Perovskite cell, stacked cell, photovoltaic module, electric device, and power generation device

Abstract

The present application relates to a perovskite cell, a stacked cell, a photovoltaic module, an electric device, and a power generation device. The perovskite cell comprises a perovskite thin film, the perovskite thin film comprises a perovskite material and a modifier, the modifier comprises lead iodide and an ammonium salt, and the ammonium salt comprises at least one of compounds having a structural formula as shown in formula (1): R1R2R3R4N+Y- (1), wherein in formula (1), R1 comprises one of substituted or unsubstituted C4-C20 alkyl groups; R2-R4 each independently comprise one of a hydrogen atom and a substituted or unsubstituted C1-C20 alkyl group; Y- comprises a halogen ion and / or a pseudohalide ion, and N is a nitrogen atom.

Description

Perovskite cell, laminated cell, photovoltaic module, power consuming device and power generating device Cross-reference to related applications

[0001] This application is based on Chinese Patent Application No. 202410864578.5, filed on June 28, 2024, entitled “Perovskite cell, laminated cell, photovoltaic module, power consuming device and power generating device”, which is incorporated by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of solar cells, in particular to a perovskite cell, a laminated cell, a photovoltaic module, a power consuming device and a power generating device. BACKGROUND

[0003] Perovskite solar cells are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite-type crystal materials. They are the third generation of solar cells and have many advantages such as high photoelectric conversion efficiency, simple manufacturing process, and low production cost. In recent years, they have been extensively studied. However, there is still a certain distance to the commercialization and large-scale application of perovskite cells. One of the key problems to be solved is how to improve the stability of perovskite cells. SUMMARY

[0004] In view of the above problems, in a first aspect, the present application provides a perovskite cell, which includes a perovskite thin film, the perovskite thin film comprising a perovskite material and a modifier, the modifier comprising lead iodide and an ammonium salt, the ammonium salt comprising at least one of the compounds having the structural formula shown in the following formula (1):

[0005] R1R2R3R4N + Y - (1);

[0006] In formula (1), R1 comprises one of substituted or unsubstituted C4-C20 alkyl, and R2-R4 each independently comprises one of hydrogen atom, substituted or unsubstituted C1-C20 alkyl;

[0007] Y - comprising halogen ions and / or halogen-like ions, and N is a nitrogen atom.

[0008] The perovskite battery provided in the application includes a perovskite thin film, and the perovskite thin film contains a modifier, and the modifier contains lead iodide and an ammonium salt, and the ammonium salt includes at least one of a compound having a structural formula shown in formula (1), and the carbon chains corresponding to R1 and the carbon chains possibly present in R2-R4 can effectively reduce the surface tension of a precursor solution used for preparing the perovskite thin film, improve the uniformity of solute (including a precursor material for forming a perovskite material and excess lead iodide) distribution in the precursor solution, and thus improve the uniformity of the distribution of the excess lead iodide in the perovskite crystallization process. At the same time, the ammonium salt can also form a complex with the excess lead iodide, that is, the crystallization rate of the lead iodide can be slowed down by coordinating the ammonium salt with Pb, so that the excess lead iodide is uniformly distributed in the grain boundary when crystallizing instead of accumulating into large particles, and thus the uniformity of the distribution of the excess lead iodide in the perovskite thin film can be further effectively improved, thereby facilitating the improvement of the stability of the perovskite battery.

[0009] In some embodiments, one or both of the following conditions are met:

[0010] (1) the halide ion comprises one or more of Cl - , Br - , I - , and F - ;

[0011] (2) the pseudohalide ion comprises one or more of CN - , SCN - , OCN - , N3 - , CF4SO4 - , HCOO - , C6H5S - , CH3COO - , CF3COO - , BH4 - , CH3S - , ClO4 - , BF4 - , and BCl4 - .

[0012] In the ammonium salt, the halide ion or the pseudohalide ion can play a certain passivation role on the A ion site defects of the perovskite material, thereby facilitating the reduction of the perovskite bulk phase defects and the improvement of the crystallization quality of the perovskite thin film.

[0013] In some embodiments, the substituted substituents each independently include one or more of a carboxyl group, a hydroxyl group, a sulfonic acid group, a phenyl group, and a methoxy group.

[0014] In some embodiments, R1 comprises one of substituted or unsubstituted C4-C16 alkyl, and each of R2-R4 independently comprises one of hydrogen atom, substituted or unsubstituted C1-C16 alkyl. In this way, the crystallization quality of the perovskite thin film is further improved, and the photoelectric conversion efficiency and stability of the perovskite cell are further improved.

[0015] In some embodiments, the ammonium salt comprises one or more of butyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium cyanide, dodecyl dimethyl benzyl ammonium bromide, dodecyl dimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium chloride, and hexadecyl tributyl ammonium bromide.

[0016] In some embodiments, the molar ratio of the lead iodide to the perovskite material in the perovskite thin film is (5-15):100.

[0017] In some embodiments, the molar ratio of the lead iodide to the perovskite material in the perovskite thin film is (5-10):100.

[0018] In this way, the lead iodide is in excess, and the excess lead iodide is coordinated with the ammonium salt, which slows down the crystallization rate by coordinating the ammonium salt with Pb, and makes the excess lead iodide uniformly distributed in the grain boundary during crystallization, reducing the accumulation of lead iodide particles. In this way, the uniformity of the distribution of the excess lead iodide is effectively improved, thereby improving the stability of the perovskite cell.

[0019] In some embodiments, the molar ratio of the lead iodide to the ammonium salt in the perovskite thin film is (10-150):1.

[0020] In some embodiments, the molar ratio of the lead iodide to the ammonium salt in the perovskite thin film is (30-80):1.

[0021] In this way, the lead iodide and the ammonium salt can form better coordination, further slowing down the crystallization rate, and making the excess lead iodide more uniformly distributed in the grain boundary during crystallization, thereby further improving the stability of the perovskite cell.

[0022] In some embodiments, the composition of the perovskite material comprises ABX3, wherein A ion is a monovalent cation, B ion is a divalent metal cation, and X ion is a monovalent anion, wherein the A ion comprises one or more of organic cation, Li + , Na + , K + , Rb + , and Cs + ; and the B ion comprises Pb 2+ , Sn 2+one or more of Be 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ Zn 2+ Ge 2+ Fe 2+ Co 2+ Cu 2+ and Ni 2+ ; the X ion comprises one or more of F - Cl - Br - I - CN - SCN - OCN - N3 - CF4SO4 - HCOO - C6H5S - CH3COO - CF3COO - BH4 - CH3S - ClO4 - BF4 - and BCI4 - .

[0023] In some embodiments, the organic cation comprises one or more of methylamine ion, ethylamine ion, propylamine ion, butylamine ion, pentylamine ion, hexylamine ion, formamidinium ion, and imidazolium ion.

