Perovskite solar cells and their manufacturing methods, photovoltaic modules, systems and power consumption devices

Abstract

A perovskite solar cell and a method for manufacturing the same, a photovoltaic module, a system, and a power consumption device, wherein the perovskite solar cell comprises a transparent electrode layer and a perovskite layer provided thereon in order, an electron transport layer and a metal electrode, the electron transport layer comprises an organic electron transport material, a first additive and a second additive, the first additive comprises one or more of polymethyl methacrylate, methacrylate-methyl methacrylate copolymer, 4-vinylpyridine-styrene copolymer, polyacrylonitrile and poly4-vinylpyridine, and the second additive comprises one or more of the compound of formula I and the compound of formula II. The perovskite solar cell has relatively high photoelectric conversion efficiency and good stability.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to Chinese Patent Application No. 202310855619.X, filed on 12 July 2023, titled "Perovskite Solar Cell and Method for Manufacturing the Same, Photovoltaic Module, System and Power Consumption Device," which is incorporated into this application in its entirety by reference.

[0002] This application relates to the field of solar cell technology, and more particularly to perovskite solar cells and methods for manufacturing the same, photovoltaic modules, systems, and power consumption devices. [Background technology]

[0003] With the rapid development of the new energy sector, solar cells are widely applied in fields such as industry, commerce, agriculture, and telecommunications. Perovskite solar cells (PSCs) are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite-type crystalline materials. They are the current third generation of solar cells and have various advantages such as high photoelectric conversion efficiency, simple manufacturing process, and low production cost, and have been the subject of much research in recent years.

[0004] With the maturation of processes for organic electron transport layer materials such as fullerene derivatives, naphthalene diimides, and perylene diimides, and the continuous decline in prices, organic electron transport layer materials are gradually being applied to large-scale industrial production. Organic electron transport layer materials can improve the hysteresis phenomenon of devices and, to some extent, improve the photoelectric conversion efficiency of devices. However, the photoelectric conversion efficiency of perovskite solar cells using current organic electron transport layer materials still needs further improvement, and the stability of these cells is relatively poor.

[0005] Therefore, improving the photoelectric conversion efficiency and stability of perovskite solar cells that use organic materials as electron transport layers is one of the important problems that need to be solved urgently in this field.

Summary of the Invention

Problems to be Solved by the Invention

[0006] This application is made in view of the above problems, and one of its objects is to provide a perovskite solar cell having a relatively high photoelectric conversion efficiency and good stability.

Means for Solving the Problems

[0007] To achieve the above object, the first aspect of this application provides a perovskite solar cell, which includes a transparent electrode layer, a perovskite layer, an electron transport layer, and a metal electrode provided in sequence on the transparent electrode layer. The electron transport layer includes an organic electron transport material, a first additive, and a second additive. The first additive includes one or more of polymethyl methacrylate, methacrylic acid-methyl methacrylate copolymer, 4-vinylpyridine-styrene copolymer, polyacrylonitrile, and poly-4-vinylpyridine. The second additive includes one or more of the compounds of formula I and the compounds of formula II:

Chemical Formula

[0008] The perovskite solar cell of this application is characterized by adding a specific organic polymer as a first additive to an electron transport layer using an organic electron transport material, and adding a specific quaternary ammonium salt and / or tertiary amine molecule as a second additive. The introduction of the first additive, an organic polymer, can improve the dispersibility of the organic electron transport material in the solution forming the electron transport layer, improve the uniformity of the electron transport layer film, and reduce the water molecule entry channels in the electron transport layer. The second additive, a quaternary ammonium salt, can significantly improve the conductivity of the electron transport layer film. The second additive, a tertiary amine molecule, can improve the intermolecular bonding force of the organic electron transport material. The quaternary ammonium salt and tertiary amine molecule can form a passivation layer with the perovskite interface during the molecular crystallization process of the electron transport layer, thereby reducing the diffusion of perovskite ions. The combined action of the specific first and second additives can improve the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0009] In any embodiment, with respect to the total mass of the electron transport layer, the mass fraction of the first additive is 1% to 5%, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%. In this way, the photoelectric conversion efficiency and stability of the perovskite solar cell can be further improved.

[0010] In any embodiment, the second additive comprises the compound of formula I and the compound of formula II, with a mass ratio of (0.5-2):1 between the compound of formula I and the compound of formula II. In this way, the photoelectric conversion efficiency and stability of the perovskite solar cell can be further improved.

[0011] In any embodiment, the compound of formula I comprises one or more of tetrabutylammonium tetrafluoroborate, hexa-bisammonium iodide, and dodecyltrimethylammonium bromide.

[0012] In any embodiment, the compound of formula II comprises one or more of 1,7-bis(dimethylamino)heptane, tris(dimethylaminopropyl)amine, and 9,9-bis[3-(dimethylamino)propyl]fluorene.

[0013] In any embodiment, the thickness of the electron transport layer is 25 nm to 45 nm.

[0014] In any embodiment, the organic electron transport material comprises one or more of the following: fullerene derivatives, naphthalene diimides and their derivatives, and perylene diimides and their derivatives.

[0015] A second aspect of this application provides a method for manufacturing a perovskite solar cell, the method being: Steps to provide a transparent electrode layer and The process includes the steps of sequentially forming a perovskite layer, an electron transport layer, and a metal electrode on a transparent electrode layer. Here, the solution forming the electron transport layer comprises a solvent and a solute dispersed in the solvent, the solute comprising an organic electron transport material, a first additive and a second additive.

[0016] By adding specific first and second additives to the electron transport layer solution, the photoelectric conversion efficiency and stability of perovskite solar cells can be improved.

[0017] In any embodiment, the solvent comprises a first organic solvent and a second organic solvent, the boiling point of the first organic solvent being 38°C to 90°C, and the boiling point of the second organic solvent being 110°C to 210°C. Thus, the first organic solvent is a low-boiling point solvent, and the second organic solvent is a high-boiling point solvent. By using the mixed solvent of the first and second organic solvents, the organic electron transport material, the first additive, and the second additive can be dispersed in this mixed solvent system. This optimizes the crystal order and uniformity of the organic electron transport material molecules and the first and second additives, inducing molecular orientation, thereby enhancing the thin-film quality and conductivity of the electron transport layer, and improving the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0018] In any embodiment, the first organic solvent includes one or more of chloroform, dichloromethane, and tetrahydrofuran.

[0019] In any embodiment, the second organic solvent includes one or more of chlorobenzene, o-dichlorobenzene, toluene, o-xylene, anisole, 2-methylanisole, 2-chlorophenol, and 1,2,3,4-tetrahydronaphthalene.

[0020] In any embodiment, the volume fraction of the first organic solvent is 20% to 80% of the total volume of the solvent, and the volume fraction of the second organic solvent is 20% to 80%.

[0021] In any embodiment, with respect to the total mass of the solution, the mass fraction of the first additive is 0.2‰ to 1‰, the mass fraction of the second additive is 0.1‰ to 0.4‰, and the mass fraction of the organic electron transport material is 1.86% to 1.97%.

[0022] In any embodiment, with respect to the total mass of the solute, the mass fraction of the first additive is 1% to 5%, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%.

[0023] A third aspect of this application provides a photovoltaic module including a perovskite solar cell of the first aspect of this application.

[0024] A fourth aspect of this application provides a photovoltaic system including a photovoltaic module of the third aspect of this application.

