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

Abstract

The invention provides a perovskite solar cell, a photovoltaic module, a power utilization device and a power generation device. The perovskite solar cell comprises a first electrode, a perovskite layer, an electron transport layer and a second electrode. The perovskite layer and the electron transport layer are stacked between the first electrode and the second electrode, and the material of the electron transport layer comprises one or more of compounds with structures shown in the following formula (I). The perovskite solar cell provided by the invention has relatively high photoelectric conversion efficiency.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to a perovskite solar cell, photovoltaic module, electrical device, and power generation device. Background Technology

[0002] Perovskite solar cells (PSCs) are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite crystal materials. They are currently the third generation of solar cells and have many advantages such as high photoelectric conversion efficiency, simple manufacturing process, and low production cost. They have been extensively studied in recent years.

[0003] Perovskite solar cells can be classified into nip (non-particle) and pin (non-particle) structures based on their functional layer configurations. Due to these differences in functional layer configurations, nip and pin structures have different requirements for charge transport and extraction, thus necessitating different requirements for electron transport layer materials. Y6 is a widely used non-fullerene acceptor material in organic solar cells. Methods have been attempted to structurally improve Y6, providing a polymeric electron transport material with thiophene-modified Y6 as the structural unit, and applying it to pin-structure perovskite solar cells; however, its photoelectric conversion efficiency requires further improvement. Summary of the Invention

[0004] Based on this, this application provides a perovskite solar cell with high photoelectric conversion efficiency, as well as a photovoltaic module, electrical device and power generation device including the perovskite solar cell.

[0005] A first aspect of this application provides a perovskite solar cell, comprising a first electrode, a perovskite layer, an electron transport layer, and a second electrode; the perovskite layer and the electron transport layer are stacked between the first electrode and the second electrode, and the material of the electron transport layer comprises one or more compounds with the structure shown in formula (I):

[0006]

[0007] in,

[0008] X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0009] Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0010] Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0011] Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0012] Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

[0013] This application provides a material with the structure shown in Formula (I) as the electron transport layer of a perovskite solar cell. It is an improvement on the Y6 structure, specifically by introducing fluorine atoms to replace the acetonitrile groups on both sides of the molecular structure, which can effectively improve the photoelectric conversion efficiency of the cell.

[0014] In some of these embodiments, each Ar independently includes the following groups:

[0015]

[0016] X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups. Indicates the connection site.

[0017] Using Ar groups with appropriate structures can enhance the overall planar rigidity of the molecular structure, strengthen the stacking between molecules, improve charge transport capacity, and thus improve the photoelectric conversion efficiency of the battery.

[0018] In some embodiments, the material of the electron transport layer comprises one or more compounds with the structure shown in formula (I-1):

[0019]

[0020] X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups.

[0021] Compounds with the structure shown in formula (I-1) can enhance the overall planar rigidity of the molecular structure while improving the electron transport efficiency of the material and thus the photoelectric conversion efficiency of the battery.

[0022] In some of these implementations, X includes S.

[0023] In some of these implementations, Y1 and Y2 each independently include S.

[0024] Using sulfur atoms is more conducive to improving electron injection and transport efficiency, and the compound has good stability.

[0025] In some of these embodiments, each R1 independently comprises a C5 to C15 alkyl group.

[0026] In some embodiments, each R2 independently comprises a C5 to C15 alkyl group.

[0027] By rationally controlling the number of C atoms in the substituents R1 and R2 in the compound structure, the molecular structure and spatial configuration of the material can be appropriately adjusted, making the electron transport channels between molecules smoother, thereby improving the electron migration efficiency and obtaining better photoelectric conversion efficiency.

[0028] In some embodiments, the material of the electron transport layer comprises one or more of the following compounds:

[0029]

[0030]

[0031] In some embodiments, the thickness of the electron transport layer is 20 nm to 30 nm.

[0032] In some embodiments, the material of the perovskite layer includes Cs. a FA b MA c Pb d Sn e I f Br g Where a is 0 to 0.25, b is 0.75 to 1, c is 0 to 0.1, d is 0.5 to 1, e is 0 to 0.5, f is 2 to 3, and g is 0 to 1.

[0033] In some embodiments, the perovskite layer is disposed between the first electrode and the electron transport layer, and the first electrode includes a transparent conductive electrode.

[0034] A second aspect of this application provides an organic compound having the structure shown in formula (I):

[0035]

[0036] in,

[0037] X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0038] Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0039] Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0040] Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0041] Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

[0042] In some of these embodiments, each Ar independently includes the following groups:

[0043]

[0044] X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups. Indicates the connection site.

