Perovskite cell and preparation method thereof, photovoltaic module, power utilization device and power generation device

Abstract

The invention relates to a perovskite cell and a preparation method thereof, a photovoltaic module, a power utilization device and a power generation device. The perovskite cell comprises a first electrode layer, a hole transport layer, a perovskite layer, a P-type electron donor material layer, an electron transport layer and a second electrode layer which are stacked in sequence, the electron transport layer comprises an N-type electron acceptor material. The perovskite cell has significant progress in the aspects of efficiency and stability.

Description

Technical Field

[0001] This application relates to the field of perovskite solar cell technology, specifically to a perovskite solar cell and its preparation method, a photovoltaic module, an electrical device, and a power generation device. Background Technology

[0002] With the rapid development of the new energy field, solar cells have been widely used in aerospace, industry, commerce, agriculture, and communications. Perovskite solar cells are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite crystalline materials. They represent the third generation of solar cells and have promising development prospects. Currently, however, perovskite solar cells still require further improvement in terms of efficiency and stability. Summary of the Invention

[0003] The purpose of this application is to provide a perovskite solar cell and its preparation method, photovoltaic module, power supply device and power generation device, which mainly improves the efficiency of the cell by setting a P-type electron donor material layer.

[0004] Therefore, this application provides a perovskite solar cell, which includes a first electrode layer, a hole transport layer, a perovskite layer, a P-type electron donor material layer, an electron transport layer, and a second electrode layer stacked sequentially; the electron transport layer includes an N-type electron acceptor material.

[0005] By setting the aforementioned P-type electron donor material layer, on the one hand, the P-type electron donor material provides a high LUMO energy level, forming a potential barrier with the perovskite layer, reducing nonradiative recombination at the interface, and increasing the open-circuit voltage V of the device. OC On the other hand, a nanoscale bulk heterojunction interpenetrating network forms at the interface between the P-type electron donor material layer and the N-type electron acceptor material in the electron transport layer. This structure is called a quasi-planar heterojunction. The P-type donor material and the N-type acceptor material form a separate bilayer structure, and the bulk heterojunction interpenetrating network generated at the interface can further promote electron and hole separation at the interface, thereby effectively improving the efficiency of perovskite solar cells.

[0006] In any embodiment, the P-type electron donor material contains at least one of the following elements: fluorine, sulfur, oxygen, nitrogen, and silicon.

[0007] When the p-type electron donor material contains the aforementioned heteroatoms, it can coordinate with the metal cations in the perovskite layer, thereby reducing the defect state density of the perovskite and improving the stability of the device.

[0008] In any embodiment, the P-type electron donor material includes at least one selected from the group consisting of PM6, PTB7-Th, D18, P3HT, PTQ10, and J71.

[0009] The aforementioned p-type electron donor materials have heteroatom-containing groups that can interact with uncoordinated Pb in the perovskite layer. 2+ Sn 2+ Isocoordination effectively passivates iodine vacancy defects on the perovskite surface, reduces the defect state density of the perovskite, and further improves the efficiency and stability of the device.

[0010] In any embodiment, the N-type electron acceptor material comprises fullerene or a derivative thereof.

[0011] Fullerenes and their derivatives have high electrical conductivity, which helps to increase short-circuit current density. SC and fill factor FF.

[0012] In any embodiment, the N-type electron acceptor material further includes a non-fullerene electron transport material.

[0013] By using N-type non-fullerene electron transport materials as electron acceptors in the electron transport layer, the light absorption range of perovskite solar cells can be extended. This allows for the formation of cascaded energy levels between N-type electron donor molecules and fullerene acceptor molecules, providing additional photogenerated electrons and increasing the short-circuit current density. SC Furthermore, non-fullerene electron transport materials can also help improve the aggregation of fullerene derivatives, making the electron transport layer more compact and stable.

[0014] In any embodiment, in the electron transport layer, the mass ratio of the fullerene or its derivative to the non-fullerene electron transport material is 1:(0.05 to 0.5).

[0015] When the above mass ratio is used, fullerenes and their derivatives can provide high electrical conductivity and electron mobility, while non-fullerene acceptors can expand the light absorption range of optoelectronic devices and inhibit the self-aggregation of fullerenes and their derivatives, thereby improving the photoelectric conversion efficiency and stability of the devices.

[0016] In any embodiment, the non-fullerene electron transport material comprises at least one selected from the group consisting of: ITIC, IT-4F, IEICO-4F, Y6, L8-BO, BTP-eC9, PY-IT, and N2200.

