WO2025237014A1 - 钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置 - Google Patents

钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置

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Publication number
WO2025237014A1
WO2025237014A1 PCT/CN2025/090474 CN2025090474W WO2025237014A1 WO 2025237014 A1 WO2025237014 A1 WO 2025237014A1 CN 2025090474 W CN2025090474 W CN 2025090474W WO 2025237014 A1 WO2025237014 A1 WO 2025237014A1
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perovskite
group
groups
carbon atoms
solar cell
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English (en)
French (fr)
Inventor
尹昭怡
周家正
陈俊超
孟轲
贾博宇
安心怡
郑义
郭永胜
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Contemporary Amperex Technology Co Ltd
Contemporary Amperex Future Energy Research Institute Shanghai Ltd
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Contemporary Amperex Technology Co Ltd
Contemporary Amperex Future Energy Research Institute Shanghai Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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

  • This application relates to the field of battery technology, and in particular to a perovskite battery, photovoltaic module, photovoltaic system, electrical device, and power generation device.
  • Perovskite solar cells have many advantages, such as excellent photoelectric properties, high light absorption coefficient, long carrier lifetime and long diffusion length, and have become a key research direction for next-generation photovoltaic technology.
  • a first aspect of this application provides a perovskite solar cell, the perovskite solar cell comprising a hole transport layer, a passivation layer, and a perovskite material layer stacked together; the passivation layer contains an ammonium salt compound;
  • the anionic group includes a group formed by the loss of hydrogen from at least one hydroxyl group of at least one oxyacid group in the compound of formula (1), and the cationic group includes a group formed by the gain of hydrogen from an amino group in the compound of formula (2).
  • L1 is selected from any one of alkyl groups substituted with at least one oxyacid group and oxyacid groups
  • each R1 and each R2 is independently selected from any one of H, alkyl, alkoxy, aryl groups with 6 to 13 substituted or unsubstituted cyclic atoms, and heteroaryl groups with 5 to 10 substituted or unsubstituted cyclic atoms.
  • Ar 1 is selected from substituted or unsubstituted aryl groups having 6 to 14 cyclic atoms, and L 2 is selected from alkylene groups having 1 to 3 carbon atoms;
  • n1 and n2 are each independently selected from any integer from 0 to 4.
  • an ammonium salt compound with a specific structure is set in the passivation layer between the hole transport layer and the perovskite.
  • the anionic group formed by the compound of formula (1) contains a carbazole structure, which itself has hole transport capability.
  • the presence of the carbazole group makes the compound prone to forming self-assembled micelles during film formation, which is not conducive to film spreading.
  • the presence of the -NH3 + group can destroy its self-assembly morphology, so that the ammonium salt compound can be better dispersed during film formation, forming a more uniform film layer.
  • the cation group formed by the compound of formula (2) also contains a specific aromatic group structure, which can generate a conjugation effect with the carbazole group in the anionic group, further improving the carrier extraction capability and/or carrier transport capability of the interface.
  • the side reactions between the hole transport layer and the perovskite material layer can be reduced, which can improve the photoelectric conversion efficiency and stability of the perovskite solar cell, thereby increasing the lifespan of the perovskite solar cell.
  • a molecule of compound (1) contains one or more oxyacid groups. When it contains multiple oxyacid groups, at least one hydroxyl group in at least one oxyacid group loses hydrogen. When M hydroxyl groups in multiple oxyacid groups in a molecule of compound (1) lose hydrogen (M is an integer greater than or equal to 2), then M molecules of compound (2) will each gain one hydrogen, forming M cation groups, which will form a salt with the anion formed by a molecule of compound (1). In other words, in a molecule of ammonium salt compound, the sum of the valence states of the anion formed by compound (1) and the cation formed by compound (2) is 0, that is, the ammonium salt compound is electrically neutral.
  • Ar 1 is selected from an aromatic group having 6 to 14 cyclic atoms or an aromatic group having 6 to 14 cyclic atoms substituted by a substituent, the substituent including any one of F, hydroxyl, alkyl having 1 to 3 carbon atoms, alkyl having 1 to 3 carbon atoms substituted by a fluorine atom, alkoxy having 1 to 3 carbon atoms, and alkoxy having 1 to 3 carbon atoms substituted by a fluorine atom.
  • Ar 1 By regulating the structure of Ar 1 to contain aromatic groups, it can be made to have strong aromaticity, that is, it can generate a strong conjugation effect with the carbazole group in the anionic group, while reducing steric hindrance and improving film quality.
  • the structure of Ar 1 is as follows:
  • Each R3 is independently selected from any one of H, F, hydroxyl, alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted by fluorine atoms, alkoxy with 1 to 3 carbon atoms, and alkoxy with 1 to 3 carbon atoms substituted by fluorine atoms.
  • n3 is selected from any integer from 0 to 5. * represents the linkage site.
  • n 3 is selected from 0, it indicates that there are no substituents on the benzene ring, and the structure is phenyl.
  • the ammonium salt compound satisfies one or both of the following conditions (1) to (2):
  • L 1 is selected from alkyl groups having 1 to 5 carbon atoms substituted by at least one oxyacid group
  • Each R1 and each R2 is independently selected from: H, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, and aryl with 6 to 10 cyclic atoms.
  • ammonium salt compound includes the compound shown in formula (I):
  • L 11 is selected from alkylene groups having 1 to 5 carbon atoms
  • a - is a group formed by losing a hydrogen atom from a hydroxyl group in the oxyacid group.
  • the oxyacid group is selected from any one of phosphonic acid groups, hypophosphite groups, sulfonic acid groups, carboxylic acid groups, boric acid groups, or silicate groups.
  • the ammonium salt compound includes at least one of the following (a) to (e):
  • L 11 is selected from alkylene groups having 1 to 5 carbon atoms
  • R 3 is selected from any one of H, F, hydroxyl, alkyl groups having 1 to 3 carbon atoms, and alkyl groups having 1 to 3 carbon atoms that have been replaced by fluorine atoms.
  • R3 is selected from F, hydroxyl group, or alkyl group having 1 to 3 carbon atoms substituted with fluorine atoms.
  • Introducing electronegative substituents such as hydroxyl, fluorine atom, or fluorine-containing alkyl groups into the cationic groups of ammonium salt compounds can further regulate the energy band at the interface and improve the interfacial carrier transport performance.
  • introducing fluorine atom or hydroxyl group into the anionic group formed in compound (1) introducing fluorine atom or hydroxyl group into the hydrophilic cationic part formed in compound (2) is more conducive to improving the wettability of the perovskite material precursor liquid on the film layer, thereby improving the film quality of the formed perovskite material layer and thus improving the stability of the battery.
  • the compound of formula (1) includes [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethylphosphonic acid, [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]carboxylic acid, and [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]carboxylic acid.
  • the compound of formula (2) includes one or more of m-fluoroanisidine, p-fluoroanisidine, o-fluoroanisidine, m-fluorophenylethylamine, p-fluorophenylethylamine, o-fluorophenylethylamine, m-fluorophenylpropanol, p-fluorophenylpropanol, o-fluorophenylpropanol, m-trifluoromethylphenylethylamine, p-trifluoromethylphenylethylamine, o-trifluoromethylphenylethylamine, p-methylphenylethylamine, m-methylphenylethylamine, o-methylphenylethylamine, p-hydroxyphenylethylamine, m-hydroxyphenylethylamine and o-hydroxyphen
  • the ammonium salt compounds formed by the compounds of formula (1) and formula (2) can be better dispersed during the film formation process, forming a more uniform film layer, which plays a role in adjusting the energy band and improving the charge extraction capability. In addition, it can reduce the side reactions between the hole transport layer and the perovskite material layer while reducing the energy level difference between the hole transport layer and the perovskite material layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery and thus improving the lifespan of the perovskite battery.
  • the hole transport layer includes at least one of inorganic hole transport materials and organic hole transport materials.
  • the hole transport layer comprises nickel oxide.
  • oxyacid groups are formed into ammonium salts, and the structure of the cation portion is controlled.
  • it can block the side reactions between high-valence nickel ions (Ni 3+ , Ni 4+ , etc.) and perovskite. This improves the film-forming ability of the ammonium salt compound, reduces the energy level difference between it and the perovskite material layer, and further improves the carrier extraction and/or carrier transport capabilities at the interface, effectively improving the photoelectric conversion efficiency and stability of perovskite solar cells.
  • the passivation layer satisfies one or both of the following conditions (1) and (2):
  • One side of the passivation layer is in direct contact with the perovskite material layer, and the other side is in direct contact with the hole transport layer;
  • the thickness of the passivation layer is 0.1 nm to 5 nm.
  • the perovskite solar cell further includes an electron transport layer, a first electrode, and a second electrode.
  • the first electrode is disposed on the side of the hole transport layer away from the perovskite material layer
  • the second electrode is disposed on the side of the perovskite material layer away from the hole transport layer.
  • the electron transport layer is disposed between the second electrode and the perovskite material layer.
  • An electron transport layer can enhance the efficiency of electron extraction and transport, thereby further improving the conversion efficiency of perovskite solar cells.
  • the perovskite solar cell further includes a hole-blocking layer disposed between the electron transport layer and the second electrode.
  • Hole blocking layers can block holes from passing through, significantly improving the electron collection rate at the interface, thereby reducing the probability of electrons and holes recombinating at the interface.
  • the perovskite solar cell satisfies one or more of the following conditions:
  • the thickness of the hole transport layer is 20nm to 100nm;
  • the thickness of the perovskite material layer is 500 nm to 800 nm;
  • the thickness of the electron transport layer is 20nm to 30nm;
  • the thickness of the hole blocking layer is 5nm to 10nm.
  • a second aspect of this application provides a method for preparing the perovskite solar cell of the first aspect, comprising the following steps:
  • the hole transport layer and the perovskite material layer are sequentially formed; and before the step of forming the perovskite material layer, the following step is also included:
  • the passivation layer is formed on the surface of the hole transport layer using raw materials including the ammonium salt compound.
  • a third aspect of this application provides a photovoltaic module, including the perovskite cell of the first aspect.
  • a fourth aspect of this application provides a photovoltaic system including the photovoltaic module of the third aspect.
  • a fifth aspect of this application provides an electrical device, including a perovskite cell of the first aspect or a photovoltaic module of the third aspect.
  • a sixth aspect of this application provides a power generation device, including a perovskite cell of the first aspect or a photovoltaic module of the third aspect.
  • Figure 1 is a schematic diagram of a perovskite solar cell according to an embodiment of this application.
  • Perovskite solar cell 11. First electrode; 12. Hole transport layer; 13. Passivation layer; 14. Perovskite material layer; 15. Electron transport layer; 16. Hole blocking layer; 17. Second electrode.
  • the term "and/or” is merely a description of the relationship between related objects, indicating that three relationships can exist.
  • a and/or B can represent: A existing alone, A and B existing simultaneously, and B existing alone.
  • the character "/" in this document generally indicates that the preceding and following related objects have an "or" relationship.
  • multiple refers to two or more (including two), similarly, “multiple sets” refers to two or more (including two sets), and “multiple pieces” refers to two or more (including two pieces).
  • alkyl refers to a group formed by the loss of one hydrogen atom from an alkane, such as methyl atom from the loss of one hydrogen atom from methane
  • alkylene group refers to a group formed by the loss of two hydrogen atom from an alkane, such as methylene atom from the loss of two hydrogen atom from methane.