[0045] In some embodiments, the organic compound includes one of compounds with the structure shown in formula (I-1):

[0046]

[0047] X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups.

[0048] A third aspect of this application provides an electronic transport material comprising the organic compound described in the second aspect.

[0049] A fourth aspect of this application provides a photovoltaic module, comprising the perovskite solar cell described in the first aspect, the organic compound described in the second aspect, or the electron transport material described in the third aspect.

[0050] The fifth aspect of this application provides an electrical device comprising the perovskite solar cell described in the first aspect, the organic compound described in the second aspect, the electron transport material described in the third aspect, or the photovoltaic module described in the fourth aspect.

[0051] A sixth aspect of this application provides a power generation device, comprising the perovskite solar cell described in the first aspect, the organic compound described in the second aspect, the electron transport material described in the third aspect, or the photovoltaic module described in the fourth aspect. Attached Figure Description

[0052] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0053] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell according to one embodiment of this application.

[0054] Wherein, 100: transparent conductive electrode, 200: hole transport layer, 300: perovskite layer, 400: electron transport layer, 500: hole blocking layer, and 600: second electrode. Detailed Implementation

[0055] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0057] The "range" disclosed in this application can be defined in the form of 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 specific range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be included or excluded independently, and they can be combined arbitrarily; 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 ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are also 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" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥ 2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0058] In this application, the terms "multiple" or "various" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" means one or more types.

[0059] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0060] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding.

[0061] Those skilled in the art will understand that the order in which the steps are written in the methods of various embodiments or examples does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) can 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.

[0062] In this application, unless otherwise specified, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0063] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0064] In this application, the use of the word "comprising" to describe open-ended technical features or solutions does not exclude additional members beyond those listed unless otherwise specified. It can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond those listed. For example, the phrase "X comprises S" can mean that X is S or X is selected from S, or it can mean that X is another group comprising S.

[0065] In this application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C2-C10 alkyl," refer to alkyl groups containing 2 to 20 carbon atoms, and each occurrence can independently be C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, or C20 alkyl. Suitable examples include, but are not limited to: 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), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3) ), 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), 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).

[0066] The term "alkoxy" refers to a group with the structure -O-alkyl, usually denoted by RO-, meaning that the alkyl group (R) as defined above is attached to an adjacent group via an oxygen atom. Phrases containing this term, such as "C2-C20 alkoxy," refer to alkyl moieties containing 2 to 20 carbon atoms, and each occurrence can be independently C2alkoxy, C4alkoxy, C5alkoxy, C6alkoxy, C7alkoxy, C8alkoxy, C9alkoxy, C12alkoxy, C15alkoxy, C17alkoxy, and C20alkoxy.

[0067] The term "alkylthio" refers to a group with the structure -S-alkyl, i.e., an alkyl group as defined above, connected to an adjacent group via a sulfur atom. Phrases containing this term, such as "C2-C20 alkylthio", refer to alkyl moieties containing 2 to 20 carbon atoms, and each occurrence can be independently C2 alkylthio, C4 alkylthio, C5 alkylthio, C6 alkylthio, C7 alkylthio, C8 alkylthio, C9 alkylthio, C12 alkylthio, C15 alkylthio, C17 alkylthio, and C20 alkylthio.

[0068] In this application, the term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic rings, at least one is an aromatic ring system. For example, "C6-C15 aryl" refers to an aryl group containing 6 to 15 carbon atoms, and each occurrence can be independently C6 aryl, C7 aryl, C8 aryl, C10 aryl, or C15 aryl.

[0069] In this application, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, an O atom, an S atom, etc. For example, "5- to 10-membered heteroaryl" refers to a heteroaryl group containing 5 to 10 ring atoms, and each occurrence can be independently 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered heteroaryl.

[0070] In this application, the term "halogen" refers to F, Cl, Br, or I.

[0071] Solar cells, also known as photovoltaic cells, are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect. Perovskite solar cells are solar cells that utilize perovskite material as the light-absorbing material. Compared with other solar cells, perovskite solar cells have high photoelectric conversion efficiency. The photoelectric conversion principle of perovskite solar cells is as follows: Incident light (e.g., sunlight) enters the device and reaches the perovskite layer, where it is absorbed. Under the excitation of the incident light, the perovskite layer generates electron-hole pairs. Under the action of an electric field, the holes and electrons separate; the electrons are transported to one electrode, while the holes are transported to the other electrode. Subsequently, a circuit is formed through an external circuit, which can be used to drive a load.

