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 a structure as shown in the following formula (I). The perovskite solar cell has relatively high photoelectric conversion efficiency and relatively low cost.

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-inverted) and pin (inverted) structures based on their functional layer configurations. Due to the different functional layer configurations, nip and pin structures have different requirements for charge transport and extraction, thus necessitating different requirements for electron transport layer materials. Traditional pin-structure perovskite solar cells typically use C0... 60 Methyl [6,6]-phenyl-C61-butyrate (PCBM) has been used as an electron transport layer, but its high cost necessitates a proactive search for alternative materials. Methods exist to replace C with Nb2O5 or materials containing naphthalene tetracarbodiimide (NDI) or perylene tetracarbodiimide (PDI) structural units. 60 While comparable to PCBM, both have photoelectric conversion efficiency (PCE) that needs 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 includes one or more compounds having the structure shown in formula (I):

[0006]

[0007] in,

[0008] n is 2, 3, 4 or 5;

[0009] X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br;

[0010] Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group;

[0011] Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

[0012] This application provides a material with the structure shown in formula (I) as an electron transport layer for perovskite solar cells, which can achieve high photoelectric conversion efficiency while reducing costs, and is particularly suitable for improving the photoelectric conversion efficiency of inverted perovskite solar cells.

[0013] In one embodiment, each repeating unit contains an Ar group that independently comprises a phenyl group or a 5- to 6-membered heteroaryl group. The use of phenyl groups or 5- to 6-membered heteroaryl groups enhances the overall planar rigidity of the molecular structure and improves photoelectric conversion efficiency.

[0014] In one embodiment, the Ar in each repeating unit independently includes the following groups:

[0015]

[0016] Z includes O, S, or Se.

[0017] By employing this 5-membered heteroaryl group, the overall planar rigidity of the molecular structure can be enhanced, further improving the ability to extract charge and increasing photoelectric conversion efficiency.

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

[0019]

[0020] By properly controlling the number of perylenetetracarboxydiimide structures, it is possible to improve device efficiency while giving the material good solubility or a low melting and boiling point, making it suitable for different production processes, such as solvent methods or vapor deposition methods.

[0021] In one embodiment, the material of the electron transport layer comprises one or more of the following compounds:

[0022]

[0023]

[0024] In one embodiment, 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 photoelectric conversion efficiency.

[0025] In one embodiment, the material of the perovskite layer includes Cs. a FAb MA c Pb d Sn e I f Br g Where 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, thereby comprehensively improving photoelectric conversion efficiency.

[0026] In one embodiment, the perovskite layer is disposed between the first electrode and the 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, thus improving its photoelectric conversion efficiency.

[0027] A second aspect of this application provides an organic compound having the structure shown in formula (I):

[0028]

[0029] n is 2, 3, 4 or 5;

[0030] X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br;

[0031] Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group;

[0032] Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

[0033] The aforementioned organic compounds can be used as materials for the electron transport layer of perovskite solar cells, improving device efficiency while maintaining low cost.

[0034] In one embodiment, the Ar in each repeating unit independently includes the following groups:

[0035]

[0036] Z includes O, S, or Se.

[0037] In one embodiment, the organic compound has the structure shown in formula (I-1):

[0038]

[0039] A third aspect of this application provides an electronic transport material comprising the organic compound described in the second aspect.

[0040] 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.

[0041] 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.

[0042] 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

[0043] 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:

[0044] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell according to one embodiment of this application.

[0045] Wherein, 100: transparent conductive electrode, 200: hole transport layer, 300: perovskite layer, 400: electron transport layer, 500: hole blocking layer, and 600: second electrode layer. Detailed Implementation

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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 "X1 comprises H" can mean that X1 is H or X1 is selected from H, or it can mean that X1 is another group comprising H.

[0056] 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 "C1-C10 alkyl," refer to alkyl groups containing 1 to 20 carbon atoms, and each occurrence can independently be C1 alkyl, 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: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)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 (- CH2CH2CH(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).

[0057] 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, and for polycyclic rings, at least one is an aromatic ring system. For example, "C6-C8 aryl" refers to an aryl group containing 6 to 8 carbon atoms, and each occurrence can be independently C6, C7, or C8 aryl. Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene, and their derivatives.

[0058] 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 8-membered heteroaryl" refers to a heteroaryl group containing 5 to 8 ring atoms, and each occurrence can be independently of a 5-membered, 6-membered, 7-membered, or 8-membered heteroaryl. Suitable examples include, but are not limited to: furanyl, thiopheneyl, pyrroleyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, oxadiazolyl, thiazolyl, tetrazolyl, indolyl, carbazolyl, pyridinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, and isoquinolinyl.

[0059] 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.

