Perovskite cell, photovoltaic module, photovoltaic system, power utilization device and power generation device

Abstract

The invention relates to a perovskite cell, a photovoltaic module, a photovoltaic system, a power utilization device and a power generation device. The perovskite cell comprises a hole transport layer, a passivation layer and a perovskite material layer which are arranged in a stacked mode. The passivation layer contains an ammonium salt compound; in the ammonium salt compound, an anion group comprises a group formed after at least one hydroxyl group in at least one oxyacid group in a compound shown in a formula (1) loses hydrogen, and a cation group comprises a group formed after an amino group in a compound shown in a formula (2) obtains hydrogen. The perovskite cell has excellent photoelectric conversion efficiency and stability.

Description

Technical Field

[0001] 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. Background Technology

[0002] 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.

[0003] However, the photoelectric conversion efficiency and stability of solar cells made from traditional perovskite material layers and hole transport layer materials are very limited, which reduces their lifetime and makes it difficult for traditional perovskite solar cells to meet increasingly demanding application requirements.

[0004] Therefore, traditional technologies still need improvement. Summary of the Invention

[0005] Therefore, it is necessary to provide a perovskite cell, photovoltaic module, photovoltaic system, electrical device, and power generation device, aiming to improve the photoelectric conversion efficiency and stability of the perovskite cell.

[0006] This application is achieved through the following technical solution.

[0007] 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;

[0008] In the 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).

[0009] , ;

[0010] Wherein, L1 is selected from any one of alkyl groups substituted with at least one oxyacid group and oxyacid groups, and 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.

[0011] Ar1 is selected from substituted or unsubstituted aryl groups with 6 to 14 cyclic atoms, and L2 is selected from alkylene groups with 1 to 3 carbon atoms;

[0012] n1 and n2 are each independently selected from any integer from 0 to 4.

[0013] In the above perovskite solar cell, an ammonium salt compound with a specific structure is set in the passivation layer between the hole transport layer and the perovskite. Among the ammonium salt compounds, the anionic group formed by the compound of formula (1) contains a carbazole structure, which itself has hole transport capability. However, 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. After synergistic effect with the cation formed by the compound of formula (2), -NH3 + The presence of the functional groups can disrupt the self-assembly morphology, allowing the ammonium salt compound to be better dispersed during film formation, forming a more uniform film layer. It also reduces the probability of side reactions between the hole transport layer and the perovskite material layer, and can regulate the energy band and improve charge extraction capability. Simultaneously, the cationic group formed by the compound in formula (2) contains a specific aromatic group structure, which can conjugate with the carbazole group in the anionic group, further improving the carrier extraction capability and / or carrier transport capability at the interface. Thus, while reducing the energy level difference between the hole transport layer and the perovskite material layer, it also reduces side reactions between them, improving the photoelectric conversion efficiency and stability of the perovskite battery, thereby increasing its lifetime.

[0014] It can be understood that 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.

[0015] In some embodiments, Ar1 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.

[0016] By regulating the structure of Ar1 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.

[0017] In some embodiments, the structure of Ar1 is as follows:

[0018] ,

[0019] 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.

[0020] It should be noted that: In the case where n3 is selected from 0, it indicates that there are no substituents on the benzene ring, and the structure is phenyl.

[0021] In some embodiments, the ammonium salt compound satisfies one or both of the following conditions (1) to (2):

[0022] (1) L1 is selected from alkyl groups having 1 to 5 carbon atoms substituted by at least one oxyacid group;

[0023] (2) Each R1 and each R2 are 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.

[0024] In some embodiments, the ammonium salt compound includes the compound shown in formula (I):

[0025] ;

[0026] Among them, L 11 Selected from alkylene groups having 1 to 5 carbon atoms, A - It is a group formed by losing a hydrogen atom from a hydroxyl group in the oxyacid group.

[0027] In some embodiments, 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.

[0028] In some embodiments, the ammonium salt compound includes at least one of the following (a) to (e):

[0029]

[0030]

[0031] ;

[0032] L 11 R3 is selected from alkylene groups having 1 to 5 carbon atoms, and R3 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.