  • a fused-ring aryl group is a group formed by two or more monoaromatic rings connected by two shared adjacent ring atoms, i.e., a fused ring. Furthermore, the ⁇ electrons of an aromatic group should satisfy 4n+2 (Hückel's rule).
  • Heteroaryl refers to a group in which at least one cyclic atom is a heteroatom and has aromaticity. Heteroatoms include, but are not limited to, N, P, O, and S.
  • ring-forming atoms refers to the number of atoms that form a ring when the ring is replaced by a substituent, and the atoms contained in the substituent are not included in the ring-forming atoms.
  • substituted or unsubstituted means that the defined group may or may not be substituted.
  • substituted it should be understood that it may be substituted by a group acceptable in the art, including but not limited to: any one or more combinations of C1-10 alkyl groups and halogens; when there are multiple combinations, they may be linked by forming a single bond; at the same time, if the defined group is substituted by a substituent, for example, an alkyl group with 1 to 5 carbon atoms substituted by at least one oxyacid group, wherein the number of carbon atoms does not include the carbon atoms in the substituent.
  • the single bonds connecting the substituents extend through the corresponding ring, indicating that the substituent can be attached to any position on the ring, for example...
  • the linking site of the substituent R3 to the benzene ring can be any substituted site on the benzene ring; furthermore, when the same substituent R3 appears multiple times on the same group (i.e., n3 is greater than or equal to 2), it can be independently selected from different groups, for example...
  • the benzene ring has 5 substitutable sites, meaning n3 can be 5.
  • Each R3 can be the same or different. When R3 is H, it means there are no substituents, and in this case, it is a phenyl group.
  • Room temperature generally refers to 4°C ⁇ 30°C, and more specifically 20 ⁇ 5°C.
  • the excessive energy level difference between the traditional perovskite material layer and the hole transport layer can lead to poor contact, material instability, and excessive defects, all of which reduce the photoelectric conversion efficiency and stability of solar cells, thus shortening their lifespan.
  • nickel oxide is used as the hole transport material.
  • nickel oxide is considered a semiconductor material with a wide bandgap and good conductivity, making it an ideal material for the hole transport layer and capable of efficiently transporting holes
  • the excessive energy level difference between the traditional perovskite material layer and nickel oxide coupled with the unavoidable high-valence nickel ions ( Ni3+ , Ni4+ , etc.) in nickel oxide, easily reacts with the perovskite material, accelerating its degradation. This significantly limits the stability of perovskite solar cells.
  • organic self-assembled molecules with oxyacid groups are often used to modify the hole transport layer to modulate its energy levels.
  • traditional organic self-assembled molecules with oxyacid groups have poor film-forming effects, limiting their ability to modulate energy bands and improve charge extraction capabilities.
  • Traditional techniques focus on controlling the framework structure of the self-assembled molecules connected to the oxyacid groups in an attempt to improve their ability to modulate energy bands and improve charge extraction capabilities, but the improvement is limited.
  • One embodiment of this application provides a perovskite solar cell, which includes a hole transport layer, a passivation layer and a perovskite material layer stacked together; the passivation layer contains an ammonium salt compound.
  • the anionic group includes the group formed after at least one hydroxyl group in at least one oxyacid group of the compound of formula (1) loses hydrogen, and the cationic group includes the group formed after the amino group in the compound of formula (2) gains a hydrogen atom:
  • L1 is selected from any one of alkyl groups substituted with at least one oxyacid group and oxyacid groups
  • each R1 and each R2 is independently selected from any one of H, alkyl, alkoxy, aryl groups with 6 to 13 substituted or unsubstituted cyclic atoms, and heteroaryl groups with 5 to 10 substituted or unsubstituted cyclic atoms.
  • Ar 1 is selected from substituted or unsubstituted aryl groups having 6 to 14 cyclic atoms, and L 2 is selected from alkylene groups having 1 to 3 carbon atoms;
  • n1 and n2 are each independently selected from any integer from 0 to 4.
  • an ammonium salt compound with a specific structure is set in the passivation layer between the hole transport layer and the perovskite.
  • the anionic group formed by the compound of formula (1) contains a carbazole structure, which itself has hole transport capability.
  • the presence of the carbazole group makes the compound prone to forming self-assembled micelles during film formation, which is not conducive to film spreading.
  • the presence of the -NH3 + group can destroy its self-assembly morphology, so that the ammonium salt compound can be better dispersed during film formation, forming a more uniform film layer.
  • the cation group formed by the compound of formula (2) also contains a specific aromatic group structure, which can generate a conjugation effect with the carbazole group in the anionic group, further improving the carrier extraction capability and/or carrier transport capability of the interface.
  • the side reactions between the hole transport layer and the perovskite material layer can be reduced, which can improve the photoelectric conversion efficiency and stability of the perovskite solar cell, thereby increasing the lifespan of the perovskite solar cell.
  • a molecule of compound (1) contains one or more oxyacid groups. When it contains multiple oxyacid groups, at least one hydroxyl group in at least one oxyacid group loses hydrogen. When M hydroxyl groups in multiple oxyacid groups in a molecule of compound (1) lose hydrogen (M is an integer greater than or equal to 2), then M molecules of compound (2) will each gain one hydrogen, forming M cation groups, which will form a salt with the anion formed by a molecule of compound (1). In other words, in a molecule of ammonium salt compound, the sum of the valence states of the anion formed by compound (1) and the cation formed by compound (2) is 0, that is, the ammonium salt compound is electrically neutral.
  • Ar 1 is selected from an aromatic group having 6 to 14 cyclic atoms or an aromatic group having 6 to 14 cyclic atoms substituted by a substituent, the substituent including any one of F, hydroxyl, alkyl having 1 to 3 carbon atoms, alkyl having 1 to 3 carbon atoms substituted by a fluorine atom, alkoxy having 1 to 3 carbon atoms, and alkoxy having 1 to 3 carbon atoms substituted by a fluorine atom.
  • Ar 1 By regulating the structure of Ar 1 to contain aromatic groups, it can be made to have strong aromaticity, that is, it can generate a strong conjugation effect with the carbazole group in the anionic group, while reducing steric hindrance and improving film quality.
  • the substituents include any one of F, hydroxyl, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, propyl, methoxy, ethoxy, and propoxy.
  • the number of ring atoms mentioned above is 6, 7, 8, 9, 10, 11, 12, 13 or 14.
  • Ar 1 is selected from an aromatic group having 6 to 10 cyclic atoms or an aromatic group having 6 to 10 cyclic atoms substituted by a substituent.
  • the structure of Ar 1 is as follows:
  • Each R3 is independently selected from any one of H, F, hydroxyl, alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted by fluorine atoms, alkoxy with 1 to 3 carbon atoms, and alkoxy with 1 to 3 carbon atoms substituted by fluorine atoms.
  • n3 is selected from any integer from 0 to 5. * represents the linkage site.
  • each R3 is independently selected from any one of H, F, hydroxyl, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, propyl, methoxy, ethoxy, and propoxy.
  • the structure of Ar 1 is as shown in any of the following configurations:
  • L1 is selected from alkyl groups having 1 to 5 carbon atoms that are substituted with at least one oxyacid group.
  • the values in “1 to 5” above include the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values in the embodiments and the following point values: 1, 2, 3, 4 or 5.
  • L1 is selected from alkyl groups having 1 to 4 carbon atoms that are substituted with at least one oxyacid group.
  • L1 alkyl chain length can improve carrier extraction performance while reducing steric hindrance and improving film quality.
  • the structure of L1 is: -AL11- * , where L11 is selected from alkylene groups having 1 to 5 carbon atoms, A- is a group formed by losing a hydrogen atom from a hydroxyl group in an oxyacid group, and * represents a linking site.
  • the oxyacid group is selected from any one of phosphonic acid groups, hypophosphite groups, sulfonic acid groups, carboxylic acid groups, boric acid groups, or silicate groups; thus, the structures of the groups formed after one hydroxyl group of the oxyacid group loses a hydrogen atom are shown below:
  • each R1 and each R2 is independently selected from: H, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and aryl groups having 6 to 10 cyclic atoms.
  • each R1 and each R2 may be the same or different.
  • each R1 and each R2 is independently selected from: H, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an aryl group having 6 to 8 cyclic atoms.
  • each R1 and each R2 is independently selected from any one of H, methyl, ethyl, propyl, methoxy, ethoxy, and phenyl.
  • ammonium salt compound includes the compound shown in formula (I):
  • L 11 is selected from alkylene groups having 1 to 4 carbon atoms.
  • L11 is selected from methylene, ethylene, propylene, and butylene.
  • the oxyacid group is selected from any one of phosphonic acid groups, hypophosphite groups, sulfonic acid groups, and carboxylic acid groups.
  • Adjusting the types of hydrochloric acid groups can further improve the stability of perovskite solar cells.
  • the ammonium salt compound includes at least one of the following (a) to (e):
  • R3 is selected from any one of H, F, hydroxyl, alkyl group having 1 to 3 carbon atoms, and alkyl group having 1 to 3 carbon atoms that has been replaced by fluorine atoms.
  • R3 is selected from any one of hydroxyl, F, or alkyl groups having 1 to 3 carbon atoms substituted with fluorine atoms.
  • R3 is selected from F, monofluoromethyl, difluoromethyl, and trifluoromethyl.
  • Introducing electronegative substituents such as hydroxyl, fluorine atom, or fluorine-containing alkyl groups into the cationic groups of ammonium salt compounds can further regulate the energy band at the interface and improve the interfacial carrier transport performance.
  • introducing fluorine atom or hydroxyl group into the anionic group formed in compound (1) introducing fluorine atom or hydroxyl group into the hydrophilic cationic part formed in compound (2) is more conducive to improving the wettability of the perovskite material precursor liquid on the film layer, thereby improving the film quality of the formed perovskite material layer and thus improving the stability of the battery.
  • the hole transport layer includes at least one of inorganic hole transport materials and organic hole transport materials.
  • the aforementioned inorganic hole transport materials and organic hole transport materials can be various hole transport materials commonly used in the field, including but not limited to at least one of the following materials and their derivatives: nickel oxide, zinc oxide, molybdenum oxide, 2,2',7,7'-tetratetra(N,N-p-methoxyaniline)-9,9'-spirodifluorene (Spiro-OMeTAD), and at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine].
  • the hole transport layer comprises nickel oxide.
  • oxyacid groups are formed into ammonium salts, and the structure of the cation portion is controlled.
  • it can block the side reactions between high-valence nickel ions (Ni 3+ , Ni 4+ , etc.) and perovskite. This improves the film-forming ability of the ammonium salt compound, reduces the energy level difference between it and the perovskite material layer, and further improves the carrier extraction and/or carrier transport capabilities at the interface, effectively improving the photoelectric conversion efficiency and stability of perovskite solar cells.
  • one side of the passivation layer is in direct contact with the perovskite material layer. Further, the other side of the passivation layer is in direct contact with the hole transport layer.
  • the thickness of the passivation layer is 0.1 nanometers (nm) to 5 nm; it can be selected as 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm; or any range of two values.
  • the thickness of the same passivation layer may be the same or different at different locations, and the thickness of the passivation layer mentioned above is the average thickness.
  • the thickness of the hole transport layer is 20nm to 100nm; it can be selected as 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm; or any range of two values.
