Perovskite cell, photovoltaic assembly

Abstract

The present invention provides a perovskite cell and a photovoltaic assembly, the perovskite cell comprising a first electrode, a second electrode, a light-absorbing layer, a hole transport layer and an electron transport layer, the light-absorbing layer located between the first electrode and the second electrode, the hole transport layer located between the first electrode and the light-absorbing layer and the electron transport layer located between the second electrode and the light-absorbing layer. The perovskite cell further comprises a passivation layer, the passivation layer located between the hole transport layer and the light-absorbing layer, and / or the passivation layer located between the electron transport layer and the light-absorbing layer, the passivation layer comprising at least two of organic molecular passivation material, metal oxide semiconductor material and metal halide.

Description

Technical Field

[0001] This application relates to perovskite solar cells and photovoltaic assemblies.

Background Art

[0002] With the development of modern industries, the world's energy shortage and environmental pollution are becoming increasingly serious, and solar cells are being increasingly emphasized as ideal renewable energy sources. A perovskite solar cell is a solar cell that uses a perovskite material as a light absorption layer, and how to improve its energy conversion efficiency is an issue that researchers are working on. Note that the above description is only for providing background technical information related to this application and does not necessarily constitute prior art.

Summary of the Invention

[0003] This application provides a perovskite solar cell and a photovoltaic assembly that can improve the energy conversion efficiency of the perovskite solar cell.

[0004] The first aspect of this application provides a perovskite solar cell including 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. The electron transport layer is located between the second electrode and the light absorption layer. The perovskite solar cell further includes a passivation layer. 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 molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0005] 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 simultaneously has the effects of energy level alignment, interface passivation, and optimization of the crystal quality of the perovskite material, and thus contributes to an improvement in the energy conversion efficiency of the perovskite solar cell. Further, 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 is excellent in stability and can reduce the erosion of moisture and oxygen to the perovskite material, so that the stability and service life of the perovskite solar cell can be improved.

[0006] In any embodiment, the passivation layer includes an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide. The organic molecular passivation material can serve as both an interfacial adhesive and a defect passivation agent. Therefore, this material can strengthen the interfacial contact between the light absorption layer and the charge transport layer, and reduce the defect energy level density in the bulk phase and at the interface of the perovskite material due to the coordination effect of the organic molecular passivation material, making it possible to improve the film formation quality of the light absorption layer. Further, when the organic molecular passivation material is inserted into the bulk phase of the perovskite material, it exhibits an anchor effect and can suppress the precipitation of halides (such as PbI2, etc.) from the perovskite material, thereby improving the stability and service life of the perovskite solar cell. Therefore, the organic molecular passivation material exhibits a better passivation effect, and by combining it with a metal oxide semiconductor material and / or a metal halide, non-radiative recombination at defect sites is further suppressed, and the energy conversion efficiency of the perovskite solar cell is further improved.

[0007] Preferably, based on the total weight of the passivation layer, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%.

[0008] In any embodiment, the passivation layer comprises an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide. When the passivation layer simultaneously comprises an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer better combines the effects of energy level matching, interface passivation, and optimization of the crystal mass of the perovskite material, which is advantageous in improving the energy conversion efficiency of the perovskite battery, suppressing the erosion of the perovskite material by moisture and oxygen, and further improving the stability and service life of the perovskite battery.

[0009] Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal oxide semiconductor material is 40 to 60 wt%, more preferably 45 to 55 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal halide is 20 to 40 wt%, more preferably 25 to 35 wt%, relative to the total weight of the passivation layer.

[0010] In any embodiment, the passivation layer comprises an organic molecular passivation material and a metal oxide semiconductor material. Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal oxide semiconductor material is 70 to 90 wt%, more preferably 75 to 85 wt%, relative to the total weight of the passivation layer.

[0011] In any embodiment, the passivation layer comprises an organic molecular passivation material and a metal halide. Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal halide is 70 to 90 wt%, more preferably 75 to 85 wt%, relative to the total weight of the passivation layer.

[0012] In any embodiment, the thickness of the passivation layer is 30 nm or less, preferably 1 to 22 nm. When the thickness of the passivation layer falls within the above range, the perovskite battery not only gains high energy conversion efficiency and stability, but the passivation layer also gains high conductivity, which is advantageous in improving the output performance of the perovskite battery.

[0013] In any embodiment, the organic molecular passivation material comprises one or more of alkylamines and their halogenated salts, aromatic amines and their halogenated salts, aromatic heterocyclic compounds, polymers, and derivatives thereof.

[0014] In any embodiment, the aromatic heterocyclic compound comprises one or more nitrogen-containing aromatic heterocyclic compounds and their derivatives, preferably one or more carbazole, pyridine, piperidine, and their respective derivatives. When the aromatic heterocyclic compound falls within the above range, the nitrogen atom has a lone pair of electrons, allowing for better coordination with the empty orbitals of metal ions in the perovskite material. As a result, the anchoring effect is enhanced, allowing for insertion into the shallow surface of the light-absorbing layer via specific atoms and / or functional groups, further reducing interfacial defects. This suppresses non-radiative recombination at defect sites, improving the energy conversion efficiency of the perovskite battery.

[0015] In any embodiment, the polymer comprises one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives. When the polymer falls within the above range, the nitrogen atom on the amino group or aromatic heterocycle has a lone pair of electrons, allowing for better coordination with the empty orbitals of metal ions in the perovskite material. As a result, the anchoring effect is enhanced, allowing for insertion into the shallow surface of the light-absorbing layer via specific atoms and / or functional groups, further reducing interfacial defects. This suppresses non-radiative recombination at defect sites, improving the energy conversion efficiency of the perovskite battery.

[0016] In any embodiment, the organic molecular passivation material comprises 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. Preferably, the organic molecular passivation material comprises one or more of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, 2-phenylethylamine hydroiodide, and their respective derivatives.

[0017] When organic molecular passivation materials fall within the above range, they better match the energy levels of the perovskite material, more effectively passivating interface defects between the light absorption layer and the charge transport layer, as well as eigenpoint defects and grain boundary defects in the perovskite material, and further optimizing the crystal quality of the perovskite material. As a result, non-radiative recombination at defect sites is further suppressed, improving the energy conversion efficiency of the perovskite battery.

[0018] In any embodiment, the metal oxide semiconductor material comprises one or more of intrinsic metal oxide semiconductor materials, N-type metal oxide semiconductor materials, and P-type metal oxide semiconductor materials, preferably SnO2, TiO2, ZnO, NiO x CeO x It comprises MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of the respective doping materials, provided that 1 ≤ x ≤ 2.

[0019] In any embodiment, if the passivation layer is located between the hole transport layer and the light absorption layer, the metal oxide semiconductor material comprises one or more of intrinsic metal oxide semiconductor materials and P-type metal oxide semiconductor materials, preferably NiO x CeO x The material comprises MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and one or more of the respective doping materials, provided that 1 ≤ x ≤ 2. This allows for better hole transport.

[0020] In any embodiment, if the passivation layer is located between the electron transport layer and the light absorption layer, the metal oxide semiconductor material comprises one or more intrinsic metal oxide semiconductor materials and N-type metal oxide semiconductor materials, preferably one or more of SnO2, TiO2, ZnO, and their respective doping materials. This allows for better transport of free electrons.