[0017] The aforementioned N-type non-fullerene electron transport materials are all small organic molecules or polymers, which can further extend the light absorption range of photovoltaic devices, generate additional photogenerated electrons, and form cascade energy levels with P-type electron donor materials and fullerene acceptor materials, generating additional photogenerated electrons and increasing the short-circuit current density. SC Furthermore, it contains a large number of electron-rich functional groups such as F, O, and S, which can interact with unpaired Pb on the perovskite surface.2+ Sn 2+ Coordination passesivates iodine vacancy defects on the perovskite surface, reduces the defect state density of the perovskite, and further improves the efficiency and stability of the device.

[0018] In any embodiment, the mass concentration ratio of the P-type electron donor material to the N-type electron acceptor material is (0.25 to 1.5):1.

[0019] When the above mass concentration ratio is used, the P-type electron donor material and the N-type electron acceptor material can better form a quasi-planar heterojunction structure that is conducive to charge transport and extraction, thereby improving the photovoltaic performance and stability of the device.

[0020] In any embodiment, the electron transport layer further includes an additive; the additive includes at least one selected from the group consisting of: 1-chloronaphthalene, 1-phenylnaphthalene, 2-methoxynaphthalene, 1,4-diiodobenzene, 1,4-dibromobenzene, 1,4-difluorobenzene, 1,6-diiodohexane, 1,7-diiodoheptane, 1,8-diiodooctane, 1,9-diiodononane, 1,10-diiododecane, 1,11-diiodoundecane, and 1,12-diiodododecane.

[0021] By adding the above-mentioned additives, the morphology of the electron transport layer and vertical phase separation can be controlled, which is beneficial to further improve electron transport efficiency.

[0022] In any embodiment, a hole blocking layer is further provided between the electron transport layer and the second electrode layer.

[0023] By setting a hole-blocking layer to block hole transport, the electron collection efficiency at the interface is improved.

[0024] A second aspect of this application provides a photovoltaic module, including the perovskite cell of the first aspect of this application.

[0025] A third aspect of this application provides an electrical device, including a perovskite cell of the first aspect of this application or a photovoltaic module of the second aspect of this application.

[0026] The fourth aspect of this application provides a power generation device, including a perovskite cell of the first aspect of this application or a photovoltaic module of the second aspect of this application.

[0027] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application, it can be implemented according to the contents of the specification. In order to make the above and other objects, features and advantages of this application more obvious and understandable, the specific implementation methods of this application are listed below. Attached Figure Description

[0028] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. In the drawings:

[0029] Figure 1 : A schematic diagram of the structure of a perovskite solar cell according to one embodiment of this application;

[0030] Figure 2 : A schematic diagram of the structure of a perovskite solar cell according to another embodiment of this application;

[0031] Figure 3 The current density-voltage characteristic curve of a perovskite solar cell according to one embodiment of this application;

[0032] Figure 4 External quantum efficiency diagram of a perovskite solar cell according to one embodiment of this application;

[0033] Figure 5 Normalized output power diagram of a perovskite solar cell according to an embodiment of this application;

[0034] Explanation of reference numerals in the attached figures:

[0035] 101-First electrode layer; 102-Hole transport layer; 103-Perovskite layer; 104-P-type electron donor material layer; 105-Electron transport layer; 106-Hole blocking layer; 107-Second electrode layer. Detailed Implementation

[0036] Exemplary embodiments of this disclosure will now be described in more detail. It should be understood that this disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0037] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is expected that ranges of 60–110 and 80–120 are also included. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0038] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0039] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0040] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0041] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0042] This article involves materials expressed in English abbreviations, and their CAS numbers are explained below:

[0043] Table 1

[0044] abbreviations CAS number PM6 1802013-83-7 PTB7-Th 1469791-66-9 D18 2433725-54-1 P3HT 104934-50-1 PTQ10 2270233-86-6 J71 2035466-89-6 PCBM 160848-22-6 PC71BM 609771-63-3 ICBA 1207461-57-1 ITIC 1664293-06-4 IT-4F 2097998-59-7 IEICO-4F 2089044-02-8 Y6 2304444-49-1 L8-BO 2668341-40-8 BTP-eC9 2598965-39-8 PY-IT 2418532-47-3 N2200 1100243-40-0

[0045] Perovskite solar cells are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite crystalline materials. They represent the third generation of solar cells and have promising development prospects. Currently, however, perovskite solar cells still require further improvement in terms of efficiency and stability. Existing technologies have reported methods to improve charge transport through modifications to charge transport materials and interface modifications, aiming to increase cell efficiency.

[0046] This application mainly improves the structure of the battery by applying a P-type electron donor material layer between the electron transport layer and the perovskite layer of the perovskite solar cell, thereby improving interfacial recombination and electron transport, which is beneficial to improving battery efficiency.

