WO2024183488A1 - 钙钛矿电池、制备方法以及相应的用电装置 - Google Patents

钙钛矿电池、制备方法以及相应的用电装置 Download PDF

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WO2024183488A1
WO2024183488A1 PCT/CN2024/073493 CN2024073493W WO2024183488A1 WO 2024183488 A1 WO2024183488 A1 WO 2024183488A1 CN 2024073493 W CN2024073493 W CN 2024073493W WO 2024183488 A1 WO2024183488 A1 WO 2024183488A1
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layer
perovskite
nickel ions
transport layer
hole transport
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French (fr)
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苏硕剑
林翔玲
李晗芳
张帆
陈国栋
郭永胜
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Contemporary Amperex Technology Co Ltd
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Priority to KR1020257028478A priority Critical patent/KR20250133989A/ko
Priority to JP2025550627A priority patent/JP2026508354A/ja
Priority to EP24766211.7A priority patent/EP4654792A4/en
Publication of WO2024183488A1 publication Critical patent/WO2024183488A1/zh
Priority to US19/306,526 priority patent/US20250393383A1/en
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • H10K2102/351—Thickness
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to the field of perovskite cells, and in particular to a perovskite cell, a preparation method and a corresponding electrical device.
  • Perovskite cells have gradually become a hot topic in the research of new generation solar cells due to their high photoelectric conversion efficiency, simple manufacturing process, low production cost and material cost.
  • Nickel oxide as the most commonly used inorganic hole transport layer material in inverse perovskite cells, is a preferred candidate for the industrialization of perovskite cells.
  • the trivalent nickel on the surface of the nickel oxide hole transport layer will react with the A-site cations and X-site halogens in the perovskite precursor solution, thereby degrading the photoelectric conversion efficiency of the perovskite cell.
  • the erosion of the perovskite light absorption layer by water and oxygen will affect the stability of the perovskite cell to a certain extent. Therefore, the structure or performance of traditional perovskite cells still needs to be improved.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a perovskite battery, which improves the stability of the perovskite layer while ensuring the conductivity of the nickel oxide hole transport layer, thereby improving the photoelectric conversion efficiency of the battery, and its preparation method has lower cost and simple operation.
  • the present application provides a perovskite battery and a preparation method and an electrical device thereof.
  • the first aspect of the present application provides a perovskite battery, which includes a first electrode, a hole transport layer, a perovskite layer, an electron transport layer and a second electrode arranged in sequence, wherein the hole transport layer includes a body layer and a surface layer arranged on a side of the body layer close to the perovskite layer, wherein the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic number percentage of trivalent nickel ions in the surface layer is less than the atomic number percentage of trivalent nickel ions in the body layer.
  • the perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer arranged on the side of the body layer close to the perovskite layer, thereby reducing the reaction of trivalent nickel ions with perovskites 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.
  • the atomic percentage of trivalent nickel ions in the surface layer decreases gradually from the side close to the main layer to the side away from the main layer along the thickness direction of the surface layer.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions decreases along the thickness direction of the surface layer with a gradient of 0.5-4 nm, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in two adjacent gradients differs by 2-20%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions is 1-15%.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in the bulk layer is 20-65%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the thickness of the surface layer is 2-15 nm; and/or the thickness of the bulk layer is 10-40 nm.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the second aspect of the present application provides a method for preparing a perovskite battery, comprising:
  • the hole transport layer comprises a main body layer and a surface layer arranged on the side of the main body layer close to the perovskite layer, wherein the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of trivalent nickel ions in the surface layer is less than the atomic percentage of trivalent nickel ions in the main body layer.
  • the method of the present application has lower cost, simple operation, and is convenient for large-scale industrial application.
  • step (2) comprises preparing a hole transport layer on the first electrode using a nickel oxide target by a magnetron sputtering method.
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the bulk layer, the argon-oxygen ratio used is 500:(1-200).
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the surface layer, the argon-oxygen ratio used is higher than the argon-oxygen ratio used in the preparation of the bulk layer.
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the third aspect of the present application provides an electrical device, comprising the perovskite battery described in the first aspect of the present application, or a perovskite battery prepared by the method described in the second aspect of the present application, wherein the perovskite battery is used to supply power to the electrical device.
  • the perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer arranged on the side of the body layer close to the perovskite layer, thereby reducing the reaction of trivalent nickel ions with 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.
  • FIG1 is a schematic diagram of the structure of a perovskite battery in one embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "ab” represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may also include step (c), which means that step (c) can be added to the method in any order.
  • 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.
  • the “include” and “comprising” mentioned in this application represent open-ended or closed-ended expressions.
  • the “include” and “comprising” may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • Nickel oxide as the most commonly used inorganic hole transport layer material in trans-perovskite cells, is a preferred candidate for the industrialization of perovskite cells.
  • the trivalent nickel present on the surface of the hole transport layer will react with the A-position cations and X-position halogens in the perovskite precursor solution, thereby deteriorating the photoelectric conversion efficiency of the perovskite cell.
  • the erosion of the perovskite light-absorbing layer by water and oxygen will affect the stability of the perovskite cell to a certain extent.
  • the perovskite cell of the present application is provided with an interface passivation layer containing nickel (II) oxide between the hole transport layer (especially the nickel oxide (NiO x ) hole transport layer) and the perovskite layer, so that it has high photoelectric conversion efficiency and good long-term stability, and its preparation method is lower in cost and simple to operate.
  • II nickel oxide
  • the first aspect of the present application provides a perovskite cell, comprising a first electrode, a hole transport layer, a perovskite layer, an electron transport layer and a second electrode arranged in sequence, wherein the hole transport layer comprises a body layer and a surface layer arranged on a side of the body layer close to the perovskite layer, wherein the hole transport layer comprises nickel oxide containing trivalent nickel ions, and the atomic number percentage of trivalent nickel ions in the surface layer is less than the atomic number percentage of trivalent nickel ions in the body layer.
  • the perovskite battery of the present application reduces the atomic percentage of trivalent nickel ions in the surface layer arranged on the side of the body layer close to the perovskite layer, thereby reducing the reaction of trivalent nickel ions with perovskites 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.
  • the hole transport layer comprises nickel oxide containing trivalent nickel ions, wherein the nickel oxide is generally Expressed as NiO x , it may represent a compound containing oxygen and nickel.
  • the hole transport layer is a nickel oxide hole transport layer.
  • the hole transport layer may contain NiO, Ni(OH) 2 , Ni 2 O 3 , NiOOH and the like.
  • the trivalent nickel ions are usually present in the form of Ni 2 O 3 , NiOOH, etc.
  • the divalent nickel ions are usually present in the form of NiO, Ni(OH) 2 , etc.
  • the atomic percentage of trivalent nickel ions in the surface layer decreases gradually from the side close to the main layer to the side away from the main layer along the thickness direction of the surface layer.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the "gradient decrease” means that the atomic percentage of trivalent nickel ions remains unchanged within a gradient, while the atomic percentage of trivalent nickel ions in another gradient adjacent to the gradient away from the main layer decreases relative to the atomic percentage of trivalent nickel ions in the gradient.
  • the unit “nm” means nanometer.
  • the atomic percentage of trivalent nickel ions decreases along the thickness direction of the surface layer with a thickness of 0.5-4nm as a gradient.
