WO2024239140A1 - 钙钛矿电池、光伏组件 - Google Patents

钙钛矿电池、光伏组件 Download PDF

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WO2024239140A1
WO2024239140A1 PCT/CN2023/095251 CN2023095251W WO2024239140A1 WO 2024239140 A1 WO2024239140 A1 WO 2024239140A1 CN 2023095251 W CN2023095251 W CN 2023095251W WO 2024239140 A1 WO2024239140 A1 WO 2024239140A1
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Prior art keywords
perovskite
passivation
layer
metal oxide
passivation layer
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English (en)
French (fr)
Inventor
陈长松
马俊福
项翎
林祖超
周丽美
郭永胜
欧阳楚英
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to PCT/CN2023/095251 priority Critical patent/WO2024239140A1/zh
Priority to CN202380069897.0A priority patent/CN119968948A/zh
Priority to EP23937819.3A priority patent/EP4716435A4/en
Priority to KR1020257031391A priority patent/KR20250152643A/ko
Priority to JP2025555449A priority patent/JP2026511540A/ja
Publication of WO2024239140A1 publication Critical patent/WO2024239140A1/zh
Priority to US19/344,541 priority patent/US20260033120A1/en
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • 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 a perovskite cell and a photovoltaic module.
  • Perovskite cells are solar cells that use perovskite materials as light-absorbing layers. How to further improve the energy conversion efficiency of perovskite cells is the direction of researchers' efforts. The above statements are only used to provide background technical information related to this application and do not necessarily constitute prior art.
  • the present application provides a perovskite cell and a photovoltaic module, which can improve the energy conversion efficiency of the perovskite cell.
  • the present application provides a perovskite cell, comprising a first electrode, a second electrode, a light absorbing layer, a hole transport layer and an electron transport layer, wherein the light absorbing layer is located between the first electrode and the second electrode, the hole transport layer is located between the first electrode and the light absorbing layer, and the electron transport layer is located between the second electrode and the light absorbing layer, wherein the perovskite cell further comprises a passivation layer, wherein the passivation layer is located between the hole transport layer and the light absorbing layer, and/or the passivation layer is located between the electron transport layer and the light absorbing layer; the passivation layer comprises at least two of an organic molecular passivation material, a metal oxide semiconductor material and a metal halide.
  • the passivation layer can simultaneously have the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby facilitating the improvement of the energy conversion efficiency of the perovskite battery.
  • the passivation layer includes at least two of an organic molecule passivation material, a metal oxide semiconductor material, and a metal halide
  • the passivation layer has better stability and can also reduce the corrosion of the perovskite material by water and oxygen, thereby improving the stability and service life of the perovskite battery.
  • the passivation layer includes an organic molecule passivation material and a metal oxide semiconductor material and/or a metal halide.
  • the organic molecule passivation material can be used as an interface connector and a defect passivation agent at the same time, thereby enhancing the interface contact between the light absorbing layer and the charge transfer layer through the organic molecule passivation material, and can also reduce the defect state density of the perovskite material bulk and interface through the coordination effect of the organic molecule passivation material, improve the film-forming quality of the light absorbing layer, and can also embed the organic molecule passivation material into the perovskite material bulk to play an anchoring role, thereby reducing the precipitation of halides (such as PbI2 , etc.) from the perovskite material, thereby improving the stability and service life of the perovskite battery.
  • halides such as PbI2 , etc.
  • the organic molecule passivation material can play a better passivation effect, and when it is used in combination with a metal oxide semiconductor material and/or a metal halide, the non-radiative recombination at the defect can be further reduced, and the energy conversion efficiency of the perovskite battery can be further improved.
  • the content of the organic molecular passivation material is 10-30 wt %, more preferably 15-25 wt %.
  • the passivation layer includes an organic molecule passivation material, a metal oxide semiconductor material and a metal halide.
  • the passivation layer can better take into account the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite battery; it can also further reduce the corrosion of the perovskite material by water and oxygen, thereby further improving the stability and service life of the perovskite battery.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal oxide semiconductor material is 40-60wt%, more preferably 45-55wt%.
  • the content of the metal halide is 20-40wt%, more preferably 25-35wt%.
  • the passivation layer comprises an organic molecule passivation material and a metal oxide semiconductor material.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal oxide semiconductor material is 70-90wt%, more preferably 75-85wt%.
  • the passivation layer comprises an organic molecule passivation material and a metal halide.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal halide is 70-90wt%, more preferably 75-85wt%.
  • the thickness of the passivation layer is less than or equal to 30 nm, and can be 1-22 nm.
  • the perovskite battery can have higher energy conversion efficiency and stability, and can also have higher conductivity, thereby helping to improve the output performance of the perovskite battery.
  • the organic molecule passivation material includes one or more of alkylamines and halogen salts thereof, aromatic amines and halogen salts thereof, aromatic heterocyclic compounds, polymers, and their respective derivatives.
  • the aromatic heterocyclic compound includes one or more of nitrogen-containing aromatic heterocyclic rings and their derivatives, and may be selected to include one or more of carbazole, pyridine, piperidine, and their respective derivatives.
  • the nitrogen atom has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the shallow position of the light-absorbing layer through specific atoms and/or functional groups, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite battery.
  • the polymer includes one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives.
  • the nitrogen atom on the amino group or aromatic heterocyclic ring has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the shallow position of the light-absorbing layer through specific atoms and/or functional groups, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite battery.
  • the organic molecule passivation material includes one or more of N,N-diethylaniline, 2-phenylethylamine hydroiodide, dopamine, 9,9-bis(4-aminophenyl)fluorene, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 4-pyridinecarboxylic acid, polyaniline, polypyridine, polypiperidine, and their respective derivatives.
  • the organic molecule passivation material includes one or more of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, 2-phenylethylamine hydroiodide, and their respective derivatives.
  • the organic molecular passivation material When the organic molecular passivation material is within the above range, it can better match the energy level of the perovskite material, better passivate the interface defects between the light absorption layer and the charge transfer layer, passivate the intrinsic point defects and grain boundary defects of the perovskite material, and better optimize the crystallization quality of the perovskite material, thereby further reducing the non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.
  • the metal oxide semiconductor material includes one or more of intrinsic metal oxide semiconductor materials, N-type metal oxide semiconductor materials, and P-type metal oxide semiconductor materials, and optionally includes one or more of SnO 2 , TiO 2 , ZnO, NiO x , CeO x , MoO 3 , NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and their respective doping materials, 1 ⁇ x ⁇ 2.
  • the metal oxide semiconductor material when the passivation layer is located between the hole transport layer and the light absorption layer, includes one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, and optionally includes one or more of NiO x , CeO x , MoO 3 , NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and their respective doping materials, 1 ⁇ x ⁇ 2.
  • NiO x , CeO x , MoO 3 NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and their respective doping materials, 1 ⁇ x ⁇ 2.
  • the metal oxide semiconductor material when the passivation layer is located between the electron transport layer and the light absorption layer, includes one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, and optionally includes one or more of SnO 2 , TiO 2 , ZnO, and their respective doping materials, thereby better transmitting free electrons.
  • the particle size of the metal oxide semiconductor material is below 100 nm, optionally below 50 nm, and more optionally 5-10 nm.
  • the metal element in the metal halide includes one or more of alkali metal elements, alkaline earth metal elements, and transition metal elements, and can optionally include one or more of K, Cs, Pb, and Cu.
  • the halogen element in the metal halide includes one or more of F, Cl, Br, and I.
  • the metal halide includes one or more of CsF, KCl, PbBr, CuI, and CuI 2 , and may optionally include one or more of KCl and CuI.
  • the electron transport material in the electron transport layer includes one or more of imide compounds, quinone compounds, fullerenes and their derivatives, a second metal oxide, silicon oxide, strontium titanate, calcium titanate, lithium fluoride, and calcium fluoride.
  • the metal element in the second metal oxide includes one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr.
  • the hole transport material in the hole transport layer includes one or more of 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene, methoxytriphenylamine-fluoroformamidine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid, poly3-hexylthiophene, triphenylamine with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, polythiophene, phosphate-based monomers, carbazole-based monomers, sulfonic acid-based monomers, triphenylamine-based monomers, aromatic monomers, a third metal oxide and cuprous thiocyan
  • the perovskite material in the light absorbing layer includes one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.
  • the electrode materials of the first electrode and the second electrode independently include organic conductive materials, inorganic conductive materials or organic-inorganic mixed conductive materials, which can be selected from one or more of poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, carbon and their derivatives.
  • organic conductive materials inorganic conductive materials or organic-inorganic mixed conductive materials, which can be selected from one or more of poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc
  • a second aspect of the present application provides a photovoltaic module, which includes the perovskite cell of the first aspect of the present application.
  • the photovoltaic module of the present application includes the perovskite cell provided by the present application, and thus has at least the same advantages as the perovskite cell.
  • FIG1 is a schematic diagram of the structure of a perovskite battery provided in some embodiments of the present application.
  • FIG. 2 is a schematic diagram of the structure of a perovskite battery provided in some other embodiments of the present application.
  • FIG3 is a schematic diagram of the structure of a perovskite battery provided in some other embodiments of the present application.
  • FIG. 4 is a schematic diagram of the structure of a perovskite battery provided in some other embodiments of the present application.
  • FIG5 is a schematic diagram of the structure of a perovskite battery provided in some other embodiments of the present application.
  • FIG6 is a schematic diagram of the structure of a perovskite battery provided in some other embodiments 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 form a scope with any upper limit combination. 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 "a-b" 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) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application are open-ended or closed-ended.
  • the “include” and “comprising” may mean 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).
  • the values of the parameters mentioned in this application can be measured by various test methods commonly used in the art, for example, they can be measured according to the test methods given in this application. Unless otherwise specified, the test temperature of each parameter is 25°C.
  • An embodiment of the present application provides a perovskite battery.
  • 1 to 6 are schematic diagrams of the structures of perovskite cells provided in some embodiments of the present application.
  • the perovskite cell includes a first electrode 1, a second electrode 5, a light absorbing layer 3, a hole transport layer 2, and an electron transport layer 4.
  • the light absorbing layer 3 is located between the first electrode 1 and the second electrode 5
  • the hole transport layer 2 is located between the first electrode 1 and the light absorbing layer 3
  • the electron transport layer 4 is located between the second electrode 5 and the light absorbing layer 3.
  • the perovskite cell further includes a passivation layer 6 , which is located between the hole transport layer 2 and the light absorbing layer 3 , and/or between the electron transport layer 4 and the light absorbing layer 3 .
  • the passivation layer 6 includes at least two of an organic molecular passivation material, a metal oxide semiconductor material and a metal halide.
  • the working principle of perovskite cells is usually as follows: under illumination, the light-absorbing layer absorbs photon energy, generates electron-hole pairs in its valence band, and the electrons are excited to the conduction band, leaving holes in the valence band.
  • the conduction band energy level of the light-absorbing layer is usually higher than the conduction band energy level of the electron transport layer, so that electrons can be transferred from the conduction band position of the light-absorbing layer to the conduction band position of the electron transport layer, and then to the conductive electrode; the valence band energy level of the light-absorbing layer is usually lower than the valence band energy level of the hole transport layer, so that holes can be transferred to the conductive electrode through the hole transport layer.
  • the light-absorbing layer includes perovskite materials, which generally use halide perovskite materials (e.g., inorganic halide perovskite materials, organic halide perovskite materials, organic-inorganic hybrid halide perovskite materials), which have the advantages of large carrier diffusion length, easily adjustable band gap, high defect tolerance and low manufacturing cost, and therefore have received widespread attention.
  • halide perovskite materials e.g., inorganic halide perovskite materials, organic halide perovskite materials, organic-inorganic hybrid halide perovskite materials
  • perovskite materials have more intrinsic point defects (such as vacancy defects, interstitial defects, and antisite defects) and grain boundary defects.
  • the light-absorbing layer also has many surface defects, mainly manifested in many holes, cracks, and other defects. The defects will capture the surrounding free electrons and holes, which are easy to recombine at the defect center (also known as non-radiative recombination), thereby increasing the energy loss of the perovskite cell and reducing the performance of the perovskite cell.