[0047] The solutions described in the embodiments of this application are applicable to perovskite cells, photovoltaic modules using perovskite cells, electrical devices using perovskite cells or photovoltaic modules, and power generation devices using perovskite cells or photovoltaic modules.

[0048] [Perovskite solar cell]

[0049] In some implementations, reference Figure 1 A perovskite solar cell is provided, comprising a first electrode layer 101, a hole transport layer 102, a perovskite layer 103, a P-type electron donor material layer 104, an electron transport layer 105, and a second electrode layer 107, which are sequentially stacked; the electron transport layer 105 comprises an N-type electron acceptor material.

[0050] By setting the aforementioned P-type electron donor material layer, on the one hand, the P-type electron donor material provides a high LUMO energy level, forming a potential barrier with the perovskite active layer, reducing nonradiative recombination at the interface, and increasing the open-circuit voltage V of the device. OC On the other hand, a nanoscale bulk heterojunction interpenetrating network forms at the interface between the P-type electron donor material layer and the N-type electron acceptor material in the electron transport layer. This structure is called a quasi-planar heterojunction. The P-type donor material and the N-type acceptor material form a separate bilayer structure, and the bulk heterojunction interpenetrating network generated at the interface can further promote electron and hole separation at the interface, thereby effectively improving the efficiency of perovskite solar cells.

[0051] P-type electron donor material layer, electron transport layer

[0052] In some embodiments, the P-type electron donor material contains at least one of the following elements: fluorine, sulfur, oxygen, nitrogen, and silicon.

[0053] When the p-type electron donor material contains the aforementioned heteroatoms, it can coordinate with the metal cations in the perovskite layer, thereby reducing the defect state density of the perovskite and improving the stability of the device.

[0054] In some embodiments, the P-type electron donor material layer includes at least one material selected from the group consisting of PM6, PTB7-Th, D18, P3HT, PTQ10, and J71.

[0055] The aforementioned p-type electron donor materials have heteroatom-containing groups that can interact with uncoordinated Pb in the perovskite layer. 2+ Sn 2+ Isocoordination effectively passivates iodine vacancy defects on the perovskite surface, reduces the defect state density of the perovskite, and further improves the efficiency and stability of the device.

[0056] In some embodiments, the thickness of the P-type electron donor material layer can be 5 to 300 nm; for example, it can be about 5 nm, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, etc.

[0057] In some embodiments, the N-type electron acceptor material includes fullerene or a derivative thereof.

[0058] Fullerenes and their derivatives have high electrical conductivity, which helps to increase short-circuit current density. SC and fill factor FF.

[0059] As examples, fullerenes or their derivatives can be listed: fullerene C 60 PCBM, PC71BM, ICBA, etc.

[0060] In some embodiments, the N-type electron acceptor material further includes a non-fullerene electron transport material.

[0061] By using N-type non-fullerene electron transport materials as electron acceptors in the electron transport layer, the light absorption range of perovskite solar cells can be extended. This allows for the formation of cascaded energy levels between N-type electron donor molecules and fullerene acceptor molecules, providing additional photogenerated electrons and increasing the short-circuit current density. SC Furthermore, non-fullerene electron transport materials can also help improve the aggregation of fullerene derivatives, making the electron transport layer more compact and stable.

[0062] In some embodiments, the mass ratio of the fullerene or its derivative to the non-fullerene electron transport material in the electron transport layer is 1:(0.05 to 0.5); for example, it can be selected from about 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, etc.

[0063] When the above mass ratio is used, fullerenes and their derivatives can provide high electrical conductivity and electron mobility, while non-fullerene acceptors can expand the light absorption range of optoelectronic devices and inhibit the self-aggregation of fullerenes and their derivatives, thereby further improving the photoelectric conversion efficiency and stability of the devices.

[0064] In some embodiments, the non-fullerene electron transport material includes at least one selected from the group consisting of: ITIC, IT-4F, IEICO-4F, Y6, L8-BO, BTP-eC9, PY-IT, and N2200.

[0065] The aforementioned N-type non-fullerene electron transport materials are all small organic molecules or polymers, which can further extend the light absorption range of photovoltaic devices, generate additional photogenerated electrons, and form cascade energy levels with P-type electron donor materials and fullerene acceptor materials, generating additional photogenerated electrons and increasing the short-circuit current density (JSC). Furthermore, they contain a large number of electron-rich functional groups such as F, O, and S, which can interact with unassociated Pb on the perovskite surface. 2+ Sn 2+ Coordination passesivates iodine vacancy defects on the perovskite surface, reduces the defect state density of the perovskite, and further improves the efficiency and stability of the device.