  • 0.5-4nm means 0.5nm-4nm.
  • the thickness of the surface layer is generally 1.5-4 nm as a gradient. In other words, the thickness of the gradient is 1.5-4 nm.
  • the thickness of the surface layer is generally 1.5-2.5 nm as a gradient. In other words, the thickness of the gradient is 1.5-2.5 nm.
  • the number of gradients in the surface layer is generally 1-10.
  • the “number of gradients” refers to the number of atomic percentages of trivalent nickel ions in the surface layer that change with the thickness of the surface layer. Starting from the side close to the bulk layer, the gradient closest to the bulk layer in the surface layer is counted as one gradient, and along the thickness direction of the surface layer to the perovskite layer, the gradients are counted as two gradients, three gradients, four gradients, and so on. The gradient closest to the perovskite layer is called the outermost gradient.
  • the number of gradients in the surface layer is typically 3-6.
  • the atomic percentage of trivalent nickel ions in two adjacent gradients differs by 2-20%.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery. It is understood that "2-20%” means 2%-20%.
  • the atomic percentage of trivalent nickel ions in two adjacent gradients differs by 2%-10%.
  • the stability of the perovskite layer is further improved while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in two adjacent gradients differs by 3.5%-6%.
  • the stability of the perovskite layer is further improved while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the outermost gradient in the surface layer directly in contact with the perovskite layer The atomic percentage of trivalent nickel ions is 1-15%.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the “outermost gradient” refers to a gradient in the surface layer on the side farthest from the body layer relative to the body layer in the hole transport layer, and the gradient layer is in direct contact with the perovskite layer.
  • the thickness of the outermost gradient may be different from the thickness of other gradients, or may be the same as the thickness of other gradients.
  • the "atomic percentage” refers to the percentage of the atomic number of the ion in the layer or gradient in which it is located, based on the total atomic number of 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, measured according to X-ray photoelectron spectroscopy (XPS).
  • the atomic percentage of trivalent nickel ions is 1-12%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions is 1-10%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions is 1-5%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in the bulk layer is 20-65%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in the bulk layer is 25-40%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in the bulk layer is 25-35%, thereby further improving the stability of the perovskite layer while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the atomic percentage of trivalent nickel ions in the bulk layer is 28-33%.
  • the stability of the perovskite layer is further improved while ensuring the electrical conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the thickness of the surface layer is 2-15 nm; and the thickness of the bulk layer is 10-40 nm.
  • the stability of the perovskite layer is further improved while ensuring the conductivity, thereby improving the photoelectric conversion efficiency of the battery.
  • the surface layer has a thickness of 2-12 nm.
  • the surface layer has a thickness of 8-12 nm.
  • the bulk layer has a thickness of 10-30 nm.
  • the bulk layer has a thickness of 10-15 nm.
  • the ratio of the number of atoms of trivalent nickel ions to that of divalent nickel ions is 1:1.
  • the total thickness of the hole transport layer is 12-50 nm.
  • the total thickness of the hole transport layer is 12-25 nm.
  • the total thickness of the hole transport layer is 18-25 nm.
  • the perovskite cell is a formal perovskite cell or an inverse perovskite cell, for example, an inverse perovskite cell.
  • the first electrode is an anode layer, which plays a role in collecting holes and is usually called a transparent electrode.
  • 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 100-1000nm, for example, 300-800nm.
  • FTO fluorine-doped tin oxide
  • ITO indium tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium zinc oxide
  • IWO indium tungsten oxide
  • the unit "cm" means centimeter.
  • the perovskite cell further comprises a transparent substrate layer, wherein the transparent substrate layer is selected from at least one of transparent glass, polyethylene terephthalate (PET), and a polyimide substrate, and the thickness of the transparent substrate layer is 0.1-3 cm.
  • the transparent substrate layer is selected from at least one of transparent glass, polyethylene terephthalate (PET), and a polyimide substrate, and the thickness of the transparent substrate layer is 0.1-3 cm.
  • the perovskite cell of the present application comprises 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 sequence.
  • the perovskite layer is a light absorption layer, that is, an active layer of a perovskite cell, which is composed of a perovskite material and is the core of the entire cell structure.
  • A is an inorganic or organic or organic-inorganic mixed cation, including at least one of an organic amine cation
  • A is at least one of methylamine (CH 3 NH 3 + ) (MA + ), formamidinium (HC(NH 2 ) 2 + ) (FA + ), cesium ion (Cs + ) and rubidium (Rb + ).
  • A is methylamine (CH 3 NH 3 + ) or formamidinium (HC(NH 2 ) 2 + ).
  • B is an inorganic or organic or organic-inorganic mixed cation, including 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.
  • B is at least one of the divalent metal ions Pb 2+ and Sn 2+ .
  • C is an inorganic or organic or organic-inorganic mixed cation.
  • C is a monovalent metal ion Ag + , etc.
  • D is an inorganic or organic or organic-inorganic mixed cation.
  • D is a trivalent metal ion such as bismuth cation Bi 3+ , antimony cation Sb 3+ , indium cation In 3+ , and the like.
  • X is an inorganic or organic or organic-inorganic mixed anion.
  • X is one or more of a halogen anion and a carboxylate anion.
  • X is a bromide ion (Br - ) or an iodide ion (I - ).
  • the unit “eV” refers to electron volts.
  • the band gap of the perovskite layer is 1.20 eV-2.30 eV.
  • the perovskite layer has a thickness of 200-800 nm.
  • the perovskite layer has a thickness of 400-600 nm.
  • the perovskite cell further comprises an electron transport layer.
  • the electron transport layer functions to efficiently transport free electrons generated by the perovskite layer, effectively block the passage of free holes, and form an ohmic contact at the interface with the perovskite active layer.
  • the material of the electron transport layer is at least one of the following materials and their derivatives and materials obtained by doping or passivation: [6,6]-phenyl-C61-butyric acid isomethyl ester (PC 61 BM), [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM), fullerene C60, fullerene C70, cyano-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthroline, hydroxyquinoline aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorine-containing phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride,
  • the material of the electron transport layer is at least one of the following materials and their derivatives and materials obtained by doping or passivation: [6,6]-phenyl-C 61 -butyric acid isomethyl ester (PC 61 BM), [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM), fullerene C60 (C60), fullerene C70 (C70), tin oxide (SnO 2 ), and zinc oxide (ZnO).
  • the thickness of the electron transport layer is 10-200 nm.
  • the electron transport layer has a thickness of 30-120 nm.
  • the electron transport layer has a thickness of 40-60 nm.
  • the perovskite cell of the present application comprises 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 sequence.
  • the second electrode is a cathode layer, which has the function of collecting free electrons.
  • the second electrode is generally an organic or inorganic or organic-inorganic hybrid 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.
  • ITO indium tin oxide
  • BZO boron-doped zinc oxide
  • AZO aluminum zinc oxide
  • IZO indium zinc oxide
  • GZO gallium zinc oxide
  • IWO indium tungsten oxide
  • Au Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof, graphite, graphene, and carbon nanotubes.
  • the second electrode is generally an organic or inorganic or organic-inorganic hybrid conductive material, including Ag, Cu, C, Au, Al, ITO, AZO, BZO or IZO.
