Solar cell and preparation method therefor, electrical device, and power generation device

Abstract

A solar cell and an electrical device. The solar cell comprises an active layer, and the active layer comprises a three-dimensional perovskite layer and a first carrier transport layer which are sequentially stacked. In the first carrier transport layer, two-dimensional perovskite is comprised on one side close to the three-dimensional perovskite layer. The solar cell has improved photovoltaic performance and thermal stability.

Description

Solar cell and preparation method thereof, electrical equipment, and power generation equipment

[0001] Cross-references

[0002] This application claims priority to Chinese Patent Application No. 202410271037.1, filed on March 8, 2024, entitled “Solar cells, methods for preparing the same, electrical equipment, and power generation equipment,” which is incorporated herein by reference in its entirety. Technical Field

[0003] The present application relates to the technical field of solar cell devices, and in particular to a solar cell and a preparation method thereof, an electrical device and a power generation device. Background Art

[0004] With the large-scale development and utilization of non-renewable energy sources such as coal and oil, their storage capacity can no longer meet the development needs of various industries such as agriculture and industry. Therefore, recycled and renewable energy has gradually become an alternative to non-renewable energy sources to promote social and industrial development. Among them, solar cell devices are widely used due to their environmental friendliness and ability to output electricity when exposed to sunlight.

[0005] Perovskite solar cells utilize perovskite-type organic metal halide semiconductors as light-absorbing materials. Compared to traditional silicon-based solar cells, they offer higher photoelectric conversion efficiency, lower manufacturing costs, and greater flexibility. However, their photovoltaic performance and thermal stability require further improvement.

[0006] Summary of the Invention

[0007] The present application provides a solar cell and a manufacturing method thereof, an electrical device and a power generation device, wherein the solar cell has improved photovoltaic performance and thermal stability.

[0008] In a first aspect, an embodiment of the present application provides a solar cell, which includes an active layer, the active layer including a three-dimensional perovskite layer and a first carrier transport layer stacked in sequence; wherein the first carrier transport layer includes a two-dimensional perovskite on a side close to the three-dimensional perovskite layer.

[0009] The two-dimensional perovskite located near the three-dimensional perovskite layer within the first carrier transport layer can increase the ion migration barrier between metal ions and anions on the surface of the three-dimensional perovskite layer, hindering the migration of ions into the first carrier transport layer, effectively passivating the material and improving the photovoltaic performance and thermal stability of the solar cell. Furthermore, the two-dimensional perovskite located within the first carrier transport layer allows the two-dimensional perovskite, which is tightly connected to the three-dimensional perovskite, to also tightly connect to the first carrier transport material. Compared to the commonly used passivation layer in solar cells, this can effectively reduce the interfacial resistance, facilitate carrier extraction and transport, and further improve the photovoltaic performance and thermal stability of the solar cell.

[0010] In any embodiment, the two-dimensional perovskite comprises a composition of A 2 X 2 A compound wherein A 2 including a monovalent organic cation, and A 2 The ionic radius is greater than or equal to 2.6 angstroms; X 2 Including monovalent halogen anions.

[0011] Cations with a size smaller than 2.6 angstroms tend to form three-dimensional perovskite compounds, which are located at the eight vertices of the octahedron in the crystal structure. 2 It is difficult for ions to enter the three-dimensional perovskite structure, and it is easy to form an organic two-dimensional perovskite structure on its surface, which increases the ion migration barrier of metal cations or anions on the surface of the three-dimensional perovskite layer, hinders the migration of ions to the first carrier transport layer, plays an effective passivation role, and improves the stability of the three-dimensional perovskite photovoltaic performance and stability of solar cells.

[0012] In any embodiment, A 2 The structural formula is shown in Formula I,

[0013] Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl groups; X 2 Including F - 、Cl - Br - , I - One or more of .

[0014] Aryl groups are beneficial to improving the transmission efficiency of the first carrier. 2 The cation radius has a passivating effect on the three-dimensional perovskite layer and is beneficial to the extraction and transmission of the first carrier.

[0015] In any embodiment, A 2The cation includes one or more of N-methyl-1-naphthylamine cation, 2-naphthylamine cation, phenylethylamine cation, m-fluorophenylethylamine cation, 2-naphthylethylamine cation, and 2-naphthylamidine cation.

[0016] In any embodiment, the three-dimensional perovskite layer comprises a composition of A 1 BX 1 3 perovskite compounds, wherein A 1 Including organic amine cations, Cs + , K + , Rb + 、Li + B includes divalent cations of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; X includes one or more of I-, Br-, Cl- and F-.

[0017] In any embodiment, the first carrier transport layer is an electron transport layer, and the first carrier transport layer further includes an electron transport material, and the electron transport material includes at least one of fullerene and its derivatives.

[0018] In any embodiment, the electron transport material includes one or more of [6,6]-phenyl-C61-butyric acid methyl ester and [6,6]-phenyl-C71-butyric acid methyl ester.