[0033] Optionally, R3 is selected from F, hydroxyl group, or alkyl group having 1 to 3 carbon atoms substituted with fluorine atoms.

[0034] 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. Moreover, compared with 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.

[0035] In some embodiments, 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 ... One or more of [-methyl]butyl]sulfonic 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-hydroxyphenylethylamine.

[0036] 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.

[0037] In some embodiments, the hole transport layer includes at least one of inorganic hole transport materials and organic hole transport materials.

[0038] In some embodiments, the hole transport layer comprises nickel oxide.

[0039] In this application, the oxyacid groups are formed into ammonium salts, and the structure of the cation moiety is controlled. When modifying a hole transport layer containing nickel oxide, it is able to block high-valence nickel ions (Ni). 3+ Ni 4+(etc.) undergo side reactions with perovskite, which improves the film-forming ability of ammonium salt compounds, reduces the energy level difference between them 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.

[0040] In some embodiments, the passivation layer satisfies one or both of the following conditions (1) and (2):

[0041] (1) 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;

[0042] (2) The thickness of the passivation layer is 0.1 nm to 5 nm.

[0043] In some embodiments, 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, and 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.

[0044] An electron transport layer can enhance the efficiency of electron extraction and transport, thereby further improving the conversion efficiency of perovskite solar cells.

[0045] In some embodiments, the perovskite solar cell further includes a hole-blocking layer disposed between the electron transport layer and the second electrode.

[0046] 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.

[0047] In some embodiments, the perovskite solar cell satisfies one or more of the following conditions:

[0048] (1) The thickness of the hole transport layer is 20nm~100nm;

[0049] (2) The thickness of the perovskite material layer is 500 nm to 800 nm;

[0050] (3) The thickness of the electron transport layer is 20nm~30nm;

[0051] (4) The thickness of the hole blocking layer is 5nm~10nm.

[0052] A second aspect of this application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0053] 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:

[0054] The passivation layer is formed on the surface of the hole transport layer using raw materials including the ammonium salt compound.

[0055] In a third aspect, this application provides a photovoltaic module, including the perovskite cell of the first aspect.

[0056] A fourth aspect of this application provides a photovoltaic system including the photovoltaic module of the third aspect.

[0057] 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.

[0058] 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. Attached Figure Description

[0059] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiments below. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0060] Figure 1 This is a schematic diagram of a perovskite solar cell according to one embodiment of this application.

[0061] Explanation of reference numerals in the attached figures:

[0062] 10. 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. Detailed Implementation

[0063] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0064] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0065] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0066] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0067] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0068] In the description of the embodiments of this application, the term "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).

[0069] In the description of the embodiments of this application, the technical terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the embodiments of this application and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of this application.

[0070] In the description of the embodiments of this application, unless otherwise expressly specified and limited, technical terms such as "installation," "connection," "joining," and "fixing" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. For those skilled in the art, the specific meaning of the above terms in the embodiments of this application can be understood according to the specific circumstances.

[0071] In this application, the term "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; the term "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.

[0072] "Aromatic" refers to an aromatic hydrocarbon group, including monocyclic aryl and fused-ring aryl groups. 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 π electrons of an aromatic group should satisfy 4n+2 (Hückel's rule).

[0073] "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.

[0074] In this application, "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. The same applies to the "ring-forming atoms" mentioned below unless otherwise specified; for example, the number of ring atoms in a benzene ring is 6, the number of ring atoms in a naphthalene ring is 10, and the number of ring atoms in a thiophene ring is 5.

[0075] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is 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.

[0076] In this application, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0077] In this application, 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... In this context, 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... In this system, 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 this is the case for a phenyl group.

[0078] Unless otherwise specified in this application, the preparation steps can be carried out at room temperature. "Room temperature" generally refers to 4℃~30℃, and more specifically 20±5℃.