[0072] Depending on the configuration of the functional layers, perovskite solar cells can be divided into nip (non-inverted) and pin (reverse) structures. Typically, in a nip structure, from bottom to top, the layers are a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. Light enters from the transparent conductive substrate, passes through the electron transport layer to reach the perovskite layer, where it absorbs the light and generates electron-hole pairs. Electrons are collected by the electron transport layer and transported to the transparent conductive substrate, while holes travel through the hole transport layer to the second electrode, generating a photocurrent. In a pin structure, from bottom to top, the layers are a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode. Light enters from the transparent conductive substrate, passes through the hole transport layer to reach the perovskite layer, where electrons are collected by the hole transport layer and transported to the transparent conductive substrate, while electrons travel through the electron transport layer to the second electrode.

[0073] Due to the different functional layer configurations, the formal and inverted structures have different requirements for charge transport and extraction, thus requiring different electron transport layer materials. In particular, in the inverted structure, the electron transport layer is located at the upper interface of the perovskite layer, and its influence on electron transport is more significant. How to effectively extract electrons is one of the key factors affecting the efficiency improvement of perovskite solar cells in the inverted structure.

[0074] Y6 material, a dithiophenothiophene(3,2-b)-pyrrolobenzothiadiazole derivative, is commonly used as an acceptor material in organic solar cells, but its application in perovskite solar cells is rarely reported. Methods have been developed to modify the structure of Y6, providing a polymeric electron transport material with thiophene-modified Y6 as the structural unit (structure shown below). However, its photoelectric conversion efficiency in inverted perovskite solar cells requires further improvement.

[0075]

[0076] One embodiment of this application provides a perovskite solar cell, comprising a first electrode, a perovskite layer, an electron transport layer, and a second electrode. The perovskite layer and the electron transport layer are stacked between the first electrode and the second electrode. The material of the electron transport layer includes one or more compounds with the structure shown in formula (I):

[0077]

[0078] in,

[0079] X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0080] Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0081] Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0082] Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0083] Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

[0084] This application provides a material with the structure shown in formula (I) as an electron transport layer for perovskite solar cells. It is an improvement on the Y6 structure, specifically by introducing fluorine atoms to replace the acetonitrile groups on both sides of the molecular structure. This effectively improves the photoelectric conversion efficiency of the cell. The likely principle is that introducing fluorine atoms to replace the acetonitrile groups on both sides of the molecular structure can adjust the electron distribution within the molecule, making it more compatible with the energy level structure of the perovskite, which is beneficial for improving electron injection and transport performance, thereby effectively improving the photoelectric conversion efficiency of the cell.

[0085] Furthermore, compared to traditional electron transport layer materials in inverted perovskite solar cells, such as C 60 Compared with methyl [6,6]-phenyl-C61-butyrate (PCBM), the electron transport layer material with the structure shown in formula (I) also has the advantage of low cost.

[0086] In some of these embodiments, each Ar independently includes the following groups:

[0087]

[0088] X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups. Indicates the connection site.

[0089] Using Ar groups with appropriate structures can enhance the overall planar rigidity of the molecular structure, strengthen the stacking between molecules, improve charge transport capacity, and thus improve the photoelectric conversion efficiency of the battery.

[0090] In some of these embodiments, each Ar independently includes the following groups:

[0091]

[0092] X1, X2, X3 and X4 each independently include H, halogens, and at least one of them is a halogen.

[0093] The use of aryl groups in Ar facilitates stronger intermolecular stacking, while the introduction of halogens enhances the electron transport efficiency of the material, thereby improving the photoelectric conversion efficiency of the battery. Furthermore, the electron transport layer material comprises one or more compounds with the structure shown in formula (I-1):

[0094]

[0095] X1, X2, X3, and X4 each independently include H, a halogen, a C1-C20 alkyl group, a C1-C20 oxygen group, a carbonyl group, an ester group, a nitro group, or a cyano group. Further, X1, X2, X3, and X4 each independently include H or a halogen, and at least one is a halogen. Compounds employing the structure shown in formula (I-1) can enhance the overall planar rigidity of the molecular structure while improving the electron transport efficiency of the material, thereby increasing the photoelectric conversion efficiency of the battery.

[0096] In some of these implementations, X includes S.

