Perovskite cell and photovoltaic module

Abstract

The invention provides a perovskite cell and a photovoltaic module, the perovskite cell comprises a first electrode, a second electrode, a light absorption layer, a hole transport layer and an electron transport layer, the light absorption layer is located between the first electrode and the second electrode, the hole transport layer is located between the first electrode and the light absorption layer, and the electron transport layer is located between the second electrode and the light absorption layer. The perovskite cell also comprises a passivation layer, and the passivation layer is located between the hole transport layer and the light absorption layer, and / or the passivation layer is located between the electron transport layer and the light absorption layer. The passivation layer includes at least two of an organic molecule passivation material, a metal oxide semiconductor material, and a metal halide.

Description

Perovskite cells and photovoltaic modules Technical Field

[0001] The present application relates to a perovskite cell and a photovoltaic module. Background Art

[0002] With the development of modern industry, global energy shortages and environmental pollution are becoming increasingly prominent. Solar cells, as an ideal renewable energy source, are gaining increasing attention. Perovskite cells are solar cells that use perovskite materials as a light-absorbing layer. Researchers are working hard to further improve the energy conversion efficiency of perovskite cells. The above statements are intended only to provide background information related to this application and do not necessarily constitute prior art.

[0003] Summary of the Invention

[0004] The present application provides a perovskite cell and a photovoltaic module, which can improve the energy conversion efficiency of the perovskite cell.

[0005] In a first aspect, the present application provides a perovskite cell, comprising a first electrode, a second electrode, a light absorbing layer, a hole transport layer, and an electron transport layer, wherein the light absorbing layer is located between the first electrode and the second electrode, the hole transport layer is located between the first electrode and the light absorbing layer, and the electron transport layer is located between the second electrode and the light absorbing layer. The perovskite cell further comprises a passivation layer, wherein the passivation layer is located between the hole transport layer and the light absorbing layer, and / or the passivation layer is located between the electron transport layer and the light absorbing layer; the passivation layer comprises at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0006] When the passivation layer includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer can simultaneously achieve energy level matching, interface passivation, and optimize the crystal quality of the perovskite material, thereby helping to improve the energy conversion efficiency of the perovskite cell. In addition, when the passivation layer includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer has better stability and can also reduce water and oxygen corrosion of the perovskite material, thereby also improving the stability and service life of the perovskite cell.

[0007] In any embodiment, the passivation layer includes an organic molecule passivation material and a metal oxide semiconductor material and / or a metal halide. The organic molecule passivation material can be used as an interface connector and a defect passivator at the same time, thereby enhancing the interface contact between the light absorbing layer and the charge transfer layer through the organic molecule passivation material, and reducing the defect state density of the perovskite material bulk and interface through the coordination effect of the organic molecule passivation material, thereby improving the film formation quality of the light absorbing layer, and further embedding the organic molecule passivation material into the perovskite material bulk to play an anchoring role, thereby reducing the precipitation of halides (such as PbI2, etc.) from the perovskite material, thereby improving the stability and service life of the perovskite cell. Therefore, the organic molecule passivation material can play a better passivation effect. When used in combination with a metal oxide semiconductor material and / or a metal halide, the non-radiative recombination at the defect can be further reduced, further improving the energy conversion efficiency of the perovskite cell.

[0008] Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30 wt %, more preferably 15-25 wt %.

[0009] In any embodiment, the passivation layer includes an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide. When the passivation layer includes the organic molecular passivation material, the metal oxide semiconductor material, and the metal halide, the passivation layer can better balance the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite cell. It can also further reduce the corrosion of the perovskite material by water and oxygen, thereby further improving the stability and service life of the perovskite cell.

[0010] Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, more preferably 15-25wt%. Optionally, based on the total weight of the passivation layer, the content of the metal oxide semiconductor material is 40-60wt%, more preferably 45-55wt%. Optionally, based on the total weight of the passivation layer, the content of the metal halide is 20-40wt%, more preferably 25-35wt%.

[0011] In any embodiment, the passivation layer comprises an organic molecular passivation material and a metal oxide semiconductor material. Optionally, based on the total weight of the passivation layer, the organic molecular passivation material comprises 10-30 wt %, more preferably 15-25 wt %. Optionally, based on the total weight of the passivation layer, the metal oxide semiconductor material comprises 70-90 wt %, more preferably 75-85 wt %.

[0012] In any embodiment, the passivation layer comprises an organic molecular passivation material and a metal halide. Optionally, the organic molecular passivation material comprises 10-30 wt %, more preferably 15-25 wt %, based on the total weight of the passivation layer. Optionally, the metal halide comprises 70-90 wt %, more preferably 75-85 wt %, based on the total weight of the passivation layer.

[0013] In any embodiment, the thickness of the passivation layer is less than or equal to 30 nm, and can be optionally 1-22 nm. When the thickness of the passivation layer is within the above range, the perovskite cell can have higher energy conversion efficiency and stability, and can also have higher conductivity, thereby helping to improve the output performance of the perovskite cell.

[0014] In any embodiment, the organic molecular passivation material includes one or more of alkylamines and their halogen salts, aromatic amines and their halogen salts, aromatic heterocyclic compounds, polymers, and their respective derivatives.

[0015] In any embodiment, the aromatic heterocyclic compound includes one or more nitrogen-containing aromatic heterocycles and their derivatives, and may optionally include one or more of carbazole, pyridine, piperidine, and their respective derivatives. When the aromatic heterocyclic compound is within the above range, the nitrogen atom has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect. Specific atoms and / or functional groups can be embedded in the shallow position of the light-absorbing layer, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite cell.

[0016] In any embodiment, the polymer includes one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives. When the polymer is within the above range, the amino group or the nitrogen atom on the aromatic heterocyclic ring has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can embed specific atoms and / or functional groups into the shallow position of the light-absorbing layer, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite cell.

[0017] In any embodiment, the organic molecule passivation material includes one or more of N,N-diethylaniline, 2-phenylethylamine hydroiodide, dopamine, 9,9-bis(4-aminophenyl)fluorene, [2-(9H-carbazol-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid, 4-pyridinecarboxylic acid, polyaniline, polypyridine, polypiperidine, and their respective derivatives. Optionally, the organic molecule passivation material includes one or more of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid, 2-phenylethylamine hydroiodide, and their respective derivatives.

[0018] When the organic molecular passivation material is within the above range, it can better match the energy level of the perovskite material, better passivate the interface defects between the light absorption layer and the charge transfer layer, passivate the intrinsic point defects and grain boundary defects of the perovskite material, and better optimize the crystallization quality of the perovskite material, thereby further reducing non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.

[0019] In any embodiment, the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material, an N-type metal oxide semiconductor material, and a P-type metal oxide semiconductor material, and optionally includes SnO2, TiO2, ZnO, NiO x 、CeO x , MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of their respective doping materials, 1≤x≤2.