[0019] In any embodiment, the first carrier transport layer is a hole transport layer, and the first carrier transport layer further includes a hole transport material, and the hole transport material includes poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD), poly-3 hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino) carbazole-spirobifluorene (CzPAF-SBF), poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), and at least one of phosphate carbazole materials.

[0020] In any embodiment, the active layer further includes a second carrier transport layer disposed on a side of the three-dimensional perovskite layer away from the first carrier transport layer; the second carriers in the second carrier transport layer are different from the first carriers in the first carrier transport layer.

[0021] In any embodiment, the solar cell further includes a first electrode and a second electrode respectively disposed on both sides of the surface of the active layer.

[0022] In any embodiment, the first carrier transport layer is prepared in a one-step process.

[0023] The one-step method involves forming the first carrier transport layer in a single step. This means the two-dimensional perovskite and the carrier transport material in the first carrier transport layer are not deposited separately. This improves the efficiency of solar cell fabrication and enables close contact between the two-dimensional perovskite and the first carrier transport material in the first carrier transport layer, reducing interfacial resistance and improving the photovoltaic performance and stability of the solar cell.

[0024] The second aspect of the present application provides a method for preparing a solar cell, comprising: providing a first electrode layer; depositing a three-dimensional perovskite layer on one side of the first electrode layer; mixing an organic cationic ammonium salt with a first carrier transport material to obtain a mixture; depositing the mixture on the three-dimensional perovskite layer to prepare a first carrier transport layer; the first carrier transport layer includes a two-dimensional perovskite on a side close to the three-dimensional perovskite layer; and providing a second electrode layer on the first carrier transport layer.

[0025] The method provided in the embodiment of the present application can prepare a two-dimensional perovskite in the first carrier transport layer close to the side of the three-dimensional perovskite layer, thereby realizing the one-step forming of the first carrier transport layer, so that the two-dimensional perovskite is in close contact with the first carrier transport material in the first carrier transport layer and the three-dimensional perovskite layer at the same time, thereby reducing the interface resistance and being beneficial to improving the photovoltaic performance and thermal stability of the solar cell.

[0026] In any embodiment, the three-dimensional perovskite layer is prepared from a three-dimensional perovskite precursor comprising BX 1 2 salt; wherein B comprises a divalent cation of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; X 1 Including one or more of I-, Br-, Cl- and F-.

[0027] In any embodiment, the organic cation in the organic cation ammonium salt has a radius greater than or equal to 2.6 angstroms.

[0028] The deposition of the above-mentioned organic cationic ammonium salt on the three-dimensional perovskite layer enables the organic cation to interact with the BX 12 salts react, but because the size of the organic cation is larger than that of the three-dimensional perovskite cation, it cannot form a three-dimensional perovskite structure, but forms a two-dimensional perovskite structure attached to the surface of the three-dimensional perovskite. In any embodiment, the cation structure of the organic cation ammonium salt is as shown in Formula I,

[0029] Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl; X2 includes Cl - Br - , I - One or more of .

[0030] In any embodiment, the organic cationic ammonium salt comprises a halide anion.

[0031] In any embodiment, the organic cationic ammonium salt includes one or more of N-methyl-1-naphthylmethylamine hydrochloride, 2-naphthylmethylamine hydrochloride, phenethylamine hydroiodide, m-fluorophenethylamine hydroiodide, 2-naphthylethylamine hydrochloride, and 2-naphthamidine hydrochloride.

[0032] In any embodiment, the first carrier transport layer includes a first carrier transport material, and the first carrier transport material includes an electron transport material or a hole transport material.

[0033] In any embodiment, the first carrier transport material comprises an electron transport material, and the electron transport material comprises [6,6]-phenyl C61 butyric acid methyl ester (PC 61 BM), [6,6]-phenyl-C71 butyric acid methyl ester (PC 71 BM), one or more of fullerenes.

[0034] In any embodiment, the mass ratio of the organic cationic ammonium salt to the first carrier transport material is 10:1-20:1.

[0035] In any embodiment, depositing a three-dimensional perovskite layer on one side of the first electrode layer includes: providing a second carrier transport layer on the first electrode layer, and depositing the three-dimensional perovskite layer on the second carrier transport layer; the second carrier transport layer includes a second carrier transport material, and the second carrier is different from the first carrier.

[0036] A third aspect of the present application provides an electrical device, including a solar cell according to any embodiment or a solar cell prepared by a preparation method according to any embodiment.

[0037] The fourth aspect of the present application provides a power generation device, comprising a solar cell according to any embodiment or a solar cell prepared by a preparation method according to any embodiment. The above description is only an overview of the technical solution of the present application. To enable a clearer understanding of the technical means of the present application, implementation can be carried out in accordance with the contents of the description. To make the above and other purposes, features, and advantages of the present application more clearly understood, the following specifically describes the specific embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present application. The same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0039] FIG1 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0040] FIG2 is a schematic structural diagram of a portion of an active layer of a solar cell provided in some embodiments of the present application. DETAILED DESCRIPTION

[0041] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0043] In the description of the embodiments of this application, the technical terms "first," "second," etc. are used only to distinguish different objects and should not be understood to indicate or imply relative importance or to implicitly indicate the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise specifically defined.