[0097] In some of these implementations, Y1 and Y2 each independently include S.

[0098] Using sulfur atoms is more conducive to improving electron injection and transport efficiency, and the compound has good stability.

[0099] In addition, by rationally controlling the number of C atoms in the substituents R1 and R2 in the compound structure, the molecular structure and spatial configuration of the material can be appropriately adjusted, making the electron transport channels between molecules smoother, thereby improving the electron migration efficiency and obtaining better photoelectric conversion efficiency.

[0100] In some embodiments, each R1 independently comprises a C5-C15 alkyl group. Further, each R1 independently comprises a C7-C10 alkyl group.

[0101] In some embodiments, each R2 independently comprises a C5-C15 alkyl group. Further, each R2 independently comprises a C11-C15 alkyl group.

[0102] Without limitation, the material of the electron transport layer includes one or more of the following compounds:

[0103]

[0104]

[0105] In some embodiments, the thickness of the electron transport layer is 20 nm to 30 nm. Reasonably controlling the thickness of the electron transport layer is more conducive to charge extraction, and at the same time, it results in high charge transport efficiency, thereby improving device efficiency. Specifically, the thickness of the electron transport layer includes, but is not limited to: 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, or any combination thereof. Further, the thickness of the electron transport layer is 20 nm to 25 nm.

[0106] In some embodiments, the material of the perovskite layer includes Cs. a FA b MA c Pb d Sn e I f Br gWhere a is 0–0.25, b is 0.75–1, c is 0–0.1, d is 0.5–1, e is 0–0.5, f is 2–3, and g is 0–1. Using appropriate materials for the perovskite layer facilitates charge extraction and provides a more matched energy level, thus comprehensively improving photoelectric conversion efficiency. Specifically, a includes, but is not limited to: 0, 0.05, 0.1, 0.15, 0.2, 0.25, or any two of the aforementioned ranges; b includes, but is not limited to: 0.75, 0.8, 0.85, 0.9, 0.95, 1, or any two of the aforementioned ranges; c includes, but is not limited to: 0, 0.03, 0.05, 0.07, 0.1, or any two of the aforementioned ranges; and d includes, but is not limited to: 0.5, 0.55, 0.6, 0.65, 0.7, 0. 75, 0.8, 0.85, 0.9, 0.95, 1, or any two of the foregoing; e includes, but is not limited to, 0, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or any two of the foregoing; f includes, but is not limited to, 2, 2.2, 2.5, 2.7, 3, or any two of the foregoing; g includes, but is not limited to, 0, 0.3, 0.5, 0.7, 1, or any two of the foregoing. Further, in the material of the perovskite layer, a is 0.05–0.25, b is 0.75–1, c is 0, d is 0.8–1, e is 0, f is 2–3, and g is 0. Without limitation, the material of the perovskite layer includes Cs. 0.05 FA 0.95 PbI3, FAPbI3, Cs 0.1 FA 0.9 PbI3, Cs 0.25 FA 0.75 PbI3 and Cs 0.25 FA 0.75 Pb 0.5 Sn 0.5 One or more of I3.

[0107] In some embodiments, the thickness of the perovskite layer is 400 nm to 1000 nm. Specifically, the thickness of the perovskite layer includes, but is not limited to, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range between the foregoing. In some embodiments, the perovskite layer is disposed between a first electrode and an electron transport layer, the first electrode comprising a transparent conductive electrode. This forms an inverted perovskite solar cell, where the material of the electron transport layer is particularly suitable for the inverted structure, improving its photoelectric conversion efficiency.

[0108] In some of these implementations, such as Figure 1 As shown, the perovskite solar cell includes a transparent conductive electrode 100, a hole transport layer 200, a perovskite layer 300, an electron transport layer 400, and a second electrode 600 stacked together. Optionally, a hole blocking layer 500 may be included between the electron transport layer 400 and the second electrode 600.

[0109] Without limitation, the transparent conductive electrode 100 is used for light incident. It may be one or more of the following materials, including but not limited to: FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), etc.

[0110] In some embodiments, the hole transport layer 200 is capable of extracting and transporting hole carriers and blocking the passage of free electrons. It may include, but is not limited to, one or more of the following materials and their derivatives: 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), nickel oxide (NiOx), poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), WO3, and other materials capable of transporting holes and blocking electrons.