[0079] The excessive energy level difference between the traditional perovskite material layer and the hole transport layer can lead to poor contact, or material instability and excessive defects, all of which reduce the photoelectric conversion efficiency and stability of solar cells, thus shortening their lifespan. This is especially true when nickel oxide is used as the hole transport material. Although 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 presence of high-valence nickel ions (Ni) in nickel oxide, further exacerbates the problem. 3+ Ni 4+ These substances can easily react with perovskite materials, accelerating the degradation of perovskite materials and thus greatly limiting the stability of perovskite solar cells.

[0080] In traditional techniques, organic self-assembled molecules with oxyacid groups are often used to modify the hole transport layer to modulate its energy levels. However, research has found that 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.

[0081] Through extensive experimental research, the technical solution described in this application, which can improve the photoelectric conversion efficiency and stability of perovskite solar cells, has been obtained.

[0082] 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.

[0083] In ammonium salt compounds, 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:

[0084] , ;

[0085] Wherein, L1 is selected from any one of alkyl groups substituted with at least one oxyacid group and oxyacid groups, and 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.

[0086] Ar1 is selected from substituted or unsubstituted aryl groups with 6 to 14 cyclic atoms, and L2 is selected from alkylene groups with 1 to 3 carbon atoms;

[0087] n1 and n2 are each independently selected from any integer from 0 to 4.

[0088] In the above perovskite solar cell, an ammonium salt compound with a specific structure is set in the passivation layer between the hole transport layer and the perovskite. Among the ammonium salt compounds, the anionic group formed by the compound of formula (1) contains a carbazole structure, which itself has hole transport capability. However, 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. After synergistic effect with the cation formed by the compound of formula (2), -NH3 + The presence of the functional groups can disrupt the self-assembly morphology, allowing the ammonium salt compound to be better dispersed during film formation, forming a more uniform film layer. It also reduces the probability of side reactions between the hole transport layer and the perovskite material layer, and can regulate the energy band and improve charge extraction capability. Simultaneously, the cationic group formed by the compound in formula (2) contains a specific aromatic group structure, which can conjugate with the carbazole group in the anionic group, further improving the carrier extraction capability and / or carrier transport capability at the interface. Thus, while reducing the energy level difference between the hole transport layer and the perovskite material layer, it also reduces side reactions between them, improving the photoelectric conversion efficiency and stability of the perovskite battery, thereby increasing its lifetime.

[0089] It can be understood that 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.

[0090] In some embodiments, Ar1 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.

[0091] By regulating the structure of Ar1 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.

[0092] In some embodiments, the substituents include any one of F, hydroxyl, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, propyl, methoxy, ethoxy, and propoxy.

[0093] The number of ring atoms mentioned above is 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0094] In some embodiments, Ar1 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.

[0095] In some embodiments, the structure of Ar1 is as follows:

[0096] ,

[0097] 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.

[0098] In some of these embodiments, each R3 is independently selected from any one of H, F, hydroxyl, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, propyl, methoxy, ethoxy, and propoxy.

[0099] In some embodiments, the structure of Ar1 is shown in any of the following configurations:

[0100]

[0101]

[0102] In some of these embodiments, L1 is selected from alkyl groups having 1 to 5 carbon atoms that are substituted with at least one oxyacid group.

[0103] The values ​​in “1~5” 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.

[0104] In some of these embodiments, L1 is selected from alkyl groups having 1 to 4 carbon atoms that are substituted with at least one oxyacid group.

[0105] Further regulation of the L1 alkyl chain length can improve carrier extraction performance while reducing steric hindrance and improving film quality.

[0106] In some embodiments, the structure of L1 is as follows: , where L 11 Selected from alkylene groups having 1 to 5 carbon atoms, A - This is a group formed when a hydroxyl group in an oxyacid group loses a hydrogen atom; * represents a linking site.

[0107] In some embodiments, 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:

[0108]

[0109] In some embodiments, 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.

[0110] In some embodiments, each R1 and each R2 may be the same or different.

[0111] In some embodiments, each R1 and each R2 is independently selected from: H, alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, and aryl groups having 6 to 8 cyclic atoms.

[0112] In some embodiments, each R1 and each R2 is independently selected from any one of H, methyl, ethyl, propyl, methoxy, ethoxy, and phenyl.