[0020] In any embodiment, when the passivation layer is located between the hole transport layer and the light absorbing layer, the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, and optionally includes NiO x 、CeO x , MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of their respective doping materials, 1≤x≤2. This allows for better hole transport.

[0021] In any embodiment, when the passivation layer is located between the electron transport layer and the light absorbing layer, the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, and optionally includes one or more of SnO2, TiO2, ZnO, and their respective doping materials, thereby enabling better transmission of free electrons.

[0022] In any embodiment, the particle size of the metal oxide semiconductor material is less than 100 nm, optionally less than 50 nm, and more optionally 5-10 nm.

[0023] In any embodiment, the metal element in the metal halide includes one or more of alkali metal elements, alkaline earth metal elements, and transition metal elements, and can optionally include one or more of K, Cs, Pb, and Cu.

[0024] In any embodiment, the halogen element in the metal halide includes one or more of F, Cl, Br, and I.

[0025] In any embodiment, the metal halide includes one or more of CsF, KCl, PbBr, CuI, and CuI2, and may optionally include one or more of KCl and CuI.

[0026] In any embodiment, the electron transport material in the electron transport layer includes one or more of imide compounds, quinone compounds, fullerenes and their derivatives, a second metal oxide, silicon oxide, strontium titanate, calcium titanate, lithium fluoride, and calcium fluoride. Optionally, the metal element in the second metal oxide includes one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr.

[0027] In any embodiment, the hole transport material in the hole transport layer includes one or more of 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene, methoxytriphenylamine-fluoroformamidine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid, poly3-hexylthiophene, triphenylamine with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-phenylamino)carbazole-spirobifluorene, polythiophene, phosphate-based monomers, carbazole-based monomers, sulfonic acid-based monomers, triphenylamine-based monomers, aromatic monomers, a third metal oxide and cuprous thiocyanate, and the metal elements in the third metal oxide include one or more of Ni, Mo and Cu.

[0028] In any embodiment, the perovskite material in the light absorbing layer includes one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.

[0029] In any embodiment, the electrode materials of the first electrode and the second electrode independently include organic conductive materials, inorganic conductive materials or organic-inorganic mixed conductive materials, which can be selected from one or more of poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, carbon and their derivatives.

[0030] A second aspect of the present application provides a photovoltaic module, which includes the perovskite cell of the first aspect of the present application.

[0031] The photovoltaic module of the present application includes the perovskite cell provided by the present application, and thus has at least the same advantages as the perovskite cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] To more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments of the present application. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on the drawings without inventive effort.

[0033] FIG1 is a schematic structural diagram of a perovskite battery provided in some embodiments of the present application.

[0034] FIG2 is a schematic structural diagram of a perovskite battery provided in some other embodiments of the present application.

[0035] FIG3 is a schematic structural diagram of a perovskite battery provided in some other embodiments of the present application.

[0036] FIG4 is a schematic structural diagram of a perovskite battery provided in some other embodiments of the present application.

[0037] FIG5 is a schematic structural diagram of a perovskite battery provided in some other embodiments of the present application.

[0038] FIG6 is a schematic structural diagram of a perovskite battery provided in some other embodiments of the present application.

[0039] In the accompanying drawings, which are not necessarily drawn to scale, the reference numerals are as follows: 1. first electrode; 2. hole transport layer; 3. light absorbing layer; 4. electron transport layer; 5. second electrode; 6. passivation layer. DETAILED DESCRIPTION

[0040] Below, the embodiments of the perovskite cell and photovoltaic module of the present application are described in detail with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially the same structures may be omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0041] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0042] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present application.

[0043] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form new technical solutions, and such technical solutions should be deemed to be included in the disclosure of this application.

[0044] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0045] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0046] Unless otherwise specified, the term "or" is used in this application to be inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied if any of the following conditions are met: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0047] Unless otherwise specified, in this application, the terms "first", "second", etc. are used to distinguish different objects rather than to describe a specific order or a primary-secondary relationship.

[0048] Unless otherwise specified, the terms used in this application have the common meanings that are commonly understood by those skilled in the art.

[0049] Unless otherwise specified, the values ​​of the parameters mentioned in this application can be measured using various test methods commonly used in the art, for example, they can be measured according to the test methods provided in this application. Unless otherwise specified, the test temperature for each parameter is 25°C.

[0050] An embodiment of the present application provides a perovskite battery.

[0051] 1 to 6 are schematic structural diagrams of perovskite cells provided in some embodiments of the present application.

[0052] As shown in Figures 1 to 6, the perovskite cell includes a first electrode 1, a second electrode 5, a light absorbing layer 3, a hole transport layer 2, and an electron transport layer 4. The light absorbing layer 3 is located between the first electrode 1 and the second electrode 5, the hole transport layer 2 is located between the first electrode 1 and the light absorbing layer 3, and the electron transport layer 4 is located between the second electrode 5 and the light absorbing layer 3.

[0053] The perovskite cell further includes a passivation layer 6 , which is located between the hole transport layer 2 and the light absorbing layer 3 , and / or between the electron transport layer 4 and the light absorbing layer 3 .

[0054] The passivation layer 6 includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0055] The operating principle of a perovskite cell is generally as follows: under illumination, the light-absorbing layer absorbs photon energy, generating electron-hole pairs in its valence band. The electrons are excited to the conduction band, leaving holes in the valence band. The conduction band energy level of the light-absorbing layer is typically higher than that of the electron transport layer, allowing electrons to transfer from the conduction band of the light-absorbing layer to the conduction band of the electron transport layer, and then to the conductive electrode. The valence band energy level of the light-absorbing layer is typically lower than that of the hole transport layer, allowing holes to transfer from the hole transport layer to the conductive electrode. When connected to an external circuit, this completes the circuit, generating a photocurrent.

[0056] The light-absorbing layer includes perovskite materials. Perovskite materials generally use halide perovskite materials (for example, inorganic halide perovskite materials, organic halide perovskite materials, and organic-inorganic hybrid halide perovskite materials). They have the advantages of large carrier diffusion length, easily adjustable band gap, high defect tolerance, and low manufacturing cost, and therefore have received widespread attention.

[0057] However, the crystallization quality of perovskite materials is poor, mainly manifested in small grain size, disordered grain stacking, and numerous grain boundaries. As a result, perovskite materials have a large number of intrinsic point defects (such as vacancies, interstitial defects, and antisite defects) and grain boundary defects. In addition, the light-absorbing layer also has a large number of surface defects, mainly manifested in numerous holes and cracks. Defects can capture surrounding free electrons and holes, and these trapped electrons and holes easily recombine at the defect center (also known as non-radiative recombination), thereby increasing the energy loss of perovskite cells and reducing the performance of perovskite cells. Moreover, compared with non-radiative recombination at intrinsic point defects or grain boundaries, non-radiative recombination at the interface between the light-absorbing layer and the charge transport layer (such as the hole transport layer or electron transport layer) is generally dominant.