[0066] In some embodiments, the mass concentration ratio of the P-type electron donor material to the N-type electron acceptor material is (0.25 to 1.5):1; for example, it can be about 0.25:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc.

[0067] When the above mass concentration ratio is used, the P-type electron donor material and the N-type electron acceptor material can better form a quasi-planar heterojunction structure that is conducive to charge transport and extraction, thereby improving the photovoltaic performance and stability of the device.

[0068] In some embodiments, the electron transport layer further includes an additive; the additive includes at least one selected from the group consisting of: 1-chloronaphthalene, 1-phenylnaphthalene, 2-methoxynaphthalene, 1,4-diiodobenzene, 1,4-dibromobenzene, 1,4-difluorobenzene, 1,6-diiodohexane, 1,7-diiodoheptane, 1,8-diiodooctane, 1,9-diiodononane, 1,10-diiododecane, 1,11-diiodoundecane, and 1,12-diiodododecane.

[0069] By adding the above-mentioned additives, the morphology of the electron transport layer and vertical phase separation can be controlled, which is beneficial to further improve electron transport efficiency.

[0070] In some implementations, the thickness of the electron transport layer can be 5 to 300 nm; for example, it can be about 5 nm, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, etc.

[0071] transparent electrode layer

[0072] In some embodiments, one of the first electrode layer or the second electrode layer is a transparent electrode layer. When the perovskite solar cell is in an inverted structure, the first electrode layer is a transparent electrode layer; when the perovskite solar cell is in a normal structure, the second electrode layer is a transparent electrode layer. In some embodiments, the perovskite solar cell is in an inverted structure.

[0073] In embodiments of this application, the transparent electrode layer is used for light incident and can be any transparent electrode known in the art.

[0074] In some embodiments, the transparent electrode includes at least one selected from the group consisting of tin oxide (ITO), indium tin oxide, fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), antimony-doped tin oxide, and indium-doped tungsten oxide.

[0075] In some embodiments, the thickness of the transparent electrode layer is 100-1000nm, and can be selected as 300-800nm; for example, it can be about 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, etc.

[0076] Hole transport layer

[0077] In the embodiments of this application, there are no particular limitations on the hole transport layer, and materials commonly used in the art can be used. Exemplarily, hole transport materials include poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly-3-hexylthiophene (P3HT), triphenylamine with a triphenylene core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), poly( 3,4-Ethylenedioxythiophene: at least one of poly(styrene sulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz).

[0078] In some implementations, the thickness of the hole transport layer can be 5 to 300 nm; for example, it can be about 5 nm, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, etc.

[0079] Perovskite layer

[0080] In the embodiments of this application, the perovskite layer is the active layer of the perovskite solar cell and is made of perovskite material.

[0081] In some embodiments, the perovskite material has the chemical formula ABX3 or A2CDX6, wherein,

[0082] A is an inorganic, organic, or mixed organic-inorganic cation, comprising at least one of organic amine cations, Cs cations, K cations, Rb cations, and Li cations; wherein the organic amine cation is selected from (NR1R2R3R4). + (R1R2N=CR3R4) + (R1R2N-C(R5)=NR3R4) + Or (R1R2N-C(NR5R6)=R3R4) + R1, R2, R3, R4, R5, and R6 are each independently selected from H, substituted or unsubstituted C1-20 alkyl groups, or substituted or unsubstituted aryl groups; A is optionally methylamino (CH3NH3) + (MA) + ), formamidinyl (HC(NH2)2+ (FA) + ), cesium ion (Cs + ) and rubidium (Rb + At least one of the following.

[0083] B is an inorganic, organic, or mixed organic-inorganic cation, including at least one of lead cation, tin cation, zinc cation, titanium cation, antimony cation, bismuth cation, nickel cation, iron cation, cobalt cation, silver cation, copper cation, gallium cation, germanium cation, magnesium cation, calcium cation, indium cation, aluminum cation, manganese cation, chromium cation, molybdenum cation, and europium cation; optionally, it is a divalent metal ion, lead cation (Pb). 2+ ) or tin cation (Sn) 2+ At least one of the following;

[0084] C is an inorganic, organic, or mixed organic-inorganic cation, optionally a monovalent metal ion, such as silver cation (Ag). + )wait;

[0085] D is an inorganic, organic, or mixed organic-inorganic cation, optionally a trivalent metal ion bismuth cation (Bi). 3+ ), antimony cation (Sb) 3+ Indium cations (In) 3+ )wait;

[0086] X is an inorganic, organic, or mixed organic-inorganic anion, optionally one or more of a halide anion and a carboxyl anion, and further optionally a bromide ion (Br). - ) or iodide ions (I - ).