[0113] In some embodiments, the ammonium salt compound includes the compound shown in formula (I):

[0114]

[0115] In some of these embodiments, L 11 Selected from alkylene groups having 1 to 4 carbon atoms.

[0116] In some of these embodiments, L 11 It is selected from any one of methylene, ethylene, propylene, and butylene.

[0117] In some embodiments, the oxyacid group is selected from any one of phosphonic acid groups, hypophosphite groups, sulfonic acid groups, and carboxylic acid groups.

[0118] Adjusting the types of hydrochloric acid groups can further improve the stability of perovskite solar cells.

[0119] In some embodiments, the ammonium salt compound includes at least one of the following (a) to (e):

[0120]

[0121]

[0122] ;

[0123] R3 is selected from any one of H, F, hydroxyl, alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 3 carbon atoms that has been replaced by fluorine atoms.

[0124] Optionally, R3 is selected from any one of hydroxyl, F, or alkyl groups having 1 to 3 carbon atoms substituted with fluorine atoms.

[0125] In some of these embodiments, R3 is selected from any one of F, monofluoromethyl, difluoromethyl, and trifluoromethyl.

[0126] 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. Moreover, compared with 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.

[0127] In some embodiments, the hole transport layer includes at least one of inorganic hole transport materials and organic hole transport materials.

[0128] 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].

[0129] In some embodiments, the hole transport layer comprises nickel oxide.

[0130] In this application, the oxyacid groups are formed into ammonium salts, and the structure of the cation moiety is controlled. When modifying a hole transport layer containing nickel oxide, it is able to block high-valence nickel ions (Ni). 3+ Ni 4+(etc.) undergo side reactions with perovskite, which improves the film-forming ability of ammonium salt compounds, reduces the energy level difference between them 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.

[0131] In some embodiments, 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.

[0132] In some embodiments, the thickness of the passivation layer is 0.1 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.

[0133] It should be noted that 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.

[0134] In some embodiments, 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.

[0135] Understandably, during the preparation process, 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:

[0136] By disassembling the battery to expose the passivation layer, and then characterizing the passivation layer interface using SEM-EDS, the presence of specific elements (such as phosphorus, sulfur, boron, etc.) in the oxyacid functional groups can be detected. FTIR infrared spectroscopy can then be used to determine the types of functional groups (R1, R2, etc.) of the substituents. Simultaneously, by dissolving the passivation layer and using NMR to obtain the proton NMR spectrum, the structure of the ammonium salt compound's hydrocarbon skeleton and the linking groups (L2, L...) can be analyzed and determined. 11 By determining the carbon chain length of the ammonium salt compound and the area integral value of the characteristic peaks in the proton spectrum, the molar ratio of each characteristic functional group can be further analyzed, and the structure of the substance contained in the passivation layer can be obtained by combining these results.

[0137] It should be noted that the above is only an example of reverse testing, and other well-known and feasible testing and analysis methods in this field can also be used.

[0138] 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. In some embodiments, the chemical formula of the perovskite material satisfies ABX3 or A2CDX6; wherein A is an inorganic cation or an organic cation or a mixture of the two, and can be a formamidinium ion (FA). + ), methylammonium ion (MA) + ) and Cs + At least one of the following; B is an inorganic metal cation, which can be Pb. 2+ Ions, Sn 2+ At least one of the ions; C is a monovalent metal cation, commonly Ag. + D is a trivalent metal cation, which can be a bismuth cation (Bi). 3+ Antimony cation Sb 3+ and indium cations In 3+ At least one of the following; X is oxygen, a halogen, or a pseudohalogen, and can be Cl. - ,Br - and I - At least one of them.

[0139] In some embodiments, the thickness of the perovskite material layer is 500nm to 800nm; it can be selected as 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm; or any range of two values.

[0140] In some embodiments, 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, and 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.

[0141] An electron transport layer can enhance the efficiency of electron extraction and transport, thereby further improving the conversion efficiency of perovskite solar cells.

[0142] In some embodiments, the thickness of the electron transport layer is 20nm to 30nm. It can be selected as 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm; or any range of two values.