[0058] Therefore, poor perovskite material crystallization quality and numerous interface defects between the light-absorbing layer and the charge transport layer are key factors affecting the performance of perovskite cells. Interface passivation is an effective strategy for achieving high-performance perovskite cells.

[0059] The passivation layer provided in the embodiment of the present application includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0060] Organic molecular passivation materials, metal oxide semiconductor materials and metal halides can easily obtain energy level structures that match perovskite materials.

[0061] Organic molecular passivation materials can act as both interface connectors and defect passivators, thereby enhancing the interface contact between the light-absorbing layer and the charge transfer layer through organic molecular passivation materials. The defect state density in the bulk and interface of the perovskite material can also be reduced through the coordination effect of the organic molecular passivation materials, thereby improving the film-forming quality of the light-absorbing layer. The organic molecular passivation materials can also be embedded in the bulk of the perovskite material to play an anchoring role, thereby reducing the precipitation of halides (such as PbI2, etc.) from the perovskite material, thereby improving the stability and service life of the perovskite battery.

[0062] Therefore, organic molecular passivation materials can passivate the interface defects between the light-absorbing layer and the charge transport layer, and can also passivate the intrinsic point defects (including vacancy defects, interstitial defects, and antisite defects) and grain boundary defects of the perovskite material, thereby improving the interface performance between the light-absorbing layer and the charge transport layer and optimizing the crystallization quality of the perovskite material, thereby reducing non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite cell. In addition, organic molecular passivation materials can also improve the film formation quality of the passivation layer, effectively blocking water and oxygen, and reducing water and oxygen corrosion of the perovskite material, thereby also improving the stability and service life of the perovskite cell.

[0063] Metal oxide semiconductor materials are highly stable and have a better energy level match with perovskite materials, which can better promote carrier transport and reduce ion migration. Furthermore, metal oxide semiconductor materials can effectively block water and oxygen, reducing water and oxygen corrosion of perovskite materials, thereby improving the stability and service life of perovskite cells.

[0064] Metal halides have high stability and can also play the role of passivating the halogen defects of perovskite materials and optimize the crystallization quality of perovskite materials.

[0065] Therefore, when the passivation layer includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer can simultaneously achieve energy level matching, interface passivation, and optimize the crystal quality of the perovskite material, thereby facilitating improved energy conversion efficiency of the perovskite cell. Furthermore, when the passivation layer includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer has better stability and can also reduce water and oxygen corrosion of the perovskite material, thereby also improving the stability and service life of the perovskite cell.

[0066] In some embodiments, the organic molecular passivation material may include one or more of alkylamines and their halogen salts, aromatic amines and their halogen salts, aromatic heterocyclic compounds, polymers, and their respective derivatives.

[0067] In some embodiments, the aromatic heterocyclic compound may optionally include one or more nitrogen-containing aromatic heterocycles and their derivatives, and more optionally include one or more of carbazole, pyridine, piperidine, and their respective derivatives. When the aromatic heterocyclic compound is within the above range, the nitrogen atom has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the shallow position of the light-absorbing layer through specific atoms and / or functional groups, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite cell.

[0068] In some embodiments, the polymer may optionally include one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives. When the polymer is within the above range, the amino group or the nitrogen atom on the aromatic heterocyclic ring has a lone pair of electrons, which can better coordinate with the empty orbital of the metal ion in the perovskite material, thereby having a better anchoring effect, and can be embedded in the shallow position of the light-absorbing layer through specific atoms and / or functional groups, thereby further reducing interface defects, thereby reducing non-radiative recombination at the defects, and improving the energy conversion efficiency of the perovskite cell.

[0069] In some embodiments, the organic molecular passivation material may include one or more of N,N-diethylaniline (DEA), 2-phenylethylamine hydroiodide (PEAI), dopamine, 9,9-bis(4-aminophenyl)fluorene (FDA), [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid, 4-pyridinecarboxylic acid, polyaniline, polypyridine, polypiperidine, and their respective derivatives.

[0070] When the organic molecular passivation material is within the above range, it can better match the energy level of the perovskite material, better passivate the interface defects between the light absorption layer and the charge transfer layer, passivate the intrinsic point defects and grain boundary defects of the perovskite material, and better optimize the crystallization quality of the perovskite material, thereby further reducing non-radiative recombination at the defects and improving the energy conversion efficiency of the perovskite battery.

[0071] The derivatives of the above-mentioned organic molecular passivation materials generally refer to products derived from the replacement of hydrogen atoms or atomic groups in the organic molecular passivation materials by other atoms or atomic groups.

[0072] In some embodiments, the organic molecular passivation material may include one or more of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), 2-phenylethylamine hydroiodide (PEAI), and their respective derivatives.

[0073] In some embodiments, the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material, an N-type metal oxide semiconductor material, and a P-type metal oxide semiconductor material. Alternatively, the metal oxide semiconductor material may include SnO2, TiO2, ZnO, NiO x (1≤x≤2), CeO x (1≤x≤2), MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of their respective doping materials.

[0074] In some embodiments, when the passivation layer 6 is located between the hole transport layer 2 and the light absorbing layer 3, the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, thereby better transporting holes. Alternatively, the metal oxide semiconductor material may include NiO x (1≤x≤2), CeO x (1≤x≤2), MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of their respective doping materials.

[0075] In some embodiments, when the passivation layer 6 is located between the electron transport layer 4 and the light absorbing layer 3, the metal oxide semiconductor material may include one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, thereby better transmitting free electrons. Alternatively, the metal oxide semiconductor material may include one or more of SnO2, TiO2, ZnO, and their respective doping materials.

[0076] When the metal oxide semiconductor material is within the above range, it can better match the energy level of the perovskite material, and can also better promote carrier transport and reduce water and oxygen corrosion of the perovskite material, thereby helping to improve the energy conversion efficiency and / or stability of the perovskite battery.

[0077] The doping material for each of the aforementioned metal oxides can independently include one or more of alkali metal elements, alkaline earth metal elements, transition metal elements, metal-poor elements, metalloid elements, halogen elements, non-metallic elements, ionic liquids, carboxylic acids, phosphoric acid, carbon derivatives, self-assembled monolayers, and polymers. Optionally, the weight content of the doping material in the metal oxide is ≤30%.

[0078] In some embodiments, the particle size of the metal oxide semiconductor material may be less than 100 nm, optionally less than 50 nm, and more optionally 5-10 nm.

[0079] In some embodiments, the metal elements in the metal halide may include one or more of alkali metal elements, alkaline earth metal elements, and transition metal elements, and may optionally include one or more of K, Cs, Pb, and Cu.

[0080] In some embodiments, the halogen element in the metal halide may include one or more of F, Cl, Br, and I.

[0081] In some embodiments, the metal halide may include one or more of CsF, KCl, PbBr, CuI, and CuI 2. When the metal halide is within the above range, it can better match the energy level of the perovskite material.