  • the second electrode is generally an organic or inorganic or organic-inorganic hybrid conductive material, including Cu, Ag, Au or a combination thereof.
  • the second electrode has a thickness of 20-200 nm.
  • the second electrode has a thickness of 60-100 nm.
  • the second electrode has a thickness of 70-90 nm.
  • a hole blocking layer may be present between the second electrode and the electron transport layer to prevent the second electrode from reacting with the perovskite and avoid a reduction in device efficiency caused by Schottky contact between the electron transport layer and the back electrode, while also having an energy level regulation effect.
  • the material of the hole blocking layer includes 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.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • LiF calcium acetylacetonate
  • LiF 8-hydroxyquinoline aluminum
  • 1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene or a combination thereof.
  • the material of the hole blocking layer includes BCP.
  • the hole blocking layer has a thickness of 0.1-30 nm.
  • the hole blocking layer has a thickness of 3-10 nm.
  • the hole blocking layer has a thickness of 4-6 nm.
  • a passivation layer may be present between the perovskite layer and the electron transport layer to passivate defects on the interface between the two.
  • a passivation layer may be present between the electron transport layer and the electrode to improve the performance of the perovskite cell.
  • 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 stacked in sequence, wherein the hole transport layer includes a body layer and a surface layer disposed on one side of the body layer close to the perovskite layer.
  • the first electrode is selected from FTO, for example.
  • the material of the body layer includes nickel oxide, for example.
  • the material of the surface layer includes nickel oxide, for example.
  • the material of the electron transport layer includes C60, for example.
  • the material of the hole blocking layer includes BCP, for example.
  • the material of the second electrode includes Cu, for example.
  • the perovskite battery 10 includes FTO 1, a nickel oxide bulk layer 2, a nickel oxide surface layer 3, a perovskite layer 4, C605, BCP 6, and Cu 7, which are stacked in sequence.
  • FTO is the first electrode
  • C60 is the electron transport layer
  • BCP is the hole blocking layer
  • Cu is the second electrode.
  • the second aspect of the present application provides a method for preparing the perovskite battery described in the first aspect of the present application, comprising:
  • the hole transport layer comprises a main body layer and a surface layer arranged on the side of the main body layer close to the perovskite layer, wherein the hole transport layer includes nickel oxide containing trivalent nickel ions, and the atomic percentage of trivalent nickel ions in the surface layer is less than the atomic percentage of trivalent nickel ions in the main body layer.
  • the method of the present application has lower cost, simple operation, and is convenient for large-scale industrial application.
  • step (2) comprises preparing a hole transport layer on the first electrode using a nickel oxide target by a magnetron sputtering method.
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the nickel-oxygen ratio of the nickel oxide target is 0.9-1.1.
  • the conditions of the magnetron sputtering method include: in the preparation of the bulk layer, the argon-oxygen ratio used is 500:(1-200).
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the bulk layer, the argon-oxygen ratio used is 500:(1-100).
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the bulk layer, the argon-oxygen ratio used is 500:(3-100).
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the bulk layer, the argon-oxygen ratio used is 500:(30-70).
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the surface layer, the argon-oxygen ratio used is higher than the argon-oxygen ratio used in the preparation of the bulk layer.
  • the perovskite cell of the first aspect of the present application can be prepared more simply.
  • the conditions of the magnetron sputtering method include: in the preparation of the surface layer, different argon-oxygen ratios are used in the preparation of different gradients so as to obtain different atomic percentage gradients of trivalent nickel ions.
  • the conditions of the magnetron sputtering method include: in the process of preparing different gradients from the bulk layer side to the perovskite layer side along the thickness direction of the surface layer, the argon-oxygen ratio used is gradually increased.
  • step (2) includes preparing a nickel oxide layer by DC magnetron sputtering, and the argon-oxygen ratio when sputtering the main layer is 500/5; when sputtering the surface layer, the argon-oxygen ratio is changed every 2 nm, and the argon-oxygen ratio of the first 2 nm is 500/4, the argon-oxygen ratio of the second 2 nm is 500/3, ..., the argon-oxygen ratio of the fifth 2 nm (i.e., the outermost gradient) is 500/0, and so on.
  • step (1) includes providing a transparent conductive oxide layer on the transparent substrate layer to obtain a first electrode attached to the transparent substrate layer.
  • the first electrode attached to the transparent substrate layer may also be a commercially available product.
  • the transparent substrate layer such as conductive glass
  • the transparent substrate layer can be further cleaned, for example, by ultrasonic cleaning with water, acetone, and isopropyl alcohol in sequence, for example, for 1-30 minutes, and then blow-dried, and then placed in a UV ozone machine for further cleaning, for example, for 1-20 minutes.
  • step (3) comprises coating the perovskite precursor solution on the hole transport layer, and then pre-drying it by vacuuming, followed by annealing, for example, annealing at a temperature of 80-120° C. for 20-40 minutes, and cooling to obtain the perovskite layer.
  • the coating method may be spin coating, blade coating, slit coating, spray coating, etc.
  • the perovskite precursor solution used in step (3) is prepared by the following steps: dissolving a perovskite precursor material (e.g., at least one of iodoformamidine, lead iodide, methylamine bromide, methylamine iodide, cesium iodide, lead bromide, etc.) in a solvent (e.g., dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or N-methylpyrrolidone) (NMP), etc.), stir evenly, and filter to obtain a perovskite precursor solution.
  • a perovskite precursor material e.g., at least one of iodoformamidine, lead iodide, methylamine bromide, methylamine iodide, cesium iodide, lead bromide, etc.
  • a solvent e.g., dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or N-methyl
  • a second electrode is prepared.
  • the preparation of the second electrode can be carried out by conventional methods in the art.
  • the electrode can be prepared by evaporation.
  • an electron transport layer may be prepared.
  • the electron transport layer is prepared using conventional techniques in the art.
  • the electron transport layer may be prepared using a spin coating method, an evaporation method, or the like.
  • the third aspect of the present application provides an electrical device, comprising the perovskite battery described in the first aspect of the present application, or a perovskite battery prepared by the method described in the second aspect of the present application, wherein the perovskite battery is used to supply power to the electrical device.
  • the power-consuming device is a common device including the perovskite battery of the present application, such as the communication field, transportation field, industrial and agricultural field, lighting field, etc.
  • the power-consuming device may include, for example, satellites, communication equipment, traffic lights, lighthouses, wireless telephone booths, monitoring equipment in the drilling field, power systems, camping lights, electric vehicles, electronic equipment chargers, etc.
  • a nickel oxide target with a nickel-oxygen ratio of 1:1 was used to magnetron sputter a bulk layer with a thickness of 12 nm at an argon-oxygen ratio of 500:50 at a sputtering power of 2000 watts (W), and then a surface layer was magnetron sputtered at an argon-oxygen ratio of 500:3.
  • the precursor solution is coated on the nickel oxide layer; the sample is then transferred to a vacuum chamber and allowed to stand for 120 seconds (s) at a vacuum degree below 100 Pa to allow the precursor solution to solidify into a film; the solidified sample is placed on a hot stage for annealing at a temperature of 150 degrees Celsius (°C) for 30 minutes; after annealing, a 500nm thick perovskite layer is obtained.