[0021] In any embodiment, the particle size of the metal oxide semiconductor material is 100 nm or less, preferably 50 nm or less, and more preferably 5 to 10 nm.

[0022] In any embodiment, the metal element in the metal halide includes one or more alkali metal elements, alkaline earth metal elements, and transition metal elements, preferably one or more of K, Cs, Pb, and Cu.

[0023] In any embodiment, the halogen element in the metal halide includes one or more of F, Cl, Br, and I.

[0024] In any embodiment, the metal halide comprises one or more of CsF, KCl, PbBr, CuI, and CuI2, preferably one or more of KCl and CuI.

[0025] In any embodiment, the electron transport material in the electron transport layer comprises one or more of imide compounds, quinone compounds, fullerenes and their derivatives, second metal oxides, silicon dioxide, strontium titanate, calcium titanate, lithium fluoride, and calcium fluoride, and preferably the metal element in the second metal oxide comprises one or more of Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr.

[0026] In any embodiment, the hole transport material in the hole transport layer comprises one or more of the following: 2,2',7,7'-tetrakis(N,N-methoxyanilino)-9,9'-spirobifluorene, methoxytriphenylamine-fluoroformamidine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid, poly3-hexylthiophene, triptycene-cored triphenylamine, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-anilino)carbazole-spirobifluorene, polythiophene, phosphate monomolecule, carbazole monomolecule, sulfonic acid monomolecule, triphenylamine monomolecule, aromatic monomolecule, tertiary metal oxide, and cuprous thiocyanate, wherein the metal element in the tertiary metal oxide comprises one or more of Ni, Mo, and Cu.

[0027] In any embodiment, the perovskite material in the light-absorbing layer includes one or more of the following: an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.

[0028] In any embodiment, the electrode materials of the first electrode and the second electrode each independently comprise an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material, preferably one or more of the following: poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimond-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, carbon, and its derivatives.

[0029] A second aspect of the present application provides a photovoltaic assembly including a perovskite cell according to the first aspect of the present application.

[0030] The photovoltaic assembly of the present invention includes a perovskite cell according to the present invention and therefore has at least the same advantages as the said perovskite cell. [Brief explanation of the drawing]

[0031] To more clearly explain the technical solutions in the embodiments of this application, the drawings necessary for the embodiments of this application are briefly described below. It should be understood that the drawings shown below represent only a few embodiments of this application, and those skilled in the art can obtain further drawings based on these drawings without requiring any creative effort.

[0032] [Figure 1] This is a schematic diagram of the structure of a perovskite battery according to some embodiments of the present invention. [Figure 2] This is a schematic diagram of the structure of a perovskite battery according to some other embodiments of the present invention. [Figure 3] This is a schematic diagram of the structure of a perovskite battery according to some other embodiments of the present invention. [Figure 4] This is a schematic diagram of the structure of a perovskite battery according to some other embodiments of the present invention. [Figure 5] This is a schematic diagram of the structure of a perovskite battery according to some other embodiments of the present invention. [Figure 6] This is a schematic diagram of the structure of a perovskite battery according to some other embodiments of the present invention.

[0033] In drawings, the drawings are not drawn according to actual proportions. [Explanation of Symbols]

[0034] 1. First electrode 2. Hole transport layer 3. Light absorption layer 4. Electron transport layer 5. Second electrode 6. Passivation layer. [Modes for carrying out the invention]

[0035] Embodiments specifically disclosing the perovskite cell and photovoltaic assembly of this application will be described in detail with reference to the drawings as appropriate. However, unnecessary details may be omitted. For example, detailed explanations of well-known matters and redundant explanations of structures that are actually the same may be omitted. This is to avoid making the following explanation unnecessarily long and to make it easily understandable to those skilled in the art. The drawings and the following explanation are provided to enable those skilled in the art to fully understand this application and are not intended to limit the topics described in the claims.

[0036] The “range” disclosed herein is defined in the form of a lower bound and an upper bound, and a given range is defined by selecting one lower bound and one upper bound, the selected lower and upper bounds defining the boundaries of a particular range. Such a limited range may or may not include the endpoints, and any combination is possible, that is, any lower bound can be combined with any upper bound to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 are also conceivable. Similarly, if the minimum range values ​​1 and 2 are listed, and the maximum range values ​​3, 4 and 5 are listed, then the ranges 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5 are all conceivable. In this application, unless otherwise specified, the numerical range “a-b” means an abbreviated expression for any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" are listed in this specification, and "0 to 5" is merely an abbreviated expression for combinations of these numbers. Also, when a parameter is described as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0037] All embodiments and optional embodiments of the present application can be combined to form new technical solutions unless otherwise specified, and such technical solutions should be considered to be included in the disclosure of the present application.

[0038] All of the technical features and selectable technical features of this application can be combined to form new technical solutions unless otherwise specified, and such technical solutions should be considered to be included in the disclosure of this application.

[0039] All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, if the method includes steps (a) and (b), it indicates that the method may include steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, if the method mentioned above may further include step (c), it indicates that step (c) may be added to the method in any order, for example, that the method may include steps (a), (b), and (c), or steps (a), (c), and (b), or steps (c), (a), and (b), and so on.

[0040] As used herein, “includes” and “inclusive” refer to both open and closed forms unless otherwise specified. For example, “includes” and “inclusive” may include or include other components not listed, or may include or include only the listed components.

[0041] In this application, unless otherwise specified, the term “or” is 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 by either A being true (or existing) and B being false (or not existing), A being false (or not existing) and B being true (or existing), or both A and B being true (or existing).

[0042] Unless otherwise specified, terms such as "first," "second," etc., in this application are used to distinguish between different objects and are not used to describe a specific order or hierarchical relationship.

[0043] Unless otherwise stated, terms used in this application have the same meanings as those generally understood by those skilled in the art.

[0044] Unless otherwise stated, the numerical values ​​of each parameter described herein can be measured by various test methods commonly used in the art, for example, according to the test methods shown herein. Unless otherwise stated, the test temperature for each parameter is 25°C.

[0045] The embodiments of this application provide a perovskite battery.

[0046] Figures 1 to 6 are schematic diagrams of the structure of a perovskite battery according to several embodiments of the present invention.

[0047] 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.

[0048] The perovskite cell further includes a passivation layer 6, which is located between the hole transport layer 2 and the light absorption layer 3, and / or between the electron transport layer 4 and the light absorption layer 3.

[0049] The passivation layer 6 comprises at least two of the following: an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0050] The operating principle of a perovskite battery is generally as follows: Under light irradiation, the light-absorbing layer absorbs photon energy, generating electron-hole pairs in its valence band. Electrons are excited to the conduction band, leaving holes in the valence band. Since the conduction band level of the light-absorbing layer is usually higher than that of the electron-transporting layer, electrons move from the conduction band of the light-absorbing layer to the conduction band of the electron-transporting layer, and then to the conductive electrode. On the other hand, since the valence band level of the light-absorbing layer is usually lower than that of the hole-transporting layer, holes are transported to the conductive electrode via the hole-transporting layer. When an external circuit is connected, a closed circuit is formed, and a photocurrent is generated.

[0051] The light-absorbing layer contains a perovskite material, and the perovskite material commonly used is a halide perovskite material (e.g., inorganic halide perovskite material, organic halide perovskite material, and organic-inorganic hybrid halide perovskite material). Perovskite materials have attracted widespread attention because they offer advantages such as long carrier diffusion length, easy band gap adjustment, high defect tolerance, and low manufacturing cost.