  • the non-radiative recombination at the interface between the light absorbing layer and the charge transport layer (such as the hole transport layer or the electron transport layer) is usually dominant.
  • Interface passivation is an effective strategy to obtain high-performance perovskite cells.
  • the passivation layer provided in the embodiment of the present application includes at least two of an organic molecular passivation material, a metal oxide semiconductor material and a metal halide.
  • Organic molecular passivation materials, metal oxide semiconductor materials and metal halides can easily obtain energy level structures that match perovskite materials.
  • Organic molecular passivation materials can act as both interface connectors and defect passivators, thereby enhancing the interface contact between the light-absorbing layer and the charge transport layer through organic molecular passivation materials.
  • the defect state density in the bulk and interface of the perovskite material can also be reduced through the coordination effect of the organic molecular passivation materials, thereby improving the film-forming quality of the light-absorbing layer.
  • the organic molecular passivation materials can also be embedded in the bulk of the perovskite material to play an anchoring role, thereby reducing the precipitation of halides (such as PbI2 , etc.) from the perovskite material, thereby improving the stability and service life of the perovskite battery.
  • organic molecular passivation materials can passivate the interface defects between the light absorption layer and the charge transport layer, and can also passivate the intrinsic point defects (including vacancy defects, interstitial defects and antisite defects) and grain boundary defects of the perovskite material, thereby improving the interface performance between the light absorption layer and the charge transport layer, and optimizing the crystallization quality of the perovskite material, thereby reducing the non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.
  • organic molecular passivation materials can also improve the film-forming quality of the passivation layer, effectively blocking water and oxygen, and reducing the erosion of water and oxygen on the perovskite material, thereby improving the stability and service life of the perovskite battery.
  • Metal oxide semiconductor materials have high stability. In addition, they have better energy level matching with perovskite materials, which can better promote carrier transport and reduce ion migration. At the same time, metal oxide semiconductor materials can also effectively block water and oxygen, reduce water and oxygen corrosion of perovskite materials, and thus improve the stability and service life of perovskite batteries.
  • Metal halides have high stability and can also play the role of passivating the halogen defects of perovskite materials and optimize the crystallization quality of perovskite materials.
  • the passivation layer when the passivation layer includes at least two of an organic molecule passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer can simultaneously have the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby facilitating the improvement of the energy conversion efficiency of the perovskite battery.
  • the passivation layer when the passivation layer includes at least two of an organic molecule passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer has better stability and can also reduce the corrosion of the perovskite material by water and oxygen, thereby improving the stability and service life of the perovskite battery.
  • the organic molecule passivation material may include one or more of alkylamines and halogen salts thereof, aromatic amines and halogen salts thereof, aromatic heterocyclic compounds, polymers, and their respective derivatives.
  • the aromatic heterocyclic compound may include one or more of nitrogen-containing aromatic heterocyclic rings and their derivatives, and may further include one or more of carbazole, pyridine, piperidine, and their respective derivatives.
  • the nitrogen atom has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the light absorbing layer through specific atoms and/or functional groups.
  • the surface position can be further reduced, thereby reducing the interface defects, thereby reducing the non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.
  • the polymer may optionally include one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives.
  • the nitrogen atom on the amino group or aromatic heterocyclic ring has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the shallow position of the light-absorbing layer through specific atoms and/or functional groups, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite battery.
  • the organic molecular passivation material may include one or more of N,N-diethylaniline (DEA), 2-phenylethylamine hydroiodide (PEAI), dopamine, 9,9-bis(4-aminophenyl)fluorene (FDA), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 4-pyridinecarboxylic acid, polyaniline, polypyridine, polypiperidine, and their respective derivatives.
  • DEA N,N-diethylaniline
  • PEAI 2-phenylethylamine hydroiodide
  • FDA 9,9-bis(4-aminophenyl)fluorene
  • FDA 9,9-bis(4-aminoph
  • the organic molecular passivation material When the organic molecular passivation material is within the above range, it can better match the energy level of the perovskite material, better passivate the interface defects between the light absorption layer and the charge transfer layer, passivate the intrinsic point defects and grain boundary defects of the perovskite material, and better optimize the crystallization quality of the perovskite material, thereby further reducing the non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.
  • the derivatives of the above-mentioned organic molecular passivation materials generally refer to products derived from the replacement of hydrogen atoms or atomic groups in the organic molecular passivation materials by other atoms or atomic groups.
  • the organic molecular passivation material may include one or more of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), 2-phenylethylamine hydroiodide (2-Phenylethylamine Hydroiodide, PEAI), and their respective derivatives.
  • the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material, an N-type metal oxide semiconductor material, and a P-type metal oxide semiconductor material.
  • the metal oxide semiconductor material may include one or more of SnO 2 , TiO 2 , ZnO, NiO x (1 ⁇ x ⁇ 2), CeO x (1 ⁇ x ⁇ 2), MoO 3 , NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and their respective doping materials.
  • the metal oxide semiconductor material when the passivation layer 6 is located between the hole transport layer 2 and the light absorption layer 3, the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, thereby better transporting holes.
  • the metal oxide semiconductor material may include one or more of NiO x (1 ⁇ x ⁇ 2), CeO x (1 ⁇ x ⁇ 2), MoO 3 , NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and their respective doping materials.
  • the metal oxide semiconductor material when the passivation layer 6 is located between the electron transport layer 4 and the light absorption layer 3, the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, thereby better transmitting free electrons.
  • the metal oxide semiconductor material may include one or more of SnO 2 , TiO 2 , ZnO, and their respective doping materials.
  • the metal oxide semiconductor material When the metal oxide semiconductor material is within the above range, it can better match the energy level of the perovskite material, and can also better promote carrier transport and reduce water and oxygen corrosion of the perovskite material, thereby helping to improve the energy conversion efficiency and/or stability of the perovskite battery.
  • the doping materials of the above-mentioned metal oxides can independently include alkali metal elements, alkaline earth metal elements, One or more of transition metal elements, poor metal elements, metalloid elements, halogen elements, non-metallic elements, ionic liquids, carboxylic acids, phosphoric acid, carbon derivatives, self-assembled monomolecules, and polymers.
  • the weight content of the doping material in the metal oxide is ⁇ 30%.
  • the particle size of the metal oxide semiconductor material may be less than 100 nm, optionally less than 50 nm, and more optionally 5-10 nm.
  • the metal element in the metal halide may include one or more of alkali metal elements, alkaline earth metal elements, and transition metal elements, and may optionally include one or more of K, Cs, Pb, and Cu.
  • the halogen element in the metal halide may include one or more of F, Cl, Br, and I.
  • the metal halide may include one or more of CsF, KCl, PbBr, CuI, CuI 2.
  • the metal halide is within the above range, the energy level of the perovskite material can be better matched.
  • the metal halide may include one or more of CsF, KCl, and PbBr, and may be selected to include one or more of KCl and PbBr.
  • the size of the halogen anion is small, which can better reduce the lattice distortion of the perovskite crystal and is also conducive to stress release, thereby better optimizing the crystal quality of the perovskite material.
  • the metal halide may include one or more of CuI, CuI 2.
  • the metal halide is within the above range, carrier transport can be better promoted.
  • the passivation layer may include an organic molecular passivation material as well as a metal oxide semiconductor material and/or a metal halide.
  • Organic molecular passivation materials can be used as interface connectors and defect passivators at the same time, so that the interface contact between the light absorbing layer and the charge transport layer can be enhanced by the organic molecular passivation materials, and the defect state density of the bulk phase and interface of the perovskite material can be reduced by the coordination effect of the organic molecular passivation materials, thereby improving the film quality of the light absorbing layer.
  • the organic molecular passivation materials can also be embedded in the bulk phase of the perovskite material to play an anchoring role, thereby reducing the precipitation of halides (such as PbI2 , etc.) from the perovskite material, thereby improving the stability and service life of the perovskite battery.
  • the organic molecular passivation material can play a better passivation effect.
  • the non-radiative recombination at the defects can be further reduced, and the energy conversion efficiency of the perovskite battery can be further improved.
  • the content of the organic molecular passivation material is 10-30wt%, optionally 15-25wt%.
  • the organic molecular passivation material itself has a slightly poor stability, so when its content is within the above range, it is also beneficial to improve the stability and service life of the perovskite battery.
  • the passivation layer 6 may include an organic molecule passivation material, a metal oxide semiconductor material, and a metal halide.
  • the passivation layer can better take into account the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite battery; it can also further reduce the corrosion of the perovskite material by water and oxygen, thereby further improving the stability and service life of the perovskite battery.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal oxide semiconductor material is 40-60wt%, more preferably 45-55wt%.
  • the content of the metal halide is 20-40wt%, more preferably 25-35wt%.
  • the passivation layer 6 may include an organic molecule passivation material and a metal oxide semiconductor material.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal oxide semiconductor material is 70-90wt%, more preferably 75-85wt%.
  • the passivation layer 6 may include an organic molecule passivation material and a metal halide.
  • the content of the organic molecule passivation material is 10-30wt%, more preferably 15-25wt%.
  • the content of the metal halide is 70-90wt%, more preferably 75-85wt%.
  • the thickness of the passivation layer 6 may be less than or equal to 30 nm, and may be 1-22 nm, 1-17 nm, 2-22 nm, 2-17 nm, 4-22 nm, or 4-17 nm.
  • the perovskite battery can have higher energy conversion efficiency and stability, and can also have higher conductivity, thereby helping to improve the output performance of the perovskite battery.
  • the light absorbing layer 3 may include a perovskite material.
  • the perovskite material can transport both electrons and holes.
  • the type of perovskite material is not specifically limited and can be selected according to actual needs.
  • the perovskite material in the light absorbing layer can include one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.
  • the molecular formula of the perovskite material may be ABX 3 , where A represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, B represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, and X represents an inorganic anion, an organic anion, or an organic-inorganic mixed anion.
  • A includes one or more of CH 3 NH 3 + (MA + ), CH(NH 2 ) 2 + (FA + ), Li + , Na + , K + , Rb + , and Cs + .
  • A includes one or more of CH 3 NH 3 + , CH(NH 2 ) 2 + , and Cs + .
  • B includes one or more of Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , and Ni 2+ .
  • B includes one or both of Pb 2+ and Sn 2+ .
  • X includes one or more of F ⁇ , Cl ⁇ , Br ⁇ , and I ⁇ .
  • X includes one or more of Cl ⁇ , Br ⁇ , and I ⁇ .
  • the molecular formula of the perovskite material may also be A' 2 CDX' 6 , where A' represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, C represents a monovalent metal cation, D represents a trivalent metal cation, and X' represents an inorganic anion, an organic anion, or an organic-inorganic mixed anion.
  • A' includes one or more of CH 3 NH 3 + (MA + ), CH(NH 2 ) 2 + (FA + ), Li + , Na + , K + , Rb + , and Cs + .
  • A' includes one or more of CH 3 NH 3 + , CH(NH 2 ) 2 + , and Cs + .
  • C includes at least one of Li + , Na + , K + , Rb + , Cs + , and Ag + .
  • D includes at least one of In 3+ and Bi 3+ .
  • X' includes one or more of F - , Cl - , Br - , and I - .
  • X' includes one or more of Cl - , Br - , and I - .
  • the perovskite material may include, but is not limited to, CH 3 NH 3 PbI 3 (MAPbI 3 ), CH(NH 2 ) 2 PbI 3 (FAPbI 3 ), CsPbI 3 , CsPbI 2 Br, CsPbIBr 2 , Cs 2 NaInCl 6 , Cs 2 KBiCl 6 , One or more of Cs 2 AgInCl 6 .
  • the thickness of the light absorbing layer 3 is not specifically limited and can be selected according to actual needs.
  • the thickness of the light absorbing layer 3 can be 50-2000 nm.
  • the electron transport layer 4 includes an electron transport material.
  • the type of electron transport material is not specifically limited and can be selected according to actual needs.