  • step (5) placing the device obtained in step (5) into a LN-F300 evaporator, and evaporating a metal electrode Cu on the hole blocking layer under a vacuum condition of 10 -5 Pa to prepare a second electrode layer with a thickness of 80 nm; and obtaining the perovskite cell.
  • Example 1 The steps of Example 1 were repeated, except that in step 2), a 2 nm gradient surface layer was sputtered at an argon-oxygen ratio of 500:30, and a 2 nm outermost layer was sputtered at an argon-oxygen ratio of 500:5.
  • Example 1 The steps of Example 1 were repeated, except that in step 2), a 2nm first gradient surface layer was sputtered at an argon-oxygen ratio of 500:39, a 2nm second gradient surface layer was sputtered at an argon-oxygen ratio of 500:25, and a 2nm outermost layer was sputtered at an argon-oxygen ratio of 500:5.
  • step 2) a 2nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:41, a 2nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:30, a 2nm third gradient surface layer is sputtered at an argon-oxygen ratio of 500:16, and a 2nm outermost layer is sputtered at an argon-oxygen ratio of 500:5.
  • step 2 a 2nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:43, a 2nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:35, a 2nm third gradient surface layer is sputtered at an argon-oxygen ratio of 500:25, a 2nm fourth gradient surface layer is sputtered at an argon-oxygen ratio of 500:16, and a 2nm outermost layer is sputtered at an argon-oxygen ratio of 500:5.
  • Example 1 The steps of Example 1 are repeated, except that: in step 2), a 2nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:45, a 2nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:39, a 2nm third gradient surface layer is sputtered at an argon-oxygen ratio of 500:32, a 2nm fourth gradient surface layer is sputtered at an argon-oxygen ratio of 500:25, a 2nm fifth gradient surface layer is sputtered at an argon-oxygen ratio of 500:16, and a 2nm outermost layer is sputtered at an argon-oxygen ratio of 500:5.
  • step 2nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:45
  • a 2nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:39
  • a 2nm third gradient surface layer is
  • Example 6 The steps of Example 6 were repeated, except that in step 2) the thickness of the bulk layer was 10 nm.
  • Example 6 The steps of Example 6 were repeated, except that in step 2) the thickness of the bulk layer was 30 nm.
  • Example 1 The steps of Example 1 are repeated, except that: in step 2), a 12 nm main layer is sputtered at an argon-oxygen ratio of 500:30, a 2 nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:25, a 2 nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:20, a 2 nm third gradient surface layer is sputtered at an argon-oxygen ratio of 500:14, a 2 nm fourth gradient surface layer is sputtered at an argon-oxygen ratio of 500:10, and a 2 nm outermost layer is sputtered at an argon-oxygen ratio of 500:5.
  • step 2 nm main layer is sputtered at an argon-oxygen ratio of 500:30
  • a 2 nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:25
  • Example 1 The steps of Example 1 are repeated, except that: in step 2), a 12 nm main layer is sputtered at an argon-oxygen ratio of 500:60, a 2 nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:50, a 2 nm second gradient surface layer is sputtered at an argon-oxygen ratio of 500:41, a 2 nm third gradient surface layer is sputtered at an argon-oxygen ratio of 500:30, a 2 nm fourth gradient surface layer is sputtered at an argon-oxygen ratio of 500:16, and a 2 nm outermost layer is sputtered at an argon-oxygen ratio of 500:5.
  • step 2 nm main layer is sputtered at an argon-oxygen ratio of 500:60
  • a 2 nm first gradient surface layer is sputtered at an argon-oxygen ratio of 500:50
  • Example 10 The steps of Example 10 were repeated, except that the thickness of the bulk layer and the atomic percentage of trivalent nickel ions were changed.
  • Example 2 The steps of Example 2 were repeated, except that in step 2), a 2 nm outermost layer was sputtered at an argon to oxygen ratio of 500:0.
  • Example 2 The steps of Example 2 were repeated, except that in step 2), a 2 nm outermost layer was sputtered at an argon to oxygen ratio of 500:1.
  • Example 2 The steps of Example 2 were repeated, except that in step 2), a 2 nm outermost layer was sputtered at an argon to oxygen ratio of 500:16.
  • Example 2 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.
  • Example 1 The steps of Example 1 were repeated, except that the surface layer preparation in step 2) was not performed.
  • Example 1 The steps of Example 1 were repeated, except that the outermost layer of 2 nm was sputtered at an argon to oxygen ratio of 500:30.
  • the number of divalent nickel ions and trivalent nickel ions in the bulk layer and the surface layer of the hole transport layer was determined by X-ray photoelectron spectroscopy (XPS), which was performed on a K-Alpha spectrometer (manufactured by Thermo Fisher).
  • XPS X-ray photoelectron spectroscopy
  • the percentage of divalent nickel or trivalent nickel ion atoms the number of divalent nickel or trivalent nickel ion atoms/the number of all nickel ion atoms in the layer or gradient.
  • A represents the percentage of trivalent nickel ion atoms in the layer or gradient.
  • the test was conducted according to the national standard IEC61215, where the test was conducted under illumination using a Keithley 2400 digital source meter.
  • the light source was provided by a solar simulator using a 450W xenon lamp with a UV filter, and the light emitted by 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 illumination.