[0087] In some embodiments, the band gap of the perovskite layer is 1.20 eV-2.30 eV.

[0088] In some embodiments, the thickness of the perovskite layer is 200-800 nm; for example, it can be about 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, etc.

[0089] Back electrode layer

[0090] In some embodiments, one of the first electrode layer or the second electrode layer is a back electrode layer. When the perovskite solar cell is inverted, the second electrode layer is the back electrode layer; when the perovskite solar cell is upright, the first electrode layer is the back electrode layer. In some embodiments, the perovskite solar cell is inverted.

[0091] In some embodiments, the back electrode layer may be selected from metallic or carbon materials. For example, the material of the back electrode layer may include at least one selected from the group consisting of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), molybdenum (Mo), tungsten (W) and its alloys, graphite, graphene, and carbon nanotubes.

[0092] In some embodiments, the thickness of the back electrode layer is 20-1000 nm; for example, it can be about 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, etc.

[0093] Cavity barrier

[0094] In some embodiments, optionally, a hole blocking layer may be provided between the second electrode layer and the electron transport layer to prevent the second electrode from reacting with the perovskite and to avoid the reduction in device efficiency caused by the Schottky contact between the electron transport layer and the second electrode, while also having an energy level modulation function.

[0095] In some embodiments, the hole-blocking layer is made of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, also known as copper bath), calcium acetylacetonate, LiF, aluminum 8-hydroxyquinoline, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene or combinations thereof; BCP may be selected as the material.

[0096] In some embodiments, the thickness of the hole blocking layer is 3-30 nm, optionally 3-10 nm, and further optionally 4-6 nm; for example, it can be about 3 nm, 5 nm, 10 nm, 20 nm, 30 nm, etc.

[0097] Therefore, in one embodiment of this application, reference is made to Figure 2 The perovskite solar cell of this application includes a first electrode layer 101, a hole transport layer 102, a perovskite layer 103, a P-type electron donor material layer 104, an electron transport layer 105, a hole blocking layer 106, and a second electrode layer 107, which are stacked sequentially.

[0098] transparent substrate

[0099] In some embodiments, the perovskite solar cell may optionally include a transparent substrate layer disposed on the surface of the transparent electrode layer away from the perovskite layer. The transparent substrate layer is selected from at least one of transparent glass, polyethylene terephthalate (PET), and polyimide substrate, and has a thickness of 0.1-3 cm.

[0100] Therefore, in one embodiment of this application, the perovskite solar cell of this application includes a transparent substrate layer, a transparent electrode layer, a hole transport layer, a perovskite layer, a P-type electron donor material layer, an electron transport layer, and a back electrode layer stacked sequentially.

[0101] Encapsulation film, sealant

[0102] In some embodiments, the perovskite solar cell further includes an encapsulating film disposed along a direction perpendicular to the thickness of the perovskite solar cell. For example, the encapsulating film is disposed on the surface of the second electrode layer away from the perovskite layer.

[0103] In some embodiments, the encapsulating film includes at least one of epoxy encapsulating adhesive, silicone encapsulating adhesive, polyurethane encapsulating adhesive, UV-curable encapsulating adhesive, ethylene-vinyl acetate copolymer, polyvinyl butyral, ethylene octene copolymer, polyisobutylene, polyolefin encapsulating adhesive, and butyl rubber.

[0104] In some embodiments, the thickness of the encapsulating film is 0.5-1 mm.

[0105] In some embodiments, the perovskite solar cell further includes a sealant disposed along a direction parallel to the thickness of the perovskite solar cell. For example, the sealant is disposed at the periphery of the first electrode layer, the hole transport layer, the perovskite layer, the p-type electron donor material layer, the electron transport layer, and the second electrode layer. The sealant may be selected from at least one of, for example, butyl rubber, epoxy resin, silicone encapsulant, polyurethane encapsulant, and UV-curable encapsulant.

[0106] Methods for preparing perovskite solar cells

[0107] In some embodiments, a method for preparing a perovskite solar cell according to any embodiment of this application is provided, which includes: providing or preparing a first electrode layer, preparing a hole transport layer, preparing a perovskite layer, preparing a p-type electron donor material layer, preparing an electron transport layer, and preparing a second electrode layer; optionally, it may also include: providing or preparing a transparent substrate layer and preparing a hole blocking layer.