[0082] In some embodiments, the metal halide may include one or more of CsF, KCl, and PbBr, and may optionally include one or more of KCl and PbBr. When the metal halide is within the above range, the size of the halogen anion is smaller, which can better reduce the lattice distortion of the perovskite crystal and facilitate stress release, thereby better optimizing the crystallization quality of the perovskite material.

[0083] In some embodiments, the metal halide may include one or more of CuI and CuI 2 . When the metal halide is within the above range, carrier transport can be better promoted.

[0084] In some embodiments, the passivation layer may include an organic molecular passivation material as well as a metal oxide semiconductor material and / or a metal halide.

[0085] Organic molecular passivation materials can act as both interface connectors and defect passivators, thereby enhancing the interface contact between the light-absorbing layer and the charge transport layer through the organic molecular passivation material. Furthermore, the defect state density in the bulk and interface of the perovskite material can be reduced through the coordination effect of the organic molecular passivation material, thereby improving the film-forming quality of the light-absorbing layer. Furthermore, the organic molecular passivation material can be embedded in the bulk of the perovskite material, acting as an anchor, thereby reducing the precipitation of halides (such as PbI2, etc.) from the perovskite material, thereby improving the stability and service life of the perovskite cell. Therefore, the organic molecular passivation material can achieve a better passivation effect. When used in combination with metal oxide semiconductor materials and / or metal halides, it can further reduce non-radiative recombination at defects and further improve the energy conversion efficiency of the perovskite cell.

[0086] Optionally, the content of the organic molecular passivation material is 10-30 wt %, optionally 15-25 wt %, based on the total weight of the passivation layer. The organic molecular passivation material itself has slightly poor stability, so when its content is within the above range, it is also beneficial to improve the stability and service life of the perovskite cell.

[0087] In some embodiments, the passivation layer 6 may include an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide. When the passivation layer includes an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer can better balance energy level matching, interface passivation, and the optimization of the crystal quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite cell. It can also further reduce the corrosion of the perovskite material by water and oxygen, thereby further improving the stability and service life of the perovskite cell.

[0088] Optionally, the organic molecular passivation material comprises 10-30 wt %, more preferably 15-25 wt %, based on the total weight of the passivation layer. Optionally, the metal oxide semiconductor material comprises 40-60 wt %, more preferably 45-55 wt %, based on the total weight of the passivation layer. Optionally, the metal halide comprises 20-40 wt %, more preferably 25-35 wt %, based on the total weight of the passivation layer.

[0089] When the content of organic molecular passivation materials, metal oxide semiconductor materials and metal halides is within the above range, the advantages of each component can be better utilized, which is conducive to further improving the energy conversion efficiency, stability and service life of perovskite batteries.

[0090] In some embodiments, the passivation layer 6 may include an organic molecular passivation material and a metal oxide semiconductor material. Optionally, the organic molecular passivation material comprises 10-30 wt %, more preferably 15-25 wt %, based on the total weight of the passivation layer. Optionally, the metal oxide semiconductor material comprises 70-90 wt %, more preferably 75-85 wt %, based on the total weight of the passivation layer.

[0091] In some embodiments, the passivation layer 6 may include an organic molecular passivation material and a metal halide. Optionally, the organic molecular passivation material comprises 10-30 wt %, more preferably 15-25 wt %, based on the total weight of the passivation layer. Optionally, the metal halide comprises 70-90 wt %, more preferably 75-85 wt %, based on the total weight of the passivation layer.

[0092] In some embodiments, the thickness of the passivation layer 6 may be less than or equal to 30 nm, and may be selected from 1-22 nm, 1-17 nm, 2-22 nm, 2-17 nm, 4-22 nm, and 4-17 nm. When the thickness of the passivation layer is within the above range, the perovskite cell can have higher energy conversion efficiency and stability, and can also have higher conductivity, thereby helping to improve the output performance of the perovskite cell.

[0093] In some embodiments, the light absorbing layer 3 may include a perovskite material. As an intrinsic semiconductor material, the perovskite material can transport both electrons and holes.

[0094] The type of perovskite material is not specifically limited and can be selected according to actual needs. In some embodiments, the perovskite material in the light absorbing layer can include one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.

[0095] The molecular formula of the perovskite material can be ABX3, where A represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, B represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, and X represents an inorganic anion, an organic anion, or an organic-inorganic mixed anion.

[0096] As an example, A includes CH3NH3 + (MA + )、CH(NH2)2 + (FA + )、Li + 、Na + , K + , Rb + 、Cs + Optionally, A includes CH3NH3 +、CH(NH2)2 + 、Cs + One or more of

[0097] As an example, B includes Pb 2+ 、Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ 、Zn 2+ 、Ge 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ Optionally, B includes Pb 2+ 、Sn 2+ One or both of .

[0098] As an example, X includes F - 、Cl - Br - , I - Optionally, X includes Cl - Br - , I - One or more of .

[0099] The molecular formula of the perovskite material can also be A'2CDX'6, where A' represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, C represents a monovalent metal cation, D represents a trivalent metal cation, and X' represents an inorganic anion, an organic anion, or an organic-inorganic mixed anion.

[0100] As an example, A' comprises CH3NH3 + (MA + )、CH(NH2)2 + (FA + )、Li + 、Na + , K + , Rb + 、Cs + Optionally, A' comprises CH3NH3 + 、CH(NH2)2 + 、Cs + One or more of

[0101] As an example, C includes Li + 、Na + , K + , Rb + 、Cs + 、Ag+ At least one of .

[0102] As an example, D includes In 3+ 、Bi 3+ At least one of .

[0103] As an example, X' includes F - 、Cl - Br - , I - Optionally, X' includes Cl - Br - , I - One or more of .

[0104] In some embodiments, the perovskite material may include, but is not limited to, one or more of CH3NH3PbI3(MAPbI3), CH(NH2)2PbI3(FAPbI3), CsPbI3, CsPbI2Br, CsPbIBr2, Cs2NaInCl6, Cs2KBiCl6, and Cs2AgInCl6.

[0105] The thickness of the light absorbing layer 3 is not particularly limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the light absorbing layer 3 can be 50-2000 nm.

[0106] The electron transport layer 4 includes an electron transport material. The type of electron transport material is not specifically limited and can be selected according to actual needs. For example, the electron transport material can include an organic electron transport material, an inorganic electron transport material, or an organic-inorganic hybrid electron transport material.

[0107] In some embodiments, the electron transport material may include one or more of an imide compound, a quinone compound, fullerene and its derivatives, a second metal oxide, silicon oxide, strontium titanate (SrTiO3), calcium titanate (CaTiO3), lithium fluoride (LiF), and calcium fluoride (CaF2). Alternatively, the metal element in the second metal oxide may include one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr.

[0108] Alternatively, the electron transport material may include SnO2, TiO2, [6,6]-phenyl C 61 -Methyl butyrate (PC 61 BM), [6,6]-phenyl C 71 -Methyl butyrate (PC 71When the electron transport material is within the above range, the bottom energy level of its conduction band can better match the bottom energy level of the conduction band of the light absorbing layer, thereby facilitating the transmission of electrons.