[0052] However, perovskite materials have inferior crystal quality, mainly exhibiting characteristics such as small grain size, disordered particle deposition, and numerous grain boundaries. As a result, perovskite materials have a large number of eigenpoint defects (vacancy defects, lattice defects, antisite defects, etc.) and grain boundary defects. Furthermore, the light-absorbing layer has a large number of surface defects, mainly pores and cracks. These defects trap surrounding free electrons and holes, and the trapped electrons and holes readily recombine at the defect center (also called non-radiative recombination). Consequently, perovskite batteries experience increased energy loss and reduced performance. Moreover, non-radiative recombination at the interface between the light-absorbing layer and the charge transport layer (e.g., hole transport layer or electron transport layer) is usually dominant compared to non-radiative recombination at eigenpoint defects and grain boundaries.

[0053] Therefore, the poor crystal quality of the perovskite material and the numerous interface defects between the light-absorbing layer and the charge-transport layer are key factors hindering the improvement of perovskite battery performance. Interface passivation is an effective strategy for obtaining high-performance perovskite batteries.

[0054] The passivation layer according to the embodiment of the present application comprises at least two of the following: an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide.

[0055] Organic molecular passivation materials, metal oxide semiconductor materials, and metal halides can easily obtain energy level structures that are compatible with perovskite materials.

[0056] Organic molecular passivation materials can combine the functions of an interfacial adhesive and a defect passivation agent. Therefore, these materials can enhance interfacial contact between the light absorption layer and the charge transport layer, and the coordination effect of the organic molecular passivation material reduces the defect level density in the bulk phase and interface of the perovskite material, thereby improving the film deposition quality of the light absorption layer. Furthermore, the insertion of the organic molecular passivation material into the bulk phase of the perovskite material exerts an anchoring effect, suppressing the deposition of halides (e.g., PbI2) from the perovskite material. This improves the stability and service life of perovskite batteries.

[0057] Therefore, organic molecular passivation materials can not only passivate defects at the interface between the light absorption layer and the charge transport layer, but can also further passivate eigenpoint defects (vacancy defects, lattice defects, antisite defects) and grain boundary defects in the perovskite material. As a result, the interface properties between the light absorption layer and the charge transport layer are improved, the crystal quality of the perovskite material is optimized, non-radiative recombination at defect sites is reduced, and energy conversion efficiency is improved. Furthermore, organic molecular passivation materials also enhance the film deposition quality of the passivation layer itself, effectively blocking moisture and oxygen and suppressing their erosion into the perovskite material, thereby further improving the stability and service life of perovskite batteries.

[0058] Metal oxide semiconductor materials possess high stability and excellent energy level matching with perovskite materials, allowing for accelerated carrier transport and reduced ion transfer. Simultaneously, metal oxide semiconductor materials effectively block moisture and oxygen, suppressing their erosion of the perovskite material. This, in turn, improves the stability and lifespan of perovskite batteries.

[0059] Metal halides possess high stability and play a role in passivating halogen defects in perovskite materials, while also optimizing the crystal quality of the perovskite material.

[0060] Therefore, when the passivation layer contains at least two of the following: organic molecular passivation material, metal oxide semiconductor material, and metal halide, the passivation layer simultaneously provides the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby contributing to improved energy conversion efficiency of the perovskite battery. Furthermore, when the passivation layer contains at least two of the following: organic molecular passivation material, metal oxide semiconductor material, and metal halide, the passivation layer exhibits excellent stability and can reduce the erosion of the perovskite material by moisture and oxygen, thereby improving the stability and service life of the perovskite battery.

[0061] In some embodiments, the organic molecular passivation material may include one or more of alkylamines and their halogenated salts, aromatic amines and their halogenated salts, aromatic heterocyclic compounds, polymers, and derivatives thereof.

[0062] In some examples, the aromatic heterocyclic compound preferably comprises at least one nitrogen-containing aromatic heterocyclic compound and its derivatives, and more preferably one or more of carbazole, pyridine, piperidine, and their respective derivatives. When the aromatic heterocyclic compound falls within the above range, the nitrogen atom has a lone pair of electrons, allowing it to coordinate better with the empty orbitals of metal ions in the perovskite material. As a result, the anchoring effect is enhanced, allowing for insertion into the shallow surface of the light-absorbing layer via specific atoms and / or functional groups, further reducing interfacial defects. This suppresses non-radiative recombination at defect sites, improving the energy conversion efficiency of the perovskite battery.

[0063] In some embodiments, the polymer may preferably comprise one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives. When the polymer falls within this range, the nitrogen atoms on the amino group or aromatic heterocycle have lone pairs of electrons, allowing for better coordination with the empty orbitals of metal ions in the perovskite material. As a result, the anchoring effect is enhanced, allowing for insertion into the shallow surface of the light-absorbing layer via specific atoms and / or functional groups, further reducing interfacial defects. This suppresses non-radiative recombination at defect sites, improving the energy conversion efficiency of the perovskite battery.

[0064] In some examples, the organic molecular passivation material may include one or more of the following: N,N-diethylaniline (DEA), 2-phenylethylamine hydroiodide (PEAI), dopamine, 9,9-bis(4-aminophenyl)fluorene (FDA), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [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.

[0065] When organic molecular passivation materials fall within the above range, they better match the energy levels of the perovskite material, more effectively passivating interface defects between the light absorption layer and the charge transport layer, as well as eigenpoint defects and grain boundary defects in the perovskite material, and further optimizing the crystal quality of the perovskite material. As a result, non-radiative recombination at defect sites is further suppressed, improving the energy conversion efficiency of the perovskite battery.

[0066] The derivatives of each of the above-mentioned organic molecular passivation materials typically refer to compounds derived by substituting hydrogen atoms or groups of atoms within the organic molecular passivation material with other atoms or groups of atoms.

[0067] In some examples, the organic molecular passivation material may contain one or more of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), 2-phenylethylamine hydroiodide (PEAI), and their respective derivatives.

[0068] In some embodiments, the metal oxide semiconductor material may include one or more of intrinsic metal oxide semiconductor materials, N-type metal oxide semiconductor materials, and P-type metal oxide semiconductor materials. Preferably, the metal oxide semiconductor material is SnO2, TiO2, ZnO, NiO x (1≦x≦2), CeO x (1≦x≦2), may include one or more of MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and their respective doping materials.

[0069] In some embodiments, when the passivation layer 6 is located between the hole transport layer 2 and the light absorption layer 3, the metal oxide semiconductor material may include one or more intrinsic metal oxide semiconductor materials or P-type metal oxide semiconductor materials, thereby enabling better hole transport. Preferably, the metal oxide semiconductor material is NiO x (1≦x≦2), CeO x (1≦x≦2), may include one or more of MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and their respective doping materials.

[0070] In some embodiments, when the passivation layer 6 is located between the electron transport layer 4 and the light absorption layer 3, the metal oxide semiconductor material may include one or more intrinsic metal oxide semiconductor materials or N-type metal oxide semiconductor materials, thereby enabling better transport of free electrons. Preferably, the metal oxide semiconductor material may include one or more of SnO2, TiO2, ZnO, and their respective doping materials.

[0071] When metal oxide semiconductor materials fall within the above range, they may better match the energy levels of the perovskite material, accelerating carrier transport and suppressing the erosion of moisture and oxygen into the perovskite material, thereby contributing to improved energy conversion efficiency and / or stability of the perovskite battery.