[0108] In some embodiments, the perovskite solar cell has an inverted structure, and its fabrication method includes: providing or fabricating a transparent electrode layer, fabricating a hole transport layer, fabricating a perovskite layer, fabricating a P-type electron donor material layer, fabricating an electron transport layer, and fabricating a back electrode layer.

[0109] In some embodiments, the transparent electrode layer is provided, and the transparent electrode layer needs to be cleaned before the hole transport layer is prepared, for example, by ultrasonic cleaning with a cleaning agent (including but not limited to surfactants), ethanol, acetone, isopropanol, and deionized water.

[0110] In some embodiments, the hole transport layer, perovskite layer, P-type electron donor material layer, electron transport layer, and optional hole blocking layer described in this application can be prepared by at least one of the following methods: chemical bath deposition, electrochemical deposition, chemical vapor deposition, physical epitaxial growth, thermal evaporation, atomic layer deposition, magnetron sputtering, spin coating of precursor solution, slot coating of precursor solution, blade coating of precursor solution, and mechanical pressing.

[0111] In some embodiments, the method for preparing the p-type electron donor material layer includes: dissolving the p-type electron donor material in an organic solvent to obtain a p-type electron donor material solution; spin-coating the p-type electron donor material solution onto the perovskite layer; and annealing to obtain the p-type electron donor material layer. The organic solvent may be at least one selected from chlorobenzene, chloroform, o-dichlorobenzene, and o-xylene. In some embodiments, the spin-coating speed is 1000–5000 rpm, the spin-coating method can be dynamic spin-coating or static spin-coating, and the spin-coating time is 20–60 s. In some embodiments, the concentration of the p-type electron donor material solution is 1–10 mg / mL.

[0112] In some embodiments, the method for preparing the electron transport layer includes: dissolving an N-type electron acceptor material (fullerene or its derivative, optionally a non-fullerene electron transport material) and optional additives for forming the electron transport layer in an organic solvent to obtain an electron transport layer solution; spin-coating the electron transport layer solution onto the P-type electron donor material layer, and annealing to obtain the electron transport layer. The organic solvent may be at least one of chlorobenzene, chloroform, o-dichlorobenzene, and o-xylene. In some embodiments, the concentration of the electron transport layer solution is 5–35 mg / mL. In some embodiments, the volume percentage of the additive in the electron transport layer solution is 0.1 vol%–1 vol%. In some embodiments, the spin-coating speed is 1000–5000 rpm, the spin-coating method can be dynamic spin-coating or static spin-coating, and the spin-coating time is 20–60 s.

[0113] In some embodiments, the back electrode layer can be prepared using methods known in the art, such as thermal evaporation.

[0114] Photovoltaic modules, electrical appliances, power generation devices

[0115] In some embodiments, a photovoltaic module is provided, which includes the perovskite cell in any embodiment of this application.

[0116] In some embodiments, an electrical device is provided, which includes a perovskite cell or a photovoltaic module as described in any embodiment of this application.

[0117] In some embodiments, the electrical device can be used in, for example, the communications field, transportation field, industrial and agricultural field, lighting field, etc. The electrical device may include, for example, satellites, communication equipment, traffic lights, lighthouses, wireless telephone booths, monitoring equipment in the oil drilling field, power systems, camping lights, electric vehicles, electronic device chargers, building curtain walls, etc.

[0118] In some embodiments, a power generation device is provided, which includes a perovskite cell or a photovoltaic module as described in any embodiment of this application.

[0119] Example

[0120] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0121] Example 1

[0122] A perovskite solar cell is provided, the preparation method of which includes:

[0123] (1) Provide a transparent electrode layer

[0124] Using FTO as a transparent electrode layer, ultrasonically clean it with dish soap and water for 15 minutes, then rub it clean with clean rubber gloves. Then, ultrasonically clean it sequentially with deionized water, ethanol, acetone, and isopropanol, each time for 15 minutes. Finally, dry it with nitrogen gas for later use.

[0125] (2) Preparation of hole transport layer

[0126] In this embodiment, nickel oxide (NiOx) is used as the transport layer material, and it is prepared using a magnetron sputtering process. Specifically, the cleaned transparent conductive substrate FTO is transferred to a vacuum chamber, and a mechanical pump and a molecular pump are used to evacuate the vacuum to 3 × 10⁻⁶. -4 Below Pa, a sputtering power of 70 W, a sputtering intensity of 0.3 Pa, and a sputtering time of 10 min were selected to prepare a NiOx film with a thickness of 30 nm.

[0127] (3) Preparation of perovskite layer

[0128] Using Cs 0.05 MA 0.1 FA 0.85 PbI3 is used as the material for the perovskite layer.