[0109] The thickness of the electron transport layer 4 is not particularly limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the electron transport layer 4 can be 1-300 nm.

[0110] The hole transport layer 2 includes a hole transport material. The type of hole transport material is not particularly limited and can be selected according to actual needs.

[0111] In some embodiments, the hole transport material may include one or more of 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly3-hexylthiophene (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, a phosphate-based single molecule, a carbazole-based single molecule, a sulfonic acid-based single molecule, a triphenylamine-based single molecule, an aromatic single molecule, a third metal oxide, and cuprous thiocyanate (CuSCN). Optionally, the metal elements in the third metal oxide may include one or more of Ni, Mo and Cu.

[0112] The thickness of the hole transport layer 2 is not particularly limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the hole transport layer 2 can be 5-1000 nm.

[0113] In some embodiments, when the passivation layer 6 is located between the hole transport layer 2 and the light absorbing layer 3, the valence band top (VBM) energy level of the light absorbing layer 3 is less than the valence band top (VBM) energy level of the passivation layer 6 and less than the valence band top (VBM) energy level of the hole transport layer 2. This facilitates better hole transport.

[0114] In some embodiments, when the passivation layer 6 is located between the electron transport layer 4 and the light absorbing layer 3, the conduction band bottom (CBM) energy level of the electron transport layer 4 is less than the conduction band bottom (CBM) energy level of the passivation layer 6 and less than the conduction band bottom (CBM) energy level of the light absorbing layer 3. This facilitates better electron transport.

[0115] The energy band distribution of each film layer can be measured by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS).

[0116] In some embodiments, the electrode materials of the first electrode 1 and the second electrode 5 can each independently include an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material. For example, the electrode materials of the first electrode 1 and the second electrode 5 can each independently include one or more of a conductive polymer, a metal, a transparent metal conductive oxide, carbon, and derivatives thereof. As an example, the electrode materials of the first electrode 1 and the second electrode 5 can each independently include poly(3,4-ethylenedioxythiophene) (PEDOT), polythiophene, polyacetylene, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium-doped zinc oxide (IZO), gold, silver, aluminum, copper, carbon, and derivatives thereof.

[0117] In some embodiments, the electrode material of one of the first electrode 1 and the second electrode 5 may include a transparent metal conductive oxide, which may be one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).

[0118] In some embodiments, the perovskite cell further includes a substrate, such as a glass substrate, and a transparent metal conductive oxide may be disposed on the surface of the substrate.

[0119] In some embodiments, the electrode material of one of the first electrode 1 and the second electrode 5 may include one or more of metal, carbon and derivatives thereof, and may optionally include one or more of gold, silver, aluminum, copper, carbon and derivatives thereof.

[0120] The thickness of the first electrode 1 is not particularly limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the first electrode 1 can be 10 nm-500 nm.

[0121] The thickness of the second electrode 5 is not particularly limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the second electrode 5 can be 10 nm-500 nm.

[0122] The perovskite cell provided in the embodiments of the present application may be a regular structure cell or a reverse structure cell.

[0123] In some embodiments, as shown in FIG1 , the first electrode 1 is the light-incident side, and the perovskite cell (transverse structure cell) sequentially includes the first electrode 1, the hole transport layer 2, the passivation layer 6, the light absorption layer 3, the electron transport layer 4, and the second electrode 5. In some embodiments, as shown in FIG2 , the first electrode 1 is the light-incident side, and the perovskite cell (transverse structure cell) sequentially includes the first electrode 1, the hole transport layer 2, the light absorption layer 3, the passivation layer 6, the electron transport layer 4, and the second electrode 5. In some embodiments, as shown in FIG1 , the first electrode 1 is the light-incident side, and the perovskite cell (transverse structure cell) sequentially includes the first electrode 1, the hole transport layer 2, the passivation layer 6, the light absorption layer 3, the passivation layer 6, the electron transport layer 4, and the second electrode 5.

[0124] In some embodiments, as shown in FIG4 , the second electrode 5 is on the light-incident side, and the perovskite cell (formal structure cell) sequentially includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light-absorbing layer 3, the hole transport layer 2, and the first electrode 1. In some embodiments, as shown in FIG5 , the second electrode 5 is on the light-incident side, and the perovskite cell (formal structure cell) sequentially includes the second electrode 5, the electron transport layer 4, the light-absorbing layer 3, the passivation layer 6, the hole transport layer 2, and the first electrode 1. In some embodiments, as shown in FIG6 , the second electrode 5 is on the light-incident side, and the perovskite cell (formal structure cell) sequentially includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light-absorbing layer 3, the passivation layer 6, the hole transport layer 2, and the first electrode 1.

[0125] Optionally, the passivation layer 6 is located between the charge transport layer and the light absorbing layer near the light incident side. For a regular structure cell, the charge transport layer is an electron transport layer, and for a trans-structure cell, the charge transport layer is a hole transport layer. In this case, the light absorbing layer is formed after the passivation layer, so that the passivation layer can better promote the crystallization of the perovskite material, thereby making the perovskite cell have a higher energy conversion efficiency.

[0126] In some embodiments, the first electrode 1 is the light-entering side, and the perovskite cell (inverted structure cell) includes the first electrode 1, the hole transport layer 2, the passivation layer 6, the light absorption layer 3, the electron transport layer 4, and the second electrode 5 in sequence; the passivation layer 6 includes an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide; based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, optionally 15-25wt%; the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, and optionally includes NiO x (1≤x≤2), CeO x (1≤x≤2), MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of their respective doping materials.

[0127] In some embodiments, the second electrode 5 is the light-entering side, and the perovskite cell (formal structure cell) includes the second electrode 5, the electron transport layer 4, the passivation layer 6, the light absorption layer 3, the passivation layer 6, the hole transport layer 2 and the first electrode 1 in sequence; the passivation layer 6 includes an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide; based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, optionally 15-25wt%; the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, and can optionally include one or more of SnO2, TiO2, ZnO, and their respective doping materials.

[0128] The perovskite cell provided in the embodiments of the present application is not limited to the above structure, and may also include other functional layers.

[0129] Perovskite cells can be prepared according to methods known in the art.

[0130] As shown in Figures 1 to 3, an exemplary preparation method includes the steps of providing a first electrode 1, forming a hole transport layer 2 on the first electrode 1, forming a light absorption layer 3 on the hole transport layer 2, forming an electron transport layer 4 on the light absorption layer 3, forming a second electrode on the electron transport layer 4, and forming a passivation layer 6 on the hole transport layer 2 and then forming the light absorption layer 3, and / or forming the passivation layer 6 on the light absorption layer 3 and then forming the electron transport layer 4.