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Abstract

本申请涉及一种钙钛矿电池、制备方法以及相应的用电装置，该钙钛矿电池包括依次设置的第一电极、空穴传输层、钙钛矿层、电子传输层和第二电极，其中空穴传输层包含本体层和设置在本体层靠近钙钛矿层一侧的表面层，其中空穴传输层包括含有三价镍离子的氧化镍，表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比；以及涉及相应的制备方法和用电装置。

Description

钙钛矿电池、制备方法以及相应的用电装置
交叉引用
本申请引用于2023年03月06日递交的名称为“钙钛矿电池、制备方法以及相应的用电装置”的第202310201482.6号中国专利申请，其通过引用被全部并入本申请。
技术领域
本申请涉及钙钛矿电池领域，特别是涉及一种钙钛矿电池、制备方法以及相应的用电装置。
背景技术
随着新能源领域的快速发展，太阳能电池已广泛应用于军事、航天、工业、商业、农业和通信等领域。钙钛矿电池凭借其高光电转换效率、简单的制作工艺、低的生产成本和材料成本等优势而逐渐成为新一代太阳能电池研究的热点。
氧化镍作为反式钙钛矿电池中最常用的无机空穴传输层材料，是钙钛矿电池实现产业化的优选候选者。然而氧化镍空穴传输层表面存在的三价镍会与钙钛矿前驱液中的A位阳离子和X位卤素反应，进而劣化钙钛矿电池的光电转换效率。同时水氧对于钙钛矿吸光层的侵蚀在一定程度上会影响钙钛矿电池的稳定性。因此，传统的钙钛矿电池的结构或性能仍有待改进。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种钙钛矿电池，其在保证氧化镍空穴传输层的导电率的情况下提高钙钛矿层的稳定性，从而提高了电池的光电转化效率，并且其制备方法成本更低、操作简单。
为了达到上述目的，本申请提供了一种钙钛矿电池及其制备方法、用电装置。
本申请的第一方面提供了一种钙钛矿电池，其包括依次设置的第一电极、空穴传输层、钙钛矿层、电子传输层和第二电极，其中所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
本申请的钙钛矿电池通过将设置在所述本体层靠近钙钛矿层一侧的表面层的三价镍离子的原子数百分比降低，减少了三价镍离子与钙钛矿层中的钙钛矿的反应，从而提高了钙钛矿层的稳定性；并且保证了含有氧化镍的空穴传输层的导电率，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，所述表面层中三价镍离子的原子数百分比沿表面层的厚度方向从靠近本体层的一侧向远离本体层的一侧呈梯度减少。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，三价镍离子的原子数百分比沿表面层的厚度方向以0.5-4nm的厚度为一个梯度减少。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，相邻两个梯度中的三价镍离子的原子数百分比相差2-20％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度中，三价镍离子的原子数百分比为1-15％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，所述本体层中三价镍离子的原子数百分比为20-65％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的任意实施方式中，所述表面层厚度为2-15nm；和/或，所述本体层的厚度为10-40nm。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
本申请的第二方面提供一种制备钙钛矿电池的方法，包括：
(1)提供第一电极；
(2)在所述第一电极上制备空穴传输层；
(3)在所述空穴传输层上制备钙钛矿层；
(4)在所述钙钛矿层上制备电子传输层；
(5)在所述电子传输层上制备第二电极，得到所述钙钛矿电池；
其中，所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
本申请的方法成本更低、操作简单，便于大规模工业应用。
在本申请的任意实施方式中，步骤(2)包括利用氧化镍靶材使用磁控溅射方法在所述第一电极上制备空穴传输层。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在本申请的任意实施方式中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(1-200)。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在本申请的任意实施方式中，磁控溅射方法的条件包括：在表面层制备中，所用氩氧比高于本体层制备中所用氩氧比。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
本申请的第三方面提供了一种用电装置，包括本申请第一方面所述的钙钛矿电池，或如本申请第二方面所述的方法制备所得的钙钛矿电池，所述钙钛矿电池用于向所述用电装置供电。
本申请的钙钛矿电池通过将设置在所述本体层靠近钙钛矿层一侧的表面层的三价镍离子的原子数百分比降低，减少了三价镍离子与钙钛矿层中的钙钛矿的反应，并且保证了含有氧化镍的空穴传输层的导电率，从而提高了电池的光电转化效率。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。在附图中：
图1为本申请的一实施方式中的钙钛矿电池的结构示意图。
附图标记说明：
1-FTO；2-氧化镍本体层；3-氧化镍表面层；4-钙钛矿层；5-C60；6-BCP；7-Cu；10-
钙钛矿电池。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的钙钛矿电池及其制备方法、相应的用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
氧化镍作为反式钙钛矿电池中最常用的无机空穴传输层材料，是钙钛矿电池实现产业化的优选候选者。然而空穴传输层表面存在的三价镍会与钙钛矿前驱液中的A位阳离子和X位卤素反应，进而劣化钙钛矿电池的光电转换效率。同时水和氧对钙钛矿吸光层的侵蚀在一定程度上会影响钙钛矿电池的稳定性。本申请的钙钛矿电池在空穴传输层(特别是氧化镍(NiOx)空穴传输层)与钙钛矿层之间设置包含氧化镍(II)的界面钝化层，使其具有高的光电转换效率和良好的长期稳定性，并且其制备方法成本更低、操作简单。
钙钛矿电池
在一些实施方式中，本申请的第一方面提供了一种钙钛矿电池，其包括依次设置的第一电极、空穴传输层、钙钛矿层、电子传输层和第二电极，其中所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
本申请的钙钛矿电池通过将设置在所述本体层靠近钙钛矿层一侧的表面层的三价镍离子的原子数百分比降低，减少了三价镍离子与钙钛矿层中的钙钛矿的反应，从而提高了钙钛矿层的稳定性；并且保证了含有氧化镍的空穴传输层的导电率，从而提高了电池的光电转化效率。
在一些实施方式中，所述空穴传输层包括含有三价镍离子的氧化镍，其中氧化镍一般 表示为NiOx，其可代表含有氧和镍的化合物。
在一些实施方式中，所述空穴传输层为氧化镍空穴传输层。
在一些实施方式中，所述空穴传输层中可存在NiO、Ni(OH)2、Ni2O3、NiOOH等物质。
在一些实施方式中，所述空穴传输层中，三价镍离子通常以Ni2O3、NiOOH等形式存在，二价镍离子通常以NiO、Ni(OH)2等形式存在。
在本申请的一些实施方式中，所述表面层中三价镍离子的原子数百分比沿表面层的厚度方向从靠近本体层的一侧向远离本体层的一侧呈梯度减少。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
所述“呈梯度减少”是指三价镍离子的原子数百分比在一个梯度内保持不变，而紧邻的设置在该梯度远离本体层一侧的另一个梯度中的三价镍离子的原子数百分比相对于该梯度内的三价镍离子的原子数百分比减少。
在本申请中，单位“nm”是指纳米。
在本申请的一些实施方式中，三价镍离子的原子数百分比沿表面层的厚度方向以0.5-4nm的厚度为一个梯度减少。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。可理解，“0.5-4nm”意指0.5nm-4nm。