[0024] In some embodiments, the composition of the perovskite material comprises APb x1 B’ 1-x1 X3, 0 < x1< 1, B’ comprises one or more of Sn 2+ Be 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ Zn 2+ Ge 2+ Fe 2+ Co 2+ Cu 2+ and Ni 2+ .

[0025] In some embodiments, the composition of the perovskite material comprises Cs y FA 1-y Pb x2 B’ 1-x2 Iz Br 3-z , 0 < y < 1, 0 < x2 < 1, 0 < z < 3, and FA is formamidinium.

[0026] In some embodiments, the perovskite thin film comprises perovskite grains, the perovskite grains comprise the perovskite material, and the average grain size of the perovskite grains is 1 μm to 2 μm.

[0027] In this way, the micron-sized grains facilitate a reduction in the number of grain boundaries, which can reduce the defect density in the perovskite thin film, improve the crystalline quality of the thin film, reduce non-radiative recombination of holes and electrons, and improve the performance of the perovskite cell.

[0028] In some embodiments, the perovskite cell further comprises a first electrode layer, a first charge transport layer, a second charge transport layer, and a second electrode layer arranged in layers, and the perovskite thin film is disposed between the first charge transport layer and the second charge transport layer.

[0029] In a second aspect, the present application provides a method for preparing a perovskite cell, comprising a step of preparing a perovskite thin film, the step of preparing the perovskite thin film comprising:

[0030] According to the composition of the perovskite material, a precursor material corresponding to the composition of the perovskite material is prepared, mixed with a modifier and a solvent to prepare a precursor solution; wherein the modifier comprises lead iodide and an ammonium salt, and the ammonium salt comprises at least one of the compounds having the structural formula shown in formula (1) below:

[0031] R1R2R3R4N + Y - (1),

[0032] In formula (1), R1 comprises one of substituted or unsubstituted C4 to C20 alkyl groups, R2 to R4 each independently comprise one of hydrogen atoms, substituted or unsubstituted C1 to C20 alkyl groups; Y - comprises halide ions and / or halide-like ions, and N is a nitrogen atom;

[0033] The precursor solution is shaped and annealed to prepare the perovskite thin film.

[0034] The modifier comprises lead iodide and an ammonium salt, the ammonium salt comprising at least one of the compounds having the structural formula shown in formula (1), the carbon chain corresponding to R1 in the compound, and the carbon chains possibly present in R2 to R4, can effectively reduce the surface tension of the precursor solution for preparing the perovskite thin film, improve the uniformity of the distribution of the solute (which comprises the precursor material for forming the perovskite material and the excess lead iodide) in the precursor solution, thereby improving the uniformity of the distribution of the excess lead iodide in the perovskite crystallization process. At the same time, the ammonium salt can also form a complex with the excess lead iodide, that is, the crystallization rate of the lead iodide can be slowed down by coordinating the ammonium salt with Pb, so that the excess lead iodide is uniformly distributed in the grain boundary when crystallizing, instead of accumulating into large particles, which can further effectively improve the uniformity of the distribution of the excess lead iodide in the perovskite thin film, thereby facilitating the improvement of the stability of the perovskite battery.

[0035] In a third aspect, the present application provides a stacked battery comprising the perovskite battery of the first aspect of the present application or the perovskite battery prepared by the method of the second aspect of the present application.

[0036] In a fourth aspect, the present application provides a photovoltaic module comprising the perovskite battery of the first aspect of the present application, the perovskite battery prepared by the method of the second aspect of the present application or the stacked battery of the third aspect of the present application.

[0037] In a fifth aspect, the present application provides an electrical device comprising at least one of the perovskite battery of the first aspect of the present application, the perovskite battery prepared by the method of the second aspect of the present application, the stacked battery of the third aspect of the present application and the photovoltaic module of the fourth aspect of the present application.

[0038] In a sixth aspect, the present application provides a power generation device comprising at least one of the perovskite battery of the first aspect of the present application, the perovskite battery prepared by the method of the second aspect of the present application, the stacked battery of the third aspect of the present application and the photovoltaic module of the fourth aspect of the present application.

[0039] The details of one or more embodiments of the application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the application will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF DRAWINGS

[0040] To better describe and illustrate the embodiments or examples of the application disclosed herein, reference can be made to one or more drawings. Additional details or examples used to describe the drawings should not be considered limiting to the scope of the disclosed application, the presently described embodiments or examples, and the best mode of these applications as presently understood. Moreover, in all the drawings, like reference numerals refer to like parts throughout the various drawings. Among the drawings:

[0041] FIG. 1 is a schematic view of a structure of a perovskite cell according to an embodiment of the present application.

[0042] FIG. 2 is a schematic view of a structure of a perovskite cell according to an embodiment of the present application.

[0043] FIG. 3 is a surface morphology view of a perovskite thin film prepared in Example 1.

[0044] FIG. 4 is a surface morphology view of a perovskite thin film prepared in Comparative Example 1.

[0045] FIG. 5 is a schematic view of a power consuming device using a perovskite cell according to an embodiment of the present application as a power source.

[0046] BRIEF DESCRIPTION OF DRAWINGS DETAILED DESCRIPTION

[0047] Hereinafter, some embodiments of the perovskite cell, the stacked cell, the photovoltaic module, and the power consuming device according to the present application will be described in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed description is omitted. For example, there will be cases where detailed description of matters known well, repetitive description of substantially identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided so that those skilled in the art can fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0048] The ranges disclosed herein are intended to be "open" ranges, i.e., the upper and lower limits of the range are not included. The ranges are also intended to include any and all sub-ranges of the same, wherein each sub-range includes each integer within the range. For example, a range of 0-10 is intended to include any and all sub-ranges between (and including) the minimum value of zero and the maximum value of ten, that is, any one or a combination of the following sub-ranges: 1-10, 3-7, 5-6, and so on, in combination with each of the following: 0-10, 0.1-10, 1-10, 2-10, 3-10, 4-10, 5-10, 6-10, 7-10, 8-10, 9-10, 0-9, 0-8, 0-7, 0-6, 0-5, 0-4, 0-3, 0-2, 0-1, 1-2, 1-3, 2-4, 2-5, 3-5, 3-6, 4-7, 5-7, 6-8, 7-9, and so on, each and every sub-range of 0-10. The same applies to ranges having a lower limit of zero. Unless otherwise specifically stated, the scope of a range includes the minimum and maximum values of the range. It is specifically intended that the scope of each range include the minimum value and the maximum value, unless otherwise indicated.

[0049] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions.

[0050] Unless otherwise specified, all steps of the present application can be performed in sequence or randomly, preferably in sequence. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method also comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0051] In the present application, "a plurality of", "a plurality of", etc. are not specifically limited, which means more than two or equal to two in quantity. For example, "one or more" means one or more than two.

[0052] In the present application, the terms "first", "second", "third", "fourth" and the like in the "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are used only for descriptive purposes and cannot be construed as indicating or implying relative importance or quantity, nor can they be construed as implying the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration and description, and should be understood as not constituting a closed limitation on the quantity.

