Organic compounds, perovskite precursor solutions, perovskite films, perovskite batteries and power consumption devices

Abstract

The present application relates to organic compounds, perovskite precursor solutions, perovskite films, perovskite batteries and power consumption devices, the organic compounds comprising a cation M and an anion Q associated with the cation M, wherein M is CH3NH3 + , CH5N2 + , Cs + and C2H5NH3 + and Q is HPO x - and H2NO y - wherein x and y are each independently an integer of 2 to 4.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application references Chinese Patent Application No. 202310286101.9, filed on March 22, 2023, entitled "Organic Compound, Perovskite Precursor Solution, Perovskite Film, Perovskite Battery and Power Consumption Device," the entire contents of which are incorporated herein by reference.

[0002] The present application relates to the field of solar cell technology, in particular to organic compounds, perovskite precursor solutions, perovskite films, perovskite cells and power consuming devices. [Background technology]

[0003] With the rapid development of new energy fields, solar cells have been widely used in military, space, industry, commerce, agriculture, and communications. Perovskite cells have gradually become a hot topic in next-generation solar cell research due to their advantages of high photoelectric conversion efficiency, simple fabrication process, low production costs, and low material costs. Currently, perovskite cells have poor long-term stability due to the limitations of precursor stability. Therefore, how to modify precursors to enhance the long-term stability of perovskite cells is of great importance for their use. Summary of the Invention

[0004] The purpose of this application is to provide an organic compound, a perovskite precursor solution, a perovskite film, a perovskite battery, and a power consuming device that can enhance the long-term stability of perovskite batteries.

[0005] To achieve the above object, a first aspect of the present application provides an organic compound, the organic compound comprising a cation M and an anion Q associated with the cation M, wherein the M is a methylamine ion (CH3NH3 + ), formamidine ion (CH5N2 + ), cesium ions (Cs +) and ethylamine ion (C2H5NH3 + ), wherein Q is one or more of HPO x - and H2NO y - wherein x and y are each independently an integer of 2 to 4.

[0006] The organic compound according to the present application contains an anion Q, which is used as an additive (passivator) in perovskite cells. In particular, when used in the fabrication of the perovskite layer, the anion Q can interact with the perovskite intermediate phase before annealing the perovskite layer, slowing down the rate of crystal nucleation, reducing grain boundary defects, realizing in-situ passivation of defects at the grain boundaries, reducing the generation of grain boundary recombination sites, extending carrier lifetime, and further improving the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0007] In some embodiments of the present application, the organic compound is selected from the group consisting of methylamine hypophosphite (MAH2PO2), formamidine hypophosphite (FAH2PO2), cesium hypophosphite (CsH2PO2), ethylamine hypophosphite (C2H5NH3H2PO2), methylamine hypophosphite (MAH2PO3), formamidine hypophosphite (FAH2PO3), cesium hypophosphite (CsH2PO3), ethylamine hypophosphite (C2H5NH3H2PO3), phosphate The compound may include one or more of methylamine (MAH2PO4), formamidine phosphate (FAH2PO4), cesium phosphate (CsH2PO4), ethylamine phosphate (C2H5NH3H2PO4), MAH2NO2, FAH2NO2, CsH2NO2, C2H5NH3H2NO2, MAH2NO3, FAH2NO3, CsH2NO3, C2H5NH3H2NO3, MAH2NO4, FAH2NO4, CsH2NO4, C2H5NH3H2NO4.

[0008] In some embodiments of the present application, the organic compound is one or more of CH3NH3H2PO4, CH5N2H2PO4, CsH2PO4, C2H5NH3H2PO4, CH3NH3H2PO3, CH3NH3H2PO2.

[0009] A second aspect of the present application further provides a perovskite precursor solution, the perovskite precursor solution comprising an organic compound according to the first aspect of the present application and a perovskite precursor material.

[0010] The perovskite precursor solution according to the present application comprises the organic compound of the first aspect of the present application, i.e., the organic compound is added to the perovskite precursor solution as an additive (passivator), and when the perovskite precursor solution is used to prepare a perovskite material, the organic compound can slow down the rate of crystal nucleation, reduce grain boundary defects, achieve in-situ passivation of defects at grain boundaries, reduce the generation of grain boundary recombination sites, extend carrier lifetime, and further improve the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0011] In some embodiments of the present application, the perovskite precursor material comprises an organic halide ABX3, where A is CH3NH3 + , CH5N2 + , Cs + and C2H5NH3 + B includes one or more of Pb, Sn, and Ge; and X includes F. - , Cl - , Br - and I - It includes one or more of the following.