在一些实施方式中，通常沿表面层的厚度方向以1.5-4nm的厚度为一个梯度。换言之，一个梯度的厚度为1.5-4nm。
在一些实施方式中，通常沿表面层的厚度方向以1.5-2.5nm的厚度为一个梯度。换言之，一个梯度的厚度为1.5-2.5nm。
在一些实施方式中，表面层中的梯度数量通常为1-10个。所述“梯度数量”是指表面层中三价镍离子的原子数百分比随表面层厚度变化的数量。从靠近本体层一侧开始计算，表面层中最靠近本体层的一个梯度计为一梯度，沿表面层的厚度方向至钙钛矿层，将梯度依次计为二梯度、三梯度、四梯度……，依次类推，最靠近钙钛矿层一侧的梯度称为最外侧梯度。
在一些实施方式中，表面层中的梯度数量通常为3-6个。
在本申请的一些实施方式中，相邻两个梯度中的三价镍离子的原子数百分比相差2-20％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。可理解，“2-20％”意指2％-20％。
在一些实施方式中，相邻两个梯度中的三价镍离子的原子数百分比相差2％-10％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，相邻两个梯度中的三价镍离子的原子数百分比相差3.5％-6％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的一些实施方式中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度 中，三价镍离子的原子数百分比为1-15％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
所述“最外侧梯度”是指在空穴传输层中，相对于本体层而言，表面层在最远离本体层的一侧中的一个梯度，该梯度层与钙钛矿层直接接触。所述最外侧梯度的厚度可以不同于其他梯度的厚度，也可以与其他梯度的厚度相同。
在本申请中，所述“原子数百分比”是指所述离子的原子数在其所在层或梯度中的百分比，基于所在层或梯度的总原子数计。所述原子数是指所述离子在其所在层或梯度中的原子数量，根据X射线光电子能谱(XPS)测量。
在一些实施方式中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度中，三价镍离子的原子数百分比为1-12％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度中，三价镍离子的原子数百分比为1-10％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度中，三价镍离子的原子数百分比为1-5％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的一些实施方式中，所述本体层中三价镍离子的原子数百分比为20-65％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，所述本体层中三价镍离子的原子数百分比为25-40％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，所述本体层中三价镍离子的原子数百分比为25-35％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，所述本体层中三价镍离子的原子数百分比为28-33％。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在本申请的一些实施方式中，所述表面层厚度为2-15nm；以及所述本体层的厚度为10-40nm。由此，进一步在保证电导率的同时提高钙钛矿层的稳定性，从而提高了电池的光电转化效率。
在一些实施方式中，所述表面层厚度为2-12nm。
在一些实施方式中，所述表面层厚度为8-12nm。
在一些实施方式中，所述本体层的厚度为10-30nm。
在一些实施方式中，所述本体层的厚度为10-15nm。
在一些实施方式中，在本体层中，三价镍离子与二价镍离子的原子数的比例为1：1。
在一些实施方式中，所述空穴传输层的总厚度为12-50nm。
在一些实施方式中，所述空穴传输层的总厚度为12-25nm。
在一些实施方式中，所述空穴传输层的总厚度为18-25nm。
在一些实施方式中，所述钙钛矿电池为正式钙钛矿电池或反式钙钛矿电池，例如为反式钙钛矿电池。
在一些实施方式中，所述第一电极为阳极层，其起到收集空穴的作用，通常称为透明电极。
在一些实施方式中，所述第一电极选自氟掺杂的氧化锡(FTO)、氧化铟锡(ITO)、掺铝氧化锌(AZO)、掺硼氧化锌(BZO)、氧化铟锌(IZO)和氧化铟钨(IWO)中的至少一种，第一电极层的厚度为100-1000nm，例如为300-800nm。
在本申请中，单位“cm”是指厘米。
在一些实施方式中，所述钙钛矿电池还包含透明基底层，所述透明基底层选自透明玻璃、聚对苯二甲酸乙二醇酯(PET)、聚酰亚胺基底中的至少一种，所述透明基底层的厚度为0.1-3cm。
因此，在本申请的一个实施方式中，本申请的钙钛矿电池包含依次层叠设置的透明基底层、第一电极、氧化镍空穴传输层、钙钛矿层、电子传输层和第二电极。
在一些实施方式中，所述钙钛矿层为光吸收层，即钙钛矿电池的活性层，由钙钛矿材料组成，该层是整个电池结构的核心位置。
在一些实施方式中，所述钙钛矿层的材料的化学式为ABX3或A2CDX6，其中A为无机或有机或有机-无机混合阳离子，包含有机胺阳离子、Cs阳离子、K阳离子、Rb阳离子和Li阳离子中的至少一种；所述有机胺阳离子选自(NR1R2R3R4)+、(R1R2N＝CR3R4)+、(R1R2N-C(R5)＝NR3R4)+或(R1R2N-C(NR5R6)＝R3R4)+，其中，R1、R2、R3、R4、R5和R6各自独立地选自H、取代或非取代的C1-20烷基或取代或非取代的芳基。
在一些实施方式中，A为甲胺基(CH3NH3 +)(MA+)，甲脒基(HC(NH2)2 +)(FA+)，铯离子(Cs+)和铷(Rb+)中的至少一种。例如A为甲胺基(CH3NH3 +)或甲脒基(HC(NH2)2 +)。
B为无机或有机或有机-无机混合阳离子，包括铅、锡、锌、钛、锑、铋、镍、铁、钴、银、铜、镓、锗、镁、钙、铟、铝、锰、铬、钼和铕中的至少一种。例如B为二价金属离子Pb2+和Sn2+中的至少一种。
C为无机或有机或有机-无机混合阳离子。例如C为一价金属离子Ag+等。
D为无机或有机或有机-无机混合阳离子。例如D为三价金属离子铋阳离子Bi3+、锑阳离子Sb3+、铟阳离子In3+等。
X为无机或有机或有机-无机混合阴离子。例如X为卤素阴离子和羧酸根阴离子中的一种或多种。例如X为溴离子(Br-)或碘离子(I-)。
在本申请中，单位“eV”是指电子伏特。
在一些实施方式中，所述钙钛矿层的带隙为1.20eV-2.30eV。
在一些实施方式中，所述钙钛矿层的厚度为200-800nm。
在一些实施方式中，所述钙钛矿层的厚度为400-600nm。
在一些实施方式中，所述钙钛矿电池还包含电子传输层。
在一些实施方式中，所述电子传输层的作用为高效的传输钙钛矿层产生的自由电子，有效的阻挡自由空穴的通过，且与钙钛矿活性层的界面处形成欧姆接触。
在一些实施方式中，所述电子传输层的材料为以下材料及其衍生物及其经掺杂或钝化所得的材料中的至少一种：[6，6]-苯基-C61-丁酸异甲酯(PC61BM)、[6,6]-苯基-C71-丁酸甲酯(PC71BM)、富勒烯C60、富勒烯C70、含氰基的聚苯乙炔、含硼的聚合物、浴铜灵、红菲咯啉、羟基喹啉铝、噁二唑化合物、苯并咪唑化合物、萘四甲酸化合物、苝衍生物、氧化膦化合物、硫化膦化合物、含氟基的酞菁、氧化钛、氧化锌、氧化铟、氧化锡、氧化镓、硫化锡、硫化铟、氟化锂、氟化钠、氟化镁和硫化锌。
在一些实施方式中，所述电子传输层的材料为以下材料及其衍生物及其经掺杂或钝化所得的材料中的至少一种：[6,6]-苯基-C61-丁酸异甲酯(PC61BM)、[6,6]-苯基-C71-丁酸甲酯(PC71BM)、富勒烯C60(C60)、富勒烯C70(C70)、氧化锡(SnO2)、氧化锌(ZnO)。
在一些实施方式中，所述电子传输层的厚度为10-200nm。
在一些实施方式中，所述电子传输层的厚度为30-120nm。
在一些实施方式中，所述电子传输层的厚度为40-60nm。