[0072] Each of the above metal oxide doping materials may independently contain one or more of alkali metal elements, alkaline earth metal elements, transition metal elements, base metal elements, metalloid elements, halogen elements, nonmetal elements, ionic liquids, carboxylic acids, phosphoric acid, carbon derivatives, self-assembled monomolecules, and polymers. Preferably, the weight content of the doping material in the metal vapor is ≤30%.

[0073] In some embodiments, the particle size of the metal oxide semiconductor material may be 100 nm or less, preferably 50 nm or less, and more preferably 5 to 10 nm.

[0074] In some examples, the metal element in the metal halide may include one or more alkali metal elements, alkaline earth metal elements, and transition metal elements, and preferably one or more of K, Cs, Pb, and Cu.

[0075] In some embodiments, the halogen element in the metal halide may include one or more of F, Cl, Br, and I.

[0076] In some embodiments, the metal halide may include one or more of CsF, KCl, PbBr, CuI, and CuI2. When the metal halide falls within the above range, it can be better matched to the energy levels of the perovskite material.

[0077] In some embodiments, the metal halide may include one or more of CsF, KCl, and PbBr, preferably one or more of KCl and PbBr. When the metal halide falls within the above range, the small size of the halogen anions allows for more effective suppression of lattice distortion in the perovskite crystal and contributes to stress relaxation. As a result, the crystal quality of the perovskite material can be further optimized.

[0078] In some embodiments, the metal halide may include one or more of CuI and CuI2. When the metal halide falls within the above range, carrier transport can be better accelerated.

[0079] In some embodiments, the passivation layer may include an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide.

[0080] Organic molecular passivation materials can combine the functions of an interfacial adhesive and a defect passivation agent. Therefore, these materials can enhance interfacial contact between the light absorption layer and the charge transport layer, and the coordination effect of the organic molecular passivation material reduces the defect level density in the bulk phase and interface of the perovskite material, thereby improving the film deposition quality of the light absorption layer. Furthermore, the insertion of the organic molecular passivation material into the bulk phase of the perovskite material exerts an anchoring effect, suppressing the deposition of halides (e.g., PbI2) from the perovskite material, thereby improving the stability and service life of the perovskite battery. Consequently, organic molecular passivation materials exhibit superior passivation effects, and by using them in combination with metal oxide semiconductor materials and / or metal halides, non-radiative recombination at defect sites is further suppressed, further improving the energy conversion efficiency of the perovskite battery.

[0081] Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, and more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Since the organic molecular passivation material has relatively low stability, its content being within the above range is advantageous in improving the stability and service life of the perovskite battery.

[0082] 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 simultaneously includes an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, the passivation layer better combines the effects of energy level matching, interface passivation, and optimization of the crystal mass of the perovskite material, which is advantageous in improving the energy conversion efficiency of the perovskite battery, suppressing the erosion of the perovskite material by moisture and oxygen, and further improving the stability and service life of the perovskite battery.

[0083] Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal oxide semiconductor material is 40 to 60 wt%, more preferably 45 to 55 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal halide is 20 to 40 wt%, more preferably 25 to 35 wt%, relative to the total weight of the passivation layer.

[0084] When the content of organic molecular passivation materials, metal oxide semiconductor materials, and metal halides falls within the above range, the properties of each component can be more effectively utilized, which is advantageous in improving the energy conversion efficiency, stability, and service life of perovskite batteries.

[0085] In some embodiments, the passivation layer 6 may contain an organic molecular passivation material and a metal oxide semiconductor material. Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal oxide semiconductor material is 70 to 90 wt%, more preferably 75 to 85 wt%, relative to the total weight of the passivation layer.

[0086] In some embodiments, the passivation layer 6 may contain an organic molecular passivation material and a metal halide. Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal halide is 70 to 90 wt%, more preferably 75 to 85 wt%, relative to the total weight of the passivation layer.

[0087] In some embodiments, the thickness of the passivation layer 6 is 30 nm or less, preferably 1 - 22 nm, 1 - 17 nm, 2 - 22 nm, 2 - 17 nm, 4 - 22 nm, or 4 - 17 nm. When the thickness of the passivation layer is within the above range, not only will the perovskite battery have high energy conversion efficiency and stability, but the passivation layer will also have high conductivity, which is advantageous for improving the output performance of the perovskite battery.

[0088] In some embodiments, the light absorption layer 3 may contain a perovskite material. As an intrinsic semiconductor material, the perovskite material can transport electrons or holes.

[0089] The type of perovskite material is not particularly limited and can be selected according to actual needs. In some embodiments, the perovskite material in the light absorption layer may include one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic - inorganic hybrid halide perovskite material.

[0090] The molecular formula of the perovskite material is represented as ABX3, where A represents an inorganic cation, an organic cation, or an organic - inorganic hybrid cation, B represents an inorganic cation, an organic cation, or an organic - inorganic hybrid cation, and X represents an inorganic anion, an organic anion, or an organic - inorganic hybrid anion.

[0091] Exemplarily, A is CH3NH3 + (MA + ), CH(NH2)2 + (FA + ), Li + , Na + , K + , Rb + , and Cs + and includes one or more of them. Preferably, A is CH3NH3 + , CH(NH2)2 + , and Cs + and includes one or more of them. For example, B is Pb 2+ Sn 2+ Be 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ Zn 2+ , Ge 2+ Fe 2+ Co 2+ , and Ni 2+ Includes one or more of the following. Preferably, B is Pb 2+ Sn 2+ It includes one or two of the following.

[0092] For example, X is F - Cl - , Br - , and I - It includes one or more of the following. Preferably, X is Cl - , Br - , and I - Includes one or more of the following.

[0093] Furthermore, the molecular formula of the perovskite material may be A'2CDX'6, where A' represents an inorganic cation, an organic cation, or an organic-inorganic hybrid 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 hybrid anion.

[0094] For example, A' is CH3NH3 + (MA + ), CH(NH2)2 + (Fa + ), Li + na + , K + , Rb + , and Cs + It includes one or more of the following. Preferably, A' is CH3NH3 + CH(NH2)2 + , and Cs + Includes one or more of the following.

[0095] For example, C is Li+ na + , K + , Rb + , Cs + , and Ag + It includes at least one of the following.

[0096] For example, D is In 3+ , and Bi 3+ It includes at least one of the following.

[0097] For example, X' is F - Cl - , Br - , and I - It includes one or more of the following. Preferably, X' is Cl - , Br - , and I - Includes one or more of the following.

[0098] In some examples, the perovskite material includes, but is not limited to, one or more of the following: CH3NH3PbI3 (MAPbI3), CH(NH2)2PbI3 (FAPbI3), CsPbI3, CsPbI2Br, CsPbIBr2, Cs2NaInCl6, Cs2KBiCl6, and Cs2AgInCl6.

[0099] The thickness of the light-absorbing layer 3 is not particularly limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the light-absorbing layer 3 is 50 to 2000 nm.

[0100] The electron transport layer 4 includes an electron transport material. The type of electron transport material is not particularly limited and can be selected according to actual requirements. For example, the electron transport material may include an organic electron transport material, an inorganic electron transport material, or an organic-inorganic hybrid electron transport material.