[0111] In some embodiments, the hole blocking layer 500 can improve electron extraction performance and block hole transport. It may include, but is not limited to, one or more of the following materials and their derivatives: tin oxide and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

[0112] Without limitation, the second electrode 600 comprises a conductive material. Further, the conductive material can be an organic conductive material, an inorganic conductive material, or a combination thereof. Non-limiting examples of inorganic conductive materials include metallic conductive materials; further, metallic conductive materials can include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), or any suitable mixture of the aforementioned elements. The conductive material can include a conductive oxide; further, the conductive material can be a conductive oxide; non-limiting examples of conductive oxides can include one or more of FTO, ITO, IWO, AZO, etc.

[0113] In some embodiments, the perovskite solar cell further includes a substrate layer disposed on the side of the transparent conductive electrode 100 away from the perovskite layer 300 for supporting the perovskite solar cell. The substrate layer can be, but is not limited to, a glass substrate or a flexible substrate. In some embodiments, the flexible substrate layer may be made of, for example (but not limited to), an organic polymer material, and further, may be a mixture of one or more of the following materials in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0114] Understandably, perovskite solar cells can be fabricated using conventional methods in the art. Specifically, the fabrication method for a perovskite solar cell, which is a formal structure, includes the following steps:

[0115] Step 1: Etch and clean the transparent conductive electrode, then dry;

[0116] Step 2: Fabricate an electron transport layer on a transparent conductive electrode;

[0117] Step 3: Prepare a perovskite layer on the electron transport layer;

[0118] Step 4: Prepare a hole transport layer on the perovskite layer;

[0119] Step 5: Fabricate a second electrode on the hole transport layer.

[0120] Specifically, the perovskite solar cell has an inverted structure, and its fabrication method includes the following steps:

[0121] Step 1: Etch and clean the transparent conductive electrode, then dry;

[0122] Step 2: Fabricate a hole transport layer on a transparent conductive electrode;

[0123] Step 3: Prepare a perovskite layer on the electron transport layer;

[0124] Step 4: Prepare an electron transport layer on the perovskite layer;

[0125] Step 5: Fabricate a second electrode layer on the hole transport layer.

[0126] Without limitation, the layers can be prepared by spin coating or vapor deposition.

[0127] In other embodiments of this application, an organic compound is provided having the structure shown in formula (I):

[0128]

[0129] in,

[0130] X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0131] Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio;

[0132] Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0133] Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group;

[0134] Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

[0135] The aforementioned organic compounds can serve as materials for the electron transport layer of perovskite solar cells, thereby improving device efficiency. Understandably, when used as materials for the electron transport layer of perovskite solar cells, they offer similar solutions and advantages to those described above, and will not be elaborated upon here.

[0136] In other embodiments of this application, an electron transport material is provided, comprising the organic compound described above. This electron transport material has similar schemes and advantages to the electron transport layer in the perovskite solar cell described above, and will not be elaborated further here.

[0137] Other embodiments of this application provide a photovoltaic module, including perovskite solar cells, organic compounds, or electron transport materials as described above.

[0138] Other embodiments of this application provide an electrical device, including perovskite solar cells, organic compounds, electron transport materials, or photovoltaic modules as described above.

[0139] Other embodiments of this application provide a power generation device, including perovskite solar cells, organic compounds, electron transport materials, or photovoltaic modules as described above.

[0140] In some embodiments, the perovskite solar cell described above can be a power generation device that functions as an electrical device. The type of power generation device may include, but is not limited to, integrated power generation. The location of the power generation device may include, but is not limited to, the roof of a vehicle, the back panel, etc.

[0141] Furthermore, the aforementioned electrical devices may include mobile devices, such as electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited to these.

[0142] As another implementation method, the power supply device can be a wearable device, such as a watch.

[0143] To make the technical problems, technical solutions, and beneficial effects solved by this application clearer, the application will be further described in detail below with reference to embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this application or its application. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0144] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0145] Preparation Example 1

[0146] Preparation of (E)-YIF material for electron transport layer.

[0147] (1) Synthesis of Compound 1

[0148]

[0149] Under an Ar atmosphere, 5 mmol of 3,4-difluorophthalic anhydride was placed in a dry flask, followed by the sequential addition of 20 mL of anhydrous acetic anhydride and 10 mL of anhydrous triethylamine. The mixture was stirred at room temperature until the anhydride was completely dissolved. The reaction apparatus was then placed in an ice bath, and 6 mmol of tert-butyl acetoacetate was added dropwise to the mixture. After the addition was complete, the reaction mixture was stirred at room temperature for 12 hours. Then, 100 mL of ice water containing 20 mL of concentrated hydrochloric acid was added to the reaction mixture, and the apparatus was heated to 100 °C and refluxed for 2 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and most of the solvent was removed using a rotary evaporator. The residue was precipitated into 100 mL of petroleum ether and filtered to give compound 1 as a pale yellow solid. 1 H NMR (400MHz, CDCl) 3, 25℃)δ(ppm)7.72(t,J=7.4Hz,2H),3.22(s,2H). 19 F NMR (376MHz, CDCl3, 25℃) δ (ppm)-121.49 (s, 2F).