[0044] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0045] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0046] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0047] In the description of the embodiments of the present application, the technical terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the embodiments of the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they should not be understood as limiting the embodiments of the present application.

[0048] In the description of the embodiments of the present application, unless otherwise expressly specified or limited, technical terms such as "installed," "connected," "connected," and "fixed" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integration; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal connections between two components or interactions between two components. Those skilled in the art can understand the specific meanings of the above terms in the embodiments of the present application based on specific circumstances.

[0049] During the fabrication of perovskite solar cells, numerous defects inevitably form on the surface of the perovskite layer, negatively impacting the photovoltaic performance and stability of the solar cell. Interface passivation is an effective method for reducing surface defects in the perovskite layer. However, the introduction of a passivation layer increases the manufacturing process for solar cells. Furthermore, the conductivity of passivation materials is generally low, and increasing their thickness enhances the passivation effect, but at the same time limits current transmission, creating a "passivation-transmission" contradiction. Furthermore, the introduction of a passivation layer creates a new interface layer within the solar cell, resulting in less than ideal improvements in overall device performance.

[0050] Based on this, as shown in Figure 1, the first aspect of the present application provides a solar cell 1, including an active layer 11, the active layer 11 includes a three-dimensional perovskite layer 112 and a first carrier transport layer 111 stacked in sequence; wherein, the first carrier transport layer 111 includes a two-dimensional perovskite on the side close to the three-dimensional perovskite layer.

[0051] As shown in Figure 2, the three-dimensional perovskite layer includes a three-dimensional perovskite compound, which refers to a large class of compounds with the same structure as perovskite CaTiO3. Two-dimensional perovskites can be formed by crystallographic planes along the three-dimensional structure. <100> 、 <110> or <111> Cutting is performed to form three different types of layered structures, namely <100> 、 <110> or <111> Oriented layered perovskites. Compared to three-dimensional perovskites, two-dimensional perovskites have higher water stability, oxygen content, thermal stability, and lower ion migration / phase transition processes.

[0052] In some embodiments, the composition of the three-dimensional perovskite compound is A 1 BX 1 3, where A 1 Includes monovalent cations, which can be selected from one or more of monovalent organic cations and monovalent metal cations; B includes divalent metal cations; X 1 Including monovalent halide anions.

[0053] In some embodiments, the three-dimensional perovskite layer 112 has a thickness of 400 nm to 1000 nm. For example, the light absorbing layer can have a thickness of 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof. In some embodiments, the three-dimensional perovskite layer has a thickness of 500 nm to 900 nm.

[0054] The two-dimensional perovskite can be characterized by any method known in the art. As an example, it can be characterized by performing grazing-incidence small-angle X-ray diffraction on the cross section of the solar cell.

[0055] The two-dimensional perovskite located near the three-dimensional perovskite layer within the first carrier transport layer can increase the ion migration barrier between metal ions and anions on the surface of the three-dimensional perovskite layer, hindering the migration of ions into the first carrier transport layer, effectively passivating the material and improving the photovoltaic performance and stability of the solar cell. Furthermore, the two-dimensional perovskite located within the first carrier transport layer creates a close connection between the two-dimensional perovskite and the first carrier transport material. Compared to the commonly used passivation layer in solar cells, this effectively reduces the interfacial resistance and facilitates carrier extraction and transport.

[0056] In some embodiments, the two-dimensional perovskite comprises a composition of A 2 X 2 A compound wherein A 2 including a monovalent organic cation, and A 2 The ionic radius is greater than or equal to 2.6 angstroms; X 2 Including monovalent halogen anions.

[0057] As used herein, the term halogen refers to elements of Group VIIA of the periodic system, including fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and Ts.

[0058] Cations with a size smaller than 2.6 angstroms tend to form three-dimensional perovskite compounds, which are located at the eight vertices of the octahedron in the crystal structure. 2 It is difficult for ions to enter the three-dimensional perovskite structure, and it is easy to form an organic two-dimensional perovskite structure on its surface, which increases the ion migration barrier of metal cations or anions on the surface of the three-dimensional perovskite layer, hinders the migration of ions to the first carrier transport layer, plays an effective passivation role, and improves the stability of the three-dimensional perovskite photovoltaic performance and stability of solar cells.

[0059] In some embodiments, A 2 The structural formula is shown in Formula I,

[0060] Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl; X2 includes Cl - Br - , I - One or more of .