[0101] In some examples, the electron transport material may include one or more of the following: imide compounds, quinone compounds, fullerenes and their derivatives, second metal oxides, silicon dioxide, strontium titanate (SrTiO3), calcium titanate (CaTiO3), lithium fluoride (LiF), and calcium fluoride (CaF2). Preferably, the metal elements in the second metal oxide may include one or more of the following: Mg, Cd, Zn, In, Pb, W, Sb, Bi, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr.

[0102] Preferably, the electron transport material is SnO2, TiO2, [6,6]-phenyl C 61 - Methylbutyrate (PC 61 BM), [6,6]-phenyl C 71 - Methylbutyrate (PC 71 The electron transport material may contain one or more of BM), fullerene C60, and fullerene C70. When the electron transport material falls within the above range, its energy level at the lower end of the conduction band is better matched with the energy level at the lower end of the conduction band of the light absorption layer, which is advantageous for accelerating electron transport.

[0103] The thickness of the electron transport layer 4 is not particularly limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the electron transport layer 4 is 1 to 300 nm.

[0104] The hole transport layer 2 contains a hole transport material. The type of hole transport material is not particularly limited and can be selected according to actual requirements.

[0105] In some examples, the hole transport material is 2,2',7,7'-tetrakis(N,N-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS), poly3-hexylthiophene (P3H T) may contain one or more of the following: triptycene-centered triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, phosphate monomolecules, carbazole monomolecules, sulfonic acid monomolecules, triphenylamine monomolecules, aromatic monomolecules, and tertiary metal oxides and cuprous thiocyanate (CuSCN). Preferably, the metal element in the tertiary metal oxide may contain one or more of Ni, Mo, and Cu.

[0106] The thickness of the hole transport layer 2 is not particularly limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the hole transport layer 2 is 5 to 1000 nm.

[0107] In some embodiments, when the passivation layer 6 is located between the hole transport layer 2 and the light absorption layer 3, the upper valence band (VBM) energy level of the light absorption layer 3 < the upper valence band (VBM) energy level of the passivation layer 6 < the upper valence band (VBM) energy level of the hole transport layer 2. This is advantageous for better hole transport.

[0108] In some embodiments, when the passivation layer 6 is located between the electron transport layer 4 and the light absorption layer 3, the lower conduction band (CBM) energy level of the electron transport layer 4 < the lower conduction band (CBM) energy level of the passivation layer 6 < the lower conduction band (CBM) energy level of the light absorption layer 3. This is advantageous for better electron transport.

[0109] The energy band distribution of each film layer can be measured using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS).

[0110] In some embodiments, the electrode materials of the first electrode 1 and the second electrode 5 may 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 may each include one or more of conductive polymers, metals, transparent metal conductive oxides, carbon, and its derivatives. Exemplarily, the electrode material of either the first electrode 1 or the second electrode 5 may each independently include one or more of poly(3,4-ethylenedioxythiophene) (PEDOT), polythiophene, polyacetylene, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimond-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 its derivatives.

[0111] In some embodiments, the electrode material of either the first electrode 1 or the second electrode 5 may contain a transparent metal conductive oxide, preferably one or more of the following: fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimond-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).

[0112] In some embodiments, the perovskite battery further includes a substrate, such as a glass substrate. A transparent metal conductive oxide may be provided on the surface of the substrate.

[0113] In some embodiments, the electrode material of either the first electrode 1 or the second electrode 5 may contain one or more of metals, carbon, and its derivatives, preferably one or more of gold, silver, aluminum, copper, carbon, and its derivatives.

[0114] The thickness of the first electrode 1 is not particularly limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the first electrode 1 is 10 nm to 500 nm.

[0115] The thickness of the second electrode 5 is not particularly limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the second electrode 5 is 10 nm to 500 nm.

[0116] The perovskite battery according to the embodiment of the present application may be a normal structure (nip) type battery or an inverse structure (pin) type battery.

[0117] In some embodiments, as shown in Figure 1, the first electrode 1 is the light-receiving side, and the perovskite battery (inverse structure battery) includes, in order, the first electrode 1, a hole transport layer 2, a passivation layer 6, a light absorption layer 3, an electron transport layer 4, and a second electrode 5. In some embodiments, as shown in Figure 2, the first electrode 1 is the light-receiving side, and the perovskite battery (inverse structure battery) includes, in order, the first electrode 1, a hole transport layer 2, a light absorption layer 3, a passivation layer 6, an electron transport layer 4, and a second electrode 5. In some embodiments, as shown in Figure 1, the first electrode 1 is the light-receiving side, and the perovskite battery (inverse structure battery) includes, in order, the first electrode 1, a hole transport layer 2, a passivation layer 6, a light absorption layer 3, a passivation layer 6, an electron transport layer 4, and a second electrode 5.

[0118] In some embodiments, as shown in Figure 4, the second electrode 5 is the light-receiving side, and the perovskite battery (normal structure battery) comprises, in order, the second electrode 5, electron transport layer 4, passivation layer 6, light absorption layer 3, hole transport layer 2, and first electrode 1. In some embodiments, as shown in Figure 5, the second electrode 5 is the light-receiving side, and the perovskite battery (normal structure battery) comprises, in order, the second electrode 5, electron transport layer 4, light absorption layer 3, passivation layer 6, hole transport layer 2, and first electrode 1. In some embodiments, as shown in Figure 6, the second electrode 5 is the light-receiving side, and the perovskite battery (normal structure battery) comprises, in order, the second electrode 5, electron transport layer 4, passivation layer 6, light absorption layer 3, passivation layer 6, hole transport layer 2, and first electrode 1.

[0119] Preferably, the passivation layer 6 is located between the charge transport layer and the light absorption layer, closer to the light-receiving side. In the case of a normal structure battery, the charge transport layer is an electron transport layer, and in the case of an inverse structure battery, the charge transport layer is a hole transport layer. In this case, since the light absorption layer is deposited after the passivation layer, the passivation layer can further promote the crystal growth of the perovskite material, thereby enabling the perovskite battery to have a higher energy conversion efficiency.

[0120] In some embodiments, the first electrode 1 is the light-receiving side, and the perovskite battery (inverse structure battery) includes, in order, the first electrode 1, a hole transport layer 2, a passivation layer 6, a light absorption layer 3, an electron transport layer 4, and a second electrode 5. The passivation layer 6 includes an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide. The content of the organic molecular passivation material is 10 to 30 wt%, preferably 15 to 25 wt%, relative to the total weight of the passivation layer, and the metal oxide semiconductor material includes one or more of intrinsic metal oxide semiconductor materials and P-type metal oxide semiconductor materials, preferably NiO x (1≦x≦2), CeO x (1≦x≦2), may include one or more of MoO3, NiMgLiO, CuGaO2, CuGrO2, CuO, Cu2O, and their respective doping materials.

[0121] In some embodiments, the second electrode 5 is the light-receiving side, and the perovskite battery (normal structure battery) includes, in order, the second electrode 5, electron transport layer 4, passivation layer 6, light absorption layer 3, passivation layer 6, hole transport layer 2, and first electrode 1. The passivation layer 6 includes an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide. The content of the organic molecular passivation material is 10 to 30 wt%, preferably 15 to 25 wt%, relative to the total weight of the passivation layer. The metal oxide semiconductor material includes one or more intrinsic metal oxide semiconductor materials and N-type metal oxide semiconductor materials, and preferably includes one or more of SnO2, TiO2, ZnO, and their respective doping materials.