[0060] Depending on the configuration of the functional layers, perovskite solar cells can be divided into two types: nip (non-next-plate) and pin (inverted-pin) structures. In a typical 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 the perovskite layer, 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 and is first received by the hole transport layer. Of the electron-hole pairs generated in the perovskite layer, holes 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.

[0061] 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.

[0062] C 60 [6,6]-phenyl-C61-butyrate methyl ester (PCBM) is a commonly used electron transport material in perovskite solar cells with an inverse structure, achieving good photoelectric conversion efficiency. However, it also suffers from high cost, thus necessitating the search for alternative materials. Currently available methods, such as those using Nb2O5 or materials containing naphthalene tetracarbodiimide (NDI) or perylene tetracarbodiimide (PDI) structural units, do not achieve photoelectric conversion efficiencies comparable to C61-butyrate. 60 Because of this, inverted perovskite solar cells suffer from a tradeoff between high photoelectric conversion efficiency and low cost, as seen with PCBMs.

[0063] Based on this, one embodiment of this application provides a perovskite solar cell, including 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 includes one or more compounds having the structure shown in formula (I):

[0064]

[0065] in,

[0066] n is 2, 3, 4 or 5;

[0067] X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br;

[0068] Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group;

[0069] Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

[0070] This application provides a material with the structure shown in formula (I) as the electron transport layer of a perovskite solar cell, which can achieve high photoelectric conversion efficiency while reducing cost. The possible principle is as follows:

[0071] In traditional electron transport materials containing perylene tetracarbamate (PDI) structures, the PDI structure is prone to rotation, resulting in poor molecular stacking order and crystallinity, which in turn leads to poor charge transport capability. The material provided in this application links the perylene tetracarbamate (PDI) structure with Ar groups to form a molecular structure with strong planar rigidity. This structure is not easily rotated, has strong intermolecular stacking, and effectively improves charge transport capability, thus effectively improving photoelectric conversion efficiency.

[0072] In some embodiments, the Ar in each repeating unit independently comprises a phenyl or a 5- to 6-membered heteroaryl group. Employing phenyl or 5- to 6-membered heteroaryl groups enhances the overall planar rigidity of the molecular structure and improves photoelectric conversion efficiency.

[0073] In some embodiments, the Ar in each repeating unit independently includes groups as shown below:

[0074]

[0075] Z includes O, S, or Se.

[0076] By employing this 5-membered heteroaryl group, the overall planar rigidity of the molecular structure can be enhanced, further improving the ability to extract charge and increasing photoelectric conversion efficiency.

[0077] In some embodiments, n is 3 or 4. By appropriately controlling the number of connected perylenetetracarboxydiimide structures, it is possible to improve device efficiency while ensuring the material has good solubility or a low melting and boiling point, making it suitable for different manufacturing processes, such as solvent extraction or vapor deposition. Furthermore, when n is 3, the electron transport layer material includes one or more compounds having the structure shown in formula (I-1):

[0078]

[0079] Without limitation, the material of the electron transport layer includes one or more of the following compounds:

[0080]

[0081]

[0082] 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 photoelectric conversion 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.

[0083] 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 0–0.25, 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 to 0.25, b is 0.85 to 1, c is 0, d is 0.8 to 1, e is 0, f is 2 to 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 Pb0.5 Sn 0.5 One or more of I3.

[0084] 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.

[0085] In some embodiments, a perovskite layer is disposed between the first electrode and the electron transport layer, and the first electrode includes 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, thus improving its photoelectric conversion efficiency.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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).

[0090] 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.

[0091] 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.

[0092] In other embodiments of this application, an organic compound is provided having the structure shown in formula (I):

[0093]

[0094] in,

[0095] n is 2, 3, 4 or 5;

[0096] X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br;

[0097] Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group;

[0098] Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

[0099] The aforementioned organic compounds can serve as materials for the electron transport layer of perovskite solar cells, improving device efficiency while maintaining low cost. 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 further here.

[0100] 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.

[0101] Other embodiments of this application provide a photovoltaic module, including perovskite solar cells, organic compounds, or electron transport materials as described above.

[0102] Other embodiments of this application provide an electrical device, including perovskite solar cells, organic compounds, electron transport materials, or photovoltaic modules as described above.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] As another implementation method, the power supply device can be a wearable device, such as a watch.

[0107] 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.

[0108] 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.

[0109] Preparation Example 1

[0110] Preparation of P3C4, a material for the electron transport layer.

[0111]

[0112] (1) Synthesis of compound M2

[0113] 2.80 g of compound M1, 4 g of (2-trimethyltinyl)thiophene, 10 mg of Pd2(dba)3, and 20 mg of P(toly)3 were added to a 150 mL single-necked round-bottom flask under a nitrogen atmosphere. 20 mL of dehydrated and deoxygenated toluene was added, and the mixture was stirred at 110 °C for 12 h. The solution was evaporated to dryness, and column chromatography was performed using dichloromethane:petroleum ether = 1:2 (v / v) as eluent to give a purple solid in 83% yield.