  • the electron transport material can include an organic electron transport material, an inorganic electron transport material, or an organic-inorganic hybrid electron transport material.
  • the electron transport material may include one or more of imide compounds, quinone compounds, fullerenes and derivatives thereof, a second metal oxide, silicon oxide, strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ), lithium fluoride (LiF), and calcium fluoride (CaF 2 ).
  • the metal element in the second metal oxide may include one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr.
  • the electron transport material may include one or more of SnO 2 , TiO 2 , [6,6]-phenyl C 61 -butyric acid methyl ester (PC 61 BM), [6,6]-phenyl C 71 -butyric acid methyl ester (PC 71 BM), fullerene C60, and fullerene C70.
  • the electron transport material is within the above range, the bottom energy level of the conduction band of the electron transport material can better match the bottom energy level of the conduction band of the light absorbing layer, thereby facilitating the transmission of electrons.
  • the thickness of the electron transport layer 4 is not specifically limited and can be selected according to actual needs.
  • the thickness of the electron transport layer 4 can be 1-300 nm.
  • the hole transport layer 2 includes a hole transport material.
  • the type of the hole transport material is not specifically limited and can be selected according to actual needs.
  • the hole transport material may include 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly3-hexylthiophene (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, one or more of a phosphate
  • the thickness of the hole transport layer 2 is not specifically limited and can be selected according to actual needs.
  • the thickness of the hole transport layer 2 can be 5-1000 nm.
  • the valence band top (VBM) energy level of the light absorption layer 3 is less than the valence band top (VBM) energy level of the passivation layer 6 and less than the valence band top (VBM) energy level of the hole transport layer 2. This is conducive to better transport of holes.
  • the conduction band bottom (CBM) energy level of the electron transport layer 4 is less than the conduction band bottom (CBM) energy level of the passivation layer 6 and less than the conduction band bottom (CBM) energy level of the light absorption layer 3. This is conducive to better transmission of electrons.
  • the energy band distribution of each film layer can be measured by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS).
  • XPS X-ray photoelectron spectroscopy
  • UPS ultraviolet photoelectron spectroscopy
  • the electrode materials of the first electrode 1 and the second electrode 5 can independently include organic conductive materials, inorganic conductive materials, or organic-inorganic hybrid conductive materials.
  • the materials may independently include one or more of conductive polymers, metals, transparent metal conductive oxides, carbon and derivatives thereof.
  • the electrode materials of the first electrode 1 and the second electrode 5 independently include one or more of poly(3,4-ethylenedioxythiophene) (PEDOT), polythiophene, polyacetylene, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium-doped zinc oxide (IZO), gold, silver, aluminum, copper, carbon and derivatives thereof.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • FTO fluorine-doped tin oxide
  • ITO indium tin oxide
  • ATO antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium-doped zinc oxide
  • the electrode material of one of the first electrode 1 and the second electrode 5 may include a transparent metal conductive oxide, which may be one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).
  • FTO fluorine-doped tin oxide
  • ITO indium tin oxide
  • ATO antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium-doped zinc oxide
  • the perovskite cell further includes a substrate, such as a glass substrate, and a transparent metal conductive oxide may be disposed on the surface of the substrate.
  • the electrode material of one of the first electrode 1 and the second electrode 5 may include one or more of metal, carbon and derivatives thereof, and may optionally include one or more of gold, silver, aluminum, copper, carbon and derivatives thereof.
  • the thickness of the first electrode 1 is not specifically limited and can be selected according to actual needs.
  • the thickness of the first electrode 1 can be 10 nm-500 nm.
  • the thickness of the second electrode 5 is not specifically limited and can be selected according to actual needs.
  • the thickness of the second electrode 5 can be 10 nm-500 nm.
  • the perovskite cell provided in the embodiment of the present application may be a regular structure cell or a reverse structure cell.
  • the first electrode 1 is the light-incident side
  • the perovskite cell includes the first electrode 1, the hole transport layer 2, the passivation layer 6, the light absorption layer 3, the electron transport layer 4, and the second electrode 5 in sequence.
  • the first electrode 1 is the light-incident side
  • the perovskite cell includes the first electrode 1, the hole transport layer 2, the light absorption layer 3, the passivation layer 6, the electron transport layer 4, and the second electrode 5 in sequence.
  • the first electrode 1 is the light-incident side
  • the perovskite cell (transverse structure cell) includes the first electrode 1, the hole transport layer 2, the passivation layer 6, the light absorption layer 3, the passivation layer 6, the electron transport layer 4, and the second electrode 5 in sequence.
  • the second electrode 5 is the light-incident side
  • the perovskite cell includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light absorption layer 3, the hole transport layer 2, and the first electrode 1 in sequence.
  • the second electrode 5 is the light-incident side
  • the perovskite cell includes the second electrode 5, the electron transport layer 4, the light absorption layer 3, the passivation layer 6, the hole transport layer 2, and the first electrode 1 in sequence.
  • the second electrode 5 is the light-incident side
  • the perovskite cell (formal structure cell) includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light absorption layer 3, the passivation layer 6, the hole transport layer 2, and the first electrode 1 in sequence.
  • the passivation layer 6 is located between the charge transport layer and the light absorption layer close to the light incident side.
  • the charge transport layer is an electron transport layer
  • the charge transport layer is a hole transport layer.
  • the light absorption layer is formed after the passivation layer, so that the passivation layer can better promote the crystallization of the perovskite material, thereby enabling the perovskite battery to have a higher energy conversion efficiency.
  • the first electrode 1 is the light-incident side
  • the perovskite cell inverted structure cell
  • the passivation layer 6 includes an organic molecule passivation material and a metal oxide semiconductor material and/or a metal halide
  • the content of the organic molecule passivation material is 10-30wt%, and can be optionally 15-25wt%
  • the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, and can optionally include NiO x (1 ⁇ x ⁇ 2), CeO x (1 ⁇ x ⁇ 2), MoO 3 , NiMgLiO, CuGaO 2 , CuGrO 2 , CuO, Cu 2 O, and one or more of their respective doping materials.
  • the second electrode 5 is the light-entering side
  • the perovskite cell (formal structure cell) includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light absorption layer 3, the passivation layer 6, the hole transport layer 2 and the first electrode 1 in sequence
  • the passivation layer 6 includes an organic molecular passivation material and a metal oxide semiconductor material and/or a metal halide; based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, and can be optionally 15-25wt%
  • the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, and can be optionally one or more of SnO2 , TiO2 , ZnO, and their respective doping materials.
  • the perovskite cell provided in the embodiment of the present application is not limited to the above structure, and may also include other functional layers.
  • Perovskite cells can be prepared according to methods known in the art.
  • an exemplary preparation method includes the steps of providing a first electrode 1, forming a hole transport layer 2 on the first electrode 1, forming a light absorption layer 3 on the hole transport layer 2, forming an electron transport layer 4 on the light absorption layer 3, forming a second electrode on the electron transport layer 4, and forming a passivation layer 6 on the hole transport layer 2 and then forming the light absorption layer 3, and/or forming the passivation layer 6 on the light absorption layer 3 and then forming the electron transport layer 4.
  • another exemplary preparation method includes: providing a second electrode 5, forming an electron transport layer 4 on the second electrode 5, forming a light absorption layer 3 on the electron transport layer 4, forming a hole transport layer 2 on the light absorption layer 3, forming a first electrode 1 on the hole transport layer 2, and forming a passivation layer 6 on the light absorption layer 3 before forming the hole transport layer 2, and/or forming a passivation layer 6 on the electron transport layer 4 before forming the light absorption layer 3.
  • film forming methods of the above-mentioned film layers are not subject to specific restrictions, and film forming methods known in the art may be used, for example, chemical bath deposition, chemical vapor deposition, electrochemical deposition, physical epitaxial growth, thermal evaporation, atomic layer deposition, magnetron sputtering, precursor liquid spin coating, precursor liquid slit coating, precursor liquid scraping, mechanical pressing, sol-gel method, pulsed laser deposition, etc., and thermal evaporation and precursor liquid spin coating may be selected.
  • the perovskite cell provided in the embodiment of the present application can be used alone as a single-junction perovskite cell, or it can be made into a stacked cell with perovskite or other types of solar cells, such as a perovskite-perovskite stacked cell or a perovskite-crystalline silicon stacked cell.
  • the embodiment of the present application also provides a photovoltaic module, which includes the perovskite cell provided in the embodiment of the present application.
  • the perovskite cell can be used as a power source for the photovoltaic module after processes such as series-parallel connection and packaging.
  • the photovoltaic module includes a single-junction perovskite cell, a perovskite-perovskite tandem cell, or a perovskite-crystalline silicon tandem cell provided in the embodiments of the present application.
  • a glass substrate with a size of 2.0 cm ⁇ 2.0 cm covered with FTO was taken, and the surface was cleaned twice with acetone and isopropanol respectively, then immersed in deionized water for ultrasonic treatment for 10 min, and then dried in a forced air drying oven and placed in a glove box. Medium ( N2 atmosphere).
  • a 3 wt % SnO 2 nano-colloid aqueous solution was spin-coated on the FTO layer at a speed of 4000-6500 rpm, and then heated on a constant temperature hot stage at 150°C for 15 min to obtain an electron transport layer with a thickness of 50 nm.
  • a mixture of 2wt% TiO2 nanocolloid-isopropanol solution, 0.2mg/mL 2PACz-isopropanol solution and 1mg/mL KCl-isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000rpm, and then heated at 100°C on a constant temperature hot stage for 10min to obtain a passivation layer with a thickness of 17nm.
  • the weight content of each component in the passivation layer is shown in Table 1.
  • a 1.5 mol/L DMF solution of FAPbI 3 was spin-coated on the passivation layer at a speed of 3000-4500 rpm, and then heated at 100 °C on a constant temperature hot stage for 30 min. After cooling to room temperature, a light-absorbing layer with a thickness of 500 nm was obtained.
  • a chlorobenzene solution of Spiro-OMeTAD at 73 mg/mL was spin-coated on the light absorbing layer at a speed of 3000-4000 rpm to obtain a hole transport layer with a thickness of 150 nm.
  • the aforementioned sample was placed in a vacuum coating machine, and Ag electrode was evaporated on the surface of the hole transport layer under a vacuum condition of 5 ⁇ 10 -4 Pa, with an evaporation rate of 0.1 angstrom/s and a thickness of 80 nm.
  • the structure of the perovskite cell finally prepared in Example 1-1 is FTO/SnO 2 /TiO 2 +2PACz+KCl/FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • the specific parameters are shown in Table 1.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • the specific parameters are shown in Table 1.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a mixture of 2 wt% TiO2 nanocolloid-isopropanol solution and 0.2 mg/mL 2PACz-isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated at 150°C for 30 min on a constant temperature hot stage to obtain a passivation layer with a thickness of 15 nm.
  • the weight content of each component in the passivation layer is shown in Table 1.
  • the structure of the perovskite cell finally prepared in Examples 1-12 is FTO/SnO 2 /TiO 2 +2PACz/FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a mixture of 2wt% TiO2 nanocolloid-isopropanol solution and 1mg/mL KCl-isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000rpm, and then heated at 100°C on a constant temperature hot stage for 10min to obtain a passivation layer with a thickness of 15nm.
  • the weight content of each component in the passivation layer is shown in Table 1.
  • the structure of the perovskite cell finally prepared in Examples 1-13 is FTO/SnO 2 /TiO 2 +KCl/FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a mixture of 0.2 mg/mL 2PACz-isopropanol solution and 1 mg/mL KCl-isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100°C for 10 minutes to obtain a passivation layer with a thickness of 4 nm.
  • the weight content of each component in the passivation layer is shown in Table 1.
  • the structure of the perovskite cell finally prepared in Examples 1-14 is FTO/SnO 2 /2PACz+KCl/FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell was the same as Example 1-1, except that the passivation layer was not included.
  • the structure of the perovskite cell finally prepared in Comparative Example 1-1 is FTO/SnO 2 /FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a 2 wt % isopropanol solution of TiO 2 nanocolloid was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 13 nm.