[0122] The perovskite battery according to the embodiment of the present application is not limited to the above structure and may further include other functional layers.

[0123] Perovskite batteries can be manufactured by methods known in the art.

[0124] As shown in Figures 1 to 3, an exemplary manufacturing 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 further forming a light absorption layer 3 after forming a passivation layer 6 on the hole transport layer 2, and / or further forming an electron transport layer 4 after forming a passivation layer 6 on the light absorption layer 3.

[0125] As shown in Figures 4 to 6, another exemplary manufacturing 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 further forming a hole transport layer 2 after forming a passivation layer 6 on the light absorption layer 3, and / or further forming a light absorption layer 3 after forming a passivation layer 6 on the electron transport layer 4.

[0126] The method for forming each of the above film layers is not particularly limited, and methods known in the art, such as chemical bath deposition, chemical vapor deposition, electrochemical deposition, physical epitaxial deposition, vacuum deposition, atomic layer deposition, magnetron sputtering, precursor solution spin coating, precursor solution slot die coating, precursor solution blade coating, mechanical pressing, sol-gel method, and pulsed laser deposition, can be applied. Preferably, vacuum deposition and precursor solution spin coating can be used.

[0127] The perovskite battery according to the embodiment of the present application can be used alone as a single-junction perovskite battery, or it may be combined with a perovskite or other type of solar cell to form a tandem battery. Examples include a perovskite-perovskite tandem battery or a perovskite-crystalline silicon tandem battery.

[0128] The present invention further provides a photovoltaic assembly according to an embodiment of the present invention, the photovoltaic assembly comprising a perovskite cell according to an embodiment of the present invention, the perovskite cell being used as a power source for the photovoltaic assembly after undergoing processes such as series-parallel connection and sealing.

[0129] In some embodiments, the photovoltaic assembly includes a single-junction perovskite cell, a perovskite-perovskite tandem cell, or a perovskite-crystalline silicon tandem cell according to embodiments of the present application.

[0130] Examples The following examples provide a more detailed description of the contents disclosed herein, but these examples are merely illustrative, as various modifications and changes made within the scope of the contents disclosed herein will be obvious to those skilled in the art. Unless otherwise specified, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without processing, and all equipment used in the examples is commercially available.

[0131] Example 1-1 Manufacturing of FTO electrodes A glass substrate with FTO (Fiber Tone Oxide) measuring 2.0 cm x 2.0 cm is prepared. The substrate surface is then sequentially washed twice each with acetone and isopropanol. After that, it is immersed in deionized water and subjected to ultrasonic treatment for 10 minutes, then dried in a forced-air dryer, and finally stored in a glove box (N2 atmosphere).

[0132] Manufacturing of electron transport layers A 3 wt% SnO2 nanocolloid aqueous solution was spin-coated onto an FTO layer at 4000-6500 rpm, and then heated on a constant-temperature hot plate at 150°C for 15 minutes to form an electron transport layer with a thickness of 50 nm.

[0133] Manufacturing of passivation layers A mixture of 2 wt% TiO2 nanocolloid-isopropanol solution, 0.2 mg / mL 2PACz-isopropanol solution, and 1 mg / mL KCl-isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 17 nm was formed by heating on a constant temperature hot plate at 100°C for 10 minutes. The weight content of each component in the passivation layer is shown in Table 1.

[0134] Manufacturing of light-absorbing layer A 1.5 mol / L DMF solution of FAPbI3 was spin-coated onto the passivation layer at 3000-4500 rpm. Then, it was heated on a constant-temperature hot plate at 100°C for 30 minutes, followed by cooling to room temperature to form a 500 nm thick light-absorbing layer.

[0135] Hole transport layer manufacturing A chlorobenzene solution of Spiro-OMeTAD at a concentration of 73 mg / mL was spin-coated onto a light-absorbing layer at 3000-4000 rpm to form a hole transport layer with a thickness of 150 nm.

[0136] Manufacturing of popular electrodes The aforementioned sample is placed in a vacuum deposition apparatus, 5 × 10 -4 An Ag electrode was deposited on the surface of the hole transport layer under a vacuum of Pa. The deposition rate was 0.1 Å / s, and the thickness was 80 nm.

[0137] The structure of the perovskite cell finally obtained in Example 1-1 is FTO / SnO2 / TiO2+2PACz+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0138] Examples 1-2 to 1-6 The manufacturing of the perovskite cell is the same as in Example 1-1, except for the difference in the weight content of each component in the passivation layer. Please refer to Table 1 for specific parameters.

[0139] Examples 1-7 to 1-11 Aside from the difference in the thickness of the passivation layer, the manufacturing of the perovskite battery is the same as in Example 1-1. Please refer to Table 1 for specific parameters.

[0140] Examples 1-12 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0141] A mixture of 2 wt% TiO2 nanocolloid-isopropanol solution and 0.2 mg / mL 2PACz-isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 15 nm was formed by heating on a constant-temperature hot plate at 150°C for 30 minutes. Table 1 shows the weight content of each component in the passivation layer.

[0142] The structure of the perovskite cell finally obtained in Examples 1-12 is FTO / SnO2 / TiO2+2PACz / FAPbI3 / Spiro-OMeTAD / Ag.

[0143] Examples 1-13 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0144] A mixture of 2 wt% TiO2 nanocolloid-isopropanol solution and 1 mg / mL KCl-isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 15 nm was formed by heating on a constant-temperature hot plate at 100°C for 10 minutes. Table 1 shows the weight content of each component in the passivation layer.

[0145] The structure of the perovskite cell finally obtained in Examples 1-13 is FTO / SnO2 / TiO2+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0146] Examples 1-14 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0147] A mixture of 0.2 mg / mL 2PACz-isopropanol solution and 1 mg / mL KCl-isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 4 nm was formed by heating on a constant-temperature hot plate at 100°C for 10 minutes. Table 1 shows the weight content of each component in the passivation layer.

[0148] Examples 1-14: The structure of the perovskite cell finally obtained is FTO / SnO2 / 2PACz+KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0149] Comparative Example 1-1 The manufacturing of the perovskite battery is the same as in Example 1-1, except that it does not include a passivation layer.

[0150] The structure of the perovskite battery finally obtained in Comparative Example 1-1 is FTO / SnO2 / FAPbI3 / Spiro-OMeTAD / Ag.

[0151] Comparative Example 1-2 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0152] A 2 wt% TiO2 nanocolloid-isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm, and then heated on a constant-temperature hot plate at 100°C for 10 minutes to form a passivation layer with a thickness of 13 nm.

[0153] The structure of the perovskite battery finally obtained in Comparative Examples 1-2 is FTO / SnO2 / TiO2 / FAPbI3 / Spiro-OMeTAD / Ag.

[0154] Comparative Examples 1-3 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0155] A 0.2 mg / mL 2PACz isopropanol solution was spin-coated onto the electron transport layer at 5000-6000 rpm, and then heated on a constant temperature hot plate at 100°C for 10 minutes to obtain a passivation layer with a thickness of 2 nm.

[0156] The structure of the perovskite cell finally obtained in Comparative Examples 1-3 is FTO / SnO2 / 2PACz / FAPbI3 / Spiro-OMeTAD / Ag.

[0157] Comparative Example 1-4 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 1-1.