[0025] A fifth aspect of this application provides a power consumption device comprising at least one of a perovskite solar cell of the first aspect of this application and a photovoltaic module of the third aspect of this application.

[0026] The perovskite solar cell of this application can effectively improve the photoelectric conversion efficiency and stability of a perovskite solar cell using an organic electron transport material as an electron transport layer by adding a specific organic polymer as a first additive to an electron transport layer using an organic electron transport material, and adding a specific quaternary ammonium salt and / or tertiary amine molecule as a second additive.

[0027] To more clearly illustrate the technical concept of the embodiments of this application, the following briefly introduces the drawings that may be used in the embodiments of this application. It is obvious that the drawings in the following description represent only a few embodiments of this application, and those skilled in the art can obtain other drawings based on these, without requiring any creative effort. In the drawings, [Brief explanation of the drawing]

[0028] [Figure 1] Figure 1 is a schematic diagram of the structure of a perovskite solar cell according to one embodiment of this application. [Figure 2] Figure 2 is a schematic diagram of the structure of a power consumption device according to one embodiment of this application. [Modes for carrying out the invention]

[0029] Hereinafter, with appropriate reference to the drawings, several embodiments of the perovskite solar cell and its manufacturing method, photovoltaic modules, systems, and power consumption devices disclosed in this application will be described in detail. However, unnecessary details may be omitted. For example, detailed explanations of well-known matters and repeated explanations of structures that are actually the same may be omitted. This is to avoid the following description becoming unnecessarily verbose and to make it easily understandable to those skilled in the art. The drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the topics described in the claims.

[0030] The “range” disclosed in this application is limited in the form of a lower limit and an upper limit, and a given range is limited by selecting one lower limit and one upper limit, which define the boundary of a particular range. The range thus limited may or may not include the limit value, and any combination is possible, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 can also be assumed. Furthermore, if 1 and 2 are listed as the minimum range values ​​and 3, 4, and 5 are listed as the maximum range values, then ranges such as 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5 can all be assumed. In this application, unless otherwise specified, the numerical range “a-b” represents an abbreviated expression for any combination of real numbers a-b, where a and b are both real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" have already been listed in this specification, and "0 to 5" is simply an abbreviated representation of combinations of these numbers. Also, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For example, when a parameter is expressed as an integer selected from "2 to 10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0031] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical inventions.

[0032] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the fact that the method includes steps (a) and (b) means that the method may include steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, the fact that the method referred to above may further include step (c) means that step (c) may be added to the method in any order, for example the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), and so on.

[0033] Unless otherwise specified, the terms “includes” and “inclusion” as used in this application may represent an open or closed configuration. For example, the terms “includes” and “inclusion” may mean that other components not listed may be included or inclusion, or that only the listed components may be included or inclusion.

[0034] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B." Furthermore, the conditions "A or B" are all satisfied, including the condition that A is true (or exists) and B is false (or does not exist), the condition that A is false (or does not exist) but B is true (or exists), and the condition that both A and B are true (or exist).

[0035] In this application, unless otherwise specified, A (for example, B) can be understood as B representing a non-exclusive example of A, and A being not limited to B.

[0036] In this application, "multiple" and "multiple types" refer to a number greater than or equal to 2, unless otherwise specified. For example, "one or more" means one or two or more.

[0037] As used herein, “that combination,” “that any combination,” and “that any combination method” include all appropriate combination methods of any two or any two or more items from the listed items.

[0038] In this specification, the term "appropriate" as used in phrases such as "appropriate combination method," "appropriate method," and "any appropriate method" refers to a technical solution that can implement this application.

[0039] In this specification, “preferred,” “better,” “more suitable,” and “good” are used to describe embodiments or examples that have a better effect and should be understood as not constituting a limitation on the scope of protection of this application. Where multiple “preferred” terms appear in a single technical proposal, each “preferred” is independent unless otherwise specified and there is no contradiction or mutual constraint.

[0040] In this application, terms such as "furthermore," "even more," and "special" are for explanatory purposes only and indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0041] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are merely for descriptive purposes and should not be understood as indicating or suggesting relative importance or number, nor should they be understood as implicitly indicating the importance or number of the technical features being discussed. Furthermore, it should be understood that "first aspect," "second aspect," "third aspect," and "fourth aspect" are merely for the purpose of illustrating with non-exclusive examples and do not restrict the number in a closed manner.

[0042] In this application, the term "room temperature" generally refers to 4°C to 35°C, and may also refer to 20°C ± 5°C. In some embodiments of this application, room temperature refers to 20°C to 30°C.

[0043] In this application, when relating to the units of a data range, if the unit is placed only after the rightmost endpoint, it indicates that the leftmost endpoint has the same unit as the rightmost endpoint. For example, 3h~5h or 3h~5h both indicate that the units of the leftmost endpoint "3" and the rightmost endpoint "5" are all in hours (h).

[0044] The weights of the relevant components mentioned in the specification of the embodiments of this application may not only refer to the content of each component but also represent the proportional weight relationships between the components. Therefore, any proportional expansion or contraction according to the content of the relevant components in the specification of the embodiments of this application falls within the scope disclosed in the specification of the embodiments of this application. Furthermore, the weights described in the specification of the embodiments of this application may be in mass units known in the chemical industry, such as μg, mg, g, and kg.

[0045] In this specification, unless otherwise specified, “alkyl group” refers to a monovalent residue produced by the loss of one hydrogen atom from a saturated hydrocarbon containing a primary (positive) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. This term is not used in any other way around. 1~9"Alkyl group" refers to an alkyl group containing 1 to 9 carbon atoms, and each instance may be independently a C1 alkyl group, C2 alkyl group, C3 alkyl group, C4 alkyl group, C5 alkyl group, C6 alkyl group, C7 alkyl group, C8 alkyl group, or C9 alkyl group. Suitable examples include methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), and 2-butyl (s-Bu, s-butyl, -CH(CH3)CH 2CH3), 2-methyl-2-propyl(t-Bu, t-butyl, -C(CH3)3), 1-pentyl(n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl(-CH(CH3)CH2CH2CH3), 3-pentyl(-CH(CH2CH3)2), 2-methyl-2-butyl(-C(CH3)2CH2CH3), 3-methyl-2-butyl(-CH(CH3)CH(CH3)2), 3-methyl-1-butyl(-CH2CH2 CH(CH3)2), 2-methyl-1-butyl(-CH2CH(CH3)CH2CH3), 1-hexyl(-CH2CH2CH2CH2CH2CH3), 2-hexyl(-CH(CH3)CH2CH2CH2CH3), 3-hexyl(-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl(-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl(-CH(CH3)CH(CH3)CH2CH3) This includes, but is not limited to, 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), and octyl (-(CH2)7CH3).