[0061] As used herein, the term "aryl" refers to a monocyclic, bicyclic or polycyclic carbocyclic aromatic ring. Examples of aryl include, but are not limited to, phenyl, naphthyl (e.g., naphthalene-1-yl, naphthalene-2-yl), anthracenyl (e.g., anthracen-1-yl, anthracen-9-yl), phenanthrenyl (e.g., phenanthren-1-yl, phenanthren-9-yl), biphenyl (e.g., biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl), phenylnaphthyl (e.g., 1-phenylnaphthyl-2-yl, 2-phenylnaphthyl-1-yl), indanyl (e.g., indan-1-yl, indan-5-yl), indenyl (e.g., inden-1-yl, inden-5-yl), 1,2,3,4-tetrahydronaphthyl (e.g., 1,2,3,4-tetrahydronaphthyl-1-yl, 1,2,3,4- tetrahydronaphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-6-yl), 1,2-dihydronaphthalen-1-yl (e.g., 1,2-dihydronaphthalen-4-yl, 1,2-dihydronaphthalen-6-yl), fluorenyl (e.g., fluoren-1-yl, fluoren-4-yl, fluoren-9-yl), benzonorbornyl (e.g., benzonorbornyl-3-yl, benzonorbornyl-6-yl), 1,4-ethano-1,2,3,4-tetrahydronaphthalen-2-yl (e.g., 1,4-ethano-1,2,3,4-tetrahydronaphthalen-10-yl), and the like.

[0062] As used herein, the term "heteroaryl" refers to a monocyclic heterocyclic aromatic ring containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur (O, N, and S). Representative examples are pyrrolyl, pyridyl, furyl, thienyl, oxazolyl, thiazolyl, imidazolyl, carbazolyl, pyrazolyl, isothiazolyl, isoxazolyl, triazolyl (e.g., 1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl), thiadiazolyl (e.g., 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl), tetrazolyl, pyranyl, pyridazinyl, pyrimidinyl, pyrazinyl, and the like.

[0063] In this article, the term “C 1-3 "Alkyl" refers to a hydrocarbon chain radical composed of carbon and hydrogen atoms, with no unsaturated bonds in the radical, having from one to three carbon atoms, and attached to the rest of the molecule by a single bond.

[0064] The term aralkyl refers to an alkyl group substituted with an aryl group, wherein R1 is attached to the carbon in formula I via a bond from the alkyl group.

[0065] The term alkaryl refers to an aryl group substituted by an alkyl group, wherein R1 is attached to the carbon in formula I via a bond from the aryl group.

[0066] Aryl groups are beneficial to improving the transmission efficiency of the first carrier. 2The cation radius has a passivating effect on the three-dimensional perovskite layer and is beneficial to the extraction and transmission of the first carrier.

[0067] In some embodiments, A 2 The cation includes one or more of N-methyl-1-naphthylamine cation, 2-naphthylamine cation, phenylethylamine cation, m-fluorophenylethylamine cation, 2-naphthylethylamine cation and 2-naphthylamidine cation.

[0068] In some embodiments, the three-dimensional perovskite layer 112 comprises a composition of 1 BX 1 3 perovskite compounds, wherein A 1 Including organic amine cations, Cs + , K + , Rb + 、Li + B includes divalent cations of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; X includes one or more of I-, Br-, Cl- and F-.

[0069] In some embodiments, the first carrier transport layer 111 is an electron transport layer, and the first carrier transport layer 111 also includes an electron transport material. The electron transport material includes at least one of fullerene and its derivatives, and can be optionally one or more of [6,6]-phenyl-C61-butyric acid methyl ester and [6,6]-phenyl-C71-butyric acid methyl ester.

[0070] In some embodiments, the first carrier transport layer 111 is a hole transport layer, and the first carrier transport layer 111 further includes a hole transport material, wherein the hole transport material includes poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), 2,2',7,7'-tetrakis [N,N-bis (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD), poly -3 hexylthiophene (P3HT), triptycene. At least one of triphenylamine (H101) with a core, 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), and phosphate carbazole materials.

[0071] In some embodiments, the first carrier transport layer has a thickness of 15 nm to 50 nm.

[0072] In some embodiments, the thickness of the first carrier transport layer can be 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or any range therebetween. In some embodiments, the active layer 11 further includes a second carrier transport layer 113 disposed on a side of the three-dimensional perovskite layer 112 facing away from the first carrier transport layer 111; the second carriers in the second carrier transport layer 113 are different from the first carriers in the first carrier transport layer.

[0073] It is understood that the active layer of the solar cell may further include any other functional layers. For example, a hole blocking layer may be provided on the side of the electron transport layer facing away from the light absorbing layer. The hole blocking layer may include any hole blocking material, such as bathocuproine or tin dioxide. In some embodiments, the first carrier transport layer 111 is an electron transport layer, and the second carrier transport layer 113 is a hole transport layer.

[0074] In some embodiments, the first carrier transport layer 111 is a hole transport layer, and the second carrier transport layer 113 is an electron transport layer.

[0075] In some embodiments, the solar cell 1 further includes a first electrode 10 and a second electrode 12 respectively disposed on both sides of the surface of the active layer.

