 nm.

[0135] 5) Place the device obtained in step (4) into a deposition machine of model number LN-F300, and on the hole blocking layer, 10 -5 A second electrode layer with a thickness of 80 nm was fabricated by depositing a metal electrode Cu under vacuum conditions of Pa, thereby obtaining the perovskite cell.

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

[0137] Example 3 The steps of Example 1 were repeated, with the difference being that in step 2), a 2nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:39, a 2nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:25, and the 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 2nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:41, a 2nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:30, a 2nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:16, and the outermost 2nm 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 2nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:43, a 2nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:35, a 2nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:25, a 2nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:16, and the outermost 2nm 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 2nm gradient 1 surface layer was sputtered with an argon-oxygen ratio of 500:45, a 2nm gradient 2 surface layer was sputtered with an argon-oxygen ratio of 500:39, a 2nm gradient 3 surface layer was sputtered with an argon-oxygen ratio of 500:32, a 2nm gradient 4 surface layer was sputtered with an argon-oxygen ratio of 500:25, a 2nm gradient 5 surface layer was sputtered with an argon-oxygen ratio of 500:16, and the outermost 2nm layer was sputtered with an argon-oxygen ratio of 500:5.

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

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

[0143] Example 9 The steps of Example 1 were repeated, with the difference being that in step 2), a 12 nm main 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 the outermost layer was sputtered with an argon-oxygen ratio of 500:5.

[0144] Example 10 The steps of Example 1 were repeated, with the difference being that in step 2), a 12 nm main 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 the 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 only difference being the thickness of the main layer and the fractional part of an atom of trivalent nickel ions.

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

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

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

[0149] Examples 16-19 The steps of Example 2 were repeated, with the only difference being 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 only difference being that the surface layer was not fabricated in step 2).

[0151] Comparative Example 2 The steps of Example 1 were repeated, with the difference being that the outermost layer of 2 nm 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 shown in Table 1.

[0153] Parameter testing Testing the number of divalent and trivalent nickel ions in the hole transport layer and the interfacial passivation layer. X-ray photoelectron spectroscopy (XPS) was used to measure the number of divalent and trivalent nickel ions in the main and surface layers of the hole transport layer. This was performed using a K-Alpha spectrometer (manufactured by Thermo Fisher). The fraction of divalent or trivalent nickel ions = number of divalent or trivalent nickel ions / total number of nickel ions in the layer or gradient where it is located.

[0154] A represents the fraction of a hundredth of a percent of trivalent nickel ion atoms in a layer or gradient.

[0155] [Table 1] JPEG0007880505000002.jpg134170

[0156] 2. Performance measurement of perovskite batteries 1. Measurement of photoelectric conversion efficiency Tests were conducted in accordance with the national standard IEC61215, where the tests were performed under light irradiation using a Keithley 2400 digital source meter. The light source was provided by a solar simulator using a 450W xenon lamp with an UV filter, and the light emitted from the light source conformed to the AM 1.5G standard solar spectrum. The battery was connected to the digital source meter, and its photoelectric conversion efficiency was measured under light irradiation.

[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 this application all achieved excellent technical effects. The efficiencies of the perovskite batteries in Examples 1 to 16 reached 12.9% or higher, and the efficiencies of the perovskite batteries in Examples 1 to 7, 10 to 11, 13 to 14, and 16 were able to reach 15% or higher.

[0160] The technical features of the embodiments described above can be combined in any way, and for the sake of brevity, not all possible combinations of the technical features in the embodiments described above will be explained. However, as long as there are no inconsistencies in these combinations of technical features, they should be considered to fall within the scope described in the specification.

[0161] The embodiments described above are merely examples of some embodiments of this application, and although the descriptions are relatively specific and detailed, they should not be understood as limiting the scope of the patent application. It should be noted that a person skilled in the art can make several modifications and improvements without departing from the concept of this application, and all of these fall within the scope of protection of this application. Therefore, the scope of protection of the patent application should be based on the attached claims, and the specification and drawings can be used to illustrate the content of the claims. [Explanation of Symbols]

[0162] 1-FTO, 2-Nickel oxide main layer, 3-Nickel oxide surface layer, 4-Perovskite layer, 5-C60, 6-BCP, 7-Cu, 10-Perovskite battery.

Claims

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 installed on the side of the main layer closer to the perovskite layer, wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and the fractional part of an atom of trivalent nickel ions in the surface layer is smaller than the fractional part of an atom of trivalent nickel ions in the main layer.

2. The perovskite battery according to claim 1, wherein the fractional part of an atom of trivalent nickel ions in the surface layer decreases in a gradient along the thickness direction of the surface layer, from the side closer to the main body layer to the side further away from the main body layer.

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

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

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

6. The perovskite battery according to claim 1, wherein the fractional part of an atom of trivalent nickel ions in the main body layer is 20 to 65%.

7. The aforementioned perovskite cell is (1) The thickness of the surface layer is 2 to 15 nm, (2) The perovskite battery according to claim 1, having one or more of the following features: the thickness of the main body layer is 10 to 40 nm.

8. A method for manufacturing a perovskite battery, (1) The step of providing a first electrode, (2) A step of manufacturing a hole transport layer on the first electrode, (3) A step of manufacturing a perovskite layer on the hole transport layer, (4) The step of manufacturing an electron transport layer on the perovskite layer, (5) The step of manufacturing a second electrode on the electron transport layer to obtain the perovskite cell, Here, the hole transport layer includes a main layer and a surface layer located on the side of the main layer closer to the perovskite layer, wherein the hole transport layer contains nickel oxide containing trivalent nickel ions, and the fractional part of an atom of trivalent nickel ions in the surface layer is smaller than the fractional part of an atom of trivalent nickel ions in the main layer. Step (2) includes the step of manufacturing a hole transport layer on the first electrode using a magnetron sputtering method, The conditions for the magnetron sputtering method include the argon-oxygen ratio used in the production of the main layer being 500:(1-200), A method for manufacturing perovskite batteries.

9. The method according to claim 8, wherein the conditions for the magnetron sputtering method include that the argon-oxygen ratio used in the production of the surface layer is higher than the argon-oxygen ratio used in the production of the main body layer.

10. A power consumption device comprising a perovskite battery according to any one of claims 1 to 7, wherein the perovskite battery is used to supply power to the power consumption device.

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