[0143] In some embodiments, the components in the electron transport layer described above can be electron transport materials commonly used in the art, and are not limited to: methyl [6,6]-phenyl-C61-butyrate (PC) 61 BM), [6,6]-phenyl-C71-butyrate methyl ester (PC) 71BM), Fullerene C60 (C 60 ), Fullerene C70 (C 70 At least one of ), tin oxide, and zinc oxide (ZnO).

[0144] In some embodiments, the perovskite solar cell further includes a hole blocking layer disposed between the electron transport layer and the second electrode.

[0145] 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.

[0146] In some embodiments, 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.

[0147] 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.

[0148] In some embodiments, 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.

[0149] In some of these embodiments, please refer to the specific details. Figure 1 , Figure 1 One embodiment of the perovskite solar cell 10 includes 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 sequentially.

[0150] In some embodiments, the perovskite solar cell 10 described above can be a conventional perovskite solar cell (nip planar structure) or an inverted perovskite solar cell (pin planar structure).

[0151] In some embodiments, the thickness of the second electrode is 80 nm to 110 nm.

[0152] It should be noted that when the first electrode 11 is a transparent electrode, that is, the side of the first electrode 11 is the light incident side, the above-mentioned perovskite cell 10 is an inverted perovskite cell. Conversely, when 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.

[0153] In some embodiments, the first electrode 11 is a transparent conductive electrode, and the perovskite cell is an inverted perovskite cell.

[0154] In some embodiments, 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. In some embodiments, 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.

[0155] According to one embodiment of this application, a method for preparing the above-mentioned perovskite solar cell is also provided, including the following step S10.

[0156] 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:

[0157] A passivation layer is formed on the surface of the hole transport layer using raw materials including ammonium salt compounds.

[0158] Specifically, 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 hole transport layer and 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.

[0159] Specifically, 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.

[0160] In some embodiments, 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.

[0161] In some embodiments, the preparation raw materials including compounds of formula (1) and formula (2) are mixed in a solvent to form a mixed solvent; further, the total mass concentration of compounds of formula (1) and formula (2) in the mixed solvent is 0.5 mg / mL to 2 mg / mL.

[0162] In some of the embodiments, the mass ratio of compound (1) to compound (2) is 1:(0.1~10).

[0163] Optionally, the annealing temperature is 100℃~150℃ and the time is 5min~20min.

[0164] The structures and specific choices of compounds of formula (1) and formula (2) are as shown above, and will not be repeated here.

[0165] In some specific embodiments, 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). The specific structures are as follows:

[0166] .

[0167] All compounds in formula (1) above can be obtained commercially or synthesized by referring to synthetic literature in this field (e.g., DOI:10.1126 / science.abd4016), and will not be elaborated further here.

[0168] In some specific embodiments, 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-fluorophenylmethylamine), pF-PMAI (p-fluorophenylmethylamine), oF-PMAI (o-fluorophenylmethylamine), m-fluorophenylacetylamine, p-fluorophenylacetylamine, o-fluorophenylacetylamine, mOH-PEAI (m-hydroxyphenylethylamine), pOH-PEAI (p-hydroxyphenylethylamine), oOH-PEAI (o-hydroxyphenylethylamine), mMe-PEAI (m-methylphenylethylamine), pMe-PEAI (p-methylphenylethylamine), oMe-PEAI (o-methylphenylethylamine), oCF-PEAI (o-trifluoromethylphenylethylamine), mCF-PEAI (m-trifluoromethylphenylethylamine), and pCF-PEAI (p-trifluoromethylphenylethylamine).

[0169] It is understood that the other functional layers of the perovskite solar cell described above can be prepared using conventional methods in the art. For example, 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.

[0170] 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:

[0171] 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.

[0172] Optionally, the annealing temperature is 100℃~150℃, and the time is 10min~30min. 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 1.0mol / L~2.0mol / L.

[0173] The antisolvent can be selected from at least one of chlorobenzene, anisole, and diethyl ether.