  • the types of ammonium salt compounds in the passivation layer can be inferred from the raw materials used in the preparation, and can also be detected by reverse analysis of the passivation layer in the molded battery product:
  • the molar ratios of various characteristic functional groups of the ammonium salt compound can be further analyzed. By combining these analyses, the structure of the substances contained in the passivation layer can be obtained.
  • the perovskite material in the above-mentioned perovskite material layer can be any type of perovskite material in the art that is subjected to atmospheric pressure.
  • the chemical formula of the perovskite material satisfies ABX ⁇ 3 or A 2 CDX ⁇ 6 ; wherein, A is an inorganic cation or an organic cation or a mixture of the two, and can be at least one of formamidine ion (FA + ), methylammonium ion (MA + ) and Cs + ; B is an inorganic metal cation, and can be at least one of Pb 2+ ion and Sn 2+ ion; C is a monovalent metal cation, commonly Ag + ; D is a trivalent metal cation, and can be at least one of bismuth cation Bi 3+ , antimony cation Sb 3+ , and indium cation In 3+ ; X ⁇ is oxygen or a halogen
  • the thickness of the perovskite material layer is 500 nm to 800 nm; it can be selected as 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm; or any range of two values.
  • the perovskite solar cell further includes an electron transport layer, a first electrode, and a second electrode.
  • the first electrode is disposed on the side of the hole transport layer away from the perovskite material layer
  • the second electrode is disposed on the side of the perovskite material layer away from the hole transport layer.
  • the electron transport layer is disposed between the second electrode and the perovskite material layer.
  • An electron transport layer can enhance the efficiency of electron extraction and transport, thereby further improving the conversion efficiency of perovskite solar cells.
  • the thickness of the electron transport layer is 20 nm to 30 nm. It can be selected as 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm; or any range of two values.
  • the components in the electron transport layer described above may be electron transport materials commonly used in the art, and are not limited to being selected from at least one of the following: methyl [6,6]-phenyl-C61-butyrate (PC 61 BM), methyl [6,6]-phenyl-C71-butyrate (PC 71 BM), fullerene C60 (C 60 ), fullerene C70 (C 70 ), tin oxide, and zinc oxide (ZnO).
  • PC 61 BM methyl [6,6]-phenyl-C61-butyrate
  • PC 71 BM methyl [6,6]-phenyl-C71-butyrate
  • ZnO zinc oxide
  • the perovskite solar cell further includes a hole blocking layer disposed between the electron transport layer and the second electrode.
  • Hole blocking layers can block holes from passing through, significantly improving the electron collection rate at the interface, thereby reducing the probability of electrons and holes recombinating at the interface.
  • the thickness of the hole blocking layer is 5nm to 10nm; it can be selected as 5nm, 6nm, 7nm, 8nm, 9nm, 10nm; or any range of two values.
  • the hole blocking layer can be composed of hole blocking materials commonly used in the art, including, but not limited to, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and tin oxide.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • the first electrode and the second electrode may be made of various electrode materials available in the art at normal pressure, including at least one of transparent conductive oxides and conductive metals; specifically, they may be at least one of fluorine-doped tin dioxide (FTO), indium tin oxide (ITO), boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), Ag, Cu, C, Au, and Al.
  • FTO fluorine-doped tin dioxide
  • ITO indium tin oxide
  • BZO boron-doped zinc oxide
  • AZO aluminum zinc oxide
  • IZO indium zinc oxide
  • Ag Cu, C, Au, and Al.
  • Figure 1 is a perovskite solar cell 10 provided in one embodiment, including a first electrode 11, a hole transport layer 12, a passivation layer 13, a perovskite material layer 14, an electron transport layer 15, a hole blocking layer 16, and a second electrode 17, which are stacked in sequence.
  • the perovskite solar cell 10 described above can be a formal perovskite solar cell (n-i-p planar structure) or an inverted perovskite solar cell (p-i-n planar structure).
  • the thickness of the second electrode is 80 nm to 110 nm.
  • the above-mentioned perovskite cell 10 is an inverted perovskite cell.
  • the second electrode 17 is a transparent electrode, that is, the side of the second electrode is the light incident side
  • the above-mentioned perovskite cell 10 is a conventional perovskite cell.
  • the first electrode 11 is a transparent conductive electrode
  • the perovskite cell is an inverted perovskite cell.
  • the perovskite solar cell further includes a substrate disposed on the side of the transparent conductive electrode away from the other electrode.
  • the substrate structure can be made of rigid material or flexible material.
  • the substrate structure can be made of transparent glass. The material of the substrate structure can be specifically set as needed, and this application does not limit it.
  • a method for preparing the above-mentioned perovskite solar cell including the following step S10.
  • Step S10 Sequentially forming a hole transport layer and a perovskite material layer stacked together; prior to the step of forming the perovskite material layer, the following steps are also included:
  • a passivation layer is formed on the surface of the hole transport layer using raw materials including ammonium salt compounds.
  • the ammonium salt compound can be formed by first reacting the compound of formula (1) and the compound of formula (2) to form an ammonium salt compound, and then the solution of the ammonium salt compound can be coated on the surface of the hole transport layer to form a passivation layer; or the raw materials including the compound of formula (1) and the compound of formula (2) can be directly mixed and coated on the surface of the hole transport layer, and the salt is formed directly during the drying process to form a passivation layer on the surface of the hole transport layer.
  • the raw materials for preparing the hole transport layer including compounds of formula (1) and formula (2), are mixed and coated on the surface of the hole transport layer, and then annealed to form a passivation layer.
  • the mixing step is carried out in a solvent; further, the solvent includes a small molecule alcohol solvent, which may be at least one of isopropanol, propanol and ethanol.
  • the raw materials for preparation including compounds of formula (1) and (2), are mixed in a solvent to form a mixed solvent; further, the total mass concentration of compounds of formula (1) and (2) in the mixed solvent is 0.5 mg/mL to 2 mg/mL.
  • the mass ratio of compound (1) to compound (2) is 1:(0.1 to 10).
  • the annealing temperature is 100°C ⁇ 150°C and the time is 5min ⁇ 20min.
  • the compound of formula (1) includes at least one of MeO-4PACz ([4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid), MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid), MeO-3PACz ([3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid), MeO-4CACz ([4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]carboxylic acid), and MeO-4SACz ([4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]sulfonic acid).
  • MeO-4PACz [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid
  • MeO-2PACz [2-(3,6-dime
  • the compound of formula (2) includes at least one of PEAI (phenylethylamine), mF-PEAI (m-fluorophenylethylamine), pF-PEAI (p-fluorophenylethylamine), oF-PEAI (o-fluorophenylethylamine), mF-PMAI (m-fluorophenylethylamine), pF-PMAI (p-fluorophenylethylamine), oF-PMAI (o-fluorophenylethylamine), m-fluorophenylacetylamine, p-fluorophenylacetylamine, o-fluorophenylacetylamine, mOH-PEAI (m-hydroxyphenylethylamine), pOH-PEAI (p-hydroxyphenylethylamine), oOH-PEAI (o-hydroxyphenylethylamine), mMe-PEAI (m-methylphen
  • the other functional layers of the perovskite solar cell described above can be prepared using conventional methods in the art.
  • the preparation process of the hole transport layer, electron transport layer, hole blocking layer, etc. can be carried out using commonly used methods in the art, including solution methods and solid deposition methods.
  • Solution methods include any one of spin coating, spraying, blade coating, and slot coating.
  • Solid deposition methods include any one of vacuum evaporation, sputtering deposition, plasma deposition, and ion deposition.
  • the perovskite material layer described above can be obtained using conventional preparation methods in the art, such as the anti-solvent method; the specific steps are as follows:
  • a perovskite precursor solution was spin-coated onto the substrate surface, and the film was etched using an anti-solvent method, followed by annealing to prepare a perovskite material layer.
  • the annealing temperature is 100°C to 150°C, and the time is 10 minutes to 30 minutes.
  • the solvent in the perovskite precursor solution can be one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and 2-methoxyethanol, with a concentration of 1.0 mol/L to 2.0 mol/L.
  • the antisolvent can be selected from at least one of chlorobenzene, anisole, and diethyl ether.
  • a photovoltaic module which includes the perovskite cell described above.
  • the perovskite solar cells mentioned above have high light conversion efficiency and good stability, which can improve the efficiency of photovoltaic modules.
  • the aforementioned photovoltaic module includes one or more perovskite cells, which can be selected according to specific application scenarios; furthermore, the aforementioned photovoltaic module includes multiple perovskite cells, which are connected in series or in parallel to form a solar cell.
  • the photovoltaic module further includes a photovoltaic glass layer, an adhesive layer, and a backsheet.
  • the solar cell has an adhesive layer on each of its two surfaces.
  • a backsheet is provided on the surface of one adhesive layer away from the solar cell, and a photovoltaic glass layer is provided on the surface of the other adhesive layer away from the solar cell.
  • the photovoltaic glass layer and backsheet are used to protect the perovskite cells, providing sealing, insulation, and waterproofing; the adhesive layer serves to bond the photovoltaic glass layer to the cells and the backsheet to the cells.
  • the photovoltaic glass layer is made of tempered glass
  • the backsheet is made of TPT (polyvinyl fluoride) or TPE (thermoplastic elastomer)
  • the adhesive layer is made of EVA (polyethylene-polyvinyl acetate copolymer).
  • the aforementioned photovoltaic modules also include junction boxes and outer frames.
  • junction boxes are used to protect the entire photovoltaic module's power generation system. They are essentially a current transfer station. When a cell short-circuits, the junction box will automatically disconnect the short-circuited cell string.
  • the outer frame serves to support and protect the entire photovoltaic module.
  • the frame can be made of aluminum alloy, which has excellent strength and corrosion resistance.
  • silicone is used to bond and seal the connections between the frame and other parts of the photovoltaic module.
  • the photovoltaic module can convert solar energy into electrical energy, which can then be stored in batteries or used to power loads.
  • the photovoltaic module is a solar panel.
  • a photovoltaic system including the photovoltaic module described above.
  • the photovoltaic system utilizes the photovoltaic effect of the perovskite cells in the photovoltaic modules to directly convert solar radiation energy into electrical energy with high efficiency; furthermore, the photovoltaic system is a photovoltaic power generation system.
  • Photovoltaic modules are the core component of a photovoltaic power generation system.
  • the aforementioned photovoltaic system includes one or more photovoltaic modules, which can be selected according to specific application scenarios. Furthermore, when the aforementioned photovoltaic system includes multiple photovoltaic modules, the multiple photovoltaic modules form a photovoltaic array.
  • the aforementioned photovoltaic system can be a stand-alone photovoltaic power generation system or a grid-connected photovoltaic power generation system.
  • An independent photovoltaic (PV) power generation system includes a PV array, battery bank, charge controller, power electronic converter (inverter), and load. Its working principle is that solar radiation energy is first converted into electrical energy by the PV array, then converted by the power electronic converter to supply power to the load. Simultaneously, excess electrical energy is stored as chemical energy in an energy storage device after passing through the charge controller. Thus, when sunlight is insufficient, the energy stored in the battery can be converted into 220V, 50Hz AC power by the power electronic inverter, filter, and power frequency transformer to supply AC loads.
  • a grid-connected photovoltaic (PV) power generation system includes a photovoltaic array, a high-frequency DC/DC boost circuit, a power electronic converter (inverter), and system monitoring. Its working principle is that solar radiation energy is converted by the photovoltaic array, then converted into high-voltage DC by a high-frequency DC converter, and finally inverted by the power electronic inverter to output a sinusoidal alternating current to the grid that is in phase with the grid voltage.