  • the structure of the perovskite cell finally prepared in Comparative Example 1-2 is FTO/SnO 2 /TiO 2 /FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a 0.2 mg/mL 2PACz isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.
  • the structure of the perovskite cell finally prepared in Comparative Examples 1-3 is FTO/SnO 2 /2PACz/FAPbI 3 /Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 1-1.
  • a 1 mg/mL KCl isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.
  • the structure of the perovskite cell finally prepared in Comparative Examples 1-4 is FTO/SnO 2 /KCl/FAPbI 3 /Spiro-OMeTAD/Ag.
  • AM1.5G standard light source was used to simulate sunlight, and a four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the perovskite battery under the irradiation of the light source.
  • the open circuit voltage Voc, short circuit current density Jsc, and fill factor FF (Fill Factor) of the perovskite battery were obtained, and the energy conversion efficiency Eff (Efficiency) of the perovskite battery was calculated.
  • Pout, Popt, Vmpp, and Jmpp are the operating output power, incident light power, maximum power point voltage, and maximum power point current of the perovskite cell, respectively.
  • Table 1 shows the test results of Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-4.
  • a glass substrate covered with FTO with a size of 2.0 cm ⁇ 2.0 cm was taken, and the surface was cleaned twice with acetone and isopropanol respectively, then immersed in deionized water for ultrasonic treatment for 10 min, and then dried in a forced air drying oven and placed in a glove box (N 2 atmosphere).
  • a 3 wt % SnO 2 nano-colloid aqueous solution was spin-coated on the FTO layer at a speed of 4000-6500 rpm, and then heated on a constant temperature hot stage at 150°C for 15 min to obtain an electron transport layer with a thickness of 50 nm.
  • a 1.5 mol/L DMF solution of FAPbI 3 was spin-coated on the electron transport layer at a speed of 3000-4500 rpm, and then heated at 100 °C on a constant temperature hot stage for 30 min. After cooling to room temperature, a light absorbing layer with a thickness of 500 nm was obtained.
  • a mixture of 2 wt% CuO nanocolloid-isopropanol solution, 0.2 mg/mL PEAI-isopropanol solution and 1 mg/mL CuI-isopropanol solution was spin-coated on the light absorbing layer at a speed of 5000-6000 rpm, and then heated at 100° C. for 10 min on a constant temperature hot stage to obtain a passivation layer with a thickness of 17 nm.
  • the weight content of each component in the passivation layer is shown in Table 2.
  • a chlorobenzene solution of Spiro-OMeTAD at 73 mg/mL was spin-coated on the passivation layer at a speed of 3000-4000 rpm to obtain a hole transport layer with a thickness of 150 nm.
  • the aforementioned sample was placed in a vacuum coating machine, and Ag electrode was evaporated on the surface of the hole transport layer under a vacuum condition of 5 ⁇ 10 -4 Pa, with an evaporation rate of 0.1 angstrom/s and a thickness of 80 nm.
  • the structure of the perovskite cell finally prepared in Example 2-1 is FTO/SnO 2 /FAPbI 3 /CuO+PEAI+CuI/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a mixture of 2 wt% CuO nanocolloid-isopropanol solution and 0.2 mg/mL PEAI-isopropanol solution was spin-coated on the light absorbing layer at a speed of 5000-6000 rpm, and then heated at 150° C. for 30 min on a constant temperature hot stage to obtain a passivation layer with a thickness of 15 nm.
  • the weight content of each component in the passivation layer is shown in Table 2.
  • the structure of the perovskite cell finally prepared in Example 2-2 is FTO/SnO 2 /FAPbI 3 /CuO+PEAI/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a mixture of 2 wt% CuO nanocolloid-isopropanol solution and 1 mg/mL CuI-isopropanol solution was spin-coated on the light absorbing layer at a speed of 5000-6000 rpm, and then heated at 100° C. for 10 min on a constant temperature hot stage to obtain a passivation layer with a thickness of 15 nm.
  • the weight content of each component in the passivation layer is shown in Table 2.
  • the structure of the perovskite cell finally prepared in Example 2-3 is FTO/SnO 2 /FAPbI 3 /CuO+CuI/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a mixture of 0.2 mg/mL PEAI-isopropanol solution and 1 mg/mL CuI-isopropanol solution was spin-coated on the light absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100°C for 10 minutes to obtain a passivation layer with a thickness of 4 nm.
  • the weight content of each component in the passivation layer is shown in Table 2.
  • the structure of the perovskite cell finally prepared in Example 2-4 is FTO/SnO 2 /FAPbI 3 /PEAI+CuI/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a 2 wt % isopropanol solution of CuO nanocolloid was spin-coated on the light absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 13 nm.
  • the structure of the perovskite cell finally prepared in Comparative Example 2-1 is FTO/SnO 2 /FAPbI 3 /CuO/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a 0.2 mg/mL PEAI isopropanol solution was spin-coated on the light-absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.
  • the structure of the perovskite cell finally prepared in Comparative Example 2-2 is FTO/SnO 2 /FAPbI 3 /PEAI/Spiro-OMeTAD/Ag.
  • the preparation of the perovskite cell is the same as that of Example 2-1.
  • a 1 mg/mL CuI isopropanol solution was spin-coated on the light-absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.
  • the structure of the perovskite cell finally prepared in Comparative Example 2-3 is FTO/SnO 2 /FAPbI 3 /CuI/Spiro-OMeTAD/Ag.
  • Table 2 shows the test results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3. Examples 1-1 to 1-14 are the same.
  • Comparative Examples 1-2 to 1-4 and Comparative Examples 2-1 to 2-3 respectively use organic molecular passivation materials, metal oxide semiconductor materials or metal halides as passivation layers. Compared with Comparative Example 1-1, the effect of improving the energy conversion efficiency of the perovskite battery is not obvious.
  • Comparative Examples 1-2 and 2-1 use metal oxide semiconductor materials as passivation layers.
  • Metal oxide semiconductor materials have high structural stability, but their effect of promoting the crystallization quality of perovskite is limited.
  • the passivation layer of Comparative Example 2-1 is formed after the light absorption layer, which will further reduce the effect of promoting the crystallization quality of perovskite, resulting in a lack of obvious effect on improving the energy conversion efficiency of the perovskite battery.
  • Comparative Examples 1-3 and Comparative Example 2-2 use organic molecular passivation materials as the passivation layer.