[0114] Mass spectrometry: 862.4. Elemental analysis: C: 75.14%; H: 6.77%; N: 3.25%; O: 7.41%; S: 7.43%.

[0115] (2) Synthesis of compound M3

[0116] 1 g of compound M2 was added to a 150 mL single-necked round-bottom flask under a nitrogen atmosphere. 80 mL of dehydrated and deoxygenated tetrahydrofuran was added, followed by the addition of 2.5 eq (molar equivalents relative to M2) of lithium diisopropylamino (LDA) at -78 °C. The mixture was stirred at low temperature for 2 h, and then 3 eq (molar equivalents relative to M2) of trimethyltin chloride (Me3SnCl) was added, followed by slow restoration to room temperature. The solution was dissolved in dichloromethane, and the dichloromethane was then evaporated to dryness to give a purple solid in 97% yield.

[0117] Mass spectrometry: 1190.3, elemental analysis: theoretical values ​​C: 60.62%; H: 6.27%; N: 2.36%; O: 5.38%; S: 5.39%; Sn: 19.97%.

[0118] (3) Synthesis of compound M5

[0119] 680 mg of compound M4, 480 mg of M3, 15 mg of Pd2(dba)3, and 28 mg of P(toly)3 were added to a 150 mL single-necked round-bottom flask under a nitrogen atmosphere. 20 mL of dehydrated and deoxygenated toluene was added, and the mixture was stirred at 110 °C for 12 h. The solution was evaporated to dryness, and column chromatography was performed using dichloromethane:petroleum ether = 2:1 (v / v) as eluent to give a purple solid in 75% yield.

[0120] Mass spectrometry: 2391.0, elemental analysis: theoretical values ​​C: 73.22%; H: 6.65%; Cl: 5.92%; N: 3.51%; O: 8.02%; S: 2.68%.

[0121] (4) Synthesis of compound P3C4

[0122] 100 mg of compound M5 was added to a 150 mL single-necked round-bottom flask under a nitrogen atmosphere, followed by 60 mL of dehydrated toluene and 20 eq (molar equivalents of M5) of iodine (I2). The mixture was stirred at 110 °C under 365 nm light for 4 h. The solution was evaporated to dryness and then subjected to column chromatography using dichloromethane:petroleum ether = 1:1 (v / v) as eluent to give a red solid in 93% yield.

[0123] Mass spectrometry: 2383.0, elemental analysis: theoretical values ​​C: 73.47%; H: 6.33%; Cl: 5.94%; N: 3.52%; O: 8.04%; S: 2.69%. 1 H NMR (400MHz, CDCl3) δ (ppm): 11.3-11.1 (br, 3H), 11.0-10.8 (br, 2H), 10.5 (s, 2H), 10.2-9.9(m, 2H), 9.3-9.0(br, 3H), 5.7-5.2(m, 6H), 2.80-0.6(m, 132H).

[0124] Preparation Example 2

[0125] Preparation of P3F4, a material for the electron transport layer.

[0126]

[0127] (1) Synthesis of compound M7

[0128] 1 g of compound M6, 0.3 g of 18-crown-6, and 1.86 g of KF were added to a 150 mL single-necked round-bottom flask under a nitrogen atmosphere. 40 mL of dehydrated DMF was added, and the mixture was stirred at 160 °C for 8 h. After drying, column chromatography was performed using dichloromethane:petroleum ether = 1:1 (v / v) as the eluent to give red solid M7 in 31% yield.

[0129] (2) Synthesis of compound M8

[0130] 1 g of compound M7 was added to a 150 mL single-necked round-bottom flask, followed by 40 mL of dichloromethane and 100 eq (molar equivalent of M7) of elemental bromine. The mixture was stirred at room temperature for 48 h, evaporated to dryness, and subjected to column chromatography using dichloromethane:petroleum ether = 1:1 (v / v) as eluent to obtain red solid M8 in 98% yield.

[0131] The method for synthesizing compound P3F4 from compound M8 is the same as the method for synthesizing compound P3C4 from compound M4 in Preparation Example 1, and compound P3F4 is obtained.

[0132] Mass spectrometry: 2319.0, elemental analysis: theoretical values ​​C: 75.56%; H: 6.51%; F: 3.27%; N: 3.62%; O: 8.27%; S: 2.76%. The experimental values ​​differed from the theoretical values ​​by less than 0.02%. 1 H NMR (400MHz, CDCl3) δ (ppm): 11.2-11.0 (br, 3H), 10.9-10.7 (br, 2H), 10.5 (s , 2H), 10.1-9.9(m, 2H), 9.2-9.0(br, 3H), 5.6-5.2(m, 6H), 2.8-0.7(m, 132H).