[0053] In the present application, the unit related to the data range, if only with the unit after the right end point, indicates that the units of the left end point and the right end point are the same. For example, 3-5h or 3-5h indicates that the units of the left end point "3" and the right end point "5" are both h (hours).

[0054] In the present application, the term "alkyl" refers to a saturated hydrocarbon containing carbon atoms, including straight-chain or straight-chain alkyl groups. "C1-C20" alkyl refers to an alkyl group containing 1-20 carbon atoms, which can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl or C20 alkyl each time it appears. "C4-C20" alkyl refers to an alkyl group containing 4-20 carbon atoms, which can be independently C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl or C20 alkyl each time it appears.

[0055] In the present application, the term "pseudohalide" also referred to as "pseudohalide", refers to a monovalent anion similar in nature and radius to halide.

[0056] In the present application, the term "phenyl" refers to a group with a benzene ring as a functional group.

[0057] In the preparation of perovskite cells, the perovskite layer usually needs to be passivated to reduce non-radiative recombination of the device and improve photoelectric conversion efficiency. One of the common means for passivating the perovskite layer is to add excess lead iodide (PbI2) to the precursor solution. The excess PbI2 can perform defect passivation at the grain boundaries and interfaces of the perovskite thin film during the formation of the perovskite thin film, reduce non-radiative recombination of the device, and thus improve photoelectric conversion efficiency. However, the excess PbI2 is prone to accumulate into particles during the crystallization process of the perovskite thin film, which reduces the crystallization quality of the perovskite thin film, affects the light absorption performance of the perovskite layer, and not only fails to achieve good passivation effect, but also reduces the stability of the perovskite cell. Currently, some technologies attempt to regulate the concentration of the perovskite precursor solution or the annealing time of the perovskite thin film to improve the uniformity of the distribution of the excess PbI2 to some extent, but the regulation space of this method is limited, and the excess PbI2 still has a serious accumulation phenomenon during the crystallization process of the thin film.

[0058] Based on this, the present application provides a perovskite cell. By coordinating the ammonium salt with the excess lead iodide, the ammonium salt can be used to improve the accumulation of the excess PbI2 and improve the uniformity of the distribution of the excess PbI2. In addition, the two together as a modifier of the perovskite thin film can also achieve good passivation effect, improve the crystallization quality of the perovskite thin film, and improve the stability of the perovskite cell.

[0059] In a first aspect, the present application provides a perovskite cell, which comprises a perovskite thin film, the perovskite thin film comprising a perovskite material and a modifier, the modifier comprising lead iodide and an ammonium salt, the ammonium salt comprising at least one of the compounds having the structural formula shown in the following formula (1):

[0060] R1R2R3R4N + Y - (1);

[0061] In formula (1), R1 comprises one of substituted or unsubstituted C4-C20 alkyl, R2-R4 each independently comprises one of hydrogen atom, substituted or unsubstituted C1-C20 alkyl; Y - comprises halide ion and / or halide-like ion, and N is nitrogen atom.

[0062] It can be understood that the "substituted C4-C20 alkyl" or "substituted C1-C20 alkyl" described in the present application means that at least one hydrogen atom in at least one of C4-C20 alkyl is substituted by a substituent; or at least one hydrogen atom in at least one of C1-C20 alkyl is substituted by a substituent.

[0063] The perovskite battery provided in the present application comprises a perovskite thin film, and the perovskite thin film comprises a modifier, and the modifier comprises lead iodide and an ammonium salt, and the ammonium salt comprises at least one of a compound having a structural formula shown in formula (1), and the carbon chain corresponding to R1 in the compound and the carbon chain possibly existing in R2-R4 can effectively reduce the surface tension of a precursor solution used for preparing the perovskite thin film, improve the uniformity of solute (which comprises a precursor material used for forming a perovskite material and excess lead iodide) distribution in the precursor solution, and thus improve the uniformity of the distribution of the excess lead iodide in the perovskite crystallization process. At the same time, the ammonium salt can also form a complex with the excess lead iodide, that is, the crystallization rate of the lead iodide can be slowed down by coordinating the ammonium salt with Pb, so that the excess lead iodide is uniformly distributed in the grain boundary when crystallizing instead of accumulating into large particles, and thus the uniformity of the distribution of the excess lead iodide in the perovskite thin film can be further effectively improved, thereby facilitating the improvement of the stability of the perovskite battery.

[0064] In this way, on the basis of the improvement of the uniformity of the distribution of the excess lead iodide, it is beneficial to the good passivation effect of the excess lead iodide on the grain boundary; at the same time, the anions and cations contained in the aforementioned compound can also play a certain passivation role (for example, the anions can passivate X ion site defects of the perovskite material, and the cations can passivate A ion site defects of the perovskite material). Therefore, the ammonium salt cooperates with the excess lead iodide to greatly reduce the defects of the perovskite phase, effectively reduce the defect density of the perovskite thin film, reduce the number of crystal nuclei, increase the grain size, improve the crystallization quality of the perovskite thin film, and simultaneously improve the photoelectric conversion efficiency and stability of the perovskite battery comprising the perovskite thin film.

[0065] In some embodiments, the substituents each independently include one or more of a carboxyl group (-COOH), a hydroxyl group (-OH), a sulfonic acid group (-SO3H), a phenyl group, and a methoxy group (CH3O-).

[0066] The substituents included in R1-R4 in the ammonium salt can be based on the properties of each substituent, so that the perovskite battery can be adapted to different application scenarios or use environments. For example, the carboxyl group or the sulfonic acid group can make the perovskite thin film have certain alkali resistance, and thus facilitate the use of the perovskite battery in an alkali environment to a certain extent.

[0067] In some embodiments, R2-R4 each independently includes one of a substituted or unsubstituted C1-C20 alkyl group. In this way, the chain length and molecular weight of the ammonium salt can be further increased, the surface tension of the precursor solution used for preparing the perovskite thin film can be further reduced, and the uniformity of the distribution of the excess lead iodide dispersed in the precursor solution can be further improved.

[0068] In some embodiments, R1comprises one of substituted or unsubstituted C4-C16 alkyl, and R2-R4each independently comprises one of hydrogen atom, substituted or unsubstituted C1-C16 alkyl. In this way, the crystalline quality of the perovskite thin film is further improved, and the photoelectric conversion efficiency and stability of the perovskite cell are further improved.

[0069] In some embodiments, the ammonium salt comprises one or more of tetrabutylammonium bromide, tetrabutylammonium cyanide, butylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl dimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium chloride, and hexadecyl tributyl ammonium bromide.

[0070] In some embodiments, the halogen ion comprises one or more of Cl - , Br - , I - , and F - . In the ammonium salt, the halogen ion can play a certain passivation effect on the A-site defects of the perovskite material, thereby helping to reduce the perovskite bulk phase defects and improve the crystalline quality of the perovskite thin film.