  • the structural stability of the organic molecular passivation materials is poor, which results in a lack of significant effect in improving the energy conversion efficiency of the perovskite battery.
  • Comparative Examples 1-4 and Comparative Examples 2-3 use metal halides as passivation layers.
  • the carrier transport capacity of KCl is limited, which results in a lack of obvious improvement in the energy conversion efficiency of the perovskite battery.
  • the interface passivation effect of CuI is limited, which results in a lack of obvious improvement in the energy conversion efficiency of the perovskite battery.
  • the passivation layer can simultaneously have the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite battery.
  • the passivation layer includes an organic molecule passivation material and a metal oxide semiconductor material and/or a metal halide, the energy conversion efficiency of the perovskite cell can be further improved.
  • the organic molecule passivation material can be used as an interface connector and a defect passivation agent at the same time, thereby enhancing the interface contact between the light absorbing layer and the charge transfer layer through the organic molecule passivation material, and can also reduce the defect state density of the perovskite material bulk and interface through the coordination effect of the organic molecule passivation material, thereby improving the film quality of the light absorbing layer, and can also embed the organic molecule passivation material into the perovskite material bulk, play an anchoring role, thereby reducing the precipitation of halides from the perovskite material.
  • the organic molecule passivation material when used in combination with the metal oxide semiconductor material and/or the metal halide, the non-radiative recombination at the defect can be further reduced, and the energy conversion efficiency of the perovskite cell can be further improved.

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Abstract

本申请提供一种钙钛矿电池、光伏组件，钙钛矿电池包括第一电极、第二电极、吸光层、空穴传输层和电子传输层，吸光层位于第一电极与第二电极之间，空穴传输层位于第一电极与吸光层之间，电子传输层位于第二电极与吸光层之间。钙钛矿电池还包括钝化层，钝化层位于空穴传输层与吸光层之间，和/或，钝化层位于电子传输层与吸光层之间；钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种。

Description

钙钛矿电池、光伏组件 技术领域
本申请涉及一种钙钛矿电池、光伏组件。
背景技术
随着现代工业的发展，全球能源短缺和环境污染问题日益突出，太阳能电池作为理想的可再生能源受到越来越多的重视。钙钛矿(Perovskite)电池是利用钙钛矿材料作为吸光层的太阳能电池，如何进一步提升钙钛矿电池的能量转换效率是研究者努力的方向。上述的陈述仅用于提供与本申请有关的背景技术信息，而不必然地构成现有技术。
发明内容
本申请提供一种钙钛矿电池、光伏组件，其能提升钙钛矿电池的能量转换效率。
本申请第一方面提供一种钙钛矿电池，包括第一电极、第二电极、吸光层、空穴传输层和电子传输层，所述吸光层位于所述第一电极与所述第二电极之间，所述空穴传输层位于所述第一电极与所述吸光层之间，所述电子传输层位于所述第二电极与所述吸光层之间，其中，所述钙钛矿电池还包括钝化层，所述钝化层位于所述空穴传输层与所述吸光层之间，和/或，所述钝化层位于所述电子传输层与所述吸光层之间；所述钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种。
当钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种时，钝化层可以同时具有能级匹配、界面钝化、优化钙钛矿材料结晶质量的效果，进而有利于提升钙钛矿电池的能量转换效率。另外，当钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种时，钝化层的稳定性较好，并且还可以减少水氧侵蚀钙钛矿材料，由此还可以提升钙钛矿电池的稳定性和使用寿命。
在任意实施例中，所述钝化层包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物。有机分子钝化材料可以同时作为界面连接剂和缺陷钝化剂，由此可以通过有机分子钝化材料增强吸光层与电荷传输层之间的界面接触，还可以通过有机分子钝化材料的配位作用降低钙钛矿材料体相和界面的缺陷态密度，提升吸光层的成膜质量，还可以使有机分子钝化材料嵌入钙钛矿材料体相，起到锚定作用，从而减少卤化物(例如PbI2等)从钙钛矿材料中析出，进而可以提升钙钛矿电池的稳定性和使用寿命。因此，有机分子钝化材料可以起到更好地钝化效果，将其与金属氧化物半导体材料和/或金属卤化物组合使用时，可以进一步减少缺陷处的非辐射复合，进一步提升钙钛矿电池的能量转换效率。
可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。
在任意实施例中，所述钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物。当钝化层同时包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物时，可以使钝化层更好地兼顾能级匹配、界面钝化、优化钙钛矿材料结晶质量的效果，进而有利于进一步提升钙钛矿电池的能量转换效率；还可以进一步减少水氧侵蚀钙钛矿材料，进而还有利于进一步提升钙钛矿电池的稳定性和使用寿命。
可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于所述钝化层的总重量计，所述金属氧化物半导体材料的含量为40-60wt％，更可选为45-55wt％。可选地，基于所述钝化层的总重量计，所述金属卤化物的含量为20-40wt％，更可选为25-35wt％。
在任意实施例中，所述钝化层包括有机分子钝化材料和金属氧化物半导体材料。可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于所述钝化层的总重量计，所述金属氧化物半导体材料的含量为70-90wt％，更可选为75-85wt％。
在任意实施例中，所述钝化层包括有机分子钝化材料和金属卤化物。可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于所述钝化层的总重量计，所述金属卤化物的含量为70-90wt％，更可选为75-85wt％。
在任意实施例中，所述钝化层的厚度小于等于30nm，可选为1-22nm。钝化层的厚度在上述范围内时，可以使钙钛矿电池具有较高的能量转换效率和稳定性，还可以使钝化层具有较高的导电性，从而还有助于提升钙钛矿电池的输出性能。
在任意实施例中，所述有机分子钝化材料包括烷基胺及其卤素盐、芳香胺及其卤素盐、芳杂环化合物、聚合物、及其各自的衍生物中的一种或多种。
在任意实施例中，所述芳杂环化合物包括含氮芳杂环及其衍生物中的一种或多种，可选为包括咔唑、吡啶、哌啶、及其各自的衍生物中的一种或多种。芳杂环化合物在上述范围内时，氮原子上具有孤对电子，可以更好地与钙钛矿材料中的金属离子的空轨道进行配位，由此其锚定作用更好，可以通过特定原子和/或官能团嵌入吸光层浅表位置，从而可以进一步减少界面缺陷，进而可以减少缺陷处的非辐射复合，并提升钙钛矿电池的能量转换效率。
在任意实施例中，所述聚合物包括聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种。聚合物在上述范围内时，氨基或者芳杂环上的氮原子上具有孤对电子，可以更好地与钙钛矿材料中的金属离子的空轨道进行配位，由此其锚定作用更好，可以通过特定原子和/或官能团嵌入吸光层浅表位置，从而可以进一步减少界面缺陷，进而可以减少缺陷处的非辐射复合，并提升钙钛矿电池的能量转换效率。
在任意实施例中，所述有机分子钝化材料包括N,N-二乙基苯胺、2-苯乙胺氢碘酸盐、多巴胺、9,9-双(4-氨基苯基)芴、[2-(9H-咔唑-9-基)乙基]膦酸、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸、[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸、4-吡啶羧酸、聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种。可选地，所述有机分子钝化材料包括[2-(9H-咔唑-9-基)乙基]膦酸、2-苯乙胺氢碘酸盐、及其各自的衍生物中的一种或多种。
有机分子钝化材料在上述范围内时，可以更好地匹配钙钛矿材料的能级，还可以更好地钝化吸光层与电荷传输层的界面缺陷、钝化钙钛矿材料的本征点缺陷和晶界缺陷，还可以更好地优化钙钛矿材料的结晶质量，由此可以进一步减少缺陷处的非辐射复合，提升钙钛矿电池的能量转换效率。
在任意实施例中，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、N型金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，可选地包括SnO2、TiO2、ZnO、NiOx、CeOx、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种，1≤x≤2。
在任意实施例中，所述钝化层位于所述空穴传输层与所述吸光层之间时，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，可选地包括NiOx、CeOx、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种，1≤x≤2。由此可以更好地传输空穴。
在任意实施例中，所述钝化层位于所述电子传输层与所述吸光层之间时，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、N型金属氧化物半导体材料中的一种或多种，可选地包括SnO2、TiO2、ZnO、及其各自的掺杂材料中的一种或多种。由此可以更好地传输自由电子。
在任意实施例中，所述金属氧化物半导体材料的粒径在100nm以下，可选为50nm以下，更可选为5-10nm。
在任意实施例中，所述金属卤化物中的金属元素包括碱金属元素、碱土金属元素、过渡金属元素中的一种或多种，可选为包括K、Cs、Pb、Cu中的一种或多种。
在任意实施例中，所述金属卤化物中的卤素元素包括F、Cl、Br、I中的一种或多种。
在任意实施例中，所述金属卤化物包括CsF、KCl、PbBr、CuI、CuI2中的一种或多种，可选为包括KCl、CuI中的一种或多种。
在任意实施例中，所述电子传输层中的电子传输材料包括酰亚胺类化合物、醌类化合物、富勒烯及其衍生物、第二金属氧化物、氧化硅、钛酸锶、钛酸钙、氟化锂、氟化钙中的一种或多种，可选地，所述第二金属氧化物中的金属元素包括Mg、Cd、Zn、In、Pb、W、Sb、Bi、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga和Cr中的一种或多种。
在任意实施例中，所述空穴传输层中的空穴传输材料包括2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴、甲氧基三苯胺-氟代甲脒、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]、聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸、聚3-已基噻吩、三蝶烯为核的三苯胺、3,4-乙烯二氧噻吩-甲氧基三苯胺、N-(4-苯胺)咔唑-螺双芴、聚噻吩、磷酸基单分子、咔唑基单分子、磺酸基单分子、三苯胺基单分子、芳香基单分子、第三金属氧化物和硫氰酸亚铜中的一种或多种，所述第三金属氧化物中金属元素包括Ni、Mo和Cu中的一种或多种。
在任意实施例中，所述吸光层中的钙钛矿材料包括无机卤化物钙钛矿材料、有机卤化物钙钛矿材料、有机-无机杂化卤化物钙钛矿材料中的一种或多种。
在任意实施例中，所述第一电极和所述第二电极的电极材料分别独立地包括有机导电材料、无机导电材料或有机无机混合导电材料，可选为包括聚(3,4-乙烯二氧噻吩)、聚噻吩、聚乙炔、氟掺杂的氧化锡、氧化铟锡、锑掺杂的氧化锡、铝掺杂的氧化锌、硼掺杂的氧化锌、铟掺杂的氧化锌、金、银、铝、铜、碳及其衍生物中的一种或多种。
本申请第二方面提供一种光伏组件，其包括本申请第一方面的钙钛矿电池。
本申请的光伏组件包括本申请提供的钙钛矿电池，因而至少具有与所述钙钛矿电池相同的优势。
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方式，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。