[0150] (2) Synthesis of compound 2

[0151]

[0152] Compound 1 (5 mmol), Ph3P + CF2COO - (6 mmol) and toluene (20 mL) were placed in a dry round-bottom flask. The reaction suspension was then heated to 110 °C and reacted for 9 hours. The reaction mixture was poured into ice water and then extracted with dichloromethane. The resulting organic phase was washed with saturated sodium chloride solution and dried with anhydrous sodium sulfate. Most of the solvent was removed by rotary evaporator. The residue was purified by silica gel column chromatography with a 200-300 mesh to give compound 2, which was a pale yellow solid. 1 H NMR (400MHz, CDCl3, 25℃) δ (ppm) 7.58 (dd, J=8.4, 7.5Hz, 1H), 7.51 (ddd, J=9.8, 6.6, 1.1Hz, 1H), 3.32 (s, 2H). 19 F NMR (376MHz, CDCl3, 25℃) δ (ppm) -80.18 (ddd, J=31.2, 6.8, 2.9Hz, 1F), -82.56 (dt,J=30.7,2.4Hz,1F),-123.33~-123.60(m,1F),-134.01~-134.29(m,1F).

[0153] (3) Synthesis of compound 3

[0154]

[0155] Compound 2 (5 mmol), CsF (0.5 mmol), and acetonitrile (20 mL) were placed in a dry round-bottom flask and stirred thoroughly to dissolve. Trimethylcyanosilane (6 mmol) was then added dropwise. The reaction was monitored by thin-layer chromatography. After the starting material disappeared, the mixture was poured into 20 mL of ice water and extracted with chloroform. The resulting organic phase was washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. After removing most of the solvent using a rotary evaporator, the residue was purified by silica gel column chromatography (200-300 mesh) to give compound 3. 1 H NMR (400MHz, CDCl3, 25℃), δ (ppm) 8.07 (dd, J = 9.6, 6.5Hz, 1H), 7.67 (t, J = 7.7Hz, 1H), 3.54 (d, J = 2.6Hz, 2H). 19F NMR (376MHz, CDCl3, 25°C) δ (ppm) -119.08 (dd, J = 7.6, 2.8Hz, 1F), -121.12 (dd, J = 19.3, 3.0Hz, 1F), -127.40 (dd, J = 19.1, 7.5Hz, 1F).

[0156] (4) Synthesis of compound (E)-YIF

[0157]

[0158] In a 10 mL solution of compound 4 (0.1 mmol) and compound 3 (0.21 mmol) in toluene, 0.1 mL of acetic anhydride was added, followed by 1 mmol of boron trifluoride diethyl ether. The reaction was then stirred at room temperature for 1 hour. After the reaction was complete, the reaction mixture was poured into 100 mL of methanol, resulting in the precipitation of a large amount of solid. The crude product of compound (E)-YIF was obtained by filtration. The crude product of compound (E)-YIF was dissolved in a small amount of chloroform, precipitated in 50 mL of methanol, and the resulting solid was washed with methanol and n-hexane, respectively. This process was repeated three times to obtain pure compound (E)-YIF, which was a blue-black solid. 1 H NMR(400MHz CDCl325℃)δ(ppm)8.43(d,J=7.5Hz,2H),8.13(dd,J=9.8,6.4Hz,2H),7.72(t,J=7.6Hz,2H),4.82- 4.69(m,4H),3.10(t,J=7.8Hz,4H),2.24-2.07(m,2H),1.85(t,J=7.7Hz,4H),1.53-0.56(m,74H). 19 F NMR (376MHz CDC13 25℃) δ (ppm) -124.05 (d, J = 19.5Hz, 2F), -129.41 (dd, J = 19.5, 5.9Hz, 2F), -130.78 (s, 2F).