[0071] In some embodiments, the halogen-like ion comprises one or more of CN - , SCN - , OCN - , N3 - , CF4SO4 - , HCOO - , C6H5S - , CH3COO - , CF3COO - , BH4 - , CH3S - , ClO4 - , BF4 - , and BCl4 - . In the ammonium salt, the halogen-like ion can also play a certain passivation effect on the A-site defects of the perovskite material, thereby helping to reduce the perovskite bulk phase defects and improve the crystalline quality of the perovskite thin film.

[0072] In some embodiments, the molar ratio of lead iodide to perovskite material in the perovskite thin film is (5-15):100. For example, it can be 5:100, 6:100, 8:100, 10:100, 12:100, 13:100, 15:100, or any range consisting of the above values, such as (5-8):100, (6-15):100, (5-10):100.

[0073] In this way, the excess lead iodide can be distributed uniformly, on the one hand, which is conducive to the formation of complex of the excess lead iodide and the ammonium salt, slows down the crystallization rate by coordination of the ammonium salt and Pb, and makes the excess lead iodide uniformly distributed in the grain boundary during crystallization, thereby reducing the accumulation of lead iodide particles and effectively improving the uniformity of the distribution of the excess lead iodide, so as to improve the stability of the perovskite battery. On the other hand, the excess lead iodide also has a good passivation effect on the defects of the perovskite film, so that the size of the crystal grains contained in the film is increased and the crystallization quality of the film is improved.

[0074] In some embodiments, the molar ratio of the lead iodide to the perovskite material in the perovskite film is (5-10):100. For example, it can be 5:100, 6:100, 7:100, 8:100, 9:100, 10:100 or any range formed by any of the above values. In this way, on the one hand, the uniformity of the distribution of the excess lead iodide is further improved, so as to further improve the stability of the perovskite battery. On the other hand, the passivation effect of the excess lead iodide on the defects of the perovskite film is further improved, so that the crystallization quality of the film is further improved.

[0075] In some embodiments, the perovskite film contains perovskite crystal grains, the perovskite crystal grains contain perovskite material, and the average particle size of the perovskite crystal grains is 1-2 μm. For example, the average particle size of the perovskite crystal grains can be 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm or any range formed by any of the above values. In this way, the micron-level crystal grains are conducive to the reduction of the number of grain boundaries, which can reduce the defect density in the perovskite film, improve the crystallization quality of the film, reduce the non-radiative recombination of holes and electrons, and improve the performance of the perovskite battery.

[0076] For example, the average particle size of the perovskite crystal grains can be measured by the following method: SEM (scanning electron microscope) test is performed on the film surface of the perovskite film, any one crystal grain in the lens is selected, the length of the longest diagonal line of the crystal grain is measured and recorded as d1; in the same way, the lengths of the longest diagonal lines of ≥50 crystal grains (such as 100 crystal grains) are measured and the average value is calculated, which is taken as the average particle size of the perovskite crystal grains.

[0077] In some embodiments, the molar ratio of lead iodide to ammonium salt in the perovskite thin film is (10-150): 1. For example, the molar ratio of lead iodide to ammonium salt can be 150: 1, 120: 1, 100: 1, 90: 1, 80: 1, 70: 1, 60: 1, 50: 1, 40: 1, 30: 1, 20: 1, 10: 1, or within a range defined by any of the above values. In this way, better coordination between lead iodide and ammonium salt can be achieved, further slowing the crystallization rate and causing excess lead iodide to be more evenly distributed in the grain boundaries upon crystallization, thereby facilitating further improvement in the stability of the perovskite cell.

[0078] In some embodiments, the molar ratio of lead iodide to ammonium salt in the perovskite thin film is (30-80): 1. For example, the molar ratio of lead iodide to ammonium salt can be 80: 1, 70: 1, 65: 1, 55: 1, 45: 1, 35: 1, 30: 1, or within a range defined by any of the above values. In this way, better coordination between lead iodide and ammonium salt can be achieved, thereby facilitating further improvement in the stability of the perovskite cell.

[0079] In some embodiments, the molar ratio of lead iodide to ammonium salt in the perovskite thin film is (40-60): 1. In this way, better coordination between lead iodide and ammonium salt can be achieved, thereby facilitating further improvement in the stability of the perovskite cell.

[0080] In some embodiments, the perovskite material includes a composition of ABX3, where A is a monovalent cation, B is a divalent metal cation, and X is a monovalent anion.

[0081] In some embodiments, the A cation includes one or more of an organic cation, Li + , Na + , K + , Rb + , and Cs + .

[0082] In some embodiments, the organic cation includes one or more of (NR’1R’2R’3R’4) + , (R’1R’2N=CR’3R’4) + , (R’1R’2N-C(R’5)=NR’3R’4) + , and (R’1R’2N-C(NR’5R’6)=NR’3R’4) + , where R’1, R’2, R’3, R’4, R’5, and R’6 are each independently selected from H, a substituted or unsubstituted C1-C20 alkyl, or a substituted or unsubstituted aryl. Optionally, the organic amine ion includes a methylamine ion (CH3NH2 + , MA +), ethylamine ion, propylamine ion, butylamine ion, pentamine ion, hexamine ion, formamidinium ion (CH(NH2)2) + FA + At least one of ) and imidazole ions.

[0083] In some embodiments, B ions include Pb 2+ Sn 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Cu 2+ and Ni 2+ One or more of them.

[0084] In some embodiments, X ions include F - Cl - ,Br - I - CN - SCN - OCN - N3 - CF4SO4 - HCOO - C6H5S - CH3COO - CF3COO - BH4 - CH3S - ClO4 - BF4 - and BCl4 - One or more of them.

[0085] In some embodiments, the perovskite material comprises APb x1 B' 1-x1 X3, B' includes Sn 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Cu 2+ and Ni 2+ One or more of them, 0 <x1<1。

[0086] In some embodiments, the composition of the perovskite material includes Cs y FA 1-y Pb x2 B’ 1-x2 I z Br 3-z , 0 < y < 1, 0 < x2 < 1, 0 < z < 3, and FA is formamidinium.

[0087] As an example, the composition in the perovskite thin film can be tested by liquid chromatography-mass spectrometry (LC-MS). For example, the perovskite thin film can be dissolved in a polar organic solvent (e.g., propylene glycol), and then the composition (e.g., ammonium salt) contained in the thin film can be obtained by analyzing the resulting spectrum (analyzing the characteristic peaks in the spectrum). Meanwhile, by matching the EDS test, the content of each component in the perovskite thin film can be measured, so as to obtain the ratio between each component. For example, according to the content of the element corresponding to the A ion (i.e., A element), the content of the perovskite material can be calculated; according to the content of the nitrogen element, the content of the ammonium salt can be calculated; then, according to the content of the lead element and the content of the element corresponding to the A ion (i.e., A element), the content of the lead iodide can be calculated (the lead element can come from the lead iodide and the perovskite material, the content of the lead element is subtracted from the content of the lead in the perovskite material, and the remaining content of the lead corresponds to the content of the lead in the lead iodide, so the content of the lead iodide can be calculated).