[0131] As shown in Figures 4 to 6, another exemplary preparation method includes: providing a second electrode 5, forming an electron transport layer 4 on the second electrode 5, forming a light absorption layer 3 on the electron transport layer 4, forming a hole transport layer 2 on the light absorption layer 3, forming a first electrode 1 on the hole transport layer 2, and forming a passivation layer 6 on the light absorption layer 3 before forming the hole transport layer 2, and / or forming the passivation layer 6 on the electron transport layer 4 before forming the light absorption layer 3.

[0132] The film-forming methods of the above-mentioned film layers are not subject to specific restrictions and can adopt film-forming methods known in the art, for example, chemical bath deposition, chemical vapor deposition, electrochemical deposition, physical epitaxial growth, thermal evaporation, atomic layer deposition, magnetron sputtering, precursor liquid spin coating, precursor liquid slit coating, precursor liquid scraping, mechanical pressing, sol-gel method, pulsed laser deposition, etc., and thermal evaporation and precursor liquid spin coating can be selected.

[0133] The perovskite cell provided in the embodiments of the present application can be used alone as a single-junction perovskite cell, or can be made into a stacked cell with perovskite or other types of solar cells, such as a perovskite-perovskite stacked cell or a perovskite-crystalline silicon stacked cell.

[0134] An embodiment of the present application also provides a photovoltaic module, which includes the perovskite cell provided in the embodiment of the present application. The perovskite cell can be used as a power source for the photovoltaic module after processes such as series and parallel connection and packaging.

[0135] In some embodiments, the photovoltaic module includes a single-junction perovskite cell, a perovskite-perovskite tandem cell, or a perovskite-crystalline silicon tandem cell provided in the embodiments of the present application.

[0136] Example

[0137] 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.

[0138] Example 1-1

[0139] Preparation of FTO electrodes

[0140] A glass substrate covered with FTO with a size of 2.0 cm × 2.0 cm was taken, and the surface was cleaned twice with acetone and isopropanol respectively, then immersed in deionized water for ultrasonic treatment for 10 minutes, and then dried in a forced air drying oven and placed in a glove box (N2 atmosphere).

[0141] Preparation of electron transport layer

[0142] A 3 wt% SnO2 nanocolloid aqueous solution was spin-coated on the FTO layer at a speed of 4000-6500 rpm, and then heated on a constant temperature hot stage at 150°C for 15 minutes to obtain an electron transport layer with a thickness of 50 nm.

[0143] Preparation of passivation layer

[0144] A mixture of a 2 wt% TiO2 nanocolloid-isopropanol solution, a 0.2 mg / mL 2PACz-isopropanol solution, and a 1 mg / mL KCl-isopropanol solution was spin-coated on the electron transport layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a 17 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 1.

[0145] Preparation of light-absorbing layer

[0146] A 1.5 mol / L FAPbI3 DMF solution was spin-coated on the passivation layer at a speed of 3000-4500 rpm, and then heated at 100°C for 30 minutes on a constant temperature hot plate. After cooling to room temperature, a light-absorbing layer with a thickness of 500 nm was obtained.

[0147] Preparation of hole transport layer

[0148] A chlorobenzene solution of 73 mg / mL Spiro-OMeTAD was spin-coated on the light-absorbing layer at a speed of 3000-4000 rpm to obtain a hole transport layer with a thickness of 150 nm.

[0149] Preparation of Ag electrode

[0150] The above samples were placed in a vacuum coating machine at 5×10 -4 Under vacuum conditions of 1.5 Å / min, an Ag electrode was evaporated on the surface of the hole transport layer at a rate of 0.1 Å / s and a thickness of 80 nm.

[0151] The perovskite cell structure finally obtained in Example 1-1 is FTO / SnO2 / TiO2+2PACz+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0152] Examples 1-2 to 1-6

[0153] Except for the different weight contents of the components in the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1. The specific parameters are shown in Table 1.

[0154] Examples 1-7 to 1-11

[0155] Except for the different thickness of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1. The specific parameters are shown in Table 1.

[0156] Examples 1-12

[0157] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0158] A mixture of a 2 wt% TiO2 nanocolloid-isopropanol solution and a 0.2 mg / mL 2PACz-isopropanol solution was spin-coated on the electron transport layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 150°C for 30 minutes to form a 15 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 1.

[0159] The perovskite cell structure finally obtained in Examples 1-12 is FTO / SnO2 / TiO2+2PACz / FAPbI3 / Spiro-OMeTAD / Ag.

[0160] Examples 1-13

[0161] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0162] A mixture of a 2 wt% TiO2 nanocolloid-isopropanol solution and a 1 mg / mL KCl-isopropanol solution was spin-coated on the electron transport layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a 15 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 1.

[0163] The perovskite cell structure finally obtained in Examples 1-13 is FTO / SnO2 / TiO2+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0164] Examples 1-14

[0165] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0166] A mixture of a 0.2 mg / mL 2PACz-isopropanol solution and a 1 mg / mL KCl-isopropanol solution was spin-coated on the electron transport layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a 4 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 1.

[0167] The perovskite cell structure finally obtained in Examples 1-14 is FTO / SnO2 / 2PACz+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0168] Comparative Example 1-1

[0169] The preparation of the perovskite cell was the same as that of Example 1-1, except that the passivation layer was not included.

[0170] The perovskite cell structure finally obtained in Comparative Example 1-1 is FTO / SnO2 / FAPbI3 / Spiro-OMeTAD / Ag.

[0171] Comparative Example 1-2

[0172] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0173] A 2 wt % TiO2 nanocolloid isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 13 nm.

[0174] The perovskite cell structure finally obtained in Comparative Example 1-2 is FTO / SnO2 / TiO2 / FAPbI3 / Spiro-OMeTAD / Ag.

[0175] Comparative Examples 1-3

[0176] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0177] A 0.2 mg / mL 2PACz isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.

[0178] The perovskite cell structure finally obtained in Comparative Examples 1-3 is FTO / SnO2 / 2PACz / FAPbI3 / Spiro-OMeTAD / Ag.

[0179] Comparative Examples 1-4

[0180] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 1-1.

[0181] A 1 mg / mL KCl isopropanol solution was spin-coated on the electron transport layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.

[0182] The perovskite cell structure finally obtained in Comparative Examples 1-4 is FTO / SnO2 / KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0183] Test section

[0184] At 25°C, using an AM1.5G standard light source to simulate sunlight, a four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the perovskite cell under the light source. The open-circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) of the perovskite cell were obtained. The energy conversion efficiency (Eff) of the perovskite cell was calculated from this. Eff = Pout / Popt = Voc × Jsc × (Vmpp × Jmpp) / (Voc × Jsc) = Voc × Jsc × FF.

[0185] Pout, Popt, Vmpp, and Jmpp are the operating output power, incident light power, maximum power point voltage, and maximum power point current of the perovskite cell, respectively.

[0186] Table 1 shows the test results of Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-4.