[0076] In some embodiments, the first electrode 10 comprises a transparent electrode including at least one of fluorine-doped tin oxide, indium tin oxide, aluminum zinc oxide, indium zinc oxide, and gallium zinc oxide.

[0077] In some embodiments, the second electrode 12 includes at least one of fluorine-doped tin oxide, indium tin oxide, aluminum-doped zinc oxide, gallium zinc oxide, indium zinc oxide, gold, silver, copper, aluminum, nickel, chromium, bismuth, platinum, magnesium, molybdenum, tungsten, or alloys thereof, carbon, graphene, and carbon nanotubes.

[0078] In some embodiments, the thickness of the first electrode 10 is 200 nm to 1000 nm. For example, the thickness of the first electrode can be 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof.

[0079] In some embodiments, the thickness of the second electrode 12 is 20 nm to 200 nm. For example, the thickness of the second electrode 12 can be 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, or any range thereof.

[0080] In some embodiments, the first carrier transport layer 111 is prepared in a one-step process.

[0081] The one-step method involves forming the first carrier transport layer in a single step. This means that the two-dimensional perovskite and the carrier transport material in the first carrier transport layer are not deposited separately. It is understood that incompletely deposited two-dimensional perovskite precursors are inevitably present in the first carrier transport layer prepared using the one-step method.

[0082] The one-step preparation method is conducive to improving the efficiency of solar cell preparation, and can achieve close contact between the two-dimensional perovskite and the first carrier transport material in the first carrier transport layer, reduce the interface resistance, and improve the photovoltaic performance and stability of the solar cell.

[0083] In some embodiments, the solar cell 1 is an inverted pin perovskite cell, comprising a first electrode 10, a second carrier transport layer 113, a three-dimensional perovskite layer 112, a first carrier transport layer 111, and a second electrode 12 stacked in sequence, wherein the second carrier transport layer 113 is a hole transport layer, the first carrier transport layer 111 is an electron transport layer, and the first carrier transport layer 111 includes a two-dimensional perovskite on the side close to the three-dimensional perovskite layer 112.

[0084] In some embodiments, the solar cell 1 is a formal nip perovskite cell, including a first electrode 10, a second carrier transport layer 113, a three-dimensional perovskite layer 112, a first carrier transport layer 111, and a second electrode 12 stacked in sequence, wherein the second carrier transport layer 113 is an electron transport layer, the first carrier transport layer 111 is a hole transport layer, and the first carrier transport layer 111 includes a two-dimensional perovskite on the side close to the three-dimensional perovskite layer 112.

[0085] The second aspect of the present application provides a method for preparing a solar cell, comprising: providing a first electrode layer; depositing a three-dimensional perovskite layer on one side of the first electrode layer; mixing an organic cationic ammonium salt with a first carrier transport material to obtain a mixture; depositing the mixture on the three-dimensional perovskite layer to prepare a first carrier transport layer; the first carrier transport layer includes a two-dimensional perovskite on a side close to the three-dimensional perovskite layer; and providing a second electrode layer on the first carrier transport layer.

[0086] The method provided in the embodiment of the present application can prepare a two-dimensional perovskite in the first carrier transport layer close to the side of the three-dimensional perovskite layer, thereby realizing the one-step forming of the first carrier transport layer, so that the two-dimensional perovskite is in close contact with the first carrier transport material in the first carrier transport layer and the three-dimensional perovskite layer at the same time, thereby reducing the interface resistance and being beneficial to improving the photovoltaic performance and thermal stability of the solar cell.

[0087] In any embodiment, the three-dimensional perovskite layer is prepared from a three-dimensional perovskite precursor, wherein the three-dimensional perovskite precursor includes BX 1 2 salt; wherein B comprises a divalent cation of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; X 1 Including one or more of I-, Br-, Cl- and F-.

[0088] In any embodiment, the organic cation in the organic cation ammonium salt has a radius greater than or equal to 2.6 angstroms.

[0089] The deposition of the above-mentioned organic cationic ammonium salt on the three-dimensional perovskite layer enables the organic cation to interact with the BX 1 2 salts react, but because the size of the above-mentioned organic cations is larger than the cation size of the three-dimensional perovskite, it cannot form a three-dimensional perovskite structure, but instead forms a two-dimensional perovskite structure attached to the surface of the three-dimensional perovskite, as shown in Figure 2.

[0090] In some embodiments, the cation structure of the organic cationic ammonium salt is as shown in Formula I,

[0091] Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl; X2 includes Cl - Br - , I - One or more of .

[0092] In some embodiments, the organic cationic ammonium salt includes a halide anion.

[0093] In some embodiments, the organic cationic ammonium salt includes one or more of N-methyl-1-naphthylmethylamine hydrochloride, 2-naphthylmethylamine hydrochloride, phenethylamine hydroiodide, m-fluorophenethylamine hydroiodide, 2-naphthylethylamine hydrochloride, and 2-naphthamidine hydrochloride.