[0088] In some embodiments, referring to FIG. 1, the perovskite cell further includes a first electrode layer 20, a first charge transport layer 30, a second charge transport layer 50, and a second electrode layer 60 which are stacked, and the perovskite thin film 40 is arranged between the first charge transport layer 30 and the second charge transport layer 50.

[0089] In some embodiments, referring to FIG. 2, the perovskite cell further includes a substrate layer 10, a first electrode layer 20, a first charge transport layer 30, a second charge transport layer 50, and a second electrode layer 60 which are stacked, and the perovskite thin film 40 is arranged between the first charge transport layer 30 and the second charge transport layer 50.

[0090] In this application, the perovskite thin film, which can also be referred to as a perovskite layer, can serve as a light-absorbing layer in the perovskite cell.

[0091] In some embodiments, the perovskite cell provided in this application can be any one of a trans-p-i-n cell and a formal n-i-p cell.

[0092] In some embodiments, one of the “first electrode” and the “second electrode” serves as the positive electrode and can collect the electron carriers transported via the electron transport layer, and the other serves as the negative electrode and can collect the hole carriers transported via the hole transport layer.

[0093] In some embodiments, at least one of the "first electrode" and the "second electrode" is a transparent electrode for light incidence. In some embodiments, the first electrode is a transparent electrode.

[0094] In some embodiments, one of the "first charge transport layer" and the "second charge transport layer" is a hole transport layer, and the other is an electron transport layer. The electron transport layer is capable of extracting and transporting electron carriers and can block free holes. The hole transport layer is capable of extracting and transporting hole carriers and can block free electrons.

[0095] For the formal, the perovskite cell includes a transparent electrode for light incidence and an electron transport layer, a perovskite layer, a hole transport layer and a second electrode layer which are sequentially stacked on the transparent electrode.

[0096] For the reverse, the perovskite cell includes a transparent electrode for light incidence and a hole transport layer, a perovskite layer, an electron transport layer and a second electrode layer which are sequentially stacked on the transparent electrode.

[0097] When the perovskite cell works, the internal electrons of the light-absorbing layer obtain energy and escape from the constraint of the light-absorbing layer to form negatively charged electron carriers, and at the same time form positively charged hole carriers, thereby obtaining electron-hole pairs. Free electrons and free holes pass through the corresponding transport layers to move in opposite directions, so that electrons and holes flow to connect the load to form an external current, realizing the conversion of light energy to electric energy. Further, after the perovskite layer absorbs photons, electron-hole pairs are generated, and the electron-hole pairs are further dissociated to form free carriers with opposite charges. The free electrons pass through the electron transport layer to the positive electrode, and the free holes pass through the hole transport layer to the negative electrode. The two kinds of free carriers are collected by the corresponding electrodes, and further form a photocurrent in the circuit of the perovskite cell.

[0098] In some embodiments, the material of the electron transport layer can include, but is not limited to, one or more of the following materials and derivatives thereof: fullerene and derivatives thereof, imide compounds, metal oxides, metal sulfides, metal fluorides, cyano-containing polyphenylenevinylene, boron-containing polymers, bathocuproin, rubrene, aluminum quinolinol, oxadiazole compounds, quinone compounds. Among them, the fullerene and derivatives thereof include one or more of fullerene C60, fullerene C70, PCBM ([6,6]-phenyl-C61-butyric acid methyl ester), [6,6]-phenyl-C7-butyric acid methyl ester (PC71BM); the imide compounds include one or more of perylene imide materials, naphthalene imide materials, phthalimide, succinimide, N-bromosuccinimide, glutarimide or maleimide; the metal oxide, the metal element in which can include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr, such as one or more of tin oxide (SnO2), zinc oxide (ZnO), titanium oxide; metal sulfide such as indium sulfide or zinc sulfide; metal fluoride such as one or more of lithium fluoride (LiF), sodium fluoride, magnesium fluoride (MgF2), calcium fluoride (CaF2).

[0099] In some embodiments, the material of the hole transport layer can include, but is not limited to, one or more of the following materials and derivatives thereof: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (abbreviated as: PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (abbreviated as: Spiro-OMeTAD), poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (abbreviated as: PEDOT:PSS), poly-3-hexylthiophene (abbreviated as: P3HT), triptycene-core triphenylamine (abbreviated as: H101), 3,4-ethylenedioxythiazole-methoxy triphenylamine (abbreviated as: EDOT-OMeTPA), N-(4-aniline)carbazole-spirofluorene (abbreviated as: CzPAF-SBF), polythiazole, nickel oxide, molybdenum oxide (abbreviated as: MoO3), cuprous iodide (abbreviated as: (CuI), cuprous oxide (abbreviated as: CuO), [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (abbreviated as: 2PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (abbreviated as: Me-4PACz), and the like.

[0100] In some embodiments, the material of the transparent electrode can be exemplified, but is not limited to, one or more of the following materials: FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), and the like.

[0101] In some embodiments, the second electrode comprises an electrically conductive material, which can be an organic electrically conductive material, an inorganic electrically conductive material, or a combination thereof. Non-limiting examples of the inorganic electrically conductive material can be a metallic electrically conductive material, which can include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), and the like, or any suitable mixture of the foregoing. The electrically conductive material can include an electrically conductive oxide, non-limiting examples of which can include one or more of FTO, ITO, IWO, AZO, and the like.

[0102] In some embodiments, the substrate layer can be a glass substrate or a flexible substrate. The flexible substrate can include one or more of polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyethylene naphthalate, and the like.

[0103] The substrate layer involved in the embodiments or examples of the present application can be, but is not limited to, a glass substrate or a flexible substrate.

[0104] In some embodiments, the perovskite cell has no particular limitation on the size, which can be, but is not limited to, 300 millimeters (mm) x 300 mm, 1000 mm x 600 mm, 1000 mm x 2000 mm.

[0105] It can be understood that the structure of the perovskite cell involved in the present application can not be limited to the aforementioned listed structure layers. Other functional layers such as buffer layers can also be introduced according to the needs. In some embodiments, the perovskite cell can be provided with a buffer layer with a suitable energy level, which can play one or more of the following roles: reducing the energy level barrier, promoting energy level matching, improving carrier extraction efficiency, at the same time, also playing one or more of the following roles: passivating interface defect states, protecting the light absorption layer, inhibiting the oxidative decomposition of water molecules and oxygen to the cell, improving the photoelectric conversion efficiency, and improving the stability of the perovskite cell. According to the different positions of the buffer layer, the types of the buffer layer can include a buffer layer between the hole transport layer and the anode, a buffer layer between the electron transport layer and the cathode, a buffer layer between the hole transport layer and the absorption layer, a buffer layer between the electron transport layer and the absorption layer, and the like. The materials that can be used for the buffer layer in the perovskite cell can include, but are not limited to, Cu2O, NiO, AZO, BCP, tin oxide, TiO2, and the like.