图1是本申请一些实施例提供的钙钛矿电池的结构示意图。
图2是本申请另一些实施例提供的钙钛矿电池的结构示意图。
图3是本申请又一些实施例提供的钙钛矿电池的结构示意图。
图4是本申请又一些实施例提供的钙钛矿电池的结构示意图。
图5是本申请又一些实施例提供的钙钛矿电池的结构示意图。
图6是本申请又一些实施例提供的钙钛矿电池的结构示意图。
在附图中，附图未必按照实际的比例绘制。附图标记说明如下：1、第一电极；2、空穴传输层；3、吸光层；4、电子传输层；5、第二电极；6、钝化层。
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、光伏组件的实施方式。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，并且这样的技术方案应被认为包含在本申请的公开内容中。
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，并且这样的技术方案应被认为包含在本申请的公开内容中。
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，所述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)。
如果没有特别的说明，在本申请中，术语“第一”、“第二”等是用于区别不同对象，而不是用于描述特定顺序或主次关系。
除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。
除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测试方法进行测定，例如，可以按照本申请给出的测试方法进行测定。除非另有说明，各参数的测试温度均为25℃。
本申请实施例提供了一种钙钛矿电池。
图1至图6是本申请一些实施例提供的钙钛矿电池的结构示意图。
如图1至图6所示，钙钛矿电池包括第一电极1、第二电极5、吸光层3、空穴传输层2和电子传输层4。吸光层3位于第一电极1与第二电极5之间，空穴传输层2位于第一电极1与吸光层3之间，电子传输层4位于第二电极5与吸光层3之间。
钙钛矿电池还包括钝化层6，钝化层6位于空穴传输层2与吸光层3之间，和/或，钝化层6位于电子传输层4与吸光层3之间。
钝化层6包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种。
钙钛矿电池的工作原理通常为：在光照条件下，吸光层吸收光子能量，在其价带处产生电子-空穴对，电子会被激发到导带处，并在价带处留下空穴。吸光层的导带能级通常高于电子传输层的导带能级，由此电子可以从吸光层的导带位置传输至电子传输层的导带位置，继而传输至导电电极；吸光层的价带能级通常低于空穴传输层的价带能级，由此空穴可以通过空穴传输层传输至导电电极。由此接通外电路后，就会形成完整的回路，产生光生电流。
吸光层包括钙钛矿材料，钙钛矿材料通常采用卤化物钙钛矿材料(例如，无机卤化物钙钛矿材料、有机卤化物钙钛矿材料、有机-无机杂化卤化物钙钛矿材料)，其具有较大的载流子扩散长度、容易调节的带隙、高缺陷容忍度以及低制造成本等优点，因此受到了广泛关注。
但是，钙钛矿材料的结晶质量不佳，主要表现在晶粒尺寸小、晶粒无序堆积、晶界界面多等，由此导致钙钛矿材料具有较多的本征点缺陷(例如空位缺陷、间隙缺陷和反位缺陷等)和晶界缺陷。另外，吸光层还存在较多的表面缺陷，主要表现在孔洞多、裂 纹多等。缺陷会捕获周围的自由电子和空穴，这些被捕获的电子和空穴容易在缺陷中心进行复合(又称为非辐射复合)，由此会增加钙钛矿电池的能量损耗，降低钙钛矿电池的性能。并且与本征点缺陷或晶界处的非辐射复合相比，吸光层与电荷传输层(例如空穴传输层或电子传输层)之间的界面处的非辐射复合通常占主导地位。
因此，钙钛矿材料结晶质量不佳、吸光层与电荷传输层界面缺陷多是影响钙钛矿电池性能提升的关键因素。界面钝化是获得高性能钙钛矿电池的有效策略。
本申请实施例提供的钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种。
有机分子钝化材料、金属氧化物半导体材料和金属卤化物容易获得与钙钛矿材料匹配的能级结构。
有机分子钝化材料可以同时作为界面连接剂和缺陷钝化剂，由此可以通过有机分子钝化材料增强吸光层与电荷传输层之间的界面接触，还可以通过有机分子钝化材料的配位作用降低钙钛矿材料体相和界面的缺陷态密度，提升吸光层的成膜质量，还可以使有机分子钝化材料嵌入钙钛矿材料体相，起到锚定作用，从而减少卤化物(例如PbI2等)从钙钛矿材料中析出，进而可以提升钙钛矿电池的稳定性和使用寿命。
因此，有机分子钝化材料可以钝化吸光层与电荷传输层界面缺陷，还可以钝化钙钛矿材料的本征点缺陷(包括空位缺陷、间隙缺陷和反位缺陷)和晶界缺陷，从而既可以提升吸光层与电荷传输层的界面性能，还可以优化钙钛矿材料的结晶质量，进而可以减少缺陷处的非辐射复合，提升钙钛矿电池的能量转换效率。另外，有机分子钝化材料还可以提升钝化层的成膜质量，起到有效阻隔水氧、减少水氧侵蚀钙钛矿材料的作用，由此还可以提升钙钛矿电池的稳定性和使用寿命。
金属氧化物半导体材料具有高稳定性，另外，其与钙钛矿材料的能级匹配性更好，由此可以更好地促进载流子传输并减少离子迁移。同时，金属氧化物半导体材料还可以有效阻隔水氧，减少水氧侵蚀钙钛矿材料，由此还可以提升钙钛矿电池的稳定性和使用寿命。
金属卤化物具有较高的稳定性，还可以起到钝化钙钛矿材料的卤素缺陷的作用，并且还可以优化钙钛矿材料的结晶质量。
因此，当钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种时，钝化层可以同时具有能级匹配、界面钝化、优化钙钛矿材料结晶质量的效果，进而有利于提升钙钛矿电池的能量转换效率。另外，当钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种时，钝化层的稳定性较好，并且还可以减少水氧侵蚀钙钛矿材料，由此还可以提升钙钛矿电池的稳定性和使用寿命。
在一些实施例中，有机分子钝化材料可以包括烷基胺及其卤素盐、芳香胺及其卤素盐、芳杂环化合物、聚合物、及其各自的衍生物中的一种或多种。
在一些实施例中，可选地，芳杂环化合物可以包括含氮芳杂环及其衍生物中的一种或多种，更可选为包括咔唑、吡啶、哌啶、及其各自的衍生物中的一种或多种。芳杂环化合物在上述范围内时，氮原子上具有孤对电子，可以更好地与钙钛矿材料中的金属离子的空轨道进行配位，由此其锚定作用更好，可以通过特定原子和/或官能团嵌入吸光层 浅表位置，从而可以进一步减少界面缺陷，进而可以减少缺陷处的非辐射复合，并提升钙钛矿电池的能量转换效率。
在一些实施例中，可选地，聚合物可以包括聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种。聚合物在上述范围内时，氨基或者芳杂环上的氮原子上具有孤对电子，可以更好地与钙钛矿材料中的金属离子的空轨道进行配位，由此其锚定作用更好，可以通过特定原子和/或官能团嵌入吸光层浅表位置，从而可以进一步减少界面缺陷，进而可以减少缺陷处的非辐射复合，并提升钙钛矿电池的能量转换效率。
在一些实施例中，有机分子钝化材料可以包括N,N-二乙基苯胺(N,N-Diethylaniline，DEA)、2-苯乙胺氢碘酸盐(2-Phenylethylamine Hydroiodide，PEAI)、多巴胺(Dopamine)、9,9-双(4-氨基苯基)芴(9,9-Bis(4-aminophenyl)fluorene，FDA)、[2-(9H-咔唑-9-基)乙基]膦酸(2PACz)、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸、[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸、4-吡啶羧酸、聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种。
有机分子钝化材料在上述范围内时，可以更好地匹配钙钛矿材料的能级，还可以更好地钝化吸光层与电荷传输层的界面缺陷、钝化钙钛矿材料的本征点缺陷和晶界缺陷，还可以更好地优化钙钛矿材料的结晶质量，由此可以进一步减少缺陷处的非辐射复合，提升钙钛矿电池的能量转换效率。
上述各有机分子钝化材料的衍生物通常是指有机分子钝化材料中的氢原子或原子团被其他原子或原子团取代而衍生的产物。
在一些实施例中，有机分子钝化材料可以包括[2-(9H-咔唑-9-基)乙基]膦酸(2PACz)、2-苯乙胺氢碘酸盐(2-Phenylethylamine Hydroiodide，PEAI)、及其各自的衍生物中的一种或多种。
在一些实施例中，金属氧化物半导体材料可以包括本征金属氧化物半导体材料、N型金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种。可选地，金属氧化物半导体材料可以包括SnO2、TiO2、ZnO、NiOx(1≤x≤2)、CeOx(1≤x≤2)、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种。
在一些实施例中，钝化层6位于空穴传输层2与吸光层3之间时，金属氧化物半导体材料可以包括本征金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，由此可以更好地传输空穴。可选地，金属氧化物半导体材料可以包括NiOx(1≤x≤2)、CeOx(1≤x≤2)、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种。
在一些实施例中，钝化层6位于电子传输层4与吸光层3之间时，金属氧化物半导体材料可以包括本征金属氧化物半导体材料、N型金属氧化物半导体材料中的一种或多种，由此可以更好地传输自由电子。可选地，金属氧化物半导体材料可以包括SnO2、TiO2、ZnO、及其各自的掺杂材料中的一种或多种。
金属氧化物半导体材料在上述范围内时，可以更好地匹配钙钛矿材料的能级，还可以更好地促进载流子传输和减少水氧侵蚀钙钛矿材料，由此有利于提升钙钛矿电池的能量转换效率和/或稳定性。
上述各金属氧化物的掺杂材料可以各自独立地包括碱金属元素、碱土金属元素、过 渡金属元素、贫金属元素、类金属元素、卤素元素、非金属元素、离子液体、羧酸、磷酸、碳衍生物、自组装单分子、聚合物中的一种或多种。可选地，金属氧化物中的掺杂材料的重量含量≤30％。
在一些实施例中，金属氧化物半导体材料的粒径可以在100nm以下，可选为50nm以下，更可选为5-10nm。
在一些实施例中，金属卤化物中的金属元素可以包括碱金属元素、碱土金属元素、过渡金属元素中的一种或多种，可选为包括K、Cs、Pb、Cu中的一种或多种。
在一些实施例中，金属卤化物中的卤素元素可以包括F、Cl、Br、I中的一种或多种。
在一些实施例中，金属卤化物可以包括CsF、KCl、PbBr、CuI、CuI2中的一种或多种。金属卤化物在上述范围内时，可以更好地匹配钙钛矿材料的能级。
在一些实施例中，金属卤化物可以包括CsF、KCl、PbBr中的一种或多种，可选为包括KCl、PbBr中的一种或多种。金属卤化物在上述范围内时，卤素阴离子的尺寸较小，可以更好地减少钙钛矿晶体的晶格扭曲，还有利于释放应力，从而可以更好地优化钙钛矿材料的结晶质量。
在一些实施例中，金属卤化物可以包括CuI、CuI2中的一种或多种。金属卤化物在上述范围内时，可以更好地促进载流子传输。
在一些实施例中，钝化层可以包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物。
有机分子钝化材料可以同时作为界面连接剂和缺陷钝化剂，由此可以通过有机分子钝化材料增强吸光层与电荷传输层之间的界面接触，还可以通过有机分子钝化材料的配位作用降低钙钛矿材料体相和界面的缺陷态密度，提升吸光层的成膜质量，还可以使有机分子钝化材料嵌入钙钛矿材料体相，起到锚定作用，从而减少卤化物(例如PbI2等)从钙钛矿材料中析出，进而可以提升钙钛矿电池的稳定性和使用寿命。因此，有机分子钝化材料可以起到更好地钝化效果，将其与金属氧化物半导体材料和/或金属卤化物组合使用时，可以进一步减少缺陷处的非辐射复合，进一步提升钙钛矿电池的能量转换效率。
可选地，基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，可选为15-25wt％。有机分子钝化材料自身的稳定性稍差，因此当其含量在上述范围内时，还有利于提升钙钛矿电池的稳定性和使用寿命。
在一些实施例中，钝化层6可以包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物。当钝化层同时包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物时，可以使钝化层更好地兼顾能级匹配、界面钝化、优化钙钛矿材料结晶质量的效果，进而有利于进一步提升钙钛矿电池的能量转换效率；还可以进一步减少水氧侵蚀钙钛矿材料，进而还有利于进一步提升钙钛矿电池的稳定性和使用寿命。
可选地，基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于钝化层的总重量计，金属氧化物半导体材料的含量为40-60wt％，更可选为45-55wt％。可选地，基于钝化层的总重量计，金属卤化物的含量为20-40wt％，更可选为25-35wt％。
有机分子钝化材料、金属氧化物半导体材料和金属卤化物的含量在上述范围内时，可以更好地发挥各组分的优势，从而有利于进一步提升钙钛矿电池的能量转换效率、稳定性和使用寿命。
在一些实施例中，钝化层6可以包括有机分子钝化材料和金属氧化物半导体材料。可选地，基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于钝化层的总重量计，金属氧化物半导体材料的含量为70-90wt％，更可选为75-85wt％。
在一些实施例中，钝化层6可以包括有机分子钝化材料和金属卤化物。可选地，基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。可选地，基于钝化层的总重量计，金属卤化物的含量为70-90wt％，更可选为75-85wt％。
在一些实施例中，钝化层6的厚度可以小于等于30nm，可选为1-22nm，1-17nm，2-22nm，2-17nm，4-22nm，4-17nm。钝化层的厚度在上述范围内时，可以使钙钛矿电池具有较高的能量转换效率和稳定性，还可以使钝化层具有较高的导电性，从而还有助于提升钙钛矿电池的输出性能。
在一些实施例中，吸光层3可以包括钙钛矿材料。钙钛矿材料作为本征半导体材料既可以传输电子也可以传输空穴。
钙钛矿材料的种类不受具体的限制，可根据实际需求进行选择。在一些实施例中，吸光层中的钙钛矿材料可以包括无机卤化物钙钛矿材料、有机卤化物钙钛矿材料、有机-无机杂化卤化物钙钛矿材料中的一种或多种。
钙钛矿材料的分子式可以为ABX3，A表示无机阳离子、有机阳离子、或有机无机混合阳离子，B表示无机阳离子、有机阳离子、或有机无机混合阳离子，X表示无机阴离子、有机阴离子、或有机无机混合阴离子。
作为示例，A包括CH3NH3 +(MA+)、CH(NH2)2 +(FA+)、Li+、Na+、K+、Rb+、Cs+中的一种或多种。可选地，A包括CH3NH3 +、CH(NH2)2 +、Cs+中的一种或多种，
作为示例，B包括Pb2+、Sn2+、Be2+、Mg2+、Ca2+、Sr2+、Ba2+、Zn2+、Ge2+、Fe2+、Co2+、Ni2+中的一种或多种。可选地，B包括Pb2+、Sn2+中的一种或两种。