[0129] Preparation of perovskite precursor solution: 0.075 mmol CsI, 0.15 mmol MAI, 1.275 mmol FAI, and 1.5 mmol PbI₂ were dissolved in 0.9 mL of a mixed solution of DMF and DMSO (volume ratio 5:1) to prepare a 1.67 M CsI solution. 0.05 MA 0.1 FA 0.85 The PbI3 precursor solution was heated and stirred at 60°C for 1 hour, then filtered for later use.

[0130] Preparation of perovskite thin film: The NiOx-sputtered substrate (i.e., the product prepared in step (2)) was transferred to a glove box. The perovskite precursor solution was uniformly coated on the hole transport layer, and then spin-coated sequentially at 1000 rpm / 15 s and 5000 rpm / 60 s. In the second spin-coating step, 20 s before the end of the spin-coating, 150 μL of anisole was dropped onto the perovskite thin film as an antisolvent. Then, it was annealed at 110 °C for 10 min to obtain the perovskite layer.

[0131] (4) Preparation of P-type electron donor material layer

[0132] The donor molecule PM6 was dissolved in a chlorobenzene solution at a concentration of 8 mg / mL. -1 The P-type electron donor material layer was prepared by static spin coating on the perovskite layer at 4000 rpm for 30 s and then annealing at 100 °C for 5 minutes.

[0133] (5) Fabrication of electron transport layer

[0134] The first receptor molecule, PCBM, and the second receptor molecule, PY-IT, were mixed thoroughly at a mass ratio of 0.85:0.15, and then dissolved in a chlorobenzene solution to a concentration of 20 mg / mL. -1 Prepare for use. Before use, add 0.5 vol% 1-chloronaphthalene as an additive and continue stirring for 30 min. Then, spin-coat it onto a perovskite film at 5000 rpm / 40 s and anneal at 100 °C for 5 min to obtain the electron transport layer.

[0135] (6) Preparation of hole blocking layer

[0136] BCP was used as a hole-blocking layer material. BCP was dissolved in trifluoroethanol at a concentration of 1 mg / ml. -1Then, the hole blocking layer is prepared by dynamically spin-coating it onto the electron transport layer at 5000 rpm / 30s.

[0137] (7) Preparation of back electrode

[0138] The product prepared in step (6) is transferred to a vapor deposition chamber, and a metal electrode Cu is vapor deposited on the hole blocking layer. The vacuum degree of the vapor deposition chamber is less than 10. -4 Pa, with A Cu electrode with a velocity of 100 nm was deposited, and after the process was stopped, the electrode was removed, thus completing the fabrication of the perovskite solar cell.

[0139] Comparative Example 1

[0140] Except for the lack of a P-type electron donor material layer, the perovskite solar cell was prepared according to the same steps as in Example 1 to obtain the perovskite solar cell.

[0141] The perovskite solar cells prepared in Example 1 and Comparative Example 1 were subjected to the following tests:

[0142] I. Current density-voltage characteristic curve (JV characteristic curve)

[0143] In the solar simulator AM1.5G (100mW cm -2 The following test was conducted using a Keithley 2400 digital source table, and the test results are as follows: Figure 3 As shown, the specific method is as follows:

[0144] 1. Place the test fixture containing the sample cell on the sample holder, ensuring it is within the measurement plane and that the sample cell is located at the center of the solar simulator's emitted light spot (or the photovoltaic cell normal is parallel to the center line of the emitted beam from the solar simulator's light source).

[0145] 2. At 100mW cm -2 Under irradiance conditions, a mask is installed on the sample battery to be tested, and the temperature of the sample battery is controlled by a temperature monitoring device so that the temperature of the sample battery is maintained at (30±5℃) during the measurement process.

[0146] 3. Set the scanning direction, voltage range, scanning interval voltage, and scanning interval time. It is recommended that the scanning interval not exceed 0.02V, and the interval between two adjacent points not be less than 0.3s. Measure the forward and reverse scanning current-voltage characteristics of the sample battery and record the open-circuit voltage (V). OC ), short-circuit current density (J SC );

[0147] The photoelectric conversion efficiency (PCE) is calculated as follows:

[0148]

[0149] Among them, J max and V max These represent the maximum output power (P) max The corresponding current density and voltage value, P in J is the incident light power. SC V is the short-circuit current density. OC is the open-circuit voltage, and FF is the fill factor.

[0150] The test results above show that, compared with Comparative Example 1, the photoelectric conversion efficiency of the battery is significantly improved in Example 1. In particular, Example 1 shows a significant improvement in open-circuit voltage and short-circuit current density.