  • the two photovoltaic power generation systems mentioned above each have their own characteristics and can be selected according to the specific application scenario.
  • an electrical device including at least one of the above-mentioned perovskite cells and photovoltaic modules.
  • the aforementioned electrical devices may include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc.
  • the mobile device may be a mobile phone or a laptop computer, etc.
  • electric vehicles include, but are not limited to: pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.
  • a power generation device including the above-mentioned perovskite battery or photovoltaic module.
  • the aforementioned power generation devices may include, but are not limited to, solar power generator sets, etc.
  • a nickel oxide nanoparticle solution with a concentration of 10 mg/mL was spin-coated onto an FTO glass substrate using a spin coater, and then annealed on a hot plate at 150°C for 15 min to form a hole transport layer with a thickness of 60 nm.
  • the compound (MeO-4PACz) of formula (1) and the compound (mF-PEAI) of formula (2) are weighed in a glass bottle at a mass ratio of 1:1. Isopropanol solvent is added to prepare a solution with a concentration of 1 mg/mL. After thorough stirring and dissolution, the solution is filtered to obtain a clear solution. Then, in a nitrogen atmosphere, the clear solution is spin-coated on the surface of the hole transport layer. The solution is then annealed at 100°C for 10 min to form a passivation layer with an average thickness of about 1 nm. The thickness is denoted as X.
  • each of the above functional layers can be tested using any one of white light interferometer, profilometer, or optical/electrical microscope.
  • the thickness of the passivation layer is tested using an electrical microscope, and samples are taken from multiple locations of the passivation layer to obtain the average value.
  • the newly prepared perovskite solar cell was subjected to photoelectric conversion efficiency testing to obtain its initial photoelectric conversion efficiency PCE(0). Then, it was placed in an unsealed nitrogen environment and heated at 85°C in the dark for 1000 hours. Its photoelectric conversion efficiency PCE(1000) was then tested again.
  • test fixture containing the perovskite solar cell on the sample holder, ensuring it is within the measurement plane and that the cell is located at the center of the solar simulator's emitted light spot (or that the photovoltaic cell normal is parallel to the center line of the emitted beam from the solar simulator's light source).
  • Pin , Pout , Vmpp , Jmpp , Voc , Jsc , and FF represent: incident light power (100mW/ cm2 ), working output power of the tested battery, voltage at the maximum power point of the tested battery, current at the maximum power point of the tested battery, open circuit voltage, short circuit current, and fill factor, respectively.
  • Examples 2 to 4 are basically the same as Example 1, except that in step (1) the preparation of perovskite battery, the types of compounds of formula (1) and/or formula (2) are different from those in Example 1. For specific differences, please refer to the relevant parameters in Table 1.
  • Examples 5 to 10 are basically the same as Example 1, except that in step (1) the preparation of perovskite battery, the types of compounds of formula (1) and/or formula (2) are different from those in Example 1. For specific differences, please refer to the relevant parameters in Table 1.
  • Comparative Example 1 is basically the same as Example 1, except that: in step (1) the perovskite cell is not provided with a passivation layer.
  • Comparative Example 2 is basically the same as Example 1, except that in step (1) of preparing the perovskite solar cell, the passivation layer is prepared as follows:
  • the compound (MeO-4PACz) of formula (1) was placed in a glass bottle, and isopropanol solvent was added to prepare a solution with a concentration of 1 mg/mL. After thorough stirring and dissolution, the solution was filtered to obtain a clear solution. Then, in a nitrogen atmosphere, the clear solution was spin-coated onto the surface of the hole transport layer, and then annealed at 100°C for 10 min to form a passivation layer with an average thickness of about 1 nm.
  • Comparative Examples 3 and 4 are basically the same as Example 1, except that the types of compounds of formula (1) and/or formula (2) are different from those in Example 1. For specific differences, please refer to the relevant parameters in Table 1.
  • Comparative Examples 5 and 6 are basically the same as Comparative Example 2, except that in Comparative Examples 5 and 6, compound (MeO-4PACz) of formula (1) is replaced with MeO-4CACz or MeO-4SACz respectively.
  • MeO-4PACz is [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid
  • MeO-2PACz is [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethylphosphonic acid
  • MeO-3PACz is [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid
  • MeO-4SACz is [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]sulfonic acid
  • Me “O-4CACz” represents [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]carboxylic acid
  • mF-PEAI represents m-fluoroanisidine
  • pF-PEAI represents p-fluoroanisidine
  • PEAI represents phenyl