[0187] Table 1

[0188] Example 2-1

[0189] Preparation of FTO electrodes

[0190] A glass substrate covered with FTO with a size of 2.0 cm × 2.0 cm was taken, and the surface was cleaned twice with acetone and isopropanol respectively, then immersed in deionized water for ultrasonic treatment for 10 minutes, and then dried in a forced air drying oven and placed in a glove box (N2 atmosphere).

[0191] Preparation of electron transport layer

[0192] A 3 wt% SnO2 nanocolloid aqueous solution was spin-coated on the FTO layer at a speed of 4000-6500 rpm, and then heated on a constant temperature hot stage at 150°C for 15 minutes to obtain an electron transport layer with a thickness of 50 nm.

[0193] Preparation of light-absorbing layer

[0194] A 1.5 mol / L FAPbI3 DMF solution was spin-coated on the electron transport layer at a speed of 3000-4500 rpm, and then heated at 100°C for 30 minutes on a constant temperature hot stage. After cooling to room temperature, a light-absorbing layer with a thickness of 500 nm was obtained.

[0195] Preparation of passivation layer

[0196] A mixture of a 2 wt% CuO nanocolloid-isopropanol solution, a 0.2 mg / mL PEAI-isopropanol solution, and a 1 mg / mL CuI-isopropanol solution was spin-coated on the light-absorbing layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a passivation layer with a thickness of 17 nm. The weight contents of the components in the passivation layer are shown in Table 2.

[0197] Preparation of hole transport layer

[0198] A chlorobenzene solution of 73 mg / mL Spiro-OMeTAD was spin-coated on the passivation layer at a speed of 3000-4000 rpm to obtain a hole transport layer with a thickness of 150 nm.

[0199] Preparation of Ag electrode

[0200] The above samples were placed in a vacuum coating machine at 5×10 -4Under vacuum conditions of 1.5 Å / min, an Ag electrode was evaporated on the surface of the hole transport layer at a rate of 0.1 Å / s and a thickness of 80 nm.

[0201] The perovskite cell structure finally obtained in Example 2-1 is FTO / SnO2 / FAPbI3 / CuO+PEAI+CuI / Spiro-OMeTAD / Ag.

[0202] Example 2-2

[0203] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0204] A mixture of a 2 wt% CuO nanocolloid-isopropanol solution and a 0.2 mg / mL PEAI-isopropanol solution was spin-coated on the light-absorbing layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 150°C for 30 minutes to form a 15 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 2.

[0205] The perovskite cell structure finally obtained in Example 2-2 is FTO / SnO2 / FAPbI3 / CuO+PEAI / Spiro-OMeTAD / Ag.

[0206] Example 2-3

[0207] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0208] A mixture of a 2 wt% CuO nanocolloid-isopropanol solution and a 1 mg / mL CuI-isopropanol solution was spin-coated on the light-absorbing layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a 15 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 2.

[0209] The perovskite cell structure finally obtained in Example 2-3 is FTO / SnO2 / FAPbI3 / CuO+CuI / Spiro-OMeTAD / Ag.

[0210] Examples 2-4

[0211] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0212] A mixture of 0.2 mg / mL PEAI in isopropanol and 1 mg / mL CuI in isopropanol was spin-coated on the light-absorbing layer at 5000-6000 rpm. The mixture was then heated on a thermostat at 100°C for 10 minutes to form a 4 nm thick passivation layer. The weight contents of the components in the passivation layer are shown in Table 2.

[0213] The perovskite cell structure finally obtained in Example 2-4 is FTO / SnO2 / FAPbI3 / PEAI+CuI / Spiro-OMeTAD / Ag.

[0214] Comparative Example 2-1

[0215] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0216] A 2 wt % isopropanol solution of CuO nanocolloids was spin-coated on the light-absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 13 nm.

[0217] The perovskite cell structure finally obtained in Comparative Example 2-1 is FTO / SnO2 / FAPbI3 / CuO / Spiro-OMeTAD / Ag.

[0218] Comparative Example 2-2

[0219] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0220] A 0.2 mg / mL PEAI isopropanol solution was spin-coated on the light-absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.

[0221] The perovskite cell structure finally obtained in Comparative Example 2-2 is FTO / SnO2 / FAPbI3 / PEAI / Spiro-OMeTAD / Ag.

[0222] Comparative Examples 2-3

[0223] Except for the different preparation of the passivation layer, the preparation of the perovskite cell is the same as that of Example 2-1.

[0224] A 1 mg / mL CuI isopropanol solution was spin-coated on the light-absorbing layer at a speed of 5000-6000 rpm, and then heated on a constant temperature hot stage at 100° C. for 10 min to obtain a passivation layer with a thickness of 2 nm.

[0225] The perovskite cell structure finally obtained in Comparative Example 2-3 is FTO / SnO2 / FAPbI3 / CuI / Spiro-OMeTAD / Ag.

[0226] Table 2 shows the test results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3. The test method of the perovskite battery is the same as that of Examples 1-1 to 1-14.

[0227] Table 2

[0228] It can be seen from the test results in Table 1 and Table 2 that Comparative Examples 1-2 to 1-4 and Comparative Examples 2-1 to 2-3 respectively use organic molecular passivation materials, metal oxide semiconductor materials or metal halides as passivation layers. Compared with Comparative Example 1-1, the effect of improving the energy conversion efficiency of the perovskite battery is not obvious.

[0229] Comparative Examples 1-2 and 2-1 use metal oxide semiconductor materials as passivation layers. Metal oxide semiconductor materials have high structural stability, but their effect on promoting the crystallization quality of perovskite is limited. In particular, the passivation layer of Comparative Example 2-1 is formed after the light absorption layer, which further reduces the effect on promoting the crystallization quality of perovskite, resulting in an insignificant effect on improving the energy conversion efficiency of the perovskite battery.

[0230] Comparative Examples 1-3 and 2-2 use organic molecular passivation materials as the passivation layer. The structural stability of the organic molecular passivation materials is relatively poor, which results in an insignificant effect on improving the energy conversion efficiency of the perovskite battery.

[0231] Comparative Examples 1-4 and Comparative Examples 2-3 use metal halides as passivation layers. The carrier transport capacity of KCl is limited, which results in an insignificant effect on improving the energy conversion efficiency of the perovskite battery. The interface passivation effect of CuI is limited, which results in an insignificant effect on improving the energy conversion efficiency of the perovskite battery.

[0232] It can be seen from the test results in Tables 1 and 2 that by providing a passivation layer between the hole transport layer and the light absorbing layer, and / or between the electron transport layer and the light absorbing layer, and making the passivation layer include at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer can simultaneously have the effects of energy level matching, interface passivation, and optimization of the crystallization quality of the perovskite material, thereby further improving the energy conversion efficiency of the perovskite battery.