[0046] In this specification, unless otherwise specified, "heteroalkyl group" refers to an alkyl group in which at least one carbon atom is substituted with a non-carbon atom, and the non-carbon atom may be an N atom, O atom, S atom, P atom, etc. The following explanation will use O, N, and S as examples. For example, if a carbon atom bonded to an adjacent group in an alkyl group is replaced with a non-carbon O, N, or S, the resulting heteroalkyl group is an alkoxy group (e.g., -OCH3), an amino group (e.g., -NHCH3, -N(CH3)2), or a thioalkyl group (e.g., -SCH3), respectively. If a carbon atom in an alkyl group that is not directly bonded to an adjacent group is replaced with a non-carbon O, N, or S, the resulting heteroalkyl group is an alkoxyalkyl group (e.g., -CH2CH2-O-CH3), an alkylaminoalkyl group (e.g., -CH2NHCH3, -CH2N(CH3)2), or an alkylthioalkyl group (e.g., -CH2-S-CH3), respectively. When the terminal carbon atoms of an alkyl group are replaced with non-carbon atoms, the resulting heteroalkyl group may be a hydroxyalkyl group (e.g., -CH2CH2-OH), an aminoalkyl group (e.g., -CH2NH2), or a mercaptoamino group (e.g., -CH2CH2-SH). Phrases containing this term, "heteroalkyl group," such as "C1-C9 heteroalkyl group" or "C 1~9 A "heteroalkyl group" refers to a heteroalkyl group containing one to nine carbon atoms, and each instance may independently consist of a C1 heteroalkyl group, a C2 heteroalkyl group, a C3 heteroalkyl group, a C4 heteroalkyl group, a C5 heteroalkyl group, a C6 heteroalkyl group, a C7 heteroalkyl group, a C8 heteroalkyl group, or a C9 heteroalkyl group.

[0047] In this specification, unless otherwise specified, "cycloalkyl group" has the same meaning as "non-aromatic ring hydrocarbon group," and refers to a monovalent residue produced when a non-aromatic hydrocarbon (saturated or unsaturated hydrocarbon) containing a ring carbon atom loses one hydrogen atom on the ring, i.e., directly forms a monovalent linkage site on the ring. Cycloalkyl groups derived from non-aromatic saturated hydrocarbons may also be written as saturated cycloalkyl groups, and cycloalkyl groups derived from non-aromatic unsaturated hydrocarbons may also be written as unsaturated cycloalkyl groups. Cycloalkyl groups may be monocycloalkyl groups, spirocycloalkyl groups, or crosslinked cycloalkyl groups. Phrases containing this term, for example, "C3-C9 cycloalkyl groups" or "C 3~9 A "cycloalkyl group" refers to a cycloalkyl group containing 3 to 9 carbon atoms, and each instance may independently be a C3, C4, C5, C6, C7, C8, or C9 cycloalkyl group. A suitable example is the cyclopropyl group. [ka] Cyclobutyl group [ka] Cyclopentyl group [ka] Cyclohexyl group [ka] This includes, but is not limited to, a cycloheptyl group. Furthermore, a "cycloalkyl group" may further contain one or more double bonds, and a typical example of a cycloalkyl group containing a double bond is a cyclopentenyl group. [ka] (Includes, but is not limited to), cyclohexenyl group ( [ka] (including, but not limited to), cyclohexadiene group ( [ka] (Includes, but is not limited to), cyclopentadienyl group ( [ka] (Includes, but is not limited to) and cyclobutadienyl group ( [ka] (Includes, but is not limited to)

[0048] In this specification, unless otherwise specified, “heterocycloalkyl group” means a cycloalkyl group in which at least one carbon atom is substituted with a noncarbon atom, which may be an N atom, an O atom, a S atom, etc., and may be a saturated ring or a partially unsaturated ring. A phrase containing this term, for example, “C4-C9 heterocyclyl group,” means a heterocyclyl group containing four to nine carbon atoms, which, each time it appears, may be independently a C4 heteroalkyl group, a C5 heteroalkyl group, a C6 heteroalkyl group, a C7 heteroalkyl group, a C8 heteroalkyl group, or a C9 heteroalkyl group. Suitable examples include, but are not limited to, dihydropyridyl group, tetrahydropyridyl group (piperidyl group), tetrahydrothienyl group, sulfur-oxidized tetrahydrothienyl group, tetrahydrofuranyl group, tetrahydroquinolinyl group, tetrahydroisoquinolinyl group, and dihydroindolyl group.

[0049] In this specification, unless otherwise specified, "aryl group" refers to an aromatic hydrocarbon group derived from the loss of one hydrogen atom on an aromatic ring hydrocarbon compound, that is, a monovalent linkage site that directly forms on the ring, and may be a monocyclic aryl group, a fused ring aryl group, or a polycyclic aryl group, and for a polycyclic ring species, at least one is an aromatic ring system. For example, "C6~C 10The term "aryl group" refers to an aryl group containing 6 to 10 carbon atoms, and each time it appears, it may independently be a C6 aryl group, a C8 aryl group, a C9 aryl group or a C 10 aryl group. Further, for example, the term "C6-C 20 aryl group" refers to an aryl group containing 6 to 20 carbon atoms, and each time it appears, it may independently be a C6 aryl group (e.g., phenyl group), a C6 aryl group (e.g., benzocyclobutenyl group), a C8 aryl group (e.g., benzocyclobutene), a C9 aryl group (e.g., indenyl group), a C 10 aryl group (e.g., naphthyl group), a C 12 aryl group (e.g., acenaphthyl group, biphenyl group), a C 13 aryl group (e.g., fluorenyl group), a C 14 aryl group (e.g., anthracenyl group, phenanthryl group), a C 18 aryl group (e.g., triphenylene group) or a C 20 aryl group (e.g., perylene group), but is not limited thereto. Examples of suitable aromatic ring hydrocarbon compounds include, but are not limited to, benzene, benzocyclobutene, biphenyl, indene, naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, triphenylene, perylene and their derivatives.

[0050] In this specification, unless otherwise specified, the term "heteroaryl group" is a heteroaryl group having aromaticity, and may be a monovalent group formed by substituting at least one carbon atom on an aryl group with a non-carbon atom, or may be a monovalent group formed by substituting at least one carbon atom on a cyclopentadienyl group with a non-carbon atom. The non-carbon atom may be, but is not limited to, an N atom, an O atom, an S atom, etc. For example, "C1-C 10A "heteroaryl group" refers to a heteroaryl group containing 1 to 10 carbon atoms, and each time it appears, it is independently a C1 heteroaryl group (e.g., tetrazolyl group), a C2 heteroaryl group (e.g., triazolyl group, oxadiazolyl group), a C3 heteroaryl group (e.g., imidazolyl group), a C4 heteroaryl group (e.g., furyl group), a C5 heteroaryl group (e.g., pyridyl group), a C6 heteroaryl group, a C7 heteroaryl group (e.g., benzimidazole group), a C8 heteroaryl group (e.g., indolyl group), a C9 heteroaryl group (e.g., quinolinyl group), or C 10 It may also be a heteroaryl group (for example, a pyrrolobispyridyl group). Also, for example, "C3~C 20 A "heteroaryl group" refers to a heteroaryl group containing 3 to 20 carbon atoms, and each time it appears, they are independently C2 heteroaryl, C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, C6 heteroaryl, C8 heteroaryl, C9 heteroaryl, and C2 heteroaryl groups. 10 Heteroaryl group, C 12 Heteroaryl group, C 13 Heteroaryl group, C 14 Heteroaryl group, C 18 Heteroaryl group or C 20 It may be a heteroaryl group, but is not limited to them. Suitable examples include furan (C4), benzofuran (C8), thiophene (C4), benzothiophene (C8), pyrrole (C4), pyrazole (C3), triazole (C2), imidazole (C3), oxazole (C3), oxadiazole (C2), thiazole (C3), tetrazole (C1), indole (C8), carbazole (C 12), pyrroloimidazole (C5), pyrrolopyrrole (C6), thienopyrrole (C6), thienopyrrole (C6), flopyrrole (C6), flofran (C6), thienofran (C6), thienopyridine (C7), flopyridine (C7), benzoxazole (C7), benzoisoxazole (C7), benzothiazole (C7), benzoisothiazole (C7), benzimidazole (C7), pyridine (C5), pyrazine (C4), pyridazine (C4), pyrimidine (C4), triazine (C3), quinoline (C9), isoquinoline (C9), naphthyridine (C8, e.g., o-naphthyridine), quinoxaline (C8), phenanthridine (C 13 ), perimidine (C 11 This includes, but is not limited to, heteroaryl groups derived from quinazoline (C8) and quinazolinone (C8) (the number of carbon atoms is indicated in parentheses).