[0133] Example 1

[0134] This embodiment provides a perovskite solar cell, the fabrication steps of which are as follows:

[0135] 1) Preparation of the substrate

[0136] 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.

[0137] 2) Preparation of the hole transport layer

[0138] A nickel oxide layer with a thickness of 30 nm was prepared on the substrate using magnetron sputtering.

[0139] 3) Preparation of the perovskite layer

[0140] 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.

[0141] 4) Fabrication of the electron transport layer

[0142] The electron transport layer material P3C4 was dissolved in chlorobenzene at a concentration of 10 mg / mL, dropped onto the surface of the perovskite layer, spin-coated at 5000 rpm for 30 seconds, and annealed at 100 °C for 10 minutes to obtain a 23 nm electron transport layer.

[0143] 5) Preparation of hole blocking layer

[0144] Tin oxide of 20 nm was prepared on the surface of the electron transport layer using an ALD device.

[0145] 6) Fabrication of the second electrode layer

[0146] A copper electrode with a thickness of 100 nm is thermally deposited on the surface of the hole blocking layer.

[0147] The perovskite solar cell provided in Example 2 is fabricated in the same steps as in Example 1, with the main difference being that P3F4, the material of the electron transport layer, is used to replace P3C4 in equal amounts.

[0148] The perovskite solar cell provided in Example 3 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.

[0149] The perovskite solar cell provided in Example 4 is fabricated in the same steps as in Example 1, except that in step 3), the perovskite layer is FAPbI3.

[0150] The perovskite solar cell provided in Comparative Example 1 is fabricated in the same steps as in Example 1, with the main difference being that P3C4 is replaced by an equal amount of PCBM, the material of the electron transport layer.

[0151] 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 P3C4 is replaced in equal amounts with M5, the material of the electron transport layer. The structural formula of M5 is shown below:

[0152]

[0153] Photoelectric performance testing

[0154] The photoelectric conversion efficiency (PCE) of the perovskite solar cells was tested at room temperature (25°C):

[0155] 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:

[0156] PCE = P out / P in ;

[0157] =Voc ×J sc ×[(V mpp ×J mpp ) / (V oc ×J sc )] / P in ;

[0158] =V oc ×J sc ×FF / P in ;

[0159] 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.

[0160] The test results are shown in Tables 1 and 2 below:

[0161] Table 1

[0162]

[0163]

[0164] Table 2

[0165]

[0166] A comparison between Examples 1-2 and Comparative Examples 1-2 shows that Examples 1-2 connect the perylene tetracarbamate structure with Ar groups to form a molecular structure with strong planar rigidity. Compared with the easily rotatable perylene tetracarbamate structure in Comparative Example 2, this significantly improves the photoelectric conversion efficiency of the battery. Moreover, the photoelectric conversion efficiency is higher than that of the high-cost electron transport layer material PCBM (Comparative Example 1) used in current traditional methods.

[0167] Furthermore, a comparison between Example 1 and Example 3 shows that properly controlling the thickness of the electron transport layer can further improve the photoelectric conversion efficiency of the battery.

[0168] As can be seen from Examples 1 and 4, this electron transport layer can be applied to different perovskite layer materials and improve the photoelectric conversion efficiency of the battery.

[0169] 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.

[0170] 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 includes one or more compounds having the structure shown in formula (I): in, n is 2, 3, 4 or 5; X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br; Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group; Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

2. The perovskite solar cell according to claim 1, characterized in that, Each repeating unit contains an Ar group that independently includes either a phenyl group or a 5- to 6-membered heteroaryl group.

3. The perovskite solar cell according to claim 2, characterized in that, Each repeating unit contains an Ar group that independently includes the following groups: Z includes O, S, or Se.

4. The perovskite solar cell according to claim 3, characterized in that, The material of the electron transport layer includes one or more compounds having the structure shown in formula (I-1):

5. The perovskite solar cell according to any one of claims 1 to 4, 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, n is 2, 3, 4 or 5; X1, Y1, X2, and Y2 each independently include H, F, Cl, or Br; Each repeating unit contains an Ar that independently comprises a C6-C8 aryl group or a 5-8 heteroaryl group; Each repeating unit, R1, R2, R3, and R4, independently includes H or C1-C20 alkyl groups.

10. The organic compound according to claim 9, characterized in that, Each repeating unit contains an Ar group that independently includes the following groups: Z includes O, S, or Se.

11. The organic compound according to claim 10, characterized in that, It has the structure shown in equation (I-1):

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.

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