[0174] According to one embodiment of this application, a photovoltaic module is also provided, which includes the perovskite cell described above.

[0175] The perovskite solar cells mentioned above have high light conversion efficiency and good stability, which can improve the efficiency of photovoltaic modules.

[0176] 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.

[0177] In some embodiments, the photovoltaic module further includes a photovoltaic glass layer, an adhesive layer, and a backsheet.

[0178] 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.

[0179] 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.

[0180] Optionally, the photovoltaic glass layer is made of tempered glass, the backsheet is made of TPT (polyvinyl fluoride) or TPE (thermoplastic elastomer), and the adhesive layer is made of EVA (polyethylene-polyvinyl acetate copolymer).

[0181] Furthermore, the aforementioned photovoltaic modules also include junction boxes and outer frames.

[0182] 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.

[0183] 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.

[0184] Furthermore, 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.

[0185] In some embodiments, the photovoltaic module is a solar panel.

[0186] According to one embodiment of this application, a photovoltaic system is also provided, including the photovoltaic module described above.

[0187] 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.

[0188] 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.

[0189] The aforementioned photovoltaic system can be a stand-alone photovoltaic power generation system or a grid-connected photovoltaic power generation system.

[0190] 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 AC, 50Hz electrical energy through the power electronic inverter, filter, and power frequency transformer to supply AC loads.

[0191] 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.

[0192] The two photovoltaic power generation systems mentioned above each have their own characteristics and can be selected according to the specific application scenario.

[0193] According to one embodiment of this application, an electrical device is also provided, including at least one of the above-mentioned perovskite cells and photovoltaic modules.

[0194] The aforementioned electrical devices may include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc.

[0195] In some embodiments, the mobile device may be a mobile phone or a laptop computer, etc.

[0196] In some embodiments, 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.

[0197] In another embodiment of this application, a power generation device is also provided, including the above-mentioned perovskite battery or photovoltaic module.

[0198] The aforementioned power generation devices may include, but are not limited to, solar power generator sets, etc.

[0199] The present application will be described below with reference to specific embodiments, but the present application is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present application. Under the guidance of the concept of the present application, those skilled in the art should realize that certain changes made to the various embodiments of the present application will be covered by the spirit and scope of the claims of the present application.

[0200] The following are specific examples.

[0201] Example 1

[0202] (1) The specific steps for the preparation of perovskite solar cells are as follows:

[0203] 1. Expose the FTO conductive glass to the glass substrate, then wash it sequentially with surfactant, deionized water, and ethanol. After drying the solvent with a nitrogen gun, irradiate it in an ultraviolet ozone generator for later use.

[0204] 2. 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.

[0205] 3. The compound (MeO-4PACz) of formula (1) and the compound m-fluorobenzylamine (mF-PEAI) of formula (2) were weighed in a glass bottle at a mass ratio of 1:1. 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, the clear solution was spin-coated on the surface of the hole transport layer in a nitrogen atmosphere. The solution was then annealed at 100°C for 10 min to form a passivation layer with an average thickness of about 1 nm.

[0206] 4. Mix methyl iodide (FAI), cesium iodide (CsI), methyl iodide (MAI), and lead iodide (PbI2) according to the chemical formula FA. 0.85 MA 0.1 Cs 0.05 Weigh out the stoichiometric fraction of PbI3 and place it in a glass bottle. Add it to a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1. After thorough stirring and dissolution, filter the solution to prepare a precursor solution with a molar concentration of 1.8 mol / L. Then, spread the perovskite precursor solution onto the surface of the passivation layer by static spin coating. After rinsing the film with the anti-solvent anisole, anneal it at 110°C for 20 min on a hot plate to form a perovskite material layer with a thickness of 700 nm.

[0207] 5. Using vapor deposition equipment, a 25nm thick electron transport layer (C) is sequentially deposited on the surface of the titanium dioxide material layer. 60 A 5 nm thick hole-blocking layer (tin oxide) was obtained by atomic deposition, and a 100 nm thick metal electrode layer (Cu) was obtained by vacuum evaporation, thus obtaining a perovskite solar cell.

[0208] The thickness of 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.