  • Comparative analysis of the test results of Examples 1-10 and Comparative Examples 1-6 in the table above shows that when using the ammonium salt compound with the specific structure of this application to prepare perovskite solar cells, it can effectively improve the photoelectric conversion efficiency of perovskite while also improving its stability. Furthermore, when used as a passivation layer material, even when nickel oxide is used as the hole transport layer material, it can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell. Further, as shown in Examples 1-3 and 4, further controlling the types of substituents on the ring structure of the anionic group in the ammonium salt compound can further improve the photoelectric conversion efficiency and stability of the perovskite solar cell.
  • the aromatic group structure in the cationic group formed by the compound of formula (2) contains more ⁇ electrons in its conjugated system, and the stronger the conjugation effect with the carbazole group in the anionic group, thereby further improving the carrier extraction capacity and/or carrier transport capacity of the interface.

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Abstract

本申请涉及一种钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置，该钙钛矿电池包括层叠设置的空穴传输层、钝化层和钙钛矿材料层；所述钝化层含有铵盐化合物；在所述铵盐化合物中，阴离子基团包括式(1)化合物中的至少一个含氧酸基团中的至少一个羟基失去氢后形成的基团，阳离子基团包括式(2)化合物中氨基得到一个氢后形成的基团。该钙钛矿电池的光电转化效率及其稳定性优异。

Description

钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置
相关申请
本申请要求2024年05月20日申请的，申请号为2024106306743，名称为“钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置”，以及2024年05月14日申请的，申请号为2024105991983，名称为“钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及电池技术领域，特别涉及一种钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置。
背景技术
钙钛矿太阳能电池具有优异的光电特性、光吸收系数高、载流子寿命长及扩散长度较长等诸多特点，已成为下一代光伏技术研究的重点方向。
然而，传统的钙钛矿材料层和空穴传输层材料层制得的太阳能电池的光电转化效率及其稳定性非常受限，从而降低其寿命，使得传统的钙钛矿太阳能电池的性能难以满足越来越高的应用要求。
因此，传统技术仍有待改进。
发明内容
基于此，有必要提供一种钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置，旨在提高钙钛矿电池的光电转化效率及其稳定性。
本申请是通过如下的技术方案实现的。
本申请的第一方面，提供一种钙钛矿电池，所述钙钛矿电池包括层叠设置的空穴传输层、钝化层和钙钛矿材料层；所述钝化层含有铵盐化合物；
在所述铵盐化合物中，阴离子基团包括式(1)化合物中的至少一个含氧酸基团中的至少一个羟基失去氢后形成的基团，阳离子基团包括式(2)化合物中氨基得到一个氢后形成的基团：
其中，L1选自：被至少一个含氧酸基团取代的烷基和含氧酸基团中的任意一种，各R1和各R2各自独立地选自：H、烷基、烷氧基、取代或未被取代的成环原子数为6～13的芳基、取代或未被取代的成环原子数为5～10的杂芳基中的任意一种；
Ar1选自取代或未取代的成环原子数为6～14的芳香基，L2选自碳原子数为1～3的亚烷基；
n1和n2各自独立地选自0～4任一整数。
上述钙钛矿电池中，在空穴传输层和钙钛矿之间的钝化层中设置特定结构的铵盐化合物，铵盐化合物中，式(1)化合物形成的阴离子基团含有咔唑类结构，其本身就具有空穴传输能力，但咔唑基团的存在使化合物在成膜时易形成自组装胶束，不利于铺展成膜，与式(2)化合物形成的阳离子协同作用后，-NH3 +基团的存在可破坏其自组装形态，使铵盐化合物在成膜过程中能更好地分散，形成较均匀的膜层，且能降低空穴传输层与钙钛矿材料层之间发生副反应的几率，还能起到调节能带、提高电荷抽取能力的作用；同时，式(2)化合物形成的阳离子基团还含有特定的芳香基结构，可与阴离子基团中的咔唑基团产生共轭作用，进一步提高界面的载流子提取能力和/或载流子传输能力。如此，可以在降低空穴传输层和钙钛矿材料层之间的能级差的同时，降低空穴传输层和钙钛矿材料层之间的副反应，可以提高钙钛矿电池的光电转化效率及其稳定性，从而可以提高钙钛矿电池的寿命。
可理解：一分子式(1)化合物中含有一个或多个含氧酸基团，当其含有多个含氧酸基团时，其中至少一个含氧酸基团中的至少一个羟基失去氢，当一分子式(1)化合物中有多个含氧酸基团中的M个羟基失去氢时(M取大于等于2的整数)，则对应有M个式(2)化合物分子均个得到一个氢，形成M个阳离子基团，与一分子式(1)化合物形成的阴离子成盐；换言之，一分子铵盐化合物中，式(1)化合物形成的阴离子与式(2)化合物形成的阳离子的价态和为0，即铵盐化合物为电中性。
在其中一些实施例中，Ar1选自成环原子数为6～14的芳香基或被取代基取代的成环原子数为6～14的芳香基，取代基包括F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种。
调控Ar1的结构为含芳香基的结构，使其具有较强的芳香性，即能与阴离子基团中的咔唑基团产生较强的共轭作用的同时，降低空间位阻，提高成膜质量。
在其中一些实施例中，Ar1的结构如下所示：
各R3分别独立地选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种，n3选自0～5任一整数，*代表连接位点。
需要说明的是：中，n3选自0时，说明苯环上没有取代基，结构为苯基。
在其中一些实施例中，所述铵盐化合物满足如下(1)～(2)中的一个或两个条件：
(1)L1选自被至少一个含氧酸基团取代的碳原子数为1～5的烷基；
(2)各R1和各R2各自独立地选自：H、碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、成环原子数为6～10的芳基。
在其中一些实施例中，所述铵盐化合物包括式(Ⅰ)所示化合物：
其中，L11选自碳原子数为1～5的亚烷基，A-为所述含氧酸基团中的一个羟基失去一个氢后形成的基团。
在其中一些实施例中，所述含氧酸基团选自膦酸基团、次磷酸基团、磺酸基团、羧酸基团、硼酸基团或硅酸基团中的任意一种。
在其中一些实施例中，所述铵盐化合物包括如下(a)～(e)中的至少一种：
L11选自碳原子数为1～5的亚烷基，R3选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
可选地，R3选自F、羟基、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
在铵盐化合物的阳离子基团中引入电负性强的取代基：羟基、氟原子或含氟原子的烷基，可进一步调节界面处能带、提高界面载流子传输性能，且相对于在式(1)化合物形成的阴离子基团引入氟原子或羟基，在式(2)化合物形成的具有亲水性的阳离子部分引入氟原子或羟基，更有利于提高钙钛矿材料的前驱液在膜层上的浸润性，从而提高形成的钙钛矿材料层的膜层质量，进而提高电池的稳定性。
在其中一些实施例中，所述式(1)化合物包括[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基膦酸、[3-(3,6-二甲氧基-9H-咔唑-9-基)丙基]膦酸、[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]羧酸和[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]磺酸中的一种或几种；所述式(2)化合物包括间氟苯甲胺、对氟苯甲胺、邻氟苯甲胺、间氟苯乙胺、对氟苯乙胺、邻氟苯乙胺、间氟苯丙胺、对氟苯丙胺、邻氟苯丙胺、间三氟甲基苯乙胺、对三氟甲基苯乙胺、邻三氟甲基苯乙胺、对甲基苯乙胺、间甲基苯乙胺、邻甲基苯乙胺、对羟基苯乙胺、间羟基苯乙胺和邻羟基苯乙胺中的一种或几种。
上述式(1)化合物和式(2)化合物形成的铵盐化合物能在成膜过程中更好地分散，形成较均匀的膜层，起到调节能带、提高电荷抽取能力的作用；此外，还可以在降低空穴传输层和钙钛矿材料层之间的能级差的同时，降低空穴传输层和钙钛矿材料层之间的副反应，可以提高钙钛矿电池的光电转化效率及其稳定性，从而可以提高钙钛矿电池的寿命。
在其中一些实施例中，所述空穴传输层包括无机空穴传输材料和有机空穴传输材料中的至少一种。
在其中一些实施例中，所述空穴传输层包括氧化镍。
本申请中使含氧酸基团形成铵盐，并调控阳离子部分的结构，在修饰含氧化镍的空穴传输层时，能够阻挡高价镍离子(Ni3+、Ni4+等)与钙钛矿发生副反应，使铵盐化合物的成膜能力提高、降低其与钙钛矿材料层的能级差的同时，进一步提高界面的载流子提取能力和/或载流子传输能力，有效提高钙钛矿电池的光电转化效率及其稳定性。
在其中一些实施例中，所述钝化层满足如下条件(1)和(2)中的一种或两种：
(1)所述钝化层的一侧表面与所述钙钛矿材料层直接接触，另一侧表面与所述空穴传输层直接接触；
(2)所述钝化层的厚度为0.1nm～5nm。
在其中一些实施例中，所述钙钛矿电池还包括电子传输层、第一电极和第二电极，所述第一电极设于所述空穴传输层远离所述钙钛矿材料层的一侧，所述第二电极设于所述钙钛矿材料层远离所述空穴传输层的一侧，所述电子传输层设于所述第二电极和所述钙钛矿材料层之间。
电子传输层可以增强电子的提取与传输效率，进一步提高钙钛矿电池的转化效率。
在其中一些实施例中，所述钙钛矿电池还包括空穴阻挡层，所述空穴阻挡层设于所述电子传输层和所述第二电极之间。
空穴阻挡层可阻挡空穴通过，显著提高界面处的电子收集率，从而降低电子和空穴在界面处复合的几率。
在其中一些实施例中，所述钙钛矿电池满足如下条件中的一种或几种：
(1)所述空穴传输层的厚度为20nm～100nm；
(2)所述钙钛矿材料层的厚度为500nm～800nm；
(3)所述电子传输层的厚度为20nm～30nm；
(4)所述空穴阻挡层的厚度为5nm～10nm。
本申请的第二方面，提供第一方面的钙钛矿电池的制备方法，包括如下步骤：
依次形成层叠设置的所述空穴传输层和所述钙钛矿材料层；且在形成所述钙钛矿材料层的步骤之前，还包括如下步骤：
采用包括所述铵盐化合物的制备原料在所述空穴传输层表面形成所述钝化层。
本申请第三方面，提供一种光伏组件，包括第一方面的钙钛矿电池。
本申请的第四方面，提供一种光伏系统，包括第三方面的光伏组件。
本申请的第五方面，提供一种用电装置，包括第一方面的钙钛矿电池或第三方面的光伏组件。
本申请的第六方面，提供一种发电装置，包括第一方面的钙钛矿电池或第三方面的光伏组件。
附图说明
为了更清楚地说明本申请的技术方案，下面将对本申请中所使用的附图作简单介绍。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。
通过阅读对下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本申请的限制。而且在全部附图中，用相同的附图标号表示相同的部件。在附图中：
图1为本申请一实施方式的钙钛矿电池的示意图。
附图标记说明：
10、钙钛矿电池；11、第一电极；12、空穴传输层；13、钝化层；14、钙钛矿材
料层；15、电子传输层；16、空穴阻挡层；17、第二电极。
具体实施方式
下面将结合附图对本申请技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本申请的技术方案，因此只作为示例，而不能以此来限制本申请的保护范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请的说明书和权利要求书及上述附图说明中的术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的包含。
在本申请实施例的描述中，技术术语“第一”“第二”等仅用于区别不同对象，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量、特定顺序或主次关系。在本申请实施例的描述中，“多个”的含义是两个以上，除非另有明确具体的限定。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