[0158] An electron transport layer was spin-coated with a 1 mg / mL KCl isopropanol solution at 5000-6000 rpm, and then heated on a constant temperature hot plate at 100°C for 10 minutes to obtain a passivation layer with a thickness of 2 nm.

[0159] The structure of the perovskite cell finally obtained in Comparative Examples 1-4 is FTO / SnO2 / KCl / FAPbI3 / Spiro-OMeTAD / Ag.

[0160] Test method Under atmospheric conditions of 25°C, sunlight was simulated using an AM1.5G standard light source. The current-voltage characteristic curve of a perovskite cell irradiated by the light source was measured using a 4-channel digital source meter (Keithley 2440). The open-circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) of the perovskite cell were obtained, and the energy conversion efficiency (Eff) of the perovskite cell was calculated from these values.

[0161] Eff = Pout / Popt = Voc×Jsc×(Vmpp×Jmpp) / (Voc×Jsc) = Voc×Jsc×FF.

[0162] However, Pout, Popt, Vmpp, and Jmpp are the operating output power, incident light output, maximum power point voltage, and maximum power point current density of the perovskite cell, respectively.

[0163] Table 1 shows the test results for Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-4.

[0164] Table 1 JPEG2026511540000002.jpg254152

[0165] Example 2-1 Manufacturing of FTO electrodes Prepare a glass substrate with FTO (Fiber Tone Oxide) measuring 2.0 cm x 2.0 cm. Wash the substrate surface twice each with acetone and isopropanol, then immerse it in deionized water and perform ultrasonic cleaning for 10 minutes. Finally, dry it in a forced-air dryer and store it in a glove box (N2 atmosphere).

[0166] Manufacturing of electron transport layers A 3 wt% SnO2 nanocolloid aqueous solution was spin-coated onto an FTO layer at 4000-6500 rpm, and then heated on a constant-temperature hot plate at 150°C for 15 minutes to form an electron transport layer with a thickness of 50 nm.

[0167] Manufacturing of light-absorbing layer A 1.5 mol / L FAPbI3 DMF solution was spin-coated onto the electron transport layer at 3000-4500 rpm. The layer was then heated on a constant-temperature hot plate at 100°C for 30 minutes, followed by cooling to room temperature to form a 500 nm thick light-absorbing layer.

[0168] Manufacturing of passivation layers A solution prepared by mixing 2 wt% CuO nanocolloid-isopropanol solution, 0.2 mg / mL PEAI-isopropanol solution, and 1 mg / mL CuI-isopropanol solution was spin-coated onto a light-absorbing layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 17 nm was formed by heating on a constant-temperature hot plate at 100°C for 10 minutes. The weight content of each component in the passivation layer is shown in Table 2.

[0169] Hole transport layer manufacturing A chlorobenzene solution of Spiro-OMeTAD at a concentration of 73 mg / mL was spin-coated onto a passivation layer at 3000-4000 rpm to form a hole transport layer with a thickness of 150 nm.

[0170] Manufacturing of popular electrodes The aforementioned sample is placed in a vacuum deposition apparatus, 5 × 10 -4 An Ag electrode was deposited on the surface of the hole transport layer under a vacuum of Pa. The deposition rate was 0.1 Å / s, and the thickness was 80 nm.

[0171] The structure of the perovskite cell finally obtained in Example 2-1 is FTO / SnO2 / FAPbI3 / CuO+PEAI+CuI / Spiro-OMeTAD / Ag.

[0172] Example 2-2 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0173] A mixture of 2 wt% CuO nanocolloid-isopropanol solution and 1 mg / mL CuI-isopropanol solution was spin-coated onto a light-absorbing layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 15 nm was formed by heating on a constant-temperature hot plate at 150°C for 30 minutes. Table 2 shows the weight content of each component in the passivation layer.

[0174] The structure of the perovskite cell finally obtained in Example 2-2 is FTO / SnO2 / FAPbI3 / CuO+PEAI / Spiro-OMeTAD / Ag.

[0175] Examples 2-3 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0176] A mixture of 2 wt% CuO nanocolloid-isopropanol solution and 1 mg / mL CuI-isopropanol solution was spin-coated onto a light-absorbing layer at 5000-6000 rpm. The mixture was then heated on a constant-temperature hot plate at 100°C for 10 minutes to form a passivation layer with a thickness of 15 nm. Table 2 shows the weight content of each component in the passivation layer.

[0177] The structure of the perovskite cell finally obtained in Example 2-3 is FTO / SnO2 / FAPbI3 / CuO+CuI / Spiro-OMeTAD / Ag.

[0178] Examples 2-4 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0179] A mixture of 0.2 mg / mL PEAI isopropanol solution and 1 mg / mL CuI-isopropanol solution was spin-coated onto the light-absorbing layer at 5000-6000 rpm. Subsequently, a passivation layer with a thickness of 4 nm was formed by heating on a constant-temperature hot plate at 100°C for 10 minutes. Table 2 shows the weight content of each component in the passivation layer.

[0180] The structure of the perovskite cell finally obtained in Examples 2-4 is FTO / SnO2 / FAPbI3 / PEAI+CuI / Spiro-OMeTAD / Ag.

[0181] Comparative Example 2-1 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0182] A 2 wt% CuO nanocolloid-isopropanol solution was spin-coated onto a light-absorbing layer at 5000-6000 rpm, and then heated on a constant-temperature hot plate at 100°C for 10 minutes to form a passivation layer with a thickness of 13 nm.

[0183] The structure of the perovskite battery finally obtained in Comparative Example 2-1 is FTO / SnO2 / FAPbI3 / CuO / Spiro-OMeTAD / Ag.

[0184] Comparative Example 2-2 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0185] A 0.2 mg / mL isopropanol solution of PEAI was spin-coated onto a light-absorbing layer at 5000-6000 rpm, and then heated on a constant-temperature hot plate at 100°C for 10 minutes to obtain a passivation layer with a thickness of 2 nm.

[0186] The structure of the perovskite battery finally obtained in Comparative Example 2-2 is FTO / SnO2 / FAPbI3 / PEAI / Spiro-OMeTAD / Ag.

[0187] Comparative Example 2-3 Except for the difference in the manufacturing of the passivation layer, the manufacturing of the perovskite cell is the same as in Example 2-1.

[0188] A 1 mg / mL CuI isopropanol solution was spin-coated onto a light-absorbing layer at 5000-6000 rpm, and then heated on a constant-temperature hot plate at 100°C for 10 minutes to obtain a passivation layer with a thickness of 2 nm.

[0189] The structure of the perovskite battery finally obtained in Comparative Example 2-3 is FTO / SnO2 / FAPbI3 / CuI / Spiro-OMeTAD / Ag.

[0190] Table 2 shows the test results for Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3. The test method for the perovskite battery is the same as for Examples 1-1 to 1-14.

[0191] Table 2 JPEG2026511540000003.jpg146170

[0192] As can be seen from the test results in Tables 1 and 2, in Comparative Examples 1-2 to 1-4 and Comparative Examples 2-1 to 2-3, organic molecular passivation materials, metal oxide semiconductor materials, or metal halides were used as passivation layers, respectively, but the effect of improving the energy conversion efficiency of the perovskite battery compared to Comparative Example 1-1 was not clear.