[0209] (2) Performance testing, as detailed below:

[0210] 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. The efficiency retention rate Y was calculated according to the following formula:

[0211] Y = PCE(1000) / PCE(0) × 100%

[0212] The specific steps for testing photoelectric conversion efficiency are as follows:

[0213] Place the 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).

[0214] Using Guangyan's solar simulator, which complies with the national standard IEC61215, the simulation of sunlight (AM1.5G, 100mW / cm²) is performed. 2 Under illumination, the battery underwent current-voltage testing, with FTO as the positive electrode and Cu as the negative electrode. The test voltage ranged from -0.1V to 1.2V, and the battery area was 0.075cm².2 From the obtained IV curve, the short-circuit current Jsc (mA / cm) can be obtained. 2 The photoelectric conversion efficiency (PCE) is calculated using the following formula: open-circuit voltage Voc (V), fill factor FF (%), and photoelectric conversion efficiency (PCE) (%).

[0215] Calculation formula: PCE=V oc ×J sc ×FF / P in P in The incident light intensity (100mW / cm) 2 ).

[0216] Please see Table 1 for specific test results.

[0217] Examples 2-4

[0218] Examples 2-4 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.

[0219] The remaining test steps are the same as in Example 1. Please see Table 1 for the specific results.

[0220] Examples 5-10

[0221] Examples 5-10 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.

[0222] The remaining test steps are the same as in Example 1. Please see Table 1 for the specific results.

[0223] Comparative Example 1

[0224] 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.

[0225] The remaining steps are the same as in Example 1. For specific results, please see Table 1.

[0226] Comparative Example 2

[0227] 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:

[0228] 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.

[0229] The remaining steps are the same as in Example 1. For specific results, please see Table 1.

[0230] Comparative Examples 3-4

[0231] 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.

[0232] The remaining steps are the same as in Example 1. For specific results, please see Table 1.

[0233] Comparative Examples 5-6

[0234] 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.

[0235] The remaining steps are the same as those in Comparative Example 2. Please see Table 1 for the specific results.

[0236] Please refer to Table 1 for the relevant physical parameters and test results of each embodiment and comparative example.

[0237] Table 1

[0238]

[0239] Note that " / " indicates that the structure or substance does not exist.

[0240] Among them, "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, and "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 phenylethylamine, "mCF-PEAI" represents m-trifluoromethylphenylethylamine, "pMe-PEAI" represents p-methylphenylethylamine, "pOH-PEAI" represents p-hydroxyphenylethylamine, "ThEAI" represents 2-thiophene ethylamine iodine, and "ThMAI" represents 2-thiophene methylamine iodine.

[0241] 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; and when used as a passivation layer material, even if 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. Furthermore, as shown in Examples 1-3 and 4, further control of 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.

[0242] Further comparative analysis of the data from Example 1 and Comparative Examples 3-4 shows that the use of the compound of formula (2) containing an aromatic group structure to form the cationic moiety in this application can improve the photoelectric conversion efficiency and stability of the perovskite solar cell. However, when the cationic moiety in Comparative Examples 3-4 was formed by a general heteroaryl group, no such effect was observed. The reason for this phenomenon may be related to the strength of the aromaticity of the group. The aromaticity of an organic structure is related to the number of π electrons in its conjugated system. The stronger the aromaticity, the more π electrons it contains in its conjugated system, and the greater the conjugation effect. Compared with heteroaryl groups, the aromatic group structure in the cationic group formed by the compound of formula (2) contains more π 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.

[0243] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0244] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A perovskite solar cell, characterized in that, The perovskite solar cell includes a hole transport layer, a passivation layer, and a perovskite material layer stacked together. The passivation layer contains an ammonium salt compound; In the 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). ， ； Wherein, L1 is selected from any one of alkyl groups substituted with at least one oxyacid group and oxyacid groups, and 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. Ar1 is selected from substituted or unsubstituted aryl groups with 6 to 14 cyclic atoms, and L2 is selected from alkylene groups with 1 to 3 carbon atoms; n1 and n2 are each independently selected from any integer from 0 to 4.