[0106] In a second aspect, the present application provides a method for preparing a perovskite cell, which can be used to prepare the perovskite cell of the first aspect of the present application, which can include the following steps for preparing a perovskite layer (or a perovskite thin film):

[0107] S1, according to the composition of the perovskite material, taking the precursor material corresponding to the composition of the perovskite material, mixing with a modifier and a solvent to prepare a precursor solution; wherein the modifier includes lead iodide and ammonium salt, the ammonium salt includes at least one of the compounds having the structural formula shown in formula (1):

[0108] R1R2R3R4N + Y - (1),

[0109] In formula (1), R1 includes one of substituted or unsubstituted C4-C20 alkyl, R2-R4 each independently includes one of hydrogen atom, substituted or unsubstituted C1-C20 alkyl; Y - including halide ions and / or halogen-like ions, N is a nitrogen atom;

[0110] S2, the precursor solution is formed and annealed to prepare the perovskite thin film.

[0111] In this application, the excess lead iodide refers to that the precursor solution contains lead iodide, and when the precursor solution is used to prepare the perovskite thin film, there will be a surplus of lead iodide after the formation of the perovskite material. The surplus of lead iodide corresponds to the lead iodide included in the modifier, that is, the surplus of lead iodide comes from the lead iodide in the modifier. Correspondingly, the perovskite thin film prepared from the precursor solution contains lead iodide, which also corresponds to the surplus of lead iodide.

[0112] The modifier contains lead iodide and ammonium salt, and the ammonium salt includes at least one of the compounds having the structural formula shown in formula (1). The carbon chain corresponding to R1 in the compound and the carbon chain that may exist in R2 to R4 can make the ammonium salt as a long-chain molecule to effectively reduce the surface tension of the precursor solution used to prepare the perovskite thin film, improve the uniformity of the distribution of the solute (which includes the precursor material for forming the perovskite material and the excess lead iodide) in the precursor solution, thereby improving the uniformity of the distribution of the excess lead iodide in the perovskite crystallization process. At the same time, the ammonium salt can also coordinate with the excess lead iodide, that is, the coordination of the ammonium salt with Pb can slow down the crystallization rate of lead iodide, so that the excess lead iodide is uniformly distributed in the grain boundary when crystallizing, rather than accumulating into large particles. This can further effectively improve the uniformity of the distribution of the excess lead iodide in the perovskite thin film, thereby improving the stability of the perovskite battery.

[0113] Thus, on the basis of the improvement of the uniformity of the excess lead iodide distribution, it is beneficial to its good passivation effect on the grain boundary; at the same time, the anions and cations contained in the aforementioned compound can also play a certain passivation role (such as the anions can passivate the X ion site defects of the perovskite material, and the cations can passivate the A ion site defects of the perovskite material). Therefore, the ammonium salt cooperates with the excess lead iodide to greatly reduce the defects of the perovskite phase, effectively reduce the defect density of the perovskite thin film, reduce the number of crystal nuclei, increase the grain size, improve the crystalline quality of the perovskite thin film, and simultaneously improve the photoelectric conversion efficiency and stability of the perovskite battery containing the perovskite thin film.

[0114] In some embodiments, the molar amount of lead iodide in the modifier is 5% to 15% of the molar amount of the perovskite material that can be formed from the precursor material. In this way, the lead iodide can have a better passivation effect.

[0115] In some embodiments, the molar ratio of lead iodide to ammonium salt in the modifier is (10-150):1. For example, the molar ratio of lead iodide to ammonium salt can be 150:1, 120:1, 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, or within a range consisting of any of the above values.

[0116] In some embodiments, the molar ratio of lead iodide to ammonium salt in the modifier is (30-80):1. For example, the molar ratio of lead iodide to ammonium salt can be 80:1, 75:1, 65:1, 55:1, 45:1, 35:1, 30:1, or within a range consisting of any of the above values.

[0117] In some embodiments, the molar ratio of lead iodide to ammonium salt in the modifier is (40-60):1. For example, the molar ratio of lead iodide to ammonium salt can be 60:1, 55:1, 50:1, 45:1, 40:1, or within a range consisting of any of the above values.

[0118] In this way, better cooperation can be formed between lead iodide and ammonium salt, further slowing down the crystallization rate, so that the excess lead iodide is more uniformly distributed in the grain boundary during crystallization, thereby further improving the stability of the perovskite battery.

[0119] In some embodiments, the solvent in step S1 includes one or more of N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), and γ-butyrolactone (GBL).

[0120] In some embodiments, the forming in step S2 comprises: performing vacuum flash treatment after spin coating the perovskite precursor solution.

[0121] In some embodiments, the conditions of the annealing in step S2 comprise: a temperature of 80 degrees Celsius (℃) to 120℃, and a time of 5 minutes (min) to 20 min. For example, the temperature can be 80℃, 90℃, 100℃, 110℃, 120℃, or within a range formed by any of the above values; and the time can be 5 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, or within a range formed by any of the above values.

[0122] In some embodiments, the substrate layer, the first electrode layer, the first charge transport layer, the second charge transport layer, and the second electrode layer included in the perovskite cell can be prepared by methods known in the art, which are not described herein.

[0123] In a third aspect, the present application provides a stacked cell, comprising the perovskite cell of the first aspect of the present application or the perovskite cell prepared by the method of the second aspect of the present application.

[0124] In some embodiments, the stacked cell comprises a silicon-perovskite stacked cell and a perovskite-perovskite stacked cell.

[0125] It can be understood that the "silicon-perovskite stacked cell" described in the present application refers to a cell formed by connecting or connecting in parallel a silicon solar cell and a perovskite cell; and the "perovskite-perovskite stacked cell" refers to a cell formed by connecting or connecting in parallel a perovskite cell and a perovskite cell. The number of junctions of the stacked cell can be 2, 3, 4, 5, etc.

[0126] In a fourth aspect, the present application provides a photovoltaic module, comprising at least one of the perovskite cell of the first aspect of the present application, the perovskite cell prepared by the method of the second aspect of the present application, or the stacked cell of the third aspect of the present application.

[0127] It can be understood that the photovoltaic module can only comprise the perovskite cell described in the first aspect of the present application, or the perovskite cell can be combined with other solar cells. For example, the perovskite cell can be combined with a silicon solar cell.

[0128] In a fifth aspect, the present application provides an electrical device, comprising at least one of the perovskite cell of the first aspect of the present application, the perovskite cell prepared by the method of the second aspect of the present application, the stacked cell of the third aspect of the present application, and the photovoltaic module of the fourth aspect of the present application.

[0129] In a sixth aspect, the present application provides a power generation device comprising at least one of the perovskite cell of the first aspect of the present application, the perovskite cell prepared by the method of the second aspect of the present application, the stacked cell of the third aspect of the present application and the photovoltaic module of the fourth aspect of the present application.