因此，在本申请的一个实施方式中，本申请的钙钛矿电池包含依次层叠设置的透明基底层、第一电极、氧化镍空穴传输层、钙钛矿层、电子传输层和第二电极。
在一些实施方式中，所述第二电极为阴极层，其具有收集自由电子的作用。
在一些实施方式中，所述第二电极通常为有机或无机或有机-无机混合导电材料，包含氧化铟锡(ITO)、镧系金属掺杂的氧化铟、硼掺杂的氧化锌(BZO)、氧化铝锌(AZO)、氧化铟锌(IZO)、氧化镓锌(GZO)、氧化铟钨(IWO)、Au、Ag、Cu、Al、Ni、Cr、Bi、Pt、Mg、Mo、W及其合金、石墨、石墨烯、碳纳米管中的至少一种。
在一些实施方式中，所述第二电极通常为有机或无机或有机-无机混合导电材料，包含Ag、Cu、C、Au、Al、ITO、AZO、BZO或IZO。
在一些实施方式中，所述第二电极通常为有机或无机或有机-无机混合导电材料，包含Cu、Ag、Au或其组合。
在一些实施方式中，所述第二电极的厚度为20-200nm。
在一些实施方式中，所述第二电极的厚度为60-100nm。
在一些实施方式中，所述第二电极的厚度为70-90nm。
在一些实施方式中，所述第二电极和所述电子传输层之间可以存在空穴阻挡层，用于防止第二电极与钙钛矿反应，并避免电子传输层与背电极的肖特基接触引起的器件效率的降低，同时具有能级的调控作用。
在一些实施方式中，所述空穴阻挡层的材料包括2,9-二甲基-4,7-二苯基-1,10-菲啰啉(BCP，别名为浴铜灵)、乙酰丙酮钙、LiF、8-羟基喹啉铝、1,3,5-Tris(1-苯基-1H-苯并咪唑-2-基)苯或其组合。
在一些实施方式中，所述空穴阻挡层的材料包括BCP。
在一些实施方式中，所述空穴阻挡层的厚度为0.1-30nm。
在一些实施方式中，所述空穴阻挡层的厚度为3-10nm。
在一些实施方式中，所述空穴阻挡层的厚度为4-6nm。
在一些实施方式中，所述钙钛矿层和所述电子传输层之间可以存在钝化层，用于钝化两者界面上的缺陷。
在一些实施方式中，在电子传输层和电极之间可以存在钝化层以提高钙钛矿电池的性能。
在一些实施方式中，钙钛矿电池包括依次层叠设置的第一电极、空穴传输层、钙钛矿层、电子传输层、空穴阻挡层和第二电极，其中空穴传输层包括本体层和设置在本体层靠近钙钛矿层一侧的表面层。第一电极例如选自FTO。本体层的材料例如包括氧化镍。表面层的材料例如包括氧化镍。电子传输层的材料例如包括C60。空穴阻挡层的材料例如包括BCP。第二电极的材料例如包括Cu。
在一些实施方式中，结合图1，钙钛矿电池10包括依次层叠设置的FTO 1、氧化镍本体层2、氧化镍表面层3、钙钛矿层4、C605、BCP 6、Cu 7。其中，FTO为第一电极，C60为电子传输层，BCP为空穴阻挡层，Cu为第二电极。
本申请的第二方面提供了一种制备本申请的第一方面所述的钙钛矿电池的方法，包括：
(1)提供第一电极；
(2)在所述第一电极上制备空穴传输层；
(3)在所述空穴传输层上制备钙钛矿层；
(4)在所述钙钛矿层上制备电子传输层；
(5)在所述电子传输层上制备第二电极，得到所述钙钛矿电池；
其中，所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
本申请的方法成本更低、操作简单，便于大规模工业应用。
在本申请的一些实施方式中，步骤(2)包括利用氧化镍靶材使用磁控溅射方法在所述第一电极上制备空穴传输层。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在一些实施方式中，在步骤(2)中，所述氧化镍靶材的镍氧比为0.9-1.1。
在本申请的一些实施方式中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(1-200)。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在一些实施方式中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(1-100)。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在一些实施方式中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(3-100)。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在一些实施方式中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(30-70)。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在本申请的一些实施方式中，磁控溅射方法的条件包括：在表面层制备中，所用氩氧比高于本体层制备中所用氩氧比。由此，可以更简单地制备本申请第一方面的钙钛矿电池。
在本申请的一些实施方式中，磁控溅射方法的条件包括：在表面层制备中，不同梯度的制备中所用氩氧比不同，以便获得不同的三价镍离子的原子数百分比梯度。
在本申请的一些实施方式中，磁控溅射方法的条件包括：沿表面层的厚度方向从本体层一侧向钙钛矿层一侧制备不同的梯度过程中，所用氩氧比逐渐增大。
在本申请的一些实施方式中，例如，步骤(2)包括使用直流磁控溅射制备氧化镍层，溅射本体层时的氩氧比为500/5；溅射表面层时每2nm变化一次氩氧比，第一个2nm的氩氧比为500/4，第二个2nm的氩氧比为500/3，……，第五个2nm(即最外层梯度)的氩氧比为500/0，以此类推。
在一些实施方式中，步骤(1)包括在透明基底层上设置透明导电氧化物层，得到附着在透明基底层上的第一电极。或者，所述附着在透明基底层上的第一电极也可以为市售的产品。
在一些实施方式中，在步骤(1)中，可以对透明基底层例如导电玻璃进行进一步的清洗，例如用水、丙酮、异丙醇依次超声清洗，例如1-30分钟，然后吹干，再放入紫外臭氧机中进一步清洗，例如清洗1-20分钟。
在一些实施方式中，步骤(3)包括将钙钛矿前驱体溶液涂覆在所述空穴传输层上，然后使用抽真空的方法进行预干燥，接着退火，例如在80-120℃的温度下退火20-40分钟，冷却后得到所述钙钛矿层。其中所述涂覆方式可以为旋涂、刮涂、狭缝涂布、喷涂等。
在一些实施方式中，在步骤(3)中所用的钙钛矿前驱体溶液通过以下步骤制备：将钙钛矿前驱体材料(例如，碘甲脒、碘化铅、溴甲胺、碘甲胺、碘化铯、溴化铅等中的至少一种)溶于溶剂(例如，二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)或N-甲基吡咯烷酮 (NMP)等)中，搅拌均匀，过滤，得到钙钛矿前驱体溶液。
在一些实施方式中，在步骤(5)中，制备第二电极。第二电极的制备可以采用本领域中常规的方法进行。例如，可采用蒸镀的方式制备电极。
在一些实施方式中，在步骤(5)之前，可制备电子传输层。电子传输层使用本领域常规技术手段制备。例如，可采用旋涂法、蒸镀法等制备电子传输层。
本申请的第三方面提供了一种用电装置，包括本申请第一方面所述的钙钛矿电池，或如本申请第二方面所述的方法制备所得的钙钛矿电池，所述钙钛矿电池用于向所述用电装置供电。
在一些实施方式中，所述用电装置为包括本申请的钙钛矿电池的常见的设备，例如通信领域、交通领域、工农业领域、照明领域等。所述用电装置例如可包括卫星、通讯设备、交通信号灯、灯塔、无线电话亭、是有钻探领域的监测设备、电源系统、野营灯、电动汽车、电子设备充电器等。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
一、钙钛矿电池
实施例1
1)取20片规格为2.0*2.0cm的FTO导电玻璃，两端通过激光刻蚀各去掉0.35cm的FTO，裸露出玻璃基底；对所述FTO导电玻璃用500毫升(mL)的水、丙酮、异丙醇依次超声清洗各10分钟(min)；然后将清洗后的FTO导电玻璃在氮气枪下吹干溶剂，放入紫外臭氧机中进一步清洗5min；得到第一电极。
2)在所述第一电极上使用镍氧比为1：1的氧化镍靶材在溅射功率为2000瓦特(W)的条件下在氩氧比为500：50下磁控溅射厚度为12nm的本体层，然后在氩氧比为500：3的条件下磁控溅射表面层。
3)将1362毫克(mg)甲脒氢碘酸盐(FAI)、228.6mg碘化铯(CsI)和4056.9mg碘化铅(PbI2)溶解于8mL溶剂中，配制成摩尔浓度为1.1摩尔/升(mol/L)的钙钛矿前体溶液。溶剂为体积比为7：1的DMF(N,N-二甲基甲酰胺)和NMP(N-甲基吡咯烷酮)的混合物。