2. The perovskite solar cell as described in claim 1, characterized in that, Ar1 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, wherein the substituent includes 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.

3. The perovskite solar cell as described in claim 1 or 2, characterized in that, The structure of Ar1 is shown below: ， 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.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, The ammonium salt compound satisfies one or both of the following conditions (1) to (2): (1) L1 is selected from alkyl groups having 1 to 5 carbon atoms substituted by at least one oxyacid group; (2) Each R1 and each R2 are 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.

5. The perovskite solar cell according to any one of claims 1 to 4, characterized in that, The ammonium salt compound includes the compound shown in formula (Ⅰ): ； Among them, L 11 Selected from alkylene groups having 1 to 5 carbon atoms, A - It is a group formed by losing a hydrogen atom from a hydroxyl group in the oxyacid group.

6. The perovskite solar cell according to any one of claims 1 to 5, characterized in that, The oxyacid group is selected from any one of phosphonic acid group, hypophosphite group, sulfonic acid group, carboxylic acid group, boric acid group or silicate group.

7. The perovskite solar cell according to any one of claims 1 to 6, characterized in that, The ammonium salt compound includes at least one of the following (a) to (e): ； L 11 R3 is selected from alkylene groups having 1 to 5 carbon atoms, and R3 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.

8. The perovskite solar cell as described in claim 7, characterized in that, R3 is selected from any one of F, hydroxyl group, or alkyl group with 1 to 3 carbon atoms substituted by fluorine atoms.

9. The perovskite solar cell as described in claim 1, characterized in that, 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. One or more of the following sulfonic acids; the compound of formula (2) includes one or more of the following: m-fluoroanisidine, p-fluoroanisidine, o-fluoroanisidine, m-fluorophenylethylamine, p-fluorophenylethylamine, o-fluorophenylethylamine, m-fluorophenylacetamide, p-fluorophenylacetamide, o-fluorophenylacetamide, m-trifluoromethylphenylethylamine, p-trifluoromethylphenylethylamine, o-trifluoromethylphenylethylamine, p-methylphenylethylamine, m-methylphenylethylamine, o-methylphenylethylamine, p-hydroxyphenylethylamine, m-hydroxyphenylethylamine, and o-hydroxyphenylethylamine.

10. The perovskite solar cell according to any one of claims 1 to 9, characterized in that, The hole transport layer includes at least one of inorganic hole transport materials and organic hole transport materials.

11. The perovskite solar cell according to any one of claims 1 to 10, characterized in that, The hole transport layer comprises nickel oxide.

12. The perovskite solar cell according to any one of claims 1 to 11, characterized in that, The passivation layer satisfies one or both of the following conditions (1) and (2): (1) 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; (2) The thickness of the passivation layer is 0.1 nm to 5 nm.

13. The perovskite solar cell according to any one of claims 1 to 12, characterized in that, 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, and 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.

14. The perovskite solar cell as described in claim 13, characterized in that, The perovskite solar cell further includes a hole blocking layer disposed between the electron transport layer and the second electrode.

15. The perovskite solar cell as described in claim 14, characterized in that, The perovskite solar cell satisfies one or more of the following conditions: (1) The thickness of the hole transport layer is 20nm~100nm; (2) The thickness of the perovskite material layer is 500 nm to 800 nm; (3) The thickness of the electron transport layer is 20nm~30nm; (4) The thickness of the hole blocking layer is 5nm~10nm.

16. A method for preparing a perovskite solar cell according to any one of claims 1 to 15, characterized in that, Includes 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.

17. A photovoltaic module, characterized in that, Including the perovskite solar cell as described in any one of claims 1 to 15.

18. A photovoltaic system, characterized in that, Including the photovoltaic module as described in claim 17.

19. An electrical appliance, characterized in that, It includes at least one of the perovskite solar cells as described in any one of claims 1 to 15 and the photovoltaic module as described in claim 17.

20. A power generation device, characterized in that, It includes at least one of the perovskite solar cells as described in any one of claims 1 to 15 and the photovoltaic module as described in claim 17.

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