作为示例，X包括F-、Cl-、Br-、I-中的一种或多种。可选地，X包括Cl-、Br-、I-中的一种或多种。
钙钛矿材料的分子式还可以为A’2CDX’6，A’表示无机阳离子、有机阳离子、或有机无机混合阳离子，C表示一价金属阳离子，D表示三价金属阳离子，X’表示无机阴离子、有机阴离子、或有机无机混合阴离子。
作为示例，A’包括CH3NH3 +(MA+)、CH(NH2)2 +(FA+)、Li+、Na+、K+、Rb+、Cs+中的一种或多种。可选地，A’包括CH3NH3 +、CH(NH2)2 +、Cs+中的一种或多种，
作为示例，C包括Li+、Na+、K+、Rb+、Cs+、Ag+中的至少一种。
作为示例，D包括In3+、Bi3+中的至少一种。
作为示例，X’包括F-、Cl-、Br-、I-中的一种或多种。可选地，X’包括Cl-、Br-、I-中的一种或多种。
在一些实施例中，钙钛矿材料可以包括但不限于CH3NH3PbI3(MAPbI3)、CH(NH2)2PbI3(FAPbI3)、CsPbI3、CsPbI2Br、CsPbIBr2、Cs2NaInCl6、Cs2KBiCl6、 Cs2AgInCl6中的一种或多种。
吸光层3的厚度不受具体的限制，可根据实际需求进行选择。例如，在一些实施例中，吸光层3的厚度可以为50-2000nm。
电子传输层4包括电子传输材料。电子传输材料的种类不受具体的限制，可根据实际需求进行选择。例如，电子传输材料可以包括有机电子传输材料、无机电子传输材料、或有机无机杂化电子传输材料。
在一些实施例中，电子传输材料可以包括酰亚胺类化合物、醌类化合物、富勒烯及其衍生物、第二金属氧化物、氧化硅、钛酸锶(SrTiO3)、钛酸钙(CaTiO3)、氟化锂(LiF)、氟化钙(CaF2)中的一种或多种。可选地，第二金属氧化物中的金属元素可以包括Mg、Cd、Zn、In、Pb、W、Sb、Bi、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga和Cr中的一种或多种。
可选地，电子传输材料可以包括SnO2、TiO2、[6,6]-苯基C61-丁酸甲酯(PC61BM)、[6,6]-苯基C71-丁酸甲酯(PC71BM)、富勒烯C60、富勒烯C70中的一种或多种。电子传输材料在上述范围内时，其导带底能级与吸光层的导带底能级能更好地匹配，从而有利于促进电子的传输。
电子传输层4的厚度不受具体的限制，可根据实际需求进行选择。例如，在一些实施例中，电子传输层4的厚度可以为1-300nm。
空穴传输层2包括空穴传输材料。空穴传输材料的种类不受具体的限制，可根据实际需求进行选择。
在一些实施例中，空穴传输材料可以包括2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴(Spiro-OMeTAD)、甲氧基三苯胺-氟代甲脒(OMeTPA-FA)、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)、聚3-已基噻吩(P3HT)、三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚噻吩、磷酸基单分子、咔唑基单分子、磺酸基单分子、三苯胺基单分子、芳香基单分子、第三金属氧化物和硫氰酸亚铜(CuSCN)中的一种或多种。可选地，第三金属氧化物中金属元素可以包括Ni、Mo和Cu中的一种或多种。
空穴传输层2的厚度不受具体的限制，可根据实际需求进行选择。例如，在一些实施例中，空穴传输层2的厚度可以为5-1000nm。
在一些实施例中，钝化层6位于空穴传输层2与吸光层3之间时，吸光层3的价带顶(VBM)能级＜钝化层6的价带顶(VBM)能级＜空穴传输层2的价带顶(VBM)能级。由此有利于更好地传输空穴。
在一些实施例中，钝化层6位于电子传输层4与吸光层3之间时，电子传输层4的导带底(CBM)能级＜钝化层6的导带底(CBM)能级＜吸光层3的导带底(CBM)能级。由此有利于更好地传输电子。
各膜层的能带分布可通过X射线光电子能谱仪(XPS)、紫外光电子能谱仪(UPS)进行测定。
在一些实施例中，第一电极1和第二电极5的电极材料可以分别独立地包括有机导电材料、无机导电材料或有机无机混合导电材料。例如，第一电极1和第二电极5的电极材 料可以分别独立地包括包括导电聚合物、金属、透明金属导电氧化物、碳及其衍生物中的一种或多种。作为示例，第一电极1和第二电极5的电极材料分别独立地包括聚(3,4-乙烯二氧噻吩)(PEDOT)、聚噻吩、聚乙炔、氟掺杂的氧化锡(FTO)、氧化铟锡(ITO)、锑掺杂的氧化锡(ATO)、铝掺杂的氧化锌(AZO)、硼掺杂的氧化锌(BZO)、铟掺杂的氧化锌(IZO)、金、银、铝、铜、碳及其衍生物中的一种或多种。
在一些实施例中，第一电极1和第二电极5中有一个的电极材料可以包括透明金属导电氧化物，可选为包括氟掺杂的氧化锡(FTO)、氧化铟锡(ITO)、锑掺杂的氧化锡(ATO)、铝掺杂的氧化锌(AZO)、硼掺杂的氧化锌(BZO)、铟掺杂的氧化锌(IZO)中的一种或多种。
在一些实施例中，钙钛矿电池还包括基底，例如玻璃基底，基底表面可以设置透明金属导电氧化物。
在一些实施例中，第一电极1和第二电极5中有一个的电极材料可以包括金属、碳及其衍生物中的一种或多种，可选为包括金、银、铝、铜、碳及其衍生物中的一种或多种。
第一电极1的厚度不受具体的限制，可根据实际需求进行选择。例如，在一些实施例中，第一电极1的厚度可以为10nm-500nm。
第二电极5的厚度不受具体的限制，可根据实际需求进行选择。例如，在一些实施例中，第二电极5的厚度可以为10nm-500nm。
本申请实施例提供的钙钛矿电池可以为正式结构电池，也可以为反式结构电池。
在一些实施例中，如图1所示，第一电极1为入光侧，钙钛矿电池(反式结构电池)依次包括第一电极1、空穴传输层2、钝化层6、吸光层3、电子传输层4和第二电极5。在一些实施例中，如图2所示，第一电极1为入光侧，钙钛矿电池(反式结构电池)依次包括第一电极1、空穴传输层2、吸光层3、钝化层6、电子传输层4和第二电极5。在一些实施例中，如图1所示，第一电极1为入光侧，钙钛矿电池(反式结构电池)依次包括第一电极1、空穴传输层2、钝化层6、吸光层3、钝化层6、电子传输层4和第二电极5。
在一些实施例中，如图4所示，第二电极5为入光侧，钙钛矿电池(正式结构电池)依次包括第二电极5、电子传输层4、钝化层6、吸光层3、空穴传输层2和第一电极1。在一些实施例中，如图5所示，第二电极5为入光侧，钙钛矿电池(正式结构电池)依次包括第二电极5、电子传输层4、吸光层3、钝化层6、空穴传输层2和第一电极1。在一些实施例中，如图6所示，第二电极5为入光侧，钙钛矿电池(正式结构电池)依次包括第二电极5、电子传输层4、钝化层6、吸光层3、钝化层6、空穴传输层2和第一电极1。
可选地，钝化层6位于靠近入光侧的电荷传输层与吸光层之间，对于正式结构电池而言，该电荷传输层为电子传输层，对于反式结构电池而言，该电荷传输层为空穴传输层。此时，吸光层在钝化层之后成膜，由此钝化层可以更好地促进钙钛矿材料结晶，从而可以使钙钛矿电池具有更高的能量转换效率。
在一些实施例中，第一电极1为入光侧，钙钛矿电池(反式结构电池)依次包括第一电极1、空穴传输层2、钝化层6、吸光层3、电子传输层4和第二电极5；钝化层6包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物；基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，可选为15-25wt％；金属氧化物半导体材料包括本征金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，可选地包括NiOx (1≤x≤2)、CeOx(1≤x≤2)、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种。
在一些实施例中，第二电极5为入光侧，钙钛矿电池(正式结构电池)依次包括第二电极5、电子传输层4、钝化层6、吸光层3、钝化层6、空穴传输层2和第一电极1；钝化层6包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物；基于钝化层的总重量计，有机分子钝化材料的含量为10-30wt％，可选为15-25wt％；金属氧化物半导体材料包括本征金属氧化物半导体材料、N型金属氧化物半导体材料中的一种或多种，可选为包括SnO2、TiO2、ZnO、及其各自的掺杂材料中的一种或多种。
本申请实施例提供的钙钛矿电池不限于上述结构，还可包含其他功能层。
钙钛矿电池可按照本领域已知的方法制备。
如图1至图3所示，一个示例性制备方法包括步骤：提供第一电极1，在第一电极1上形成空穴传输层2，在空穴传输层2上形成吸光层3，在吸光层3上形成电子传输层4，在电子传输层4上形成第二电极，以及在空穴传输层2上形成钝化层6后再形成吸光层3，和/或，在吸光层3上形成钝化层6后再形成电子传输层4。
如图4至图6所示，另一示例性制备方法包括：提供第二电极5，在第二电极5上形成电子传输层4，在电子传输层4上形成吸光层3，在吸光层3上形成空穴传输层2，在空穴传输层2上形成第一电极1，以及在吸光层3上形成钝化层6后再形成空穴传输层2，和/或，在电子传输层4上形成钝化层6后再形成吸光层3。
上述各膜层的成膜方法不受具体的限制，可采用本领域已知的成膜方法，例如，化学浴沉积法、化学气相沉积法、电化学沉积法、物理外延生长法、热蒸镀法、原子层沉积法、磁控溅射法、前驱液旋涂法、前驱液狭缝涂布法、前驱液刮涂法、机械压合法、溶胶凝胶法、脉冲激光沉积法等，可选为热蒸镀法和前驱液旋涂法。
本申请实施例提供的钙钛矿电池可以作为单结钙钛矿电池单独使用，也可以与钙钛矿型或其他类型的太阳能电池制成叠层电池，例如钙钛矿-钙钛矿叠层电池或钙钛矿-晶硅叠层电池等。
本申请实施例还提供一种光伏组件，光伏组件包括本申请实施例提供的钙钛矿电池，钙钛矿电池可以经串并联和封装等工序后用作光伏组件的电源。
在一些实施例中，光伏组件包括本申请实施例提供的单结钙钛矿电池、钙钛矿-钙钛矿叠层电池或钙钛矿-晶硅叠层电池。
实施例
下述实施例更具体地描述了本申请公开的内容，这些实施例仅仅用于阐述性说明，因为在本申请公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
实施例1-1
制备FTO电极
取规格为2.0cm×2.0cm的覆盖有FTO的玻璃基底，表面依次用丙酮和异丙醇分别清洗2次，之后浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱 中(N2氛围)。
制备电子传输层
以4000-6500rpm的速度在FTO层上旋涂3wt％的SnO2纳米胶体水溶液，之后在恒温热台上以150℃加热15min，得到电子传输层，厚度为50nm。
制备钝化层
以5000-6000rpm的速度在电子传输层上旋涂2wt％的TiO2纳米胶体-异丙醇溶液、0.2mg/mL的2PACz-异丙醇溶液以及1mg/mL的KCl-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为17nm。钝化层中各组分的重量含量如表1所示。
制备吸光层
以3000-4500rpm的速度在钝化层上旋涂1.5mol/L的FAPbI3的DMF溶液，之后在恒温热台上以100℃加热30min，冷却至室温后，得到吸光层，厚度为500nm。
制备空穴传输层
以3000-4000rpm的速度在吸光层上旋涂73mg/mL的Spiro-OMeTAD的氯苯溶液，得到空穴传输层，厚度为150nm。
制备Ag电极
将前述样品放入真空镀膜机，在5×10-4Pa的真空条件下在空穴传输层表面蒸镀Ag电极，蒸镀速率0.1埃/s，厚度为80nm。
实施例1-1最终制得的钙钛矿电池结构为FTO/SnO2/TiO2+2PACz+KCl/FAPbI3/Spiro-OMeTAD/Ag。
实施例1-2至1-6
除钝化层中各组分的重量含量不同之外，钙钛矿电池的制备与实施例1-1相同，具体参数详见表1。
实施例1-7至1-11
除钝化层的厚度不同之外，钙钛矿电池的制备与实施例1-1相同，具体参数详见表1。
实施例1-12
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂2wt％的TiO2纳米胶体-异丙醇溶液与0.2mg/mL的2PACz-异丙醇溶液的混合液，之后在恒温热台上以150℃加热30min，得到钝化层，厚度为15nm。钝化层中各组分的重量含量如表1所示。
实施例1-12最终制得的钙钛矿电池结构为FTO/SnO2/TiO2+2PACz/FAPbI3/Spiro-OMeTAD/Ag。
实施例1-13
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂2wt％的TiO2纳米胶体-异丙醇溶液与1mg/mL的KCl-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为15nm。钝化层中各组分的重量含量如表1所示。
实施例1-13最终制得的钙钛矿电池结构为FTO/SnO2/TiO2+KCl/FAPbI3/Spiro-OMeTAD/Ag。
实施例1-14
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂0.2mg/mL的2PACz-异丙醇溶液与1mg/mL的KCl-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为4nm。钝化层中各组分的重量含量如表1所示。
实施例1-14最终制得的钙钛矿电池结构为FTO/SnO2/2PACz+KCl/FAPbI3/Spiro-OMeTAD/Ag。
对比例1-1
除不包含钝化层之外，钙钛矿电池的制备与实施例1-1相同。
对比例1-1最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/Spiro-OMeTAD/Ag。
对比例1-2
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂2wt％的TiO2纳米胶体的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为13nm。
对比例1-2最终制得的钙钛矿电池结构为FTO/SnO2/TiO2/FAPbI3/Spiro-OMeTAD/Ag。
对比例1-3
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂0.2mg/mL的2PACz的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为2nm。
对比例1-3最终制得的钙钛矿电池结构为FTO/SnO2/2PACz/FAPbI3/Spiro-OMeTAD/Ag。
对比例1-4
除钝化层的制备不同之外，钙钛矿电池的制备与实施例1-1相同。
以5000-6000rpm的速度在电子传输层上旋涂1mg/mL的KCl的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为为2nm。
对比例1-4最终制得的钙钛矿电池结构为FTO/SnO2/KCl/FAPbI3/Spiro-OMeTAD/Ag。
测试部分
在25℃、大气环境下，使用AM1.5G标准光源模拟太阳光，使用四通道数字源表(Keithley 2440)测量光源照射下钙钛矿电池的伏安特性曲线，得到钙钛矿电池的开路电压Voc、短路电流密度Jsc、填充因子FF(Fill Factor)，由此计算钙钛矿电池的能量转换效率Eff(Efficiency)。
Eff＝Pout/Popt＝Voc×Jsc×(Vmpp×Jmpp)/(Voc×Jsc)＝Voc×Jsc×FF。