[0094] In some embodiments, the first carrier transport layer includes a first carrier transport material, and the first carrier transport material includes an electron transport material or a hole transport material.

[0095] In some embodiments, the first carrier transport material comprises an electron transport material, and the electron transport material comprises [6,6]-phenyl C61 butyric acid methyl ester (PC 61 BM), [6,6]-phenyl-C71 butyric acid methyl ester (PC 71BM), one or more of fullerenes.

[0096] In some embodiments, the mass ratio of the organic cationic ammonium salt to the first carrier transport material is 10:1-20:1.

[0097] In some embodiments, the mass ratio of the organic cationic ammonium salt to the first carrier transport material can be 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, or any range therebetween.

[0098] The mass ratio of the organic cationic ammonium salt to the first carrier transport material within the above range can not only ensure the transport efficiency of the first carrier in the first carrier transport layer, but also effectively form a two-dimensional perovskite, thereby improving the stability of the solar cell.

[0099] In some embodiments, depositing a three-dimensional perovskite layer on one side of the first electrode layer includes: providing a second carrier transport layer on the first electrode layer, and depositing a three-dimensional perovskite layer on the second carrier transport layer; the second carrier transport layer includes a second carrier transport material, and the second carrier is different from the first carrier.

[0100] A third aspect of the present application provides an electrical device, including a solar cell according to any embodiment or a solar cell prepared by a preparation method according to any embodiment.

[0101] A fourth aspect of the present application provides a power generation device comprising a solar cell according to any embodiment or a solar cell prepared by any embodiment of the preparation method. In some embodiments, the solar cell or solar cell assembly can be used as a power generation device for an electrical device. Types of power generation devices may include, but are not limited to, integrated power generation.

[0102] The electrical devices may include, but are not limited to, mobile devices such as mobile phones, tablet computers, laptop computers, calculators, watches, cars, electric trains, ships, satellites, power generation systems, etc.

[0103] The location of the power generation device may include but is not limited to the roof, back panel, etc. of the car.

[0104] The following examples describe the present disclosure in more detail and are intended to be illustrative only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used directly without further processing, and all instruments used in the examples are commercially available.

[0105] Example

[0106] Preparation method

[0107] Example 1

[0108] An embodiment of the present application provides a method for manufacturing a solar cell, the method comprising the following steps:

[0109] Preparation of the first electrode: Specifications: 2.0×2.0 cm 2 Fluorine-doped tin oxide transparent conductive glass (FTO conductive glass) was removed by laser etching at both ends of the FTO conductive glass by 0.35 cm, exposing the glass substrate; the etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropyl alcohol, and then dried with nitrogen gas for use as the first electrode;

[0110] Preparation of hole transport layer: FTO conductive glass was treated with UV ozone, and then nickel oxide (NiO) with a thickness of about 30nm was magnetron sputtered. x ), annealing at 300°C for 60 min to obtain a hole transport layer;

[0111] Preparation of the perovskite light-absorbing layer: A one-step process was used to prepare the perovskite light-absorbing layer. A perovskite precursor solution was spin-coated on the prepared hole transport layer at 4000 rpm for 40 seconds. Around the 10th second after spin coating, 300 μL of anti-solvent was added dropwise. The film was then placed on a hot plate and annealed at 120°C for 60 minutes to obtain a 500 nm thick perovskite light-absorbing layer.

[0112] The perovskite precursor solution was prepared by dissolving 116.91 mg of cesium iodide, 94.19 mg of methylamine chloride, 1440.94 mg of formamidine iodine, 4356.54 mg of lead iodide, 66.06 mg of lead bromide, and 111.97 mg of methylamine bromide in 6 mL of a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), wherein the volume ratio of DMF to DMSO was 4:1, and the antisolvent was anisole;

[0113] Preparation of the first carrier transport layer: Prepare 20 mg / mL of [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM) in chlorobenzene solution, to which 2-naphthylmethylamine hydrochloride, [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 The mass ratio of BM to 2-naphthylmethylamine hydrochloride was 10:1. The mixture was stirred and dissolved, filtered, and then spin-coated on the perovskite surface at a spin-coating speed of 4000 rpm for 30 seconds. The mixture was annealed at 100°C for 10 minutes. The thickness of the first carrier transport layer was 20 nm.

[0114] Preparation of hole blocking layer: put the film with the first carrier transport layer into the evaporation apparatus, and wait until the evaporation vacuum reaches 5×10 -4 Pa, 8 nm of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) was evaporated at a rate of 0.1 A / s to serve as a hole blocking layer.

[0115] Preparation of the second electrode: Place the film with the hole blocking layer into the evaporation apparatus and wait until the vacuum degree of evaporation reaches 5×10 -4 Pa, an 80 nm metal back electrode Ag was evaporated at a rate of 0.1 A / s as the second electrode.