将前驱体溶液涂布于氧化镍层上；然后样品被转移至真空腔，在100帕(Pa)的真空度以下静置120秒(s)，使得前体溶液固化成膜；将固化后的样品置于热台上进行退火处理，退火处理的温度为150摄氏度(℃)，退火处理的时间为30min；退火处理后，得到500nm厚的钙钛矿层。
4)在步骤(3)所得的钙钛矿层上以1500转/秒(rpm/s)旋涂PC61BM，100℃下退火10min，得到50nm厚的电子传输层；紧接着在所述电子传输层上以5000rpm/s旋涂浓度为0.5毫克/毫升(mg/mL)的BCP于异丙醇中的溶液，得到5nm厚的空穴阻挡层。
5)将步骤(5)获得的器件放入LN-F300型号的蒸镀机，在所述空穴阻挡层上在10-5Pa真空条件下蒸镀金属电极Cu，制备80nm厚的第二电极层；得到所述钙钛矿电池。
实施例2
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：30溅射2nm一梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例3
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：39溅射2nm一梯度表面层，以氩氧比500：25溅射2nm二梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例4
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：41溅射2nm一梯度表面层，以氩氧比500：30溅射2nm二梯度表面层，以氩氧比500：16溅射2nm三梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例5
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：43溅射2nm一梯度表面层，以氩氧比500：35溅射2nm二梯度表面层，以氩氧比500：25溅射2nm三梯度表面层，以氩氧比500：16溅射2nm四梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例6
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：45溅射2nm一梯度表面层，以氩氧比500：39溅射2nm二梯度表面层，以氩氧比500：32溅射2nm三梯度表面层，以氩氧比500：25溅射2nm四梯度表面层，以氩氧比500：16溅射2nm五梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例7
重复实施例6的步骤，不同之处在于：在步骤2)中本体层厚度为10nm。
实施例8
重复实施例6的步骤，不同之处在于：在步骤2)中本体层厚度为30nm。
实施例9
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：30溅射12nm本体层，以氩氧比500：25溅射2nm一梯度表面层，以氩氧比500：20溅射2nm二梯度表面层，以氩氧比500：14溅射2nm三梯度表面层，以氩氧比500：10溅射2nm四梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例10
重复实施例1的步骤，不同之处在于：在步骤2)中以氩氧比500：60溅射12nm本体层，以氩氧比500：50溅射2nm一梯度表面层，以氩氧比500：41溅射2nm二梯度表面层，以氩氧比500：30溅射2nm三梯度表面层，以氩氧比500：16溅射2nm四梯度表面层，以氩氧比500：5溅射2nm最外层。
实施例11-12
重复实施例10的步骤，不同之处在于：改变本体层的厚度和三价镍离子的原子数百分比。
实施例13
重复实施例2的步骤，不同之处在于：在步骤2)中以氩氧比500：0溅射2nm最外层。
实施例14
重复实施例2的步骤，不同之处在于：在步骤2)中以氩氧比500：1溅射2nm最外层。
实施例15
重复实施例2的步骤，不同之处在于：在步骤2)中以氩氧比500：16溅射2nm最外层。
实施例16-19
重复实施例2的步骤，不同之处在于：改变第一梯度层的厚度和最外层的厚度。
对比例1：空穴传输层不含表面层
重复实施例1的步骤，不同之处在于：不进行步骤2)中的表面层制备。
对比例2
重复实施例1的步骤，不同之处在于：以氩氧比500：30溅射2nm最外层。
上述实施例和对比例中得到的钙钛矿电池的产品参数见表1。
参数测试
空穴传输层和界面钝化层的二价镍离子和三价镍离子原子数的测试
通过X射线光电子能谱(XPS)对空穴传输层本体层和表面层中的二价镍离子和三价镍离子原子数进行测定，其在K-Alpha型号的光谱仪(厂家赛默飞)上进行。其中：
二价镍或三价镍离子原子数百分比＝二价镍或三价镍离子原子数/所在层或梯度中所有镍离子原子数。
A代表层或梯度中三价镍离子原子数百分比。
表1各实施例和对比例的钙钛矿电池的产品参数

二、钙钛矿电池的性能测定
1、光电转化效率测定
根据国家标准IEC61215进行测试，其中测试是在光照的情况下，使用Keithley 2400数字源表进行的，光源通过使用带有紫外光过滤器的450W氙灯的太阳光模拟器提供，光源发出的光符合AM 1.5G标准太阳光谱。电池与数字源表连接，光照下测其光电转化效率。
按照上述过程分别测试上述实施例和对比例中得到的钙钛矿电池，具体数值参见表2。
表2各实施例和对比例的钙钛矿电池的光电转化效率
从表1和表2可以看出，本申请的钙钛矿电池的效率均取得了优异的技术效果，实施例1-16的钙钛矿电池的效率达到12.9％以上，其中，实施例1-7、实施例10-11、实施例13-14和实施例16的钙钛矿电池的效率可达到15％以上。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准，说明书及附图可以用于解释权利要求的内容。

Claims (12)

  1. 一种钙钛矿电池，包括依次设置的第一电极、空穴传输层、钙钛矿层、电子传输层和第二电极，其中所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
  2. 根据权利要求1所述的钙钛矿电池，其中，所述表面层中三价镍离子的原子数百分比沿表面层的厚度方向从靠近本体层的一侧向远离本体层的一侧呈梯度减少。
  3. 根据权利要求2所述的钙钛矿电池，其中，三价镍离子的原子数百分比沿表面层的厚度方向以0.5-4nm的厚度为一个梯度减少。
  4. 根据权利要求2或3所述的钙钛矿电池，其中，相邻两个梯度中的三价镍离子的原子数百分比相差2-20％。
  5. 根据权利要求2-4任一项所述的钙钛矿电池，其中，在所述表面层中与所述钙钛矿层直接接触的最外侧梯度中，三价镍离子的原子数百分比为1-15％。
  6. 根据权利要求1-5任一项所述的钙钛矿电池，其中，所述本体层中三价镍离子的原子数百分比为20-65％。
  7. 根据权利要求1-6任一项所述的钙钛矿电池，其中，所述钙钛矿电池具备如下特征中的一个或多个：
    (1)所述表面层厚度为2-15nm；
    (2)所述本体层的厚度为10-40nm。
  8. 一种制备钙钛矿电池的方法，包括：
    (1)提供第一电极；
    (2)在所述第一电极上制备空穴传输层；
    (3)在所述空穴传输层上制备钙钛矿层；
    (4)在所述钙钛矿层上制备电子传输层；
    (5)在所述电子传输层上制备第二电极，得到所述钙钛矿电池；
    其中，所述空穴传输层包含本体层和设置在所述本体层靠近钙钛矿层一侧的表面层，其中所述空穴传输层包括含有三价镍离子的氧化镍，所述表面层中三价镍离子的原子数百分比小于本体层中三价镍离子的原子数百分比。
  9. 根据权利要求8所述的方法，其中，步骤(2)包括使用磁控溅射方法在所述第一电极上制备空穴传输层。
  10. 根据权利要求9所述的方法，其中，磁控溅射方法的条件包括：在本体层制备中，所用氩氧比为500：(1-200)。
  11. 根据权利要求9或10所述的方法，其中，磁控溅射方法的条件包括：在表面层制备中，所用氩氧比高于本体层制备中所用氩氧比。
  12. 一种用电装置，包括如权利要求1-7中任一项所述的钙钛矿电池，或如权利要求8-11中任一项的方法制备所得的钙钛矿电池，所述钙钛矿电池用于向所述用电装置供电。
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