在本申请实施例的描述中，术语“多个”指的是两个以上(包括两个)，同理，“多组”指的是两组以上(包括两组)，“多片”指的是两片以上(包括两片)。
在本申请实施例的描述中，技术术语“中心”“纵向”“横向”“长度”“宽度”“厚度”“上”“下”“前”“后”“左”“右”“竖直”“水平”“顶”“底”“内”“外”“顺时针”“逆时针”“轴向”“径向”“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请实施例和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请实施例的限制。
在本申请实施例的描述中，除非另有明确的规定和限定，技术术语“安装”“相连”“连接”“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；也可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本申请实施例中的具体含义。
在本申请中，在本申请中，术语“烷基”指的是烷烃失去一个氢后形成的基团，例如甲烷失去一个氢后形成甲基；术语“烷烃亚基或亚烷基”指的是烷烃失去两个氢后形成的基团，例如甲烷失去两个氢后形成亚甲基。
“芳基”指具有芳香性的烃基，包括单环芳基及稠环芳基。稠环芳基是指两个或多个单芳香环通过共用的两个相邻的环原子连接后形成的基团，即稠环。进一步地：芳香基的π电子应满足4n+2(休克尔规则)。
“杂芳基”指至少一个成环原子是杂原子且具有芳香性的基团。杂原子包括但不限于N、P、O、S。
在本申请中，“成环原子数”表示键合成环状的原子的数目，该环被取代基所取代时，取代基所包含的原子不包括在成环原子内。关于以下所述的“环原子数”，在没有特别说明的条件下也是同样的，例如，苯环的环原子数为6，萘环的环原子数为10，噻吩的环原子数为5。
本申请中，“取代或未取代”表示所定义的基团可以被取代，也可以不被取代。当所定义的基团被取代时，应理解为任选被本领域可接受的基团所取代，包括但不限于：C1-10烷基、卤素中的任意一种或多种的组合；多种组合时，可通过形成单键连接；同时，若所定义的基团被取代基取代时，例如被至少一个含氧酸基团取代的碳原子数为1～5的烷基，其中碳原子数不包括取代基中的碳原子。
本申请中，基团中未指明连接位点时，表示基团中任选可连接位点作为连接位点。
本申请中，取代基相连的单键贯穿相应的环，表示该取代基可与环的任选位置连接，例如中，该取代基团R3与苯环的连接位点可以是该苯环上任一可取代位点；进一步地，同一基团上的同一取代基R3多次出现时(即n3大于等于2)，可独立选自不同基团，例如中，苯环的可取代位点有5个，即n3可为5，各个R3可相同或不同，R3取H时，代表不存在取代基，此时即为苯基。
在本申请中，若无特殊说明，制备步骤可在室温下进行，“室温”一般指4℃～30℃，进一步指20±5℃。
传统的钙钛矿材料层和空穴传输层材料层之间能级差过大，导致接触不良、或材料本身不稳定且缺陷过多，均会降低太阳能电池的光电转化效率及其稳定性，从而降低其寿命。尤其是采用氧化镍作为空穴传输材料时，虽然氧化镍被认为是一种具有宽带隙和良好导电性的半导体材料，是空穴传输层的理想材料，能够高效地传输空穴，但传统的钙钛矿材料层和氧化镍之间的能级差过大，且氧化镍中存在的不可避免的高价镍离子Ni3+、Ni4+等易与钙钛矿材料产生副反应，加速钙钛矿材料降解，如此，大大限制了钙钛矿电池的稳定性。
传统技术中，常采用具有含氧酸基团的有机自组装分子修饰空穴传输层以调节其能级。然而，研究发现：传统的含氧酸基团的有机自组装分子的成膜效果较差，限制了其调节能带、提高电荷抽取能力的作用，传统技术中聚焦于调控自组装分子中与含氧酸基团相连的骨架结构，以尝试提高其调节能带、提高电荷抽取能力的作用，但提升有限。
经过大量实验研究，获得本申请中能提高钙钛矿电池的光电转化效率及其稳定性的技术方案。
本申请一实施方式提供了一种钙钛矿电池，该钙钛矿电池包括层叠设置的空穴传输层、钝化层和钙钛矿材料层；钝化层含有铵盐化合物。
在铵盐化合物中，阴离子基团包括式(1)化合物中的至少一个含氧酸基团中的至少一个羟基失去氢后形成的基团，阳离子基团包括式(2)化合物中氨基得到一个氢后形成的基团：
其中，L1选自：被至少一个含氧酸基团取代的烷基和含氧酸基团中的任意一种，各R1和各R2各自独立地选自：H、烷基、烷氧基、取代或未被取代的成环原子数为6～13的芳基、取代或未被取代的成环原子数为5～10的杂芳基中的任意一种；
Ar1选自取代或未取代的成环原子数为6～14的芳香基，L2选自碳原子数为1～3的亚烷基；
n1和n2各自独立地选自0～4任一整数。
上述钙钛矿电池中，在空穴传输层和钙钛矿之间的钝化层中设置特定结构的铵盐化合物，铵盐化合物中，式(1)化合物形成的阴离子基团含有咔唑类结构，其本身就具有空穴传输能力，但咔唑基团的存在使化合物在成膜时易形成自组装胶束，不利于铺展成膜，与式(2)化合物形成的阳离子协同作用后，-NH3 +基团的存在可破坏其自组装形态，使铵盐化合物在成膜过程中能更好地分散，形成较均匀的膜层，且能降低空穴传输层与钙钛矿材料层之间发生副反应的几率，还能起到调节能带、提高电荷抽取能力的作用；同时，式(2)化合物形成的阳离子基团还含有特定的芳香基结构，可与阴离子基团中的咔唑基团产生共轭作用，进一步提高界面的载流子提取能力和/或载流子传输能力。如此，可以在降低空穴传输层和钙钛矿材料层之间的能级差的同时，降低空穴传输层和钙钛矿材料层之间的副反应，可以提高钙钛矿电池的光电转化效率及其稳定性，从而可以提高钙钛矿电池的寿命。
可理解：一分子式(1)化合物中含有一个或多个含氧酸基团，当其含有多个含氧酸基团时，其中至少一个含氧酸基团中的至少一个羟基失去氢，当一分子式(1)化合物中有多个含氧酸基团中的M个羟基失去氢时(M取大于等于2的整数)，则对应有M个式(2)化合物分子均个得到一个氢，形成M个阳离子基团，与一分子式(1)化合物形成的阴离子成盐；换言之，一分子铵盐化合物中，式(1)化合物形成的阴离子与式(2)化合物形成的阳离子的价态和为0，即铵盐化合物为电中性。
在其中一些实施例中，Ar1选自成环原子数为6～14的芳香基或被取代基取代的成环原子数为6～14的芳香基，取代基包括F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种。
调控Ar1的结构为含芳香基的结构，使其具有较强的芳香性，即能与阴离子基团中的咔唑基团产生较强的共轭作用的同时，降低空间位阻，提高成膜质量。
在其中一些实施例中，取代基包括F、羟基、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、丙基、甲氧基、乙氧基、丙氧基中的任意一种。
上述环原子数为6、7、8、9、10、11、12、13或14。
在其中一些实施例中，Ar1选自成环原子数为6～10的芳香基或被取代基取代的成环原子数为6～10的芳香基。
在其中一些实施例中，Ar1的结构如下所示：
各R3分别独立地选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种，n3选自0～5任一整数，*代表连接位点。
在其中一些实施例中，各R3分别独立地选自H、F、羟基、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、丙基、甲氧基、乙氧基、丙氧基中的任意一种。
在其中一些实施例中，Ar1的结构如下任意结构所示：
在其中一些实施例中，L1选自被至少一个含氧酸基团取代的碳原子数为1～5的烷基。
上述“1～5”中，取值包括该范围的最小值及最大值，以及这种最小值与最大值之间的每一个值，具体示例包括但不限于实施例中的点值及以下点值：1、2、3、4或5。
在其中一些实施例中，L1选自被至少一个含氧酸基团取代的碳原子数为1～4的烷基。
进一步调控L1烷基链的长度，在提高载流子提取性能的同时，降低位阻作用，提高成膜质量。
在其中一些实施例中，L1的结构为：-A-L11-＊，其中，L11选自碳原子数为1～5的亚烷基，A-为含氧酸基团中的一个羟基失去一个氢后形成的基团，*代表连接位点。
在其中一些实施例中，氧酸基团选自膦酸基团、次磷酸基团、磺酸基团、羧酸基团、硼酸基团或硅酸基团中的任意一种；由此，氧酸基团中的一个羟基失去一个氢后形成的基团的结构分别如下所示：
在其中一些实施例中，各R1和各R2各自独立地选自：H、碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、成环原子数为6～10的芳基。
在其中一些实施例中，各R1和各R2相同或不同。
在其中一些实施例中，各R1和各R2各自独立地选自：H、碳原子数为1～3的烷基、碳原子数为1～3的烷氧基、成环原子数为6～8的芳基。
在其中一些实施例中，各R1和各R2各自独立地选自：H、甲基、乙基、丙基、甲氧基、乙氧基、苯基中的任意一种。
在其中一些实施例中，铵盐化合物包括式(Ⅰ)所示化合物：
在其中一些实施例中，L11选自碳原子数为1～4的亚烷基。
在其中一些实施例中，L11选自亚甲基、亚乙基、亚丙基、亚丁基中的任意一种。
在其中一些实施例中，含氧酸基团选自膦酸基团、次磷酸基团、磺酸基团、羧酸基团的任意一种。
调控含盐酸基团的种类，可以进一步提高钙钛矿电池的稳定性。
在其中一些实施例中，铵盐化合物包括如下(a)～(e)中的至少一种：
R3选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
可选地，R3选自羟基、F、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
在其中一些实施例中，R3选自F、一氟甲基、二氟甲基、三氟甲基中的任意一种。
在铵盐化合物的阳离子基团中引入电负性强的取代基：羟基、氟原子或含氟原子的烷基，可进一步调节界面处能带、提高界面载流子传输性能，且相对于在式(1)化合物形成的阴离子基团引入氟原子或羟基，在式(2)化合物形成的具有亲水性的阳离子部分引入氟原子或羟基，更有利于提高钙钛矿材料的前驱液在膜层上的浸润性，从而提高形成的钙钛矿材料层的膜层质量，进而提高电池的稳定性。
在其中一些实施例中，空穴传输层包括无机空穴传输材料和有机空穴传输材料中的至少一种。
上述无机空穴传输材料和有机空穴传输材料可以是本领域中常用的各类空穴传输材料，包括但不限于以下材料及其衍生物中的至少一种：氧化镍、氧化锌、氧化钼、2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴(Spiro-OMeTAD)，聚[双(4-苯基)(2,4,6-三甲基苯基)胺]中的至少一种。
在其中一些实施例中，空穴传输层包括氧化镍。
本申请中使含氧酸基团形成铵盐，并调控阳离子部分的结构，在修饰含氧化镍的空穴传输层时，能够阻挡高价镍离子(Ni3+、Ni4+等)与钙钛矿发生副反应，使铵盐化合物的成膜能力提高、降低其与钙钛矿材料层的能级差的同时，进一步提高界面的载流子提取能力和/或载流子传输能力，有效提高钙钛矿电池的光电转化效率及其稳定性。
在其中一些实施例中，钝化层的一侧表面与钙钛矿材料层直接接触。进一步地，钝化层的另一侧表面与空穴传输层直接接触。
在其中一些实施例中，钝化层的厚度为0.1纳米(nm)～5nm；可选为0.1nm、0.2nm、0.3nm、0.4nm、0.5nm、0.6nm、0.7nm、0.8nm、0.9nm、1nm、1.5nm、2nm、2.5nm、3nm、3.5nm、4nm、4.5nm、5nm；或任意两个数值组成的范围。
需要说明的是，同一钝化层的各处厚度可相同或不同，上述钝化层的厚度为平均厚度。
在其中一些实施例中，空穴传输层的厚度为20nm～100nm；可选为20nm、25nm、30nm、35nm、40nm、45nm、50nm、55nm、60nm、65nm、70nm、75nm、80nm、85nm、90nm、95nm、100nm；或任意两个数值组成的范围。
可理解，在制备过程中，钝化层中的铵盐化合物种类可通过所用制备原料推知，同时也可从成型电池产品中的钝化层进行反向检测：
通过拆解电池，使钝化层暴露，然后对钝化层界面使用SEM-EDS电镜表征手段，可以探测含氧酸官能团的特定元素存在情况(如磷、硫、硼等)；并使用FTIR红外光谱仪，可以确定其取代基(R1、R2等)的官能团的种类；同时将钝化层溶解，使用NMR进行测试获得氢谱图，可以分析确定铵盐化合物碳氢骨架的结构以及连接基团(L2、L11等)的碳链长度，同时根据氢谱中特征峰的面积积分值，可以进一步分析出铵盐化合物各个特征官能团的摩尔比，综合即可获得钝化层中所含物质的结构。
需要说明的是，上述只是对反向测试进行举例说明，也可以采用本领域其他公知可行的测试分析方法进行。
上述钙钛矿材料层中的钙钛矿材料可以是本领域常压的各类钙钛矿材料。在其中一些实施例中，钙钛矿材料的化学式满足ABX`3或A2CDX`6；其中，A为无机阳离子或有机阳离子或这两种的混合物，可以是甲脒离子(FA+)、甲铵离子(MA+)和Cs+中的至少一种；B为无机金属阳离子，可以为Pb2+离子、Sn2+离子中的至少一种；C为一价金属阳离子，常见为Ag+；D为三价金属阳离子，可以为铋阳离子Bi3+、锑阳离子Sb3+、以及铟阳离子In3+中的至少一种；X`为氧或卤族元素或伪卤素元素，可以为Cl-、Br-和I-的至少一种。