[0116] The preparation methods of Examples 2-4 are basically the same as that of Example 1, except that the preparation method of the first carrier transport layer is changed.

[0117] Preparation of the first carrier transport layer of Example 2:

[0118] Prepare 20 mg / mL [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM) chlorobenzene solution, to which 2-naphthylmethylamine hydrochloride, PC 61 The mass ratio of BM to 2-naphthylmethylamine hydrochloride was 15:1. After stirring and dissolving, the mixture was filtered and then spin-coated on the perovskite surface at a spin-coating speed of 4000 rpm for 30 seconds. The mixture was annealed at 100°C for 10 minutes to obtain the first carrier transport layer.

[0119] Preparation of the first carrier transport layer of Example 3:

[0120] Prepare 20 mg / mL [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM) chlorobenzene solution, to which 2-naphthylmethylamine hydrochloride, PC 61 The mass ratio of BM to 2-naphthylmethylamine hydrochloride was 20:1. After stirring and dissolving, the mixture was filtered and then spin-coated on the perovskite surface at a spin-coating speed of 4000 rpm for 30 seconds. The mixture was annealed at 100°C for 10 minutes to obtain the first carrier transport layer.

[0121] Preparation of the first carrier transport layer of Example 4:

[0122] Prepare 20 mg / mL [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM) chlorobenzene solution, to which 2-naphthylmethylamine hydrochloride, PC 61 The mass ratio of BM to 2-naphthylmethylamine hydrochloride was 5:1. After stirring and dissolving, the mixture was filtered and then spin-coated on the perovskite surface at a spin-coating speed of 4000 rpm for 30 seconds. The mixture was annealed at 100°C for 10 minutes to obtain the first carrier transport layer.

[0123] The preparation methods of Examples 5-8 are basically the same as those of Example 1, except that the types of organic cationic ammonium salts are changed, as shown in Table 1.

[0124] The steps of Comparative Example 1 are basically the same as those of Example 1, except that 2-naphthylmethylamine hydrochloride is not added in the preparation step of the first carrier transport layer in Comparative Example 1.

[0125] The steps of Comparative Example 2 are basically the same as those of Example 1, except that:

[0126] Spin-coat a 1 mg / ml isopropanol solution of 2-naphthylmethylamine hydrochloride on the light-absorbing layer. After stirring and dissolving, spin-coat the solution at a speed of 4000 rpm for 30 seconds on the surface of the light-absorbing layer. Anneal at 100°C for 5 minutes to obtain a passivation layer.

[0127] A 20 mg / mL chlorobenzene solution of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was prepared, stirred and dissolved, and then spin-coated on the surface of the above-prepared film at a spin-coating speed of 4000 rpm for 30 seconds, and annealed at 100°C for 10 minutes to obtain the first carrier transport layer.

[0128] Table 1

[0129] Test Method

[0130] Photoelectric conversion efficiency test

[0131] The battery performance was tested using a Keithley 2400SMU and AM 1.5G solar radiation test system under a 100mW / cm2 light source. The photoelectric conversion efficiency was calculated as follows: PCE = Pout / Popt = Voc × Jsc × (Vmpp × Jmpp) / (Voc × Jsc × Popt) = Voc × Jsc × FF / Popt

[0132] Where Pout(mW / cm 2 )、Popt(mW / cm 2 )、Vmpp(V)、Jmpp(mA / cm 2 )、Voc(V)、Jsc(mA / cm 2 ) and FF are the battery operating output power, incident light power, battery maximum power point voltage, battery maximum power point current, open circuit voltage, short circuit current density and fill factor, respectively.

[0133] 2. Stability test

[0134] The solar cell was placed on a hot plate at 65°C and heated continuously at 100 mW / cm 2The photoelectric conversion efficiency is tracked over time by continuously irradiating the perovskite solar cell under a light source, and the time required for the photoelectric conversion efficiency to decay to 80% of the initial efficiency is recorded as T80. The size of this parameter indicates the thermal stability of the perovskite solar cell or battery component.

[0135] Test results

[0136] Table 2

[0137] As can be seen from Table 2, the solar cell provided in the embodiment of the present application has higher photoelectric conversion efficiency and thermal stability than the comparative example.

[0138] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A solar cell, wherein: The solar cell includes an active layer, which includes a three-dimensional perovskite layer and a first carrier transport layer stacked in sequence; wherein the first carrier transport layer includes a two-dimensional perovskite on a side close to the three-dimensional perovskite layer.

2. The solar cell according to claim 1, wherein The two-dimensional perovskite comprises a composition of A 2 X 2 A compound wherein A 2 including a monovalent organic cation, and A 2 The ionic radius of X is greater than or equal to 2.6 angstroms; 2 Including monovalent halide anions.

3. The solar cell according to claim 2, wherein A 2 The structural formula is shown in Formula I, Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl groups; X 2 Including F - 、Cl - Br - , I - One or more of .