[0159] Compound S4 was prepared using a similar method to that used for compound (E)-YIF. The structure of compound S4 is shown below:

[0160]

[0161] 1H NMR(400MHz CDCl3 25℃)δ(ppm)7.72(t,J=7.6Hz,2H),7.36-7.32(m,4H),7.21(s,2H),4.82-4.69(m,4H) ,3.10(t,J=7.8Hz,4H),2.24-2.07(m,2H),1.85(t,J=7.7Hz,4H),1.53-0.56(m,74H). 19 F NMR (376MHz CDCl3 25℃) δ (ppm)-132.81 (s, 2F).

[0162] Example 1

[0163] This embodiment provides a perovskite solar cell, the fabrication steps of which are as follows:

[0164] 1) Preparation of the substrate

[0165] The etched FTO transparent metal oxide substrate was sequentially cleaned with 2% (w / w) Triton X-100 deionized water, anhydrous ethanol, deionized water, and anhydrous ethanol. After drying, the cleaned substrate was irradiated in a UV ozone generator for 30 minutes.

[0166] 2) Preparation of the hole transport layer

[0167] A nickel oxide layer with a thickness of 30 nm was prepared on the substrate using magnetron sputtering.

[0168] 3) Preparation of the perovskite layer

[0169] 19.5 mg CsI, 695.0 mg PbI2, and 245.1 mg FAI were dissolved in 800 μL DMF and 200 μL DMSO and stirred for 30 minutes to obtain a perovskite precursor solution. Under a nitrogen atmosphere, the perovskite precursor solution was dropwise added to the surface of the hole transport layer, and spin-coated at 1000 rpm for 10 seconds, followed by spin-coating at 5000 rpm for 30 seconds, during which 150 μL of chlorobenzene was injected as an antisolvent. The resulting film was annealed at 150 °C for 10 minutes to obtain a 450 nm perovskite layer. 0.05 FA 0.95 PbI3.

[0170] 4) Fabrication of the electron transport layer

[0171] The electron transport layer material (E)-YIF was dissolved in chlorobenzene at a concentration of 10 mg / mL, dropped onto the surface of the perovskite layer, spin-coated at 3000 rpm for 30 seconds, and annealed at 100 °C for 10 minutes to obtain a 23 nm electron transport layer.

[0172] 5) Preparation of hole blocking layer

[0173] Tin oxide of 20 nm was prepared on the surface of the electron transport layer using an ALD device.

[0174] 6) Preparation of the second electrode layer

[0175] A copper electrode with a thickness of 100 nm is thermally deposited on the surface of the hole blocking layer.

[0176] The perovskite solar cell provided in Example 2 is fabricated in the same steps as in Example 1, except that in step 4), the thickness of the electron transport layer is 30 nm.

[0177] The perovskite solar cell provided in Example 3 is fabricated using the same steps as in Example 1, with the main difference being that in step 3), the perovskite layer is Cs. 0.25 FA 0.75 PbI3.

[0178] The perovskite solar cell provided in Example 4 is fabricated in the same steps as in Example 1, with the main difference being that the electron transport layer material S4 is used to replace (E)-YIF in equal amounts.

[0179] The perovskite solar cell provided in Comparative Example 1 is fabricated using the same steps as in Example 1, with the main difference being that the electron transport layer material D1 is used to replace (E)-YIF in equal amounts. The structural formula of D1 is shown below:

[0180]

[0181] The perovskite solar cell provided in Comparative Example 2 is fabricated using the same steps as in Example 1, with the main difference being that the electron transport layer material D2 is used to replace (E)-YIF in equal amounts. The structural formula of D2 is shown below:

[0182]

[0183] Photoelectric performance testing

[0184] The photoelectric conversion efficiency (PCE) of the perovskite solar cells was tested at room temperature (25°C):

[0185] Using an AAA-grade solar simulator under standard test conditions: incident light power 100mW / cm² 2 The photoelectric performance parameters of the tested battery were measured using a spectral energy of AM1.5G, and the P values ​​were obtained. out P in V mpp J mpp V oc J sc Then, calculate the PCE based on the following formula:

[0186] PCE = P out / P in ;

[0187] =V oc ×J sc ×[(V mpp ×J mpp ) / (V oc ×J sc )] / P in ;

[0188] =V oc ×J sc ×FF / P in ;

[0189] Among them, P in P out V mpp J mpp V oc J sc FF represent: incident light power, operating output power of the battery under test, voltage at the maximum power point of the battery under test, current at the maximum power point of the battery under test, open circuit voltage, short circuit current, and fill factor, respectively.