Pout、Popt、Vmpp、Jmpp分别为钙钛矿电池的工作输出功率、入射光功率、最大功率点电压和最大功率点电流。
表1示出实施例1-1至1-14和对比例1-1至1-4的测试结果。
表1

实施例2-1
制备FTO电极
取规格为2.0cm×2.0cm的覆盖有FTO的玻璃基底，表面依次用丙酮和异丙醇分别清洗2次，之后浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱中(N2氛围)。
制备电子传输层
以4000-6500rpm的速度在FTO层上旋涂3wt％的SnO2纳米胶体水溶液，之后在恒温热台上以150℃加热15min，得到电子传输层，厚度为50nm。
制备吸光层
以3000-4500rpm的速度在电子传输层上旋涂1.5mol/L的FAPbI3的DMF溶液，之后在恒温热台上以100℃加热30min，冷却至室温后，得到吸光层，厚度为500nm。
制备钝化层
以5000-6000rpm的速度在吸光层上旋涂2wt％的CuO纳米胶体-异丙醇溶液、0.2mg/mL的PEAI-异丙醇溶液以及1mg/mL的CuI-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为17nm。钝化层中各组分的重量含量如表2所示。
制备空穴传输层
以3000-4000rpm的速度在钝化层上旋涂73mg/mL的Spiro-OMeTAD的氯苯溶液，得到空穴传输层，厚度为150nm。
制备Ag电极
将前述样品放入真空镀膜机，在5×10-4Pa的真空条件下在空穴传输层表面蒸镀Ag电极，蒸镀速率0.1埃/s，厚度为80nm。
实施例2-1最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/CuO+PEAI+CuI/Spiro-OMeTAD/Ag。
实施例2-2
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂2wt％的CuO纳米胶体-异丙醇溶液与0.2mg/mL的PEAI-异丙醇溶液的混合液，之后在恒温热台上以150℃加热30min，得到钝化层，厚度为15nm。钝化层中各组分的重量含量如表2所示。
实施例2-2最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/CuO+PEAI/Spiro-OMeTAD/Ag。
实施例2-3
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂2wt％的CuO纳米胶体-异丙醇溶液与1mg/mL的CuI-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为15nm。钝化层中各组分的重量含量如表2所示。
实施例2-3最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/CuO+CuI/Spiro-OMeTAD/Ag。
实施例2-4
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂0.2mg/mL的PEAI-异丙醇溶液与1mg/mL的CuI-异丙醇溶液的混合液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为4nm。钝化层中各组分的重量含量如表2所示。
实施例2-4最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/PEAI+CuI/Spiro-OMeTAD/Ag。
对比例2-1
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂2wt％的CuO纳米胶体的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为13nm。
对比例2-1最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/CuO/Spiro-OMeTAD/Ag。
对比例2-2
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂0.2mg/mL的PEAI的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为2nm。
对比例2-2最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/PEAI/Spiro-OMeTAD/Ag。
对比例2-3
除钝化层的制备不同之外，钙钛矿电池的制备与实施例2-1相同。
以5000-6000rpm的速度在吸光层上旋涂1mg/mL的CuI的异丙醇溶液，之后在恒温热台上以100℃加热10min，得到钝化层，厚度为为2nm。
对比例2-3最终制得的钙钛矿电池结构为FTO/SnO2/FAPbI3/CuI/Spiro-OMeTAD/Ag。
表2示出实施例2-1至2-4和对比例2-1至2-3的测试结果。钙钛矿电池的测试方法与实施 例1-1至1-14相同。
表2
从表1和表2的测试结果可以看出，对比例1-2至1-4、对比例2-1至2-3分别采用有机分子钝化材料、金属氧化物半导体材料或金属卤化物作为钝化层，与对比例1-1相比，对钙钛矿电池的能量转换效率的提升效果并不明显。
对比例1-2和对比例2-1采用金属氧化物半导体材料作为钝化层，金属氧化物半导体材料具有高结构稳定性，但是其对钙钛矿结晶质量的促进效果有限，特别地，对比例2-1的钝化层在吸光层之后形成，由此会进一步降低对钙钛矿结晶质量的促进效果，导致对于钙钛矿电池的能量转换效率的提升效果不明显。
对比例1-3和对比例2-2采用有机分子钝化材料作为钝化层，有机分子钝化材料的结构稳定性较差，由此导致对于钙钛矿电池的能量转换效率的提升效果不明显。
对比例1-4和对比例2-3采用金属卤化物作为钝化层，KCl的载流子传输能力有限，由此导致对于钙钛矿电池的能量转换效率的提升效果不明显，CuI的界面钝化效果有限，由此导致对于钙钛矿电池的能量转换效率的提升效果不明显。
从表1和表2的测试结果可以看出，通过在空穴传输层与吸光层之间，和/或，电子传输层与吸光层之间设置钝化层，并使钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种，钝化层可以同时具有能级匹配、界面钝化、优化钙钛矿材料结晶质量的效果，进而可以进一步提升钙钛矿电池的能量转换效率。
从表1和表2测试结果还可以看出，钝化层包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物时，可以进一步提升钙钛矿电池的能量转换效率。这是由于，有机分子钝化材料可以同时作为界面连接剂和缺陷钝化剂，由此可以通过有机分子钝化材料增强吸光层与电荷传输层之间的界面接触，还可以通过有机分子钝化材料的配位作用降低钙钛矿材料体相和界面的缺陷态密度，提升吸光层的成膜质量，还可以使有机分子钝化材料嵌入钙钛矿材料体相，起到锚定作用，从而减少卤化物从钙钛矿材料中析出。因此，将有机分子钝化材料与金属氧化物半导体材料和/或金属卤化物组合使用时，可以进一步减少缺陷处的非辐射复合，进一步提升钙钛矿电池的能量转换效率。
从表1和表2测试结果还可以看出，当在靠近入光侧的电荷传输层与吸光层之间设置钝化层时，可以更好地提升钙钛矿电池的能量转换效率。这是由于，钝化层可以更好地 促进钙钛矿材料结晶。
以上所述，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到各种等效的修改或替换，这些修改或替换都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以权利要求的保护范围为准。

Claims (16)

  1. 一种钙钛矿电池，包括：
    第一电极；
    第二电极；
    吸光层，位于所述第一电极与所述第二电极之间；
    空穴传输层，位于所述第一电极与所述吸光层之间；以及
    电子传输层，位于所述第二电极与所述吸光层之间，
    其中，
    所述钙钛矿电池还包括钝化层，所述钝化层位于所述空穴传输层与所述吸光层之间，和/或，所述钝化层位于所述电子传输层与所述吸光层之间；
    所述钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物中的至少两种。
  2. 根据权利要求1所述的钙钛矿电池，其中，
    所述钝化层包括有机分子钝化材料以及金属氧化物半导体材料和/或金属卤化物，
    可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％。
  3. 根据权利要求1或2所述的钙钛矿电池，其中，所述钝化层包括有机分子钝化材料、金属氧化物半导体材料和金属卤化物，
    可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％；
    可选地，基于所述钝化层的总重量计，所述金属氧化物半导体材料的含量为40-60wt％，更可选为45-55wt％；
    可选地，基于所述钝化层的总重量计，所述金属卤化物的含量为20-40wt％，更可选为25-35wt％。
  4. 根据权利要求1或2所述的钙钛矿电池，其中，所述钝化层包括有机分子钝化材料和金属氧化物半导体材料，
    可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％；
    可选地，基于所述钝化层的总重量计，所述金属氧化物半导体材料的含量为70-90wt％，更可选为75-85wt％。
  5. 根据权利要求1或2所述的钙钛矿电池，其中，所述钝化层包括有机分子钝化材料和金属卤化物，
    可选地，基于所述钝化层的总重量计，所述有机分子钝化材料的含量为10-30wt％，更可选为15-25wt％；
    可选地，基于所述钝化层的总重量计，所述金属卤化物的含量为70-90wt％，更可选为75-85wt％。
  6. 根据权利要求1至5任一项所述的钙钛矿电池，其中，所述钝化层的厚度小于等于30nm，可选为1-22nm。
  7. 根据权利要求1-6任一项所述的钙钛矿电池，其中，所述有机分子钝化材料包括烷基胺及其卤素盐、芳香胺及其卤素盐、芳杂环化合物、聚合物、及其各自的衍生物中的一种或多种，
    可选地，所述芳杂环化合物包括含氮芳杂环及其衍生物中的一种或多种，更可选为包括咔唑、吡啶、哌啶、及其各自的衍生物中的一种或多种；
    可选地，所述聚合物包括聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种。
  8. 根据权利要求7所述的钙钛矿电池，其中，
    所述有机分子钝化材料包括N,N-二乙基苯胺、2-苯乙胺氢碘酸盐、多巴胺、9,9-双(4-氨基苯基)芴、[2-(9H-咔唑-9-基)乙基]膦酸、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸、[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸、4-吡啶羧酸、聚苯胺、聚吡啶、聚哌啶、及其各自的衍生物中的一种或多种，
    可选地，所述有机分子钝化材料包括[2-(9H-咔唑-9-基)乙基]膦酸、2-苯乙胺氢碘酸盐、及其各自的衍生物中的一种或多种。
  9. 根据权利要求1-8任一项所述的钙钛矿电池，其中，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、N型金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，可选地包括SnO2、TiO2、ZnO、NiOx、CeOx、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种，1≤x≤2。
  10. 根据权利要求9所述的钙钛矿电池，其中，
    所述钝化层位于所述空穴传输层与所述吸光层之间时，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、P型金属氧化物半导体材料中的一种或多种，可选地包括NiOx、CeOx、MoO3、NiMgLiO、CuGaO2、CuGrO2、CuO、Cu2O、及其各自的掺杂材料中的一种或多种，1≤x≤2；
    所述钝化层位于所述电子传输层与所述吸光层之间时，所述金属氧化物半导体材料包括本征金属氧化物半导体材料、N型金属氧化物半导体材料中的一种或多种，可选地包括SnO2、TiO2、ZnO、及其各自的掺杂材料中的一种或多种。
  11. 根据权利要求1-10任一项所述的钙钛矿电池，其中，所述金属氧化物半导体材料的粒径在100nm以下，可选为50nm以下，更可选为5-10nm。
  12. 根据权利要求1-11任一项所述的钙钛矿电池，其中，
    所述金属卤化物中的金属元素包括碱金属元素、碱土金属元素、过渡金属元素中的一种或多种，可选为包括K、Cs、Pb、Cu中的一种或多种；和/或，
    所述金属卤化物中的卤素元素包括F、Cl、Br、I中的一种或多种。
  13. 根据权利要求12所述的钙钛矿电池，其中，所述金属卤化物包括CsF、KCl、PbBr、CuI、CuI2中的一种或多种，可选为包括KCl、CuI中的一种或多种。
  14. 根据权利要求1-13任一项所述的钙钛矿电池，其中，
    所述电子传输层中的电子传输材料包括酰亚胺类化合物、醌类化合物、富勒烯及其衍生物、第二金属氧化物、氧化硅、钛酸锶、钛酸钙、氟化锂、氟化钙中的一种或多种，可选地，所述第二金属氧化物中的金属元素包括Mg、Cd、Zn、In、Pb、W、Sb、Bi、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga和Cr中的一种或多种；和/或，
    所述空穴传输层中的空穴传输材料包括2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴、甲氧基三苯胺-氟代甲脒、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]、聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸、聚3-已基噻吩、三蝶烯为核的三苯胺、3,4-乙烯二氧噻吩-甲氧基三苯胺、N-(4-苯胺)咔唑-螺双芴、聚噻吩、磷酸基单分子、咔唑基单分子、磺酸基单分子、三苯胺基单分子、芳香基单分子、第三金属氧化物和硫氰酸亚铜中的一种或多种，所述第三金属氧化物中金属元素包括Ni、Mo和Cu中的一种或多种；和/或，
    所述吸光层中的钙钛矿材料包括无机卤化物钙钛矿材料、有机卤化物钙钛矿材料、有机-无机杂化卤化物钙钛矿材料中的一种或多种。
  15. 根据权利要求1-14任一项所述的钙钛矿电池，其中，所述第一电极和所述第二电极的电极材料分别独立地包括有机导电材料、无机导电材料或有机无机混合导电材料，可选为包括聚(3,4-乙烯二氧噻吩)、聚噻吩、聚乙炔、氟掺杂的氧化锡、氧化铟锡、锑掺杂的氧化锡、铝掺杂的氧化锌、硼掺杂的氧化锌、铟掺杂的氧化锌、金、银、铝、铜、碳及其衍生物中的一种或多种。
  16. 一种光伏组件，包括根据权利要求1-15任一项所述的钙钛矿电池。
PCT/CN2023/095251 2023-05-19 2023-05-19 钙钛矿电池、光伏组件 Ceased WO2024239140A1 (zh)

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