[0130] In some embodiments, one of the above-mentioned perovskite cell, stacked cell or photovoltaic module can be used as a power generation device of an electric device. The type of the power generation device can include, but is not limited to, integrated power generation. The location of the power generation device can include, but is not limited to, the roof of a car, the backboard and the like.

[0131] Further, the above-mentioned electric device can include a mobile device such as a mobile phone, a notebook computer and the like, an electric vehicle, an electric train, a ship and a satellite, a power generation system and the like, but is not limited thereto.

[0132] FIG. 5 is an electric device as an example. The electric device is a car, which can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle and the like.

[0133] The electric device as another example can be a mobile phone, a tablet computer, a notebook computer, a calculator and the like.

[0134] The electric device as another example can be a wearable device such as a watch and the like.

[0135] Embodiments

[0136] Hereinafter, some embodiments of the present application will be described. The embodiments described below are exemplary and are intended to explain the present application only, and should not be understood as a limitation of the present application. In the embodiments, the technology or conditions not mentioned are performed according to the description above, or according to the technology or conditions described in the literature in the art or according to the product manual. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained commercially, or can be synthesized by the conventional method from the commercially available products.

[0137] In the following embodiments, "room temperature" refers to 20℃ to 30℃, which can further be 25℃.

[0138] Embodiment 1

[0139] 1) Preparation of the first electrode layer

[0140] Take FTO conductive glass with a specification of 2.0 centimeters (cm) x 2.0 cm, remove 0.35 cm of FTO at both ends by laser etching, and then sequentially ultrasonic 20 min in deionized water, detergent, ethanol, isopropanol, acetone, ethanol, deionized water, and dry with N2, as a first electrode for standby.

[0141] 2) Preparation of the hole transport layer

[0142] On the conductive glass obtained in step 1), 0.5 mg / mL of self-assembled molecule MeO-2PACz (isopropanol as solvent) was spin-coated at a rate of 2000 rpm / s for 30 s, and a hole transport layer with a thickness of 15 nm was prepared by annealing on a hot plate at 100°C for 10 min.

[0143] 3) Preparation of perovskite layer

[0144] ①According to the composition of the perovskite material, Cs 0.2 FA 0.8 PbI 1.8 Br 1.2 , 0.6 mmol of lead iodide, 0.4 mmol of lead bromide, 0.32 mmol of bromoacetamide, 0.48 mmol of iodoacetamide, 0.12 mmol of cesium iodide, and 0.08 mmol of cesium bromide were weighed and dissolved in 1 mL of solvent, which was a mixture of DMF and DMSO in a volume ratio of 4:1, and then stirred for 1 h.

[0145] Then a modifier was added, which contained 0.001 mmol of tetrabutylammonium bromide and 0.06 mmol of lead iodide (6% of the molar amount of the perovskite material), and stirred overnight, and then filtered with a 0.22 μm organic filter membrane to obtain a perovskite precursor solution.

[0146] ②100 μL of the perovskite precursor solution was taken and spin-coated on the obtained hole transport layer at 5000 rpm / s for 25 s, and then placed in a vacuum flash evaporation device for 30 s, and then transferred to a hot plate at 100°C for annealing for 10 min to prepare a perovskite film with a thickness of 500 nm.

[0147] 4) Preparation of electron transport layer

[0148] The product obtained in 3) was placed in a vacuum thermal evaporation device, vacuumed to 4×10 -4 Pa, and a 25 nm thick layer of C 60 70 was deposited as an electron transport layer, and a 7 nm thick layer of BCP (bathocuproin) was deposited as a blocking layer.

[0149] 5) Preparation of second electrode layer

[0150] A Cu counter electrode was deposited on the electron transport layer using a thermal evaporation method with a specific pattern mask to form a second electrode layer with a thickness of about 100 nm, and a perovskite battery was obtained.

[0151] Examples 2-18

[0152] Similar to the technical solutions of Example 1, the main difference is that the material for preparing the perovskite film and the amount used are changed. For details, refer to Table 1 and Table 2.

[0153] Comparative Example 1

[0154] Similar to the technical solutions of Example 1, the main difference is that in step 3) ①, the modifier does not contain tetrabutylammonium bromide, but only contains 0.06 mmol of lead iodide.

[0155] Comparative Example 2

[0156] Similar to the technical solutions of Example 1, the main difference is that in step 3) ①, the modifier does not contain lead iodide, but only contains 0.001 mmol of tetrabutylammonium bromide.

[0157] Comparative Example 3

[0158] Similar to the technical solutions of Example 1, the main difference is that in step 3) ①, an equimolar amount of tetrapropylammonium bromide is used instead of tetrabutylammonium bromide.

[0159] Table 1

[0160] Table 2

[0161] In addition, the perovskite films and perovskite cells in Examples 1-18 and Comparative Examples 1-3 were tested for relevant performance, and the results are shown in Table 3 below.

[0162] Test method

[0163] (1) Surface morphology test

[0164] The surface morphology of the perovskite film was tested using a scanning electron microscope (model: Hitachi, HD-2700).

[0165] (2) Photoelectric conversion efficiency test

[0166] Under normal temperature and pressure, the cell performance was tested under standard simulated sunlight (AM 1.5G, 100 milliwatts per square centimeter (mW / cm 2 )) to obtain the I-V curve (volt-ampere characteristic curve). According to the I-V curve and the data feedback from the test equipment (four-channel digital source meter, Keithley 2440), the short-circuit current density Jsc (unit: milliamperes per square centimeter (mA / cm 2 )), open-circuit voltage Voc (unit: volts (V)), maximum light output current Jmpp (unit: milliamperes (mA)), and maximum light output voltage Vmpp (unit: V) can be obtained.

[0167] The fill factor FF of the cell can be calculated by the formula FF = Jsc x Voc / (Jmpp x Vmpp) and is in %. The photoelectric conversion efficiency PCE of the cell can be calculated by the formula PCE = Jsc x Voc x FF / Pw and is in %; Pw represents the input power and is in milliwatt (mW).

[0168] "Normal temperature and normal pressure" refers to normal pressure: the pressure is one atmosphere at a temperature of 25°C; normal temperature refers to 20-30°C, further, it can be 25°C.

[0169] (3) Stability test

[0170] The self-stability test condition of the perovskite cell is to be stored in a nitrogen glove box at a constant temperature of 25°C in the dark. The photocurrent density-voltage curve of the cell device is tested every certain time interval and the corresponding photoelectric conversion efficiency is normalized, and finally the perovskite cell photovoltaic efficiency decay curve is obtained.

[0171] Under simulated 1 sun light, the maximum power point (MPP) tracking is used, when the cell efficiency decreases to 90% of its initial PCE, the test is stopped, and the storage time at this time is obtained, that is, the stability can be judged accordingly.