[0233] It can also be seen from the test results in Tables 1 and 2 that when the passivation layer includes an organic molecule passivation material and a metal oxide semiconductor material and / or a metal halide, the energy conversion efficiency of the perovskite cell can be further improved. This is because the organic molecule passivation material can act as an interface connector and a defect passivator at the same time, thereby enhancing the interface contact between the light-absorbing layer and the charge transport layer through the organic molecule passivation material. The defect state density in the bulk and interface of the perovskite material can also be reduced through the coordination effect of the organic molecule passivation material, thereby improving the film formation quality of the light-absorbing layer. The organic molecule passivation material can also be embedded in the bulk of the perovskite material to play an anchoring role, thereby reducing the precipitation of halides from the perovskite material. Therefore, when the organic molecule passivation material is used in combination with the metal oxide semiconductor material and / or the metal halide, the non-radiative recombination at the defects can be further reduced, further improving the energy conversion efficiency of the perovskite cell.

[0234] The test results in Tables 1 and 2 also show that when a passivation layer is placed between the charge transfer layer and the light absorption layer near the light incident side, the energy conversion efficiency of the perovskite cell can be further improved. This is because the passivation layer can better promote the crystallization of the perovskite material.

[0235] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present application, and such modifications or substitutions should be included in the scope of protection of the present application. Therefore, the scope of protection of the present application should be based on the scope of protection of the claims.

Claims

1. A perovskite battery, include: a first electrode; a second electrode; a light absorbing layer, located between the first electrode and the second electrode; a hole transport layer, located between the first electrode and the light absorbing layer; as well as an electron transport layer, located between the second electrode and the light absorbing layer, in, The perovskite cell further comprises a passivation layer, wherein the passivation layer is located between the hole transport layer and the light absorbing layer, and / or the passivation layer is located between the electron transport layer and the light absorbing layer; The passivation layer includes at least two of an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

2. The perovskite cell according to claim 1, in, The passivation layer comprises an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide, Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30 wt %, more preferably 15-25 wt %.

3. The perovskite cell according to claim 1 or 2, in, The passivation layer includes an organic molecular passivation material, a metal oxide semiconductor material and a metal halide. Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, more preferably 15-25wt%; Optionally, based on the total weight of the passivation layer, the content of the metal oxide semiconductor material is 40-60wt%, and more preferably 45-55wt%; Optionally, based on the total weight of the passivation layer, the content of the metal halide is 20-40 wt %, and more preferably 25-35 wt %.

4. The perovskite cell according to claim 1 or 2, in, The passivation layer comprises an organic molecular passivation material and a metal oxide semiconductor material, Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, more preferably 15-25wt%; Optionally, based on the total weight of the passivation layer, the content of the metal oxide semiconductor material is 70-90 wt %, and more preferably 75-85 wt %.

5. The perovskite cell according to claim 1 or 2, in, The passivation layer includes an organic molecular passivation material and a metal halide, Optionally, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10-30wt%, more preferably 15-25wt%; Optionally, based on the total weight of the passivation layer, the content of the metal halide is 70-90 wt %, and more preferably 75-85 wt %.

6. The perovskite cell according to any one of claims 1 to 5, in, The thickness of the passivation layer is less than or equal to 30 nm, and can be selected to be 1-22 nm.

7. The perovskite cell according to any one of claims 1 to 6, in, The organic molecular passivation material includes one or more of alkylamines and their halogen salts, aromatic amines and their halogen salts, aromatic heterocyclic compounds, polymers, and their respective derivatives. Optionally, the aromatic heterocyclic compound includes one or more of nitrogen-containing aromatic heterocyclic rings and their derivatives, and more optionally includes one or more of carbazole, pyridine, piperidine, and their respective derivatives; Optionally, the polymer includes one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives.

8. The perovskite cell according to claim 7, in, The organic molecular passivation material includes one or more of N,N-diethylaniline, 2-phenylethylamine hydroiodide, dopamine, 9,9-bis(4-aminophenyl)fluorene, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 4-pyridinecarboxylic acid, polyaniline, polypyridine, polypiperidine, and their respective derivatives, Optionally, the organic molecular passivation material includes one or more of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid, 2-phenylethylamine hydroiodide, and their respective derivatives.

9. The perovskite cell according to any one of claims 1 to 8, in, The metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material, an N-type metal oxide semiconductor material, and a P-type metal oxide semiconductor material, and optionally includes SnO 2 、TiO 2 、ZnO、NiO x 、CeO x 、MoO 3 、NiMgLiO、CuGaO 2 、CuGrO 2 , CuO, Cu 2 O, and one or more of their respective doping materials, 1≤x≤2.

10. The perovskite cell according to claim 9, in, When the passivation layer is located between the hole transport layer and the light absorbing layer, the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and a P-type metal oxide semiconductor material, and optionally includes NiO x 、CeO x 、MoO 3 、NiMgLiO、CuGaO 2 、CuGrO 2 , CuO, Cu 2 O, and one or more of their respective doping materials, 1≤x≤2; When the passivation layer is located between the electron transport layer and the light absorbing layer, the metal oxide semiconductor material includes one or more of an intrinsic metal oxide semiconductor material and an N-type metal oxide semiconductor material, and optionally includes SnO 2 、TiO 2 , ZnO, and one or more of their respective doping materials.

11. The perovskite cell according to any one of claims 1 to 10, in, The particle size of the metal oxide semiconductor material is below 100 nm, and may be below 50 nm, and may be further selected to be 5-10 nm.

12. The perovskite cell according to any one of claims 1 to 11, in, The metal element in the metal halide includes one or more of alkali metal elements, alkaline earth metal elements, and transition metal elements, and may be one or more of K, Cs, Pb, and Cu; and / or, The halogen element in the metal halide includes one or more of F, Cl, Br, and I.

13. The perovskite cell according to claim 12, in, The metal halide includes CsF, KCl, PbBr, CuI, CuI 2 One or more of, optionally including one or more of KCl, CuI.

14. The perovskite cell according to any one of claims 1 to 13, in, The electron transport material in the electron transport layer includes one or more of imide compounds, quinone compounds, fullerenes and their derivatives, a second metal oxide, silicon oxide, strontium titanate, calcium titanate, lithium fluoride, and calcium fluoride. Optionally, the metal element in the second metal oxide includes one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr; and / or, The hole transport material in the hole transport layer includes one or more of 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene, methoxytriphenylamine-fluoroformamidine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid, poly-3-hexylthiophene, triphenylamine with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-anilino)carbazole-spirobifluorene, polythiophene, phosphate-based monomers, carbazole-based monomers, sulfonic acid-based monomers, triphenylamine-based monomers, aromatic monomers, a third metal oxide and cuprous thiocyanate, and the metal element in the third metal oxide includes one or more of Ni, Mo and Cu; and / or, The perovskite material in the light absorbing layer includes one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.

15. The perovskite cell according to any one of claims 1 to 14, in, The electrode materials of the first electrode and the second electrode independently include organic conductive materials, inorganic conductive materials or organic-inorganic mixed conductive materials, and can be selected from one or more of poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, carbon and their derivatives.

16. A photovoltaic module comprising the perovskite cell according to any one of claims 1 to 15.

Images