[0051] In this specification, unless otherwise specified, "alkylene group" refers to a hydrocarbon group having two monovalent centers, which is derived by removing two hydrogen atoms from an alkane (or by losing one more hydrogen atom from an alkyl group), and which may be a saturated branched alkyl group or an unsaturated linear alkyl group. For example, "C1-C9 alkylene group" refers to a group in which the alkyl group contains 1 to 9 carbon atoms, and each instance may independently be a C1 alkylene group, a C2 alkylene group, a C3 alkylene group, a C4 alkylene group, a C5 alkylene group, a C6 alkylene group, a C7 alkylene group, a C8 alkylene group, or a C9 alkylene group. Appropriate examples include, but are not limited to, the methylene group (-CH2-), 1,1-ethyl group (-CH(CH3)-), 1,2-ethyl group (-CH2CH2-), 1,1-propyl group (-CH(CH2CH3)-), 1,2-propyl group (-CH2CH(CH3)-), 1,3-propyl group (-CH2CH2CH2-), and 1,4-butyl group (-CH2CH2CH2CH2-).

[0052] In this specification, unless otherwise specified, "halogen" or "halo group" refers to F, Cl, Br, or I.

[0053] In this specification, unless otherwise specified, "amino group" may be a primary amino group (-NH2), a secondary amino group (>NH), a tertiary amino group (>N-), or a quaternary amino group (>N+<).

[0054] In this specification, unless otherwise specified, a hydroxyl group is -OH, a carboxyl group is -COOH, a cyano group is -CN, a hydrazine group is -NHNH2, a sulfinic acid group is -S(=O)OH, a phosphinic acid group is (*-)2P(=O)OH, a sulfonic acid group is -S(=O)2OH, a phosphate group is (*-)P(=O)(OH)2, and a boric acid group is (*-)B(OH)2. Here, in a phosphinic acid group, * indicates that it is bonded to a carbon atom or H and at least one of them is bonded to a carbon atom, in a phosphonic acid group, * indicates that it is bonded to a carbon atom, and in a boric acid group, * indicates that it is bonded to a carbon atom.

[0055] Currently, the photoelectric conversion efficiency of perovskite solar cells using organic electron transport layer materials still needs further improvement, and the stability of these cells is relatively poor, limiting the large-scale industrial production of perovskite solar cells using organic electron transport layer materials. This application provides a perovskite solar cell that can effectively improve the photoelectric conversion efficiency and stability of perovskite solar cells by adjusting the material components that form the organic electron transport layer.

[0056] Referring to Figure 1, one embodiment of the present application provides a perovskite solar cell 1 with a transformer structure. This perovskite solar cell 1 includes a transparent electrode layer 11 and a hole transport layer 12, a perovskite layer 13, an electron transport layer 14, and a metal electrode 15, which are sequentially provided on the transparent electrode layer 11.

[0057] Here, the electron transport layer 14 comprises an organic electron transport material, a first additive and a second additive, wherein the first additive comprises one or more of polymethyl methacrylate, methacrylate-methyl methacrylate copolymer, 4-vinylpyridine-styrene copolymer, polyacrylonitrile and poly4-vinylpyridine. The second additive comprises one or more of the compounds of formula I and formula II below: [ka] Here, R1, R2, R3, R5 and R6 are each independently selected from C1-C4 alkyl groups, n1 and n2 are each independently integers from 1 to 6, m1 and m2 are each independently integers from 1 to 4, R4 and R7 are each independently alkyl groups from C1-C5, alkoxy groups from C1-C5, alkyl mercapto groups from C1-C5, aryl groups, halogens, carboxyl groups, cyano groups, or none, X is one or more of Cl, Br, I, BF4, PF6 and TFSI, and Y1 and Y2 are each independently selected from one of CH2, NH, O and S, or none. Here, "none" means that this group is H.

[0058] Conventional perovskite solar cells 1 using organic electron transport layer materials suffer from limitations in photovoltaic performance and photoelectric conversion efficiency due to the relatively low conductivity of the organic electron transport material. Simultaneously, the dispersibility of the organic electron transport material in the solvent is not sufficiently high, leading to relatively serious aggregation phenomena. This affects the uniformity of the electron transport layer 14 film, resulting in relatively poor stability of batteries using organic electron transport material as the electron transport layer 14. These factors hinder the large-scale industrial application of perovskite solar cells 1 using organic electron transport material as the electron transport layer 14.

[0059] The perovskite solar cell 1 of this application adds a specific organic polymer as a first additive to an electron transport layer 14 using an organic electron transport material, and adds a specific quaternary ammonium salt and / or tertiary amine molecule as a second additive. The introduction of the organic polymer can improve the dispersibility of the organic electron transport material in the solution forming the electron transport layer 14, reduce aggregation of the organic electron transport material, improve the uniformity of the film layer of the electron transport layer 14, and further improve the photoelectric conversion efficiency of the device. The introduction of the quaternary ammonium salt can significantly improve the conductivity of the film layer of the electron transport layer 14, thereby improving the photoelectric conversion efficiency of the perovskite solar cell. The introduction of the tertiary amine molecule can improve the bonding force with the transport layer molecules through the bonding action between the N atom and the electron transport layer 14, improve molecular orientation, and enhance the electron mobility of the electron transport layer 14.

[0060] Furthermore, the hydrophobic functional groups in the above organic polymer reduce the entry channels for water molecules in the electron transport layer 14, mitigating the reaction of water with the perovskite through the electron transport layer 14, thereby improving the stability of the device. The quaternary ammonium salt and tertiary amine molecules reduce the diffusion of perovskite ions by forming a passivation layer with the perovskite interface during the molecular crystallization process of the electron transport layer 14, suppressing the decomposition of the perovskite and improving the stability of the device. The synergistic action of the above specific first and second additives can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell 1 using the organic electron transport material.

[0061] To make it easier to understand, the electron transport layer 14 of the perovskite solar cell 1 may contain only the organic electron transport material, the first additive of the organic polymer system, and the second additive of the quaternary ammonium salt system; or it may contain only the organic electron transport material, the first additive of the organic polymer system, and the second additive of the tertiary amine molecule system; or it may contain the organic electron transport material, the first additive of the organic polymer system, the second additive of the quaternary ammonium salt system, and the second additive of the tertiary amine molecule system simultaneously.

[0062] To make it easier to understand, in the compounds of formula I and formula II described above, R1, R2, R3, R5 and R6 may each be independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, etc., n1 and n2 may each be independently 1, 2, 3, 4, and 5, and m1 and m2 may each be independently 1, 2, 3, and 4.