在其中一些实施例中，钙钛矿材料层的厚度为500nm～800nm；可选为500nm、550nm、600nm、650nm、700nm、750nm、800nm；或任意两个数值组成的范围。
在其中一些实施例中，上述钙钛矿电池还包括电子传输层、第一电极和第二电极，第一电极设于空穴传输层远离钙钛矿材料层的一侧，第二电极设于钙钛矿材料层远离空穴传输层的一侧，电子传输层设于第二电极和钙钛矿材料层之间。
电子传输层可以增强电子的提取与传输效率，进一步提高钙钛矿电池的转化效率。
在其中一些实施例中，上述电子传输层的厚度为20nm～30nm。可选为20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm、30nm；或任意两个数值组成的范围。
在其中一些实施例中，上述电子传输层中的组分可以是本领域常用的电子传输材料，非限制性地选自：[6,6]-苯基-C61-丁酸甲酯(PC61BM)、[6,6]-苯基-C71-丁酸甲酯(PC71BM)、富勒烯C60(C60)、富勒烯C70(C70)、氧化锡、氧化锌(ZnO)中的至少一种。
在其中一些实施例中，钙钛矿电池还包括空穴阻挡层，空穴阻挡层设于电子传输层和第二电极之间。
空穴阻挡层可阻挡空穴通过，显著提高界面处的电子收集率，从而降低电子和空穴在界面处复合的几率。
在其中一些实施例中，空穴阻挡层的厚度为5nm～10nm；可选为5nm、6nm、7nm、8nm、9nm、10nm；或任意两个数值组成的范围。
空穴阻挡层的组分可以是本领域常用的空穴阻挡材料，非限制性举例包括：2,9-二甲基-4,7-二苯基-1,10-菲啰啉(BCP)和氧化锡中的至少一种。
在其中一些实施例中，第一电极和第二电极可采用本领域常压的各类电极材料，包括透明导电氧化物和导电金属中的至少一种；具体可以是：掺氟二氧化锡(FTO)，掺锡氧化铟(ITO)，掺硼氧化锌(BZO)和氧化锌铝(AZO)、铟锌氧化物(IZO)、Ag、Cu、C、Au、Al中的至少一种。
在其中一些实施例中，具体请参照图1，图1是一实施方式提供的钙钛矿电池10，包括依次层叠设置的第一电极11、空穴传输层12、钝化层13、钙钛矿材料层14、电子传输层15、空穴阻挡层16、第二电极17。
在其中一些实施例中，上述钙钛矿电池10可以是正式钙钛矿电池(n-i-p平面结构)或反式钙钛矿电池(p-i-n平面结构)。
在其中一些实施例中，第二电极的厚度为80nm～110nm。
需要说明的是，当第一电极11为透明电极时，即第一电极11侧作为光入射侧，此时上述钙钛矿电池10是反式钙钛矿电池，反之当第二电极17为透明电极时，即第二电极侧作为光入射侧，此时上述钙钛矿电池10是正式钙钛矿电池。
在其中一些实施例中，第一电极11为透明导电电极，上述钙钛矿电池为反式钙钛矿电池。
在其中一些实施例中，钙钛矿电池还包括衬底，衬底设于透明导电电极远离另一电极的一侧，衬底结构可以为硬性材质，也可以为柔性材质，在一些实施例中，衬底结构可以采用透明玻璃材质，衬底结构的材质根据需要具体设置，本申请不做限定。
本申请一实施方式，还提供上述钙钛矿电池的制备方法，包括如下步骤S10。
步骤S10：依次形成层叠设置的空穴传输层和钙钛矿材料层；在形成钙钛矿材料层的步骤之前，还包括如下步骤：
采用包括铵盐化合物的制备原料在空穴传输层表面形成钝化层。
具体地，可以通过先将式(1)化合物和式(2)化合物进行成盐反应形成铵盐化合物后，再采用铵盐化合物制成溶液涂布在空穴传输层表面，形成钝化层；或是直接将包括式(1)化合物和式(2)化合物的制备原料混合处理后直接涂布在空穴传输层表面，干燥过程中直接成盐并在空穴传输层表面形成钝化层。
具体地，将包括空穴将包括式(1)化合物和式(2)化合物的制备原料混合，并涂布在空穴传输层表面，退火处理成盐形成钝化层。
在其中一些实施例中，混合的步骤在溶剂中进行；进一步地，溶剂包括小分子醇类溶剂，可为异丙醇、丙醇和乙醇中的至少一种。
在其中一些实施例中，将包括式(1)化合物和式(2)化合物的制备原料混合在溶剂中形成混合溶剂；进一步地，混合溶剂中的式(1)化合物和式(2)化合物的总质量浓度为0.5mg/mL～2mg/mL。
在其中一些实施例中，式(1)化合物和式(2)化合物的质量比为1:(0.1～10)。
可选地，退火温度为100℃～150℃，时间为5min～20min。
式(1)化合物和式(2)化合物的结构和具体选择同上所示，在此不再赘述。
在一些具体实施例中，式(1)化合物包括MeO-4PACz([4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸)、MeO-2PACz([2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸、MeO-3PACz([3-(3,6-二甲氧基-9H-咔唑-9-基)丙基]膦酸、MeO-4CACz([4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]羧酸)和MeO-4SACz([4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]磺酸)中的至少一种。具体结构如下：

上述式(1)化合物均是可以通过市购获得或参照本领域的合成文献(例如DOI:10.1126/science.abd4016)合成，在此不过多赘述。
在一些具体实施例中，式(2)化合物包括PEAI(苯乙胺)、mF-PEAI(间氟苯乙胺)、pF-PEAI(对氟苯乙胺)、oF-PEAI(邻氟苯乙胺)、mF-PMAI(间氟苯甲胺)、pF-PMAI(对氟苯甲胺)、oF-PMAI(邻氟苯甲胺)、间氟苯丙胺、对氟苯丙胺、邻氟苯丙胺、mOH-PEAI(间羟基苯乙胺)、pOH-PEAI(对羟基苯乙胺)、oOH-PEAI(邻羟基苯乙胺)、mMe-PEAI(间甲基苯乙胺)、pMe-PEAI(对甲基苯乙胺)、oMe-PEAI(邻甲基苯乙胺)、oCF-PEAI(邻三氟甲基苯乙胺)、mCF-PEAI(间三氟甲基苯乙胺)和pCF-PEAI(对三氟甲基苯乙胺)中的至少一种。
可理解：上述钙钛矿电池其他各功能层可以采用本领域常规的制备方法制备，例如上述空穴传输层、电子传输层、空穴阻挡层等的制备过程可采用本领域常用的制备方法，包括溶液法和固体沉积法，溶液法包括旋涂法、喷涂、刮涂法和狭缝涂布法等中的任意一种方法，固体沉积法包括：真空蒸镀、溅射沉积、等离子体沉积、离子沉积中的任意一种。
上述钙钛矿材料层可采用本领域常规的制备方法获得，例如反溶剂法；具体步骤如下：
在基底表面旋涂钙钛矿前驱体溶液，使用反溶剂法冲膜，然后进行退火处理，制备得到钙钛矿材料层。
可选的，退火处理的温度为100摄氏度(℃)～150℃，时间为10分钟(min)～30min。钙钛矿前驱体溶液中的溶剂可选：N,N-二甲基甲酰胺、二甲基亚砜,N-甲基吡咯烷酮和2-甲氧基乙醇中的一种或几种，浓度为1.0摩尔/升(mol/L)～2.0mol/L。
反溶剂可选：氯苯、苯甲醚、乙醚中的至少一种。
本申请一实施方式，还提供一种光伏组件，该光伏组件包括上述钙钛矿电池。
上述钙钛矿电池的光转化效率高且稳定性好，可提高光伏组件的效率。
上述光伏组件中，包括一个或多个钙钛矿电池，可根据具体的应用场景选择；进一步地，上述光伏组件中包括多个钙钛矿电池，多个钙钛矿电池串联或并联连接形成电池片。
在其中一些实施例中，上述光伏组件还包括光伏玻璃层、粘结层、背板。
电池片的两个表面分别设有粘结层，在其中一个粘结层中远离电池片的表面设有背板，在另一个粘结层中远离电池片的表面设有光伏玻璃层。
光伏玻璃层和背板用于保护保护钙钛矿电池，密封、绝缘、防水；粘结层起到粘结光伏玻璃层与电池片、粘结背板与电池片的作用。
可选地，光伏玻璃层的材质钢化玻璃，背板的材质采用TPT(聚氟乙烯)或TPE(热塑性弹性体)材质，粘结层的材质采用EVA(聚乙烯-聚醋酸乙烯酯共聚物)。
进一步地，上述光伏组件还包括接线盒及外框。
接线盒用于保护整个光伏组件的发电系统，它相当于一个电流中转站，当有电池片出现短路，接线盒会自动断开短路的电池串。
外框可以起到支撑和保护整个光伏组件的作用，边框可采用铝合金材质，强度、耐腐蚀性优异。
进一步地，通过硅胶来粘结、密封边框与光伏组件中其他部位的连接处。光伏组件可以将太阳能转化为电能，或送往蓄电池中存储起来，或推动负载工作。
在其中一些实施例中，上述光伏组件为太阳能电池板。
本申请一实施方式，还提供一种光伏系统，包括上述光伏组件。
光伏系统利用上述光伏组件中钙钛矿电池的光生伏特效应，将太阳辐射能直接转换成电能，效率高；进一步地，上述光伏系统为光伏发电系统。
光伏组件是光伏发电系统中的核心部分，上述光伏系统中，包括一个或多个光伏组件，可根据具体的应用场景选择；进一步地，上述光伏系统中包括多个光伏组件时，多个光伏组件形成光伏阵列。
上述光伏系统可以是独立光伏发电系统，也可以是并网光伏发电系统。
独立光伏发电系统包括光伏阵列、蓄电池组、充电控制器、电力电子变换器(逆变器)、负载等。其工作原理是，太阳辐射能量经过光伏阵列首先被转换成电能，然后由电力电子变换器变换后给负载供电，同时将多余的电能经过充电控制器后以化学能的形式储存在储能装置中，这样在日照不足时，储存在电池中的能量就可经过电力电子逆变器、滤波和工频变压器升压后变成交流220V、50Hz的电能供交流负载使用。
并网光伏发电系统包括光伏阵列、高频DC/DC升压电路、电力电子变换器(逆变器)和系统监控。其工作原理是，太阳辐射能量经过光伏阵列转换后，再经高频直流变换后变成高压直流电，然后经过电力电子逆变器逆变后向电网输出与电网电压相频一致的正弦交流电流。
上述两种光伏发电系统各有特点，可根据具体的应用场景选择。
本申请一实施方式，还提供一种用电装置，包括上述钙钛矿电池和光伏组件中的至少一个。
上述用电装置可以但不限于是移动设备、电动车辆、电气列车、船舶及卫星、储能系统等。
在其中一些实施例中，移动设备可以是手机或笔记本电脑等。
在其中一些实施例中，电动车辆包括但不限于：纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等。
本申请又一实施方式，还提供一种发电装置，包括上述钙钛矿电池或或光伏组件。
上述发电装置可以但不限于：太阳能发电机组等。
下面将结合具体的实施例对本申请进行了说明，但本申请并不局限于下述实施例，应当理解，所附权利要求概括了本申请的范围，在本申请构思的引导下本领域的技术人员应意识到，对本申请的各实施例所进行的一定的改变，都将被本申请的权利要求书的精神和范围所覆盖。
以下为具体实施例。
实施例1
(1)钙钛矿电池的制备，具体步骤如下：
1、把FTO导电玻璃裸露出玻璃基底，然后依次放入表面活性剂、去离子水、乙醇中依次清洗，然后在氮气枪下吹干溶剂，放入紫外臭氧机中照射，备用。
2、在FTO玻璃基板上使用匀胶机旋涂氧化镍纳米颗粒溶液，溶液浓度为10mg/mL，然后置于150℃热台上退火处理15min，形成60nm厚的空穴传输层。
3、将式(1)化合物(MeO-4PACz)与式(2)化合物间氟苯甲胺(mF-PEAI)按质量比例1：1称量投放在玻璃瓶中，加入异丙醇溶剂，制备成浓度为1mg/mL的溶液，充分搅拌溶解后过滤得到澄清溶液，然后在氮气氛围中，在空穴传输层的表面上旋涂澄清溶液，再在100℃下退火处理10min，形成平均厚度约为1nm的钝化层，厚度记作X。
4、将碘化甲醚FAI、碘化铯CsI、MAI碘甲胺、碘化铅PbI2按化学式FA0.85MA0.1Cs0.05PbI3的化学计量分数称量并投放在玻璃瓶中，加入体积比4:1的N,N-二甲基甲酰胺DMF与二甲基亚砜DMSO的混合溶剂中，充分搅拌溶解后过滤，配成摩尔浓度为1.8mol/L的前驱体溶液；然后将钙钛矿前驱体溶液通过静态旋涂铺展在钝化层表面，使用反溶剂苯甲醚冲膜后，在热台上110℃下退火20min形成钙钛矿材料层，厚度为700nm。
5、使用蒸镀设备在钛矿材料层的表面上依次蒸镀25nm厚的电子传输层(C60)、原子沉积得到5nm厚的空穴阻挡层(氧化锡)以及真空蒸镀得到100nm厚的金属电极层(Cu)，获得钙钛矿电池。
其中，上述各功能层的厚度可采用白光干涉仪、台阶仪、光学/电学显微镜中任一种测试，其中钝化层的厚度采用电学显微镜测试，且在钝化层的多个部位取样测试取平均值。
(2)性能测试，具体如下：
将刚制备好的钙钛矿电池进行光电转换效率测试，获得其初始光电转换效率PCE(0)，然后置于未封装的氮气环境中，遮光加热85℃下放置1000h，再测试其光电转换效率PCE(1000)，按照下述公式计算其效率保持率Y：
Y＝PCE(1000)/PCE(0)×100％
其中，光电转化效率测试的具体步骤如下：
将装有钙钛矿电池的测试夹具置于样品架上，使其位于测量平面内，并保证电池位于太阳模拟器出射光斑的中心位置(或光伏电池法线与太阳模拟器光源出射光束的中心线平行)。
采用光焱的太阳光模拟器，参照国家标准IEC61215，在标准模拟太阳光(AM1.5G，100mW/cm2)照射下，对电池进行电流-电压测试，FTO为正极，Cu为负极，测试电压从-0.1V～1.2V，电池面积为0.075cm2，获得的I-V曲线，可得到Pout、Pin、Vmpp、Jmpp、Voc、Jsc，然后，基于如下公式计算PCE：
PCE＝Pout/Pin；
＝Voc×Jsc×[(Vmpp×Jmpp)/(Voc×Jsc)]/Pin；
＝Voc×Jsc×FF/Pin；