[0172] Table 3

[0173] It can be seen from the comparison of Examples 1-18 and Comparative Examples 1 and 2 that when the perovskite thin film contains a modifier and the modifier contains lead iodide and the ammonium salt described in the present application, the stability and photoelectric conversion efficiency of the perovskite cell can be effectively improved. It can be seen from the comparison of Examples 1-18 and Comparative Example 3 that when the ammonium salt meets the conditions of the present application, the improvement of the stability and photoelectric conversion efficiency of the perovskite cell will have a significant effect.

[0174] Each technical feature of the above-described embodiments can be combined arbitrarily, and in order to make the description concise, all possible combinations of each technical feature in the above-described embodiments are not described, however, as long as the combination of these technical features does not exist contradictory, it should be considered as the scope of the present description.

[0175] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exerting the same effects within the scope of the technical solution of the present application are included in the technical scope of the present application. The above-described embodiments only express several embodiments of the present application, and the description is relatively detailed, but it should not be understood as a limitation on the scope of the patent. In addition, within the scope of the main idea of the present application, various modifications that can be thought of by those skilled in the art, other ways constructed by combining part of the elements of the embodiments are also included in the scope of the present application. It should be noted that for those skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the scope of protection of the present application. Therefore, the protection scope of the present application should be subject to the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A perovskite cell comprising a perovskite thin film, the perovskite thin film comprising a perovskite material and a modifier, the modifier comprising lead iodide and an ammonium salt, the ammonium salt comprising at least one of the compounds having the structural formula as shown in formula (1) below: R1R2R3R4N (1); wherein R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, alkyl, aryl, and aralkyl. + Y - (1); In formula (1), R1 includes one of substituted or unsubstituted C4-C20 alkyl, R2-R4 each independently includes one of hydrogen atom, substituted or unsubstituted C1-C20 alkyl; Y - comprising halogen ions and / or halogen-like ions, N is a nitrogen atom.

2. The perovskite cell of claim 1, wherein, One or both of the following conditions are met: (1) said halogen ion comprises one or more of Cl - , Br - , I - , and F - ; (2) the pseudohalide ion comprises one or more of CN - , SCN - , OCN - , N3 - , CF4SO4 - , HCOO - , C6H5S - , CH3COO - , CF3COO - , BH4 - , CH3S - , ClO4 - , BF4 - , and BCl4 - .

3. The perovskite cell according to claim 1 or 2, wherein, The substituted substituent each independently includes one or more of carboxyl, hydroxyl, sulfonic acid group, phenyl and methoxy.

4. The perovskite cell according to any one of claims 1 to 3, wherein, The R1 includes one of substituted or unsubstituted C4-C16 alkyl, and the R2-R4 each independently includes one of hydrogen atom, substituted or unsubstituted C1-C16 alkyl.

5. The perovskite cell according to any one of claims 1 to 4, wherein, The ammonium salt includes one or more of butyl ammonium bromide, tetrabutyl ammonium bromide, tetrabutyl ammonium cyanide, dodecyl dimethyl benzyl ammonium bromide, dodecyl dimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium chloride and hexadecyl tributyl ammonium bromide.

6. The perovskite cell according to any one of claims 1 to 5, wherein, In the perovskite thin film, the molar ratio of the lead iodide to the perovskite material is (5-15):

100.

7. The perovskite cell of claim 6, wherein, In the perovskite thin film, the molar ratio of the lead iodide to the perovskite material is (5-10):

100.

8. The perovskite cell according to any one of claims 1 to 7, wherein, In the perovskite thin film, the molar ratio of the lead iodide to the ammonium salt is (10-150):

1.

9. The perovskite cell of claim 8, wherein, In the perovskite thin film, the molar ratio of the lead iodide to the ammonium salt is (30-80):

1.

10. The perovskite cell according to any one of claims 1 to 9, wherein, The composition of the perovskite material includes ABX3, wherein A ion is monovalent cation, B ion is divalent metal cation, and X ion is monovalent anion, wherein: The A ion includes one or more of organic cations, Li + , Na + , K + , Rb + , and Cs + . The B ion includes one or more of Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , Cu 2+ , and Ni 2+ . The X ion comprises one or more of F - , Cl - , Br - , I - , CN - , SCN - , OCN - , N3 - , CF4SO4 - , HCOO - , C6H5S - , CH3COO - , CF3COO - , BH4 - , CH3S - , ClO4 - , BF4 - , and BCl4 - .

11. The perovskite cell of claim 10, wherein, The organic cation includes at least one of methylamine ion, ethylamine ion, propylamine ion, butylamine ion, pentylamine ion, hexylamine ion, formamidine ion and imidazole ion.

12. The perovskite cell according to claim 10 or 11, wherein, The composition of the perovskite material comprises APb x1 B’ 1-x1 X3, 0 < x1< 1, B’ comprises one or more of Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , Cu 2+ , and Ni 2+ .

13. The perovskite cell according to any one of claims 10 to 12, wherein, The composition of the perovskite material includes Cs y FA 1-y Pb x2 B’ 1-x2 I z Br 3-z , 0 < y < 1, 0 < x2< 1, 0 < z < 3, FA is formamidinium.

14. The perovskite cell according to any one of claims 1 to 13, wherein, The perovskite thin film comprises perovskite grains, the perovskite grains comprise the perovskite material, and the average particle size of the perovskite grains is 1-2 μm.

15. The perovskite cell according to any one of claims 1 to 14, wherein, The perovskite battery further comprises a first electrode layer, a first charge transport layer, a second charge transport layer and a second electrode layer which are arranged in layers, and the perovskite thin film is arranged between the first charge transport layer and the second charge transport layer.

16. A method for preparing a perovskite battery, comprising the step of preparing a perovskite thin film, the step of preparing a perovskite thin film comprising: According to the composition of the perovskite material, a precursor material corresponding to the composition of the perovskite material is prepared, mixed with a modifier and a solvent to prepare a precursor solution; wherein the modifier includes lead iodide and ammonium salt, and the ammonium salt includes at least one of the compounds having the structural formula shown in formula (1) as follows: R1R2R3R4N + Y - (1), In formula (1), R1 includes one of substituted or unsubstituted C4 to C20 alkyl, R2 to R4 each independently include one of hydrogen atom, substituted or unsubstituted C1 to C20 alkyl; Y - comprising halogen ions and / or halogen-like ions, N is a nitrogen atom; The precursor solution is shaped and annealed to prepare the perovskite thin film.

17. A laminated battery comprising the perovskite battery of any one of claims 1-15 or prepared by the method of claim 16.

18. A photovoltaic module comprising at least one of the perovskite battery of any one of claims 1-15, the perovskite battery prepared by the method of claim 16 and the laminated battery of claim 17.

19. An electric device comprising at least one of the perovskite cell of any one of claims 1-15, the perovskite cell prepared by the method of claim 16, the tandem cell of claim 17, and the photovoltaic module of claim 18.

20. A power generation device comprising at least one of the perovskite cell of any one of claims 1-15, the perovskite cell prepared by the method of claim 16, the tandem cell of claim 17, and the photovoltaic module of claim 18.

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