[0012] In some embodiments of the present application, A is CH5N2 + , C2H5NH3 + , Cs + It includes one or more of the following.

[0013] In some embodiments of the present application, B comprises Pb.

[0014] In some embodiments of the present application, X is Br - and I - Includes.

[0015] In some embodiments of the present application, the organic halide is FA 1-x’ Cs x’ Pb(I 1-y’ Br y’ )3, including 0 <x’<1、0<y’<1である。

[0016] In some embodiments of the present application, the molar concentration of the organic halide in the perovskite precursor solution is between 0.5 moles per liter (mol / L) and 3 mol / L, and the molar concentration of the organic compound in the perovskite precursor solution is between 0.0008×10 -2 mol / L~0.18mol / L.

[0017] In some embodiments of the present application, the molar concentration of the organic halide in the perovskite precursor solution is 0.8 mol / L to 1.5 mol / L.

[0018] In some embodiments of the present application, the molar concentration of the organic compound in the perovskite precursor solution is 0.003×10 -2 mol / L~0.1 mol / L.

[0019] In some embodiments of the present application, the molar concentration of the organic compound in the perovskite precursor solution is 0.01×10 -2 mol / L~0.01mol / L.

[0020] In some embodiments of the present application, in the perovskite precursor solution, the ratio of the molar concentration of the organic halide to the molar concentration of the organic compound is 100:(0.0008-12).

[0021] In some embodiments of the present application, the ratio of the molar concentration of the organic halide to the molar concentration of the organic compound in the perovskite precursor solution is 100:(0.001 to 10).

[0022] In some embodiments of the present application, the ratio of the molar concentration of the organic halide to the molar concentration of the organic compound in the perovskite precursor solution is 100:(0.003 to 5).

[0023] The molar concentration of the organic halide in the perovskite precursor solution is within the above range, and can provide sufficient organic luminescent material in the perovskite layer of the perovskite cell, thereby providing sufficient photoelectrons and making the luminous efficiency of the perovskite cell at a relatively high level.

[0024] In some embodiments of the present application, the perovskite precursor solution further comprises an organic solvent, wherein the organic solvent comprises one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, 2-mercaptoethanol, and 1-methyl-2-pyrrolidone.

[0025] A third aspect of the present application provides a perovskite film, formed by fabrication from a precursor solution as described in the second aspect of the present application.

[0026] The perovskite film according to the present application is prepared using a perovskite precursor solution containing the aforementioned organic compound and perovskite precursor material, and therefore has similar effects to the aforementioned perovskite precursor solution when used in a perovskite battery, and will not be further described here.

[0027] A fourth aspect of the present application provides a perovskite battery, the battery comprising a perovskite layer, the perovskite layer comprising the perovskite film of the third aspect of the present application.

[0028] In some embodiments of the present application, the perovskite layer has a thickness of 150 nanometers (nm) to 600 nm.

[0029] The perovskite layer is the light-absorbing layer, i.e., the active layer of the perovskite battery, and this layer is the core position of the entire battery structure. The thickness of the perovskite layer within this range can further improve the photoelectric conversion efficiency and long-term stability of the perovskite battery.

[0030] A fifth aspect of the present application provides a power consuming device, the power consuming device comprising the perovskite battery of the fourth aspect of the present application.

[0031] The power consuming device of the present application includes a perovskite battery according to the present application and therefore has at least the same advantages as said perovskite battery. [Brief explanation of the drawings]

[0032] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without any creative efforts. [Figure 1] 1 is a structural schematic diagram of a perovskite battery according to an embodiment of the present application; FIG. [Figure 2] 1 is a schematic diagram of a power consuming device powered by a perovskite battery according to an embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0033] Hereinafter, with appropriate reference to the drawings, embodiments specifically disclosing the organic compound, perovskite precursor solution, perovskite film, perovskite battery, and power consumption device of the present application will be described in detail. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and redundant descriptions of structures that are actually the same may be omitted. This is to avoid unnecessarily lengthening the following description and to facilitate understanding by those skilled in the art. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application, and are not intended to limit the subject matter described in the claims.

[0034] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and the resulting range is defined by selecting one lower limit and one upper limit, with the selected lower and upper limits defining the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of their extreme values, and are arbitrarily combinable; i.e., any lower limit can be combined with any upper limit to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also contemplated. Furthermore, if 1 and 2 are listed as minimum range values ​​and 3