其中，Pin、Pout、Vmpp、Jmpp、Voc、Jsc、FF分别表示：入射光功率(100mW/cm2)、被测电池的工作输出功率、被测电池最大功率点的电压、被测电池最大功率点的电流、开路电压、短路电流、填充因子。
具体测试结果请见表1。
实施例2～4
实施例2～4与实施例1基本相同，不同之处仅在于：步骤(1)钙钛矿电池的制备中，式(1)化合物和/或式(2)化合物的种类与实施例1不同，具体不同之处请见表1中相关参数。
其余测试步骤与实施例1相同，具体结果请见表1。
实施例5～10
实施例5～10与实施例1基本相同，不同之处仅在于：步骤(1)钙钛矿电池的制备中，式(1)化合物和/或式(2)化合物的种类与实施例1不同，具体不同之处请见表1中相关参数。
其余测试步骤与实施例1相同，具体结果请见表1。
对比例1
对比例1与实施例1基本相同，不同之处仅在于：步骤(1)钙钛矿电池的制备中，不设置钝化层。
其余步骤与实施例1相同，具体结果请见表1。
对比例2
对比例2与实施例1基本相同，不同之处仅在于：步骤(1)钙钛矿电池的制备中，钝化层的制备步骤如下：
将式(1)化合物(MeO-4PACz)投放在玻璃瓶中，加入异丙醇溶剂，制备成浓度为1mg/mL的溶液，充分搅拌溶解后过滤得到澄清溶液，然后在氮气氛围中，在空穴传输层的表面上旋涂澄清溶液，再在100℃下退火处理10min，形成平均厚度约为1nm的钝化层。
其余步骤与实施例1相同，具体结果请见表1。
对比例3～4
对比例3～4与实施例1基本相同，不同之处仅在于：式(1)化合物和/或式(2)化合物的种类与实施例1不同，具体不同之处请见表1中相关参数。
其余步骤与实施例1相同，具体结果请见表1。
对比例5～6
对比例5～6与对比例2基本相同，不同之处仅在于：对比例5～6中将式(1)化合物(MeO-4PACz)分别替换为MeO-4CACz或MeO-4SACz。
其余步骤与对比例2相同，具体结果请见表1。
各实施例及对比例中相关的物理参数及测试结果请见表1。
表1

注“/”代表不存在该结构或物质。
其中，“MeO-4PACz”为[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸，“MeO-2PACz”为[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基膦酸，“MeO-3PACz”为[3-(3,6-二甲氧基-9H-咔唑-9-基)丙基]膦酸，“MeO-4SACz”为[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]磺酸，“MeO-4CACz”为[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]羧酸，“mF-PEAI”为间氟苯甲胺，“pF-PEAI”为对氟苯甲胺，“PEAI”为苯乙胺，“mCF-PEAI”为间三氟甲基苯乙胺，“pMe-PEAI”为对甲基苯乙胺，“pOH-PEAI”为对羟基苯乙胺，“ThEAI”为2-噻吩乙胺碘，“ThMAI”为2-噻吩甲胺碘。
对比分析上述表中实施例1～10和对比例1～6的测试结果可知：采用本申请特定结构的铵盐化合物制备钙钛矿电池时，能起到有效提高钙钛矿光电转换效率的同时提高其稳定性的作用；且作为钝化层材料时，即使采用氧化镍作为空穴传输层材料，也能有效提高钙钛矿电池的光电转化效率及其稳定性。进一步地，由实施例1～3和实施例4可知，进一步调控铵盐化合物中阴离子基团中的环结构上的取代基种类，可进一步提高钙钛矿电池的光电转化效率及其稳定性。
进一步对比分析实施例1和对比例3～4的数据可知，本申请中采用含芳香基结构的式(2)化合物形成阳离子部分，可以提高钙钛矿电池的光电转化效率及其稳定性，而对比例3～4中换成一般的杂芳基形成阳离子部分，则未观测到有此作用。导致该现象的原因可能与基团的芳香性强弱有关，有机结构的芳香性与其共轭体系内π电子的数量有关，芳香性越强，其含有的共轭体系内π电子越多，共轭作用越大，而相对于杂芳香基，式(2)化合物形成的阳离子基团中的芳香基结构含有的轭体系内π电子更多，可与阴离子基团中的咔唑基团产生的共轭作用越强，从而能够进一步提高界面的载流子提取能力和/或载流子传输能力。
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发明专利范围的限制。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 (20)

  1. 一种钙钛矿电池，其包括层叠设置的空穴传输层、钝化层和钙钛矿材料层；所述钝化层含有铵盐化合物；
    在所述铵盐化合物中，阴离子基团包括式(1)化合物中的至少一个含氧酸基团中的至少一个羟基失去氢后形成的基团，阳离子基团包括式(2)化合物中氨基得到一个氢后形成的基团：
    其中，L1选自：被至少一个含氧酸基团取代的烷基和含氧酸基团中的任意一种，各R1和各R2各自独立地选自：H、烷基、烷氧基、取代或未被取代的成环原子数为6～13的芳基、取代或未被取代的成环原子数为5～10的杂芳基中的任意一种；
    Ar1选自取代或未取代的成环原子数为6～14的芳香基，L2选自碳原子数为1～3的亚烷基；
    n1和n2各自独立地选自0～4任一整数。
  2. 如权利要求1所述的钙钛矿电池，其中，Ar1选自成环原子数为6～14的芳香基或被取代基取代的成环原子数为6～14的芳香基，所述取代基包括F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种。
  3. 如权利要求1或2所述的钙钛矿电池，其中，Ar1的结构如下所示：
    各R3分别独立地选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基、碳原子数为1～3的烷氧基及被氟原子取代的碳原子数为1～3的烷氧基中的任意一种，n3选自0～5任一整数，*代表连接位点。
  4. 如权利要求1～3任一项所述的钙钛矿电池，其中，所述铵盐化合物满足如下(1)～(2)中的一个或两个条件：
    (1)L1选自被至少一个含氧酸基团取代的碳原子数为1～5的烷基；
    (2)各R1和各R2各自独立地选自：H、碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、成环原子数为6～10的芳基。
  5. 如权利要求1～4任一项所述的钙钛矿电池，其中，所述铵盐化合物包括式(Ⅰ)所示化合物：
    其中，L11选自碳原子数为1～5的亚烷基，A-为所述含氧酸基团中的一个羟基失去一个氢后形成的基团。
  6. 如权利要求1～5任一项所述的钙钛矿电池，其中，所述含氧酸基团选自膦酸基团、次磷酸基团、磺酸基团、羧酸基团、硼酸基团或硅酸基团中的任意一种。
  7. 如权利要求1～6任一项所述的钙钛矿电池，其中，所述铵盐化合物包括如下(a)～(e)中的至少一种：

    L11选自碳原子数为1～5的亚烷基，R3选自H、F、羟基、碳原子数为1～3的烷基、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
  8. 如权利要求7所述的钙钛矿电池，其中，R3选自F、羟基、被氟原子取代的碳原子数为1～3的烷基中的任意一种。
  9. 如权利要求1所述的钙钛矿电池，其中，所述式(1)化合物包括[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基膦酸、[3-(3,6-二甲氧基-9H-咔唑-9-基)丙基]膦酸、[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]羧酸和[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]磺酸中的一种或几种；所述式(2)化合物包括间氟苯甲胺、对氟苯甲胺、邻氟苯甲胺、间氟苯乙胺、对氟苯乙胺、邻氟苯乙胺、间氟苯丙胺、对氟苯丙胺、邻氟苯丙胺、间三氟甲基苯乙胺、对三氟甲基苯乙胺、邻三氟甲基苯乙胺、对甲基苯乙胺、间甲基苯乙胺、邻甲基苯乙胺、对羟基苯乙胺、间羟基苯乙胺和邻羟基苯乙胺中的一种或几种。
  10. 如权利要求1～9任一项所述的钙钛矿电池，其中，所述空穴传输层包括无机空穴传输材料和有机空穴传输材料中的至少一种。
  11. 如权利要求1～10任一项所述的钙钛矿电池，其中，所述空穴传输层包括氧化镍。
  12. 如权利要求1～11任一项所述的钙钛矿电池，其中，所述钝化层满足如下条件(1)和(2)中的一种或两种：
    (1)所述钝化层的一侧表面与所述钙钛矿材料层直接接触，另一侧表面与所述空穴传输层直接接触；
    (2)所述钝化层的厚度为0.1nm～5nm。
  13. 如权利要求1～12任一项所述的钙钛矿电池，其中，所述钙钛矿电池还包括电子传输层、第一电极和第二电极，所述第一电极设于所述空穴传输层远离所述钙钛矿材料层的一侧，所述第二电极设于所述钙钛矿材料层远离所述空穴传输层的一侧，所述电子传输层设于所述第二电极和所述钙钛矿材料层之间。
  14. 如权利要求13所述的钙钛矿电池，其中，所述钙钛矿电池还包括空穴阻挡层，所述空穴阻挡层设于所述电子传输层和所述第二电极之间。
  15. 如权利要求14所述的钙钛矿电池，其中，所述钙钛矿电池满足如下条件中的一种或几种：
    (1)所述空穴传输层的厚度为20nm～100nm；
    (2)所述钙钛矿材料层的厚度为500nm～800nm；
    (3)所述电子传输层的厚度为20nm～30nm；
    (4)所述空穴阻挡层的厚度为5nm～10nm。
  16. 一种钙钛矿电池的制备方法，包括如下步骤：
    依次形成层叠设置的所述空穴传输层和所述钙钛矿材料层；且在形成所述钙钛矿材料层的步骤之前，还包括如下步骤：
    采用包括铵盐化合物的制备原料在所述空穴传输层表面形成所述钝化层；
    在所述铵盐化合物中，阴离子基团包括式(1)化合物中的至少一个含氧酸基团中的至少一个羟基失去氢后形成的基团，阳离子基团包括式(2)化合物中氨基得到一个氢后形成的基团：
    其中，L1选自：被至少一个含氧酸基团取代的烷基和含氧酸基团中的任意一种，各R1和各R2各自独立地选自：H、烷基、烷氧基、取代或未被取代的成环原子数为6～13的芳基、取代或未被取代的成环原子数为5～10的杂芳基中的任意一种；
    Ar1选自取代或未取代的成环原子数为6～14的芳香基，L2选自碳原子数为1～3的亚烷基；
    n1和n2各自独立地选自0～4任一整数。
  17. 一种光伏组件，包括如权利要求1～15任一项所述的钙钛矿电池。
  18. 一种光伏系统，包括如权利要求17所述的光伏组件。
  19. 一种用电装置，包括如权利要求1～15任一项所述的钙钛矿电池和权利要求17所述的光伏组件中的至少一个。
  20. 一种发电装置，包括如权利要求1～15任一项所述的钙钛矿电池和权利要求17所述的光伏组件中的至少一个。
PCT/CN2025/090474 2024-05-14 2025-04-22 钙钛矿电池、光伏组件、光伏系统、用电装置及发电装置 Pending WO2025237014A1 (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023164877A1 (zh) * 2022-03-03 2023-09-07 宁德时代新能源科技股份有限公司 富勒烯衍生物及钙钛矿太阳能电池
US20230284520A1 (en) * 2021-12-31 2023-09-07 Contemporary Amperex Technology Co., Limited Perovskite solar cell and manufacturing method
CN117042473A (zh) * 2023-08-04 2023-11-10 深圳现象光伏科技有限公司 钙钛矿太阳能电池及其制备方法和应用
WO2024078144A1 (zh) * 2022-10-09 2024-04-18 隆基绿能科技股份有限公司 咔唑盐及其衍生物以及在制备太阳能电池中的应用

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* Cited by examiner, † Cited by third party
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US20230284520A1 (en) * 2021-12-31 2023-09-07 Contemporary Amperex Technology Co., Limited Perovskite solar cell and manufacturing method
WO2023164877A1 (zh) * 2022-03-03 2023-09-07 宁德时代新能源科技股份有限公司 富勒烯衍生物及钙钛矿太阳能电池
WO2024078144A1 (zh) * 2022-10-09 2024-04-18 隆基绿能科技股份有限公司 咔唑盐及其衍生物以及在制备太阳能电池中的应用
CN117042473A (zh) * 2023-08-04 2023-11-10 深圳现象光伏科技有限公司 钙钛矿太阳能电池及其制备方法和应用

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