[0190] The test results are shown in Tables 1 and 2 below:

[0191] Table 1

[0192]

[0193] Table 2

[0194]

[0195]

[0196] A comparison between Examples 1 and 4 and Comparative Examples 1 and 2 shows that the examples effectively improve the photoelectric conversion efficiency of the battery by introducing fluorine atoms to replace the acetonitrile groups on both sides of the molecular structure. A comparison between Examples 1 and 4 and Comparative Example 2 shows that Comparative Example 2, which uses a polymer-type electron transport material, has a significantly lower photoelectric conversion efficiency than Examples 1 and 4. This may be because polymer materials have low conductivity and electron mobility, resulting in limited improvement in the photoelectric conversion efficiency of the battery.

[0197] Furthermore, a comparison between Example 1 and Example 2 shows that properly controlling the thickness of the electron transport layer can further improve the photoelectric conversion efficiency of the battery.

[0198] As can be seen from Examples 1 and 3, the electron transport layer can be applied to different perovskite layer materials and improve the photoelectric conversion efficiency of the battery.

[0199] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0200] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A perovskite solar cell, characterized in that, The electrode comprises a first electrode, a perovskite layer, an electron transport layer, and a second electrode; the perovskite layer and the electron transport layer are stacked between the first electrode and the second electrode, and the material of the electron transport layer comprises one or more compounds with the structure shown in formula (I): in, X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio; Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio; Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group; Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group; Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

2. The perovskite solar cell according to claim 1, characterized in that, Each Ar independently includes the following groups: X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups. Indicates the connection site.

3. The perovskite solar cell according to claim 2, characterized in that, The material of the electron transport layer includes one or more compounds with the structure shown in formula (I-1): X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, It has one or more of the following characteristics: (1) X includes S; (2) Y1 and Y2 each independently include S; (3) Each R1 independently includes a C5 to C15 alkyl group; (4) Each R2 independently includes a C5 to C15 alkyl group.

5. The perovskite solar cell according to claim 1, characterized in that, The electron transport layer is made of one or more of the following compounds:

6. The perovskite solar cell according to any one of claims 1 to 5, characterized in that, The thickness of the electron transport layer is 20nm to 30nm.

7. The perovskite solar cell according to any one of claims 1 to 6, characterized in that, The material of the perovskite layer includes Cs. a FA b MA c Pb d Sn e I f Br g Where a is 0 to 0.25, b is 0.75 to 1, c is 0 to 0.1, d is 0.5 to 1, e is 0 to 0.5, f is 2 to 3, and g is 0 to 1.

8. The perovskite solar cell according to any one of claims 1 to 7, characterized in that, The perovskite layer is disposed between the first electrode and the electron transport layer, and the first electrode includes a transparent conductive electrode.

9. An organic compound, characterized in that, It has the structure shown in equation (I): in, X includes S, Se, or NR. 01 R 01 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio; Y1 and Y2 each independently include O, S, Se, or NR. 02 R 02 Including C2-C20 alkyl, C2-C20 alkoxy, or C2-C20 alkylthio; Each R1 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group; Each R2 independently comprises a C2-C20 alkyl, a C2-C20 alkoxy, or a C2-C20 alkylthio group; Each Ar independently includes substituted or unsubstituted C6-C15 aryl groups or substituted or unsubstituted 5-10 heteroaryl groups.

10. The organic compound according to claim 9, characterized in that, Each Ar independently includes the following groups: X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups. Indicates the connection site.

11. The organic compound according to claim 10, characterized in that, One of the compounds with the structure shown in formula (I-1) below: X1, X2, X3, and X4 each independently include H, halogen, C1-C20 alkyl, C1-C20 oxygen, carbonyl, ester, nitro, or cyano groups.

12. An electron transport material, characterized in that, Includes the organic compounds described in any one of claims 9 to 11.

13. A photovoltaic module, characterized in that, This includes the perovskite solar cell according to any one of claims 1 to 8, the organic compound according to any one of claims 9 to 11, or the electron transport material according to claim 12.

14. An electrical appliance, characterized in that, This includes the perovskite solar cell according to any one of claims 1 to 8, the organic compound according to any one of claims 9 to 11, the electron transport material according to claim 12, or the photovoltaic module according to claim 13.

15. A power generation device, characterized in that, This includes the perovskite solar cell according to any one of claims 1 to 8, the organic compound according to any one of claims 9 to 11, the electron transport material according to claim 12, or the photovoltaic module according to claim 13.

Images