[0151] II. External Quantum Efficiency (EQE) Curve

[0152] The quantum efficiency test was conducted using an Enlitech QE-R3011 quantum efficiency meter. Prior to the test, the light intensity was calibrated using a standard photodetector. The test results are as follows: Figure 4 As shown.

[0153] Compared to Control Example 1, Example 1 exhibits higher external quantum efficiency in both the 350–500 nm and 750–850 nm ranges. This is consistent with the test results of the JV characteristic curve.

[0154] III. Stability Testing

[0155] At 85℃, a white LED calibrated to the intensity of sunlight was used to continuously illuminate the perovskite solar cell, and the maximum output power of the perovskite solar cell was continuously tracked during this period. The test results are as follows: Figure 5 As shown.

[0156] Depend on Figure 5 It can be seen that after 500 hours of continuous aging, the normalized output power of the perovskite solar cell in Comparative Example 1 decreased significantly, with the output power decaying to about 80% of the initial value; while the normalized output power of the perovskite solar cell in Example 1 decreased slowly, and after 500 hours, the output power could still maintain about 93% of the initial value.

[0157] The relevant test results are summarized in Table 2.

[0158] Table 2

[0159]

[0160] Examples 2-8

[0161] Except for the P-type electron donor material, the materials of the first acceptor and the second acceptor in the electron transport layer, which are shown in Table 3, the perovskite solar cells were prepared according to the same steps as in Example 1, and tested. The results are shown in Table 3.

[0162] Table 3

[0163]

[0164] Examples 9-16

[0165] Except for the different mass ratio between the first and second acceptors and the different mass concentrations of the N-type electron acceptor material, the perovskite solar cells were prepared according to the same steps as in Example 1, and related tests were performed. The results are shown in Table 4.

[0166] Table 4 shows the concentration of N-type electron acceptor material, the ratio of the mass concentration of P-type electron donor material to that of N-type electron acceptor material (i.e., the sum of the first acceptor and the second acceptor) in each embodiment, and the mass ratio between the first acceptor and the second acceptor.

[0167] Table 4

[0168]

[0169] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A perovskite cell, characterized in that, The perovskite battery comprises a first electrode layer, a hole transport layer, a perovskite layer, a P-type electron donor material layer, an electron transport layer and a second electrode layer which are sequentially stacked; the electron transport layer comprises an N-type electron acceptor material.

2. The perovskite cell of claim 1, wherein, The P-type electron donor material contains at least one of the following elements: fluorine, sulfur, oxygen, nitrogen, silicon.

3. The perovskite cell according to claim 1 or 2, wherein The P-type electron donor material comprises at least one selected from the group consisting of PM6, PTB7-Th, D18, P3HT, PTQ10, J71.

4. The perovskite cell according to any one of claims 1 to 3, wherein The N-type electron acceptor material comprises at least one of a fullerene material and a derivative thereof.

5. The perovskite cell of claim 4, wherein the perovskite layer is formed by a solution process. The N-type electron acceptor material further comprises a non-fullerene electron transport material.

6. The perovskite cell of claim 5, wherein, In the electron transport layer, the mass ratio of the fullerene or its derivative to the non-fullerene electron transport material is 1:(0.05-0.5).

7. The perovskite cell according to claim 5 or 6, wherein The non-fullerene electron transport material comprises at least one selected from the group consisting of ITIC, IT-4F, IEICO-4F, Y6, L8-BO, BTP-eC9, PY-IT, N2200.

8. The perovskite cell according to any one of claims 1 to 7, wherein The mass concentration ratio of the P-type electron donor material to the N-type electron acceptor material is (0.25-1.5):

1.

9. The perovskite cell according to any one of claims 1 to 8, wherein The electron transport layer further comprises an additive; the additive comprises at least one selected from the group consisting of 1-chloronaphthalene, 1-phenylnaphthalene, 2-methoxynaphthalene, 1,4-diiodobenzene, 1,4-dibromobenzene, 1,4-difluorobenzene, 1,6-diiodohexane, 1,7-diiodoheptane, 1,8-diiodooctane, 1,9-diiodononane, 1,10-diiododecane, 1,11-diiodoundecane, 1,12-diiodododecane.

10. The perovskite cell according to any one of claims 1 to 9, wherein The electron transport layer and the second electrode layer further have a hole blocking layer therebetween.

11. A photovoltaic module, characterized by The perovskite battery of any one of claims 1-10.

12. An electrical device, characterized by The perovskite battery of any one of claims 1-10 or the photovoltaic module of claim 11.

13. A power generation device characterized by comprising: The perovskite battery of any one of claims 1-10 or the photovoltaic module of claim 11.

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