[0193] In Comparative Examples 1-2 and 2-1, a metal oxide semiconductor material was used as the passivation layer. Although metal oxide semiconductor materials have high structural stability, there are limits to their effect in improving the quality of the perovskite crystal. In particular, in Comparative Example 2-1, since the passivation layer was formed after the light absorption layer, the effect of improving the quality of the perovskite crystal was further reduced, and the effect of improving the energy conversion efficiency of the perovskite battery was not clear.

[0194] In Comparative Examples 1-3 and 2-2, organic molecular passivation materials were used as the passivation layer. However, due to the inferior structural stability of the organic molecular passivation materials, the effect of improving the energy conversion efficiency of the perovskite battery was not clear.

[0195] In Comparative Examples 1-4 and 2-3, metal halides were used as passivation layers. However, KCl has limited carrier transport capacity, so its effect on improving the energy conversion efficiency of perovskite batteries was not clear. CuI has limited interfacial passivation effect, so its effect on improving the energy conversion efficiency of perovskite batteries was not clear.

[0196] As can be seen from the test results in Tables 1 and 2, when a passivation layer is provided between the hole transport layer and the light absorption layer, and / or between the electron transport layer and the light absorption layer, and the passivation layer contains at least two of the following: organic molecular passivation material, metal oxide semiconductor material, and metal halide, the passivation layer simultaneously provides the effects of energy level matching, interface passivation, and optimization of the crystal quality of the perovskite material, thereby contributing to an improvement in the energy conversion efficiency of the perovskite battery.

[0197] Furthermore, as can be seen from the test results in Tables 1 and 2, the energy conversion efficiency of perovskite batteries is further improved when the passivation layer contains an organic molecular passivation material and a metal oxide semiconductor material and / or a metal halide. This is because the organic molecular passivation material can serve as both an interfacial adhesive and a defect passivation agent. Therefore, this material strengthens the interfacial contact between the light absorption layer and the charge transport layer, and the coordination effect of the organic molecular passivation material reduces the defect level density in the bulk phase and interface of the perovskite material, thereby improving the film deposition quality of the light absorption layer. Moreover, the insertion of the organic molecular passivation material into the bulk phase of the perovskite material exerts an anchoring effect, suppressing the deposition of halides from the perovskite material. Therefore, by using the organic molecular passivation material in combination with a metal oxide semiconductor material and / or a metal halide, non-radiative recombination at defect sites is further suppressed, and the energy conversion efficiency of perovskite batteries is further improved.

[0198] Furthermore, as can be seen from the test results in Tables 1 and 2, the energy conversion efficiency of the perovskite battery can be better improved by providing a passivation layer between the charge transport layer and the light absorption layer, which are closer to the light-receiving side. This is because the passivation layer can more effectively promote the crystallization of the perovskite material.

[0199] The above are merely specific embodiments of the present application, and the scope of protection of the present application is not limited thereto. A person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed herein, and all such modifications or substitutions should be included within 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. First electrode and The second electrode and 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 absorption layer, An electron transport layer located between the second electrode and the light absorption layer, A perovskite battery containing, The perovskite cell further includes a passivation layer, the passivation layer being located between the hole transport layer and the light absorption layer, and / or the passivation layer being located between the electron transport layer and the light absorption layer. The passivation layer comprises at least two of the following: an organic molecular passivation material, a metal oxide semiconductor material, and a metal halide, in a perovskite cell.

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

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

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

5. The passivation layer comprises an organic molecular passivation material and a metal halide. Preferably, the content of the organic molecular passivation material is 10 to 30 wt%, more preferably 15 to 25 wt%, relative to the total weight of the passivation layer. Preferably, the content of the metal halide is 70 to 90 wt%, more preferably 75 to 85 wt%, relative to the total weight of the passivation layer, in the perovskite battery according to claim 1 or 2.

6. The perovskite battery according to any one of claims 1 to 5, wherein the thickness of the passivation layer is 30 nm or less, preferably 1 to 22 nm.

7. The aforementioned organic molecular passivation material comprises one or more of alkylamines and their halogenated salts, aromatic amines and their halogenated salts, aromatic heterocyclic compounds, polymers, and their respective derivatives. Preferably, the aromatic heterocyclic compound comprises one or more nitrogen-containing aromatic heterocyclic rings and their derivatives, more preferably one or more carbazole, pyridine, piperidine and their respective derivatives. Preferably, the polymer comprises one or more of polyaniline, polypyridine, polypiperidine, and their respective derivatives, as described in any one of claims 1 to 6, the perovskite battery.

8. The aforementioned organic molecular passivation material includes one or more of the following: 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. Preferably, the perovskite battery according to claim 7 comprises one or more of the following: the organic molecular passivation material is [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, 2-phenylethylamine hydroiodide, and derivatives thereof.

9. The metal oxide semiconductor material comprises one or more of intrinsic metal oxide semiconductor materials, N-type metal oxide semiconductor materials, and P-type metal oxide semiconductor materials, preferably SnO ２ , TiO ２ ZnO, NiO ｘ , CEO ｘ MoO ３ , NiMgLiO, CuGaO ２ CuGrO ２ , CuO, Cu ２ A perovskite cell according to any one of claims 1 to 8, comprising O and one or more of the respective doping materials, wherein 1 ≤ x ≤ 2.

10. When the passivation layer is located between the hole transport layer and the light absorption 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, preferably NiO ｘ , CeO ｘ , MoO ３ , NiMgLiO, CuGaO ２ , CuGrO ２ , CuO, Cu ２ O, and includes one or more of each doping material, 1 ≤ x ≤ 2, When the passivation layer is located between the electron transport layer and the light absorption 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, preferably SnO ２ , TiO ２ The perovskite battery according to claim 9, comprising ZnO and one or more of the respective doping materials.

11. The perovskite battery according to any one of claims 1 to 10, wherein the particle size of the metal oxide semiconductor material is 100 nm or less, preferably 50 nm or less, and more preferably 5 to 10 nm.

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

13. The aforementioned metal halides are CsF, KCl, PbBr, CuI, and CuI ２ The perovskite battery according to claim 12, comprising one or more of the above, preferably comprising one or more of KCl and CuI.

14. The electron transport material in the electron transport layer comprises one or more of imide compounds, quinone compounds, fullerenes and their derivatives, second metal oxides, silicon dioxide, strontium titanate, calcium titanate, lithium fluoride, and calcium fluoride, and preferably the metal element in the second metal oxide comprises 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 comprises one or more of the following: 2,2',7,7'-tetrakis(N,N-methoxyanilino)-9,9'-spirobifluorene, methoxytriphenylamine-fluoroformamidine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid, poly3-hexylthiophene, triptycene-cored triphenylamine, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-anilino)carbazole-spirobifluorene, polythiophene, phosphate group monomolecule, carbazole group monomolecule, sulfonic acid group monomolecule, triphenylamine group monomolecule, aromatic group monomolecule, tertiary metal oxide, and cuprous thiocyanate, wherein the metal element in the tertiary metal oxide comprises one or more of Ni, Mo, and Cu, and / or The perovskite battery according to any one of claims 1 to 13, wherein 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 electrode materials of the first electrode and the second electrode each independently comprise an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material, preferably comprising one or more of the following: poly(3,4-ethylenedioxythiophene), polythiophene, polyacetylene, fluorine-doped tin oxide, indium tin oxide, antimond-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, carbon, and its derivatives, as described in any one of claims 1 to 14.

16. A photovoltaic assembly comprising a perovskite cell according to any one of claims 1 to 15.

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