[0063] In some of these embodiments, the mass fraction of the first additive is 1% to 5% of the total mass of the electron transport layer 14, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%. The amounts of the first additive, the second additive, and the organic electron transport material used in the electron transport layer 14 are within the above ranges, which can further improve the photoelectric conversion efficiency and stability of the perovskite solar cell 1.

[0064] In some of these embodiments, the second additive comprises a compound of formula I and a compound of formula II, and the mass ratio of the compound of formula I to the compound of formula II is (0.5-2):1. In this way, by simultaneously using two types of second additives, the compound of formula I and the compound of formula II, in the electron transport layer 14, and controlling the mass ratio of the compound of formula I to the compound of formula II within the range of (0.5-2):1, the photoelectric conversion efficiency and stability of the perovskite solar cell 1 can be further improved through the synergistic action of a specific amount of a quaternary ammonium salt-based second additive, a tertiary amine molecule-based second additive, an organic polymer-based first additive, and an organic electron transport material.

[0065] In some of these examples, the compound of formula I is one or more of tetrabutylammonium tetrafluoroborate, hexa-bisammonium iodide, and dodecyltrimethylammonium bromide, and the compound of formula II is one or more of 1,7-bis(dimethylamino)heptane, tris(dimethylaminopropyl)amine, and 9,9-bis[3-(dimethylamino)propyl]fluorene.

[0066] In some of these embodiments, the thickness of the electron transport layer is 25 nm to 45 nm. As can be understood, the thickness of the electron transport layer may be, but is not limited to, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, or 45 nm.

[0067] In some of these examples, the organic electron transport material comprises one or more of the following: fullerene derivatives, naphthalenediimides and their derivatives, and perylenediimides and their derivatives. Here, the fullerene derivative is PCBM([6,6]-phenyl-C 61 -Isomethyl butyrate), [6,6]-phenyl-C71-methyl butyrate (PC71BM), C 60 -PDI(C 60 -Perylenediimide, etc., may also be used.

[0068] In some of these embodiments, the transparent electrode layer 11 may be made of a transparent conductive oxide, such as FTO (fluorine-doped tin oxide, SnO2:F), ITO (tin-doped indium oxide), BZO (boron-doped zinc oxide), AZO (zinc aluminum oxide), or IZO (indium zinc oxide). The conductive oxide may be laid on a substrate, and the substrate may be a rigid substrate or a flexible substrate. In some embodiments, the substrate may be made of transparent glass.

[0069] The hole transport layer 12 may be made of hole transport materials commonly used in this field. One specific example is that the hole transport layer 12 may be made of PTAA (polytriarylamine), Spiro-OMeTAD (tetrakis(N,Np-methoxyanilino)-9,9'-spirobifluorene), or Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphate).

[0070] The perovskite layer 13 may use perovskite components commonly used in this field, the chemical formula of which satisfies ABX3 or A2CDX6, where A is an inorganic monovalent cation or an organic monovalent cation or a mixture thereof, and A is FA + MA + , Cs + , Rb + , K + DMA + EA + GA + It includes one or more of the following, where B is an inorganic divalent metal cation, and B is Pb 2+ , Ge 2+ , Cd 2+ Sb 2+ Zn 2+ Mn 2+ Ca 2+ It includes one or more of the following, where C is a noble metal cation, and generally Ag + D is a heavy metal or rare metal trivalent cation, and Bi is a bismuth cation. 3+ Antimony cation Sb 3+ , and indium cation In 3+X may be at least one of the following, where X is oxygen, a halogen element, or a pseudohalogen element, and X is I - , Br - Cl - SCN - , HCOO - CH3COO - CF3COO - CH3SO3 - CF3SO3 - 5CN - It includes one or more of the following. In one specific example, the perovskite component is Cs 0.05 MA 0.1 FA 0.85 PbI3 is used, where MA is methylammonium and FA is formamidine.

[0071] The metal electrode 15 may be an electrode commonly used in this field, such as Au, Ag, Cu, Al, or Pt. In one specific example, the metal electrode 15 is an Ag electrode.

[0072] One embodiment of this application provides a method for manufacturing the perovskite solar cell 1 described above, the manufacturing method comprising the following steps S100 to S500.

[0073] Step S100: Provide a transparent electrode layer 11.

[0074] This transparent electrode layer 11 is used as the device substrate, and specifically, FTO glass may be used for the transparent electrode layer 11. Before manufacturing the hole transport layer 12 on the transparent electrode layer 11, the transparent electrode layer 11 is first subjected to UV cleaning to remove impurities from the surface of the transparent electrode layer 11.

[0075] In one specific example, the transparent electrode layer 11 is made of FTO glass.

[0076] Step S200: A hole transport layer 12 is formed on the transparent electrode layer 11.

[0077] A solution containing a hole transport material is spin-coated onto one surface of the transparent electrode layer 11 using a spin-coating process, and after annealing, a hole transport layer 12 is formed.

[0078] Here, the spin coating process parameters (e.g., spin coating rotation speed, spin coating time, etc.) used when manufacturing the hole transport layer 12 may be specifically set according to actual conditions such as the thickness of the hole transport layer 12 to be manufactured. Similarly, the annealing temperature may be set according to actual production conditions.

[0079] To make it clear, the material forming the hole transport layer 12 may be a common hole transport material in this field.

[0080] In one specific example, PTAA is used as the hole transport material, the spin coating rotation speed is 5000 rpm / s, the spin coating time is 30 s, and the annealing temperature is 100°C.

[0081] Step S300: A perovskite layer 13 is formed on the hole transport layer 12.

[0082] A solution containing a perovskite component is spin-coated onto the surface of the hole transport layer 12, away from the transparent electrode layer 11, using a spin-coating process. After annealing, a perovskite layer 13 is formed.

[0083] Here, the spin coating process parameters (e.g., spin coating rotation speed, spin coating acceleration, spin coating time, etc.) used when manufacturing the perovskite layer 13 may be specifically set according to actual conditions such as the thickness of the perovskite layer 13 to be manufactured. The annealing temperature may also be set according to actual production conditions.

[0084] To make it easier to understand, the perovskite layer 13 may use perovskite components commonly used in this field.

[0085] In one specific example, the perovskite component is Cs 0.05MA 0.1 FA 0.85 Using PbI3, the spin coat rotation speed was 5000 rpm / s, the spin coat acceleration was 2000 rpm / s, the spin coat time was 30 s, and the annealing temperature was 100°C.

[0086] Step S400: An electron transport layer 14 is formed on the perovskite layer 13.

[0087] An electron transport layer 14 can be formed without annealing by spin-coating a solution containing an organic electron transport material, a first additive, and a second additive onto a surface of the perovskite layer 13 away from the hole transport layer 12 using a spin-coating process. This solution comprises a solvent and a solute dispersed in the solvent, where the solute includes the organic electron transport material, the first additive, and the second additive. The types of organic electron transport material, the first additive, and the second additive in the electron transport layer 14 are as described above and will not be further explained here.

[0088] To make it easier to understand, the spin-coating process parameters (e.g., spin-coating rotation speed, spin-coating time, etc.) used when manufacturing the electron transport layer 14 may be specifically set according to the actual conditions, such as the thickness of the electron transport layer 14 to be manufactured. The electron transport layer 14 may use organic electron transport materials commonly used in this field.

[0089] In one specific example, the spin-coating rotation speed is 2000 rpm / s, the spin-coating time is 30 s, and PCBM is used as the organic electron transport material.

[0090] In some embodiments, the solvent in the solution forming the electron transport layer 14 includes a first organic solvent and a second organic solvent, where the first organic solvent is a low-boiling point solvent with a boiling point of 38°C to 70°C, and the second organic solvent is a high-boiling point solvent with a boiling point of 110°C to 210°C.

[0091] In some examples, the first organic solvent includes one or more of chloroform (boiling point approximately 61°C), dichloromethane (boiling point approximately 39.75°C), and tetrahydrofuran (boiling point approximately 66°C). The second organic solvent includes one or more of chlorobenzene (boiling point approximately 132.2°C), o-dichlorobenzene (boiling point approximately 180.4°C), toluene (boiling point approximately 110.6°C), o-xylene (boiling point approximately 144.4°C), anisole (boiling point approximately 153.8°C), 2-methylanisole (boiling point approximately 170°C), 2-chlorophenol (boiling point approximately 174°C), and 1,2,3,4-tetrahydronaphthalene (boiling point approximately 207.2°C).

[0092] In some of these examples, the volume fraction of the first organic solvent is 20% to 80% of the total volume of the solvent, and the volume fraction of the second organic solvent is 20% to 80%. As can be understood, the volume fraction of the first organic solvent may be 20%, 30%, 40%, 50%, 60%, 70%, or 80%, but is not limited to these, and accordingly, the volume fraction of the second organic solvent may be 80%, 70%, 60%, 50%, 40%, 30%, or 20%, but is not limited to these. In one specific example, the volume ratio of the first organic solvent to the second organic solvent is 1:1, that is, a high-boiling point solvent and a low-boiling point solvent are mixed in equal volumes, and the volume fraction of each is 50%.

[0093] In some of these embodiments, in the solution forming the electron transport layer 14, the mass fraction of the first additive is 0.2‰ to 1‰, the mass fraction of the second additive is 0.1‰ to 0.4‰, and the mass fraction of the organic electron transport material is 1.86% to 1.97%.

[0094] In some of these embodiments, the mass fraction of the first additive in the solute forming the electron transport layer 14 is 1% to 5%, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%.

[0095] Step S500: A metal electrode 15 is formed on the electron transport layer 14.

[0096] A metal electrode 15 is manufactured on the electron transport layer 14 using a thermal evaporation process, where the deposition rate of the thermal evaporation process may be set according to the actual demand, and the material of the metal electrode 15 may be an electrode material commonly used in this field.

[0097] In one specific example, the evaporation rate is 0.2 Å / s, and a metallic Ag electrode with a thickness of 110 nm is fabricated and formed.

[0098] The method for manufacturing the perovskite solar cell 1 of this application involves spin-coating a solution containing an organic electron transport material, a first additive, and a second additive onto a perovskite layer 13 using a spin-coating process to produce an electron transport layer 14. By using the specific first and second additives of this application in the electron transport layer 14, the photoelectric conversion efficiency and stability of the perovskite solar cell 1 can be effectively improved.

[0099] Furthermore, by using a mixed solvent containing a first organic solvent and a second organic solvent, the first organic solvent is a low-boiling point solvent, and the second organic solvent is a high-boiling point solvent. The first and second organic solvents are mixed in a specific volume ratio, and the organic electron transport material, the first additive, and the second additive are dispersed in this mixed solvent system. By adjusting the volume ratio of the different solvents based on the differences in boiling point and viscosity (generally, solvents with high boiling points have relatively high viscosity, and solvents with low boiling points have relatively low viscosity) between the first and second organic solvents, the crystal order and uniformity of the organic electron transport material molecules and the first and second additives can be optimized, and molecular orientation can be induced. This enhances the thin film quality and conductivity of the electron transport layer 14, and improves the photoelectric conversion efficiency and stability of the perovskite solar cell 1.

[0100] One embodiment of this application provides a photovoltaic module including the perovskite solar cell described in this application. The photovoltaic module of this application has relatively high photoelectric conversion efficiency and relatively good stability by using the perovskite solar cell described in this application.

[0101] The above-mentioned photovoltaic module includes one or more perovskite solar cells, which may be selected depending on the specific application scenario. Furthermore, the photovoltaic module includes multiple perovskite solar cells, which are connected in series or in parallel to form a battery cell.

[0102] In some of these embodiments, the photovoltaic module further includes a photovoltaic glass layer, an adhesive layer, and a backplate.

[0103] An adhesive layer is provided on each of the two surfaces of the battery cell. A back plate is provided on the surface of one of the adhesive layers that is separated from the battery cell, and a solar power generation glass layer is provided on the surface of the other adhesive layer that is separated from the battery cell.

[0104] The photovoltaic glass layer and backplate are used to protect the perovskite solar cell, providing sealing, insulation, and waterproofing functions. The adhesive layer adheres the photovoltaic glass layer to the battery cell and the backplate to the battery cell.

[0105] Selectively, the material of the photovoltaic glass layer is tempered glass, TPT (polyfluoroethylene) or TPE (thermoplastic elastomer) is used as the material of the backplate, and EVA (polyethylene-polyvinyl acetate copolymer) is used as the material of the adhesive layer.

[0106] Furthermore, the above-mentioned solar power generation module further includes a junction box and an outer frame.

[0107] A junction box is used to protect the entire power generation system of a solar power module. It acts as a current relay station, and if a battery cell is short-circuited, the junction box automatically disconnects the short-circuited battery string.

[0108] The outer frame can support and protect the entire solar power generation module, and the frame may be made of aluminum alloy, which has excellent strength and corrosion resistance.

[0109] Furthermore, silica gel 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, send it to a battery for storage, or power the operation of a load.

[0110] In some of these embodiments, the photovoltaic power generation module is a solar cell panel.

[0111] One embodiment of this application provides a photovoltaic power generation system including the above-described photovoltaic power generation module.

[0112] The photovoltaic power generation system utilizes perovskite solar cells in the above-mentioned photovoltaic power generation module to directly convert solar radiation energy into electrical energy, resulting in high efficiency and good stability. Furthermore, the above-mentioned photovoltaic power generation system is a photovoltaic system.

[0113] A photovoltaic module is the core component of a photovoltaic system, and the photovoltaic system includes one or more photovoltaic modules, which may be selected depending on the specific application scenario. Furthermore, if the photovoltaic system includes multiple photovoltaic modules, the multiple photovoltaic modules form a photovoltaic array.

[0114] The above-mentioned photovoltaic power generation system may be an independent photovoltaic system or a grid-connected photovoltaic system.

[0115] An independent photovoltaic system includes a solar power array, battery pack, charge controller, power converter (inverter), and load. Its operating principle is that solar radiation energy is first converted into electrical energy via the solar power array, then converted again by the power converter before being supplied to the load. At the same time, any excess electrical energy is stored in an energy storage device in the form of chemical energy via the charge controller. In the event of insufficient sunlight, the energy stored in the battery is boosted by a power converter, filter, and commercial frequency transformer, and then supplied to the AC load as 220V, 50Hz AC electrical energy.

[0116] The grid-connected photovoltaic system includes a photovoltaic array, a high-frequency DC / DC boost circuit, a power-electronic converter (inverter), and a system monitor. Its operating principle is that solar radiation energy is converted by the photovoltaic array, then further converted to high-frequency DC, becoming high-voltage DC, and then converted by a power-electronic inverter to output a sinusoidal AC current with a frequency matched to the grid voltage to the grid.

[0117] The two photovoltaic systems described above each have their own characteristics and may be selected depending on the specific application scenario.

[0118] Referring to Figure 2, one embodiment of the present application provides a power consumption device 2 including the perovskite solar cell described in the present application.

[0119] In some embodiments, the power consumption device 2 is a common device including the solar cell of this application, for example, in the fields of communications, transportation, agriculture and industry, lighting, etc. The power consumption device 2 may also include, for example, satellites, communication equipment, traffic signals, lighthouses, wireless telephone booths, monitoring equipment in the field of oil drilling, power systems, camping lights, electric vehicles, electronic equipment chargers, building curtain walls, etc.

[0120] Examples of the present application are described below. The examples described below are illustrative and are used solely for the purpose of interpreting this application and should not be understood as limitations thereon. Unless specific techniques or conditions are specified in the examples, they shall be carried out in accordance with the techniques or conditions described in the literature in the art or in accordance with the product description. Unless the manufacturer is specified, the reagents or equipment used are all commonly available commercial products.

[0121] 1. Perovskite solar cells Example 1: 1)Transparent electrode layer After UV cleaning of the FTO glass, it was used as a transparent electrode layer.

[0122] 2) Manufacturing of the hole transport layer A solution containing the hole transport material PTAA was spin-coated onto a transparent electrode layer, followed by annealing to form a hole transport layer. The spin-coating rotation speed was 5000 rpm / s, the spin-coating time was 30 s, the annealing temperature was 100°C, the annealing time was 10 min, and the thickness of the hole transport layer was 15 nm.

[0123] 3) Production of perovskite layers A solution containing the perovskite component raw material is spin-coated onto a hole transport layer, annealed, and a perovskite layer is formed. Here, the spin-coating rotation speed is 5000 rpm / s, the spin-coating acceleration is 2000 rpm / s, the spin-coating time is 30 s, the annealing temperature is 100°C, the annealing time is 15 min, and the perovskite component is Cs 0.05 MA 0.1 FA 0.85 The material was PbI3, and the perovskite layer thickness was 600 nm.

[0124] 4) Manufacturing of the electron transport layer An electron transport layer solution was formed by dispersing an organic electron transport material PCBM, a first additive polymethyl methacrylate, and a second additive tetrabutylammonium tetrafluoroborate in a mixed solvent. In this electron transport layer solution, the mixed solvent was 2-methylanisole and chloroform in a volume ratio of 1:1.

[0125] The electron transport layer solution described above was spin-coated onto a perovskite layer, and after removing the solvent, the electron transport layer was formed. The spin-coating rotation speed was 2000 rpm / s, and the spin-coating time was 30 s. The mass fraction of PCBM in the electron transport layer was 94%, the mass fraction of polymethyl methacrylate was 5%, and the mass fraction of the second additive, tetrabutylammonium tetrafluoroborate, was 1%. The thickness of the electron transport layer was 40 nm.

[0126] 5) Manufacturing of metal electrodes A metallic Ag electrode was formed on the electron transport layer using a thermal evaporation process. The evaporation rate was 0.2 Å / s, and the thickness of the metallic Ag electrode was 110 nm.

[0127] Example 2: This example was almost identical to Example 1, the only difference being the type of first additive. In this example, the first additive was methacrylic acid-methyl methacrylate copolymer.

[0128] Example 3: This embodiment was almost identical to Example 1, the only difference being the type of first additive. In this embodiment, the first additive was poly-4-vinylpyridine.

[0129] Example 4: This example was almost identical to Example 1, the only difference being the type of first additive. In this example, the first additive was 4-vinylpyridine-styrene copolymer.

[0130] Example 5: This example was almost identical to Example 1, the only difference being the type of second additive in the tertiary amine molecular system. The second additive in this example was tris(dimethylaminoethyl)amine, with a CAS number of 33527-91-2.

[0131] Example 6: This example was almost identical to Example 1, the only difference being the type of second additive in the tertiary amine molecular system. The second additive in this example was 1,7-bis(dimethylamino)heptane, with a CAS number of 29333-99-1.

[0132] Example 7: This example was almost identical to Example 1, the only difference being the type of second additive in the tertiary amine molecular system. The second additive in this example was 9,9-bis[3-(dimethylamino)propyl]fluorene, with a CAS number of 1821313-63-6.

[0133] Example 8: This embodiment was almost identical to Embodiment 1, the only difference being the type of second additive. In this embodiment, the second additive used was a quaternary ammonium salt additive shown in formula I. Specifically, this second additive was bisammonium iodide, with a CAS number of 870-62-2.

[0134] Example 9: This example was almost identical to Example 1, the only difference being the type of second additive. In this example, the second additive used was a quaternary ammonium salt additive shown in formula I. Specifically, this second additive was dodecyltrimethylammonium bromide, with a CAS number of 1119-94-4.

[0135] Example 10: This embodiment was almost identical to Example 1, the only difference being the type of second additive. In this embodiment, the second additive was a mixture of a quaternary ammonium salt additive shown in formula I and a tertiary amine molecular additive shown in formula II. Specifically, the second additive was a mixture of tetrabutylammonium tetrafluoroborate (CAS number: 429-42-5) and tris(dimethylaminoethyl)amine, and the mass fraction of the quaternary ammonium salt additive in the electron transport layer was 1%, and the mass fraction of the tertiary amine molecular additive was 1%.

[0136] Example 11: This embodiment was almost identical to Embodiment 1, the only difference being the type of organic electron transport material. In this embodiment, the organic electron transport material was naphthalenediimide.

[0137] Example 12: This embodiment was almost identical to Embodiment 1, the only difference being the type of organic electron transport material. In this embodiment, the organic electron transport material was perylenediimide.

[0138] Example 13: This embodiment was almost identical to Example 1, with the only difference being the mass fractions of the organic electron transport material, the first additive, and the second additive in the electron transport layer. In this embodiment, the mass fraction of PCBM in the electron transport layer was 98%, the mass fraction of polymethyl methacrylate was 1%, and the mass fraction of the second additive, tetrabutylammonium tetrafluoroborate, was 1%.

[0139] Example 14: This example was almost identical to Example 1, the only difference being the mixed solvent used in the solution forming the electron transport layer. In this example, the mixed solvent was chlorobenzene and dichloromethane in a volume ratio of 1:2.

[0140] Comparative Example 1: This comparative example was almost identical to Example 1, the only difference being that the first and second additives were not used in the electron transport layer.

[0141] Comparative Example 2: This comparative example was almost identical to Example 1, the only difference being the type of polymer additive in the electron transport layer. In this comparative example, polyethylene was used as the polymer additive.

[0142] Comparative Example 3: This comparative example was almost identical to Example 1, the only difference being the type of second additive in the electron transport layer. In this comparative example, the second additive used was tris(3-aminopropyl)amine, with a CAS number of 4963-47-7.

[0143] 2. Measurement of Solar Cell Performance 1) Photoelectric conversion efficiency test At 25°C, a perovskite solar cell was placed in sunlight using a test fixture, and the light output density was 100 mW / cm². 2 Specifically, the test fixture and Keithley 2400 digital source meter were connected using the four-wire method. The starting voltage was set to -0.2V, the cutoff voltage to 1.2V, and the scanning speed to 200mV / s. Reverse / forward scanning was performed, and the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) were recorded.

[0144] Then, the photoelectric conversion efficiency (PCE) of the perovskite solar cell was calculated using the formula: PCE = Jsc × Voc × FF / optical power density × 100%.

[0145] 2) Photoaging test The specific test process is as follows: The perovskite solar cell is placed in sunlight at 85°C, and the light output density is 100 mW / cm². 2 The perovskite solar cells were packaged in a nitrogen gas box, the maximum output point voltage of the solar cells was dynamically monitored, and time, output, current, and voltage were recorded, and the perovskite solar cells were aged in nitrogen gas for 1000 hours.

[0146] The photoelectric conversion efficiency test described above was performed after removing the perovskite solar cell. Specifically, the test fixture and Keithley 2400 digital source meter were connected using the four-wire method, the starting voltage was set to -0.2V, the cutoff voltage to 1.2V, and the scanning speed to 200mV / s. Forward and reverse scanning was performed, and the short-circuit current density (Jsc), open-circuit voltage (Voc), and packing factor (FF) were recorded.

[0147] The photoelectric conversion efficiency (PCE) of the perovskite solar cell after photoaging was calculated and compared with that of the perovskite solar cell before aging. The results of the photoaging test indicate the stability of the perovskite solar cell. When the aging time is the same, the closer the efficiency after aging is to the initial efficiency, the better the stability of the cell.

[0148] The parameters and performance data for the perovskite solar cells in each of the above examples and comparative examples are shown in Tables 1 and 2.

[0149] [Table 1-1] [Table 1-2]

[0150] [Table 2-1] [Table 2-2]

[0151] As can be seen from the above examples and comparative examples, in the electron transport layer of the organic electron transport material in each example of this application, a specific polymer containing lone pairs of electrons such as O and N is used as the first additive, and a quaternary ammonium salt matching a specific compound of general formula I and a tertiary amine molecule of a compound of general formula II are used as the second additive, and the photoelectric conversion efficiency and stability of the perovskite solar cell are better than those of Comparative Examples 1 to 3.

[0152] Each of the technical features of the embodiments described above can be combined in any way, and for the sake of brevity, not all possible combinations of each technical feature in the embodiments described above are described; however, as long as there is no contradiction in these combinations of technical features, they should all be considered to fall within the scope described herein.

[0153] The above embodiments illustrate only a few embodiments of this application, and while their descriptions are more specific and detailed, they should not be understood as limiting the scope of the invention patent. It should be noted that a person skilled in the art can make several further modifications and improvements without departing from the inventive concept of this application, and all of these fall within the scope of protection of this application. Therefore, the scope of protection of the patent of this application should be based on the attached claims, and the specification and drawings can be used to interpret the content of the claims. [Explanation of Symbols]

[0154] 1. Perovskite solar cell, 2 power consumption equipment, 11 transparent electrode layer, 12 Hole transport layer, 13 Perovskite layer, 14 electron transport layer, 15 Metal electrode

Claims

1. A perovskite solar cell comprising a transparent electrode layer and a perovskite layer, an electron transport layer, and a metal electrode arranged sequentially on the transparent electrode layer, The electron transport layer comprises an organic electron transport material, a first additive, and a second additive. The first additive comprises one or more of polymethyl methacrylate, methacrylate-methyl methacrylate copolymer, 4-vinylpyridine-styrene copolymer, polyacrylonitrile, and poly4-vinylpyridine. The second additive comprises one or more of the compounds of formula I and formula II below: 【Chemistry 1】 Here, R １ 、R ２ 、R ３ 、R ５ and R ６ are each independently selected from the alkyl groups of C １ to C ４ , n1 and n2 are each independently an integer from 1 to 6, m1 and m2 are each independently an integer from 1 to 4, R ４ and R ７ are each independently an alkyl group of C １ to C ５ , an alkoxy group of C １ to C ５ , an alkyl mercapto group of C １ to C ５ , an aryl group, a halogen, a carboxyl group, a cyano group, or do not exist, X is one or more of Cl, Br, I, BF ４ , PF ６ and TFSA, Y １ and Y ２ are each independently selected from any one of CH ２ , NH, O and S, or do not exist, a perovskite solar cell.

2. The perovskite solar cell according to claim 1, wherein, with respect to the total mass of the electron transport layer, the mass fraction of the first additive is 1% to 5%, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%.

3. The perovskite solar cell according to claim 1, wherein the second additive comprises the compound of formula I and the compound of formula II, and the mass ratio of the compound of formula I to the compound of formula II is (0.5 to 2):

1.

4. The perovskite solar cell according to claim 1, wherein the compound of formula I comprises one or more of tetrabutylammonium tetrafluoroborate, hexa-bisammonium iodide, and dodecyltrimethylammonium bromide.

5. The perovskite solar cell according to claim 1, comprising one or more of the compound of formula II, 1,7-bis(dimethylamino)heptane, tris(dimethylaminopropyl)amine, and 9,9-bis[3-(dimethylamino)propyl]fluorene.

6. The perovskite solar cell according to claim 1, wherein the thickness of the electron transport layer is 25 nm to 45 nm.

7. The perovskite solar cell according to claim 1, wherein the organic electron transport material comprises one or more of fullerene derivatives, naphthalene diimides and their derivatives, and perylene diimides and their derivatives.

8. The step of providing the transparent electrode layer, The step includes sequentially forming the perovskite layer, the electron transport layer, and the metal electrode on the transparent electrode layer, The method for manufacturing a perovskite solar cell according to claim 1, wherein the solution forming the electron transport layer comprises a solvent and a solute dispersed in the solvent, and the solute comprises the organic electron transport material, the first additive and the second additive.

9. The method for producing a perovskite solar cell according to claim 8, wherein the solvent comprises a first organic solvent and a second organic solvent, the boiling point of the first organic solvent being 38°C to 70°C, and the boiling point of the second organic solvent being 110°C to 210°C.

10. The method for producing a perovskite solar cell according to claim 9, wherein the first organic solvent comprises one or more of chloroform, dichloromethane, and tetrahydrofuran.

11. The method for producing a perovskite solar cell according to claim 9, wherein the second organic solvent comprises one or more of chlorobenzene, o-dichlorobenzene, toluene, o-xylene, anisole, 2-methylanisole, 2-chlorophenol, and 1,2,3,4-tetrahydronaphthalene.

12. A method for producing a perovskite solar cell according to claim 9, wherein, with respect to the total volume of the solvent, the volume fraction of the first organic solvent is 20% to 80%, and the volume fraction of the second organic solvent is 20% to 80%.

13. A method for manufacturing a perovskite solar cell according to claim 8, wherein, with respect to the total mass of the solution, the mass fraction of the first additive is 0.2‰ to 1‰, the mass fraction of the second additive is 0.1‰ to 0.4‰, and the mass fraction of the organic electron transport material is 1.86% to 1.97%.

14. A method for manufacturing a perovskite solar cell according to claim 8, wherein, with respect to the total mass of the solute, the mass fraction of the first additive is 1% to 5%, the mass fraction of the second additive is 0.5% to 2%, and the mass fraction of the organic electron transport material is 93% to 98.5%.

15. A photovoltaic module comprising a perovskite solar cell as described in claim 1.

16. A solar power generation system comprising the solar power generation module described in claim 15.

17. A power consumption device comprising at least one of the perovskite solar cell described in any one of claims 1 to 7 and the photovoltaic module described in claim 15.

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