4. The solar cell according to claim 2 or 3, wherein A 2 The cation includes one or more of N-methyl-1-naphthylamine cation, 2-naphthylamine cation, phenylethylamine cation, m-fluorophenylethylamine cation, 2-naphthylethylamine cation, and 2-naphthylamidine cation.

5. The solar cell according to any one of claims 1 to 4, wherein The three-dimensional perovskite layer comprises a composition of 1 BX 1 3 perovskite compounds, wherein A 1 Including organic amine cations, Cs + , K + , Rb + 、Li + B includes divalent cations of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium; X includes one or more of I-, Br-, Cl- and F-.

6. The solar cell according to any one of claims 1 to 5, wherein The first carrier transport layer is an electron transport layer. The first carrier transport layer further comprises an electron transport material. The electron transport material comprises at least one of fullerene and its derivatives.

7. The solar cell according to any one of claims 1 to 5, wherein The first carrier transport layer is a hole transport layer, and the first carrier transport layer also includes a hole transport material, and the hole transport material includes poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD), poly-3 hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino) carbazole-spirobifluorene (CzPAF-SBF), poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), and at least one of phosphate carbazole materials.

8. The solar cell according to any one of claims 1 to 7, wherein The active layer further includes a second carrier transport layer disposed on a side of the three-dimensional perovskite layer away from the first carrier transport layer; second carriers in the second carrier transport layer are different from first carriers in the first carrier transport layer.

9. The solar cell according to any one of claims 1 to 8, wherein The solar cell further includes a first electrode and a second electrode respectively arranged on both sides of the surface of the active layer.

10. The solar cell according to any one of claims 1 to 9, wherein The first carrier transport layer is prepared in a one-step process.

11. A method for preparing a solar cell, wherein: include: providing a first electrode layer; depositing a three-dimensional perovskite layer on one side of the first electrode layer; mixing an organic cationic ammonium salt and a first carrier transport material to obtain a mixture; Depositing the mixture on the three-dimensional perovskite layer to prepare a first carrier transport layer; wherein the first carrier transport layer includes a two-dimensional perovskite on a side close to the three-dimensional perovskite layer; A second electrode layer is provided on the first carrier transport layer.

12. The preparation method according to claim 11, wherein The three-dimensional perovskite layer is prepared from a three-dimensional perovskite precursor, and the three-dimensional perovskite precursor includes BX 1 2 salt; wherein B includes divalent cations of one or more of the following elements: lead, tin, zinc, Titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium; X 1 Including one or more of I-, Br-, Cl- and F-.

13. The preparation method according to claim 11 or 12, wherein The organic cation radius in the organic cation ammonium salt is greater than or equal to 2.6 angstroms.

14. The preparation method according to any one of claims 11 to 13, wherein The cation structure of the organic cationic ammonium salt is shown in Formula I, Wherein, R1 includes unsubstituted or halogen-substituted aryl, unsubstituted or halogen-substituted heteroaryl, unsubstituted or halogen-substituted aralkyl, unsubstituted or halogen-substituted alkaryl; R2 includes hydrogen, C 1-3 One or more of alkyl; X2 includes Cl - Br - , I - One or more of .

15. The preparation method according to any one of claims 11 to 14, wherein The organic cationic ammonium salt includes a halide anion.

16. The preparation method according to any one of claims 11 to 15, wherein The organic cationic ammonium salt includes one or more of N-methyl-1-naphthylamine hydrochloride, 2-naphthylamine hydrochloride, phenethylamine hydroiodide, m-fluorophenethylamine hydroiodide, 2-naphthylethylamine hydrochloride, and 2-naphthamidine hydrochloride.

17. The preparation method according to any one of claims 11 to 16, wherein The first carrier transport layer includes a first carrier transport material, and the first carrier transport material includes an electron transport material or a hole transport material.

18. The preparation method according to claim 17, wherein The first carrier transport material includes an electron transport material, and the electron transport material includes [6,6]-phenyl C61 butyric acid methyl ester (PC 61 BM), [6,6]-phenyl-C71 butyric acid methyl ester (PC 71 BM), one or more of fullerenes.

19. The preparation method according to any one of claims 11 to 18, wherein The mass ratio of the organic cationic ammonium salt to the first carrier transport material is 10:1-20:

1.

20. The preparation method according to any one of claims 11 to 19, wherein Depositing a three-dimensional perovskite layer on one side of the first electrode layer comprises: providing a second carrier transport layer on the first electrode layer, depositing a three-dimensional perovskite layer on the second carrier transport layer; The second carrier transport layer includes a second carrier transport material, and the second carriers are different from the first carriers.

21. An electrical device, wherein: A solar cell comprising the solar cell according to any one of claims 1 to 10 or a solar cell prepared by the preparation method according to any one of claims 11 to 20.

22. A power generation device, wherein: A solar cell comprising the solar cell according to any one of claims 1 to 10 or a solar cell prepared by the preparation method according to any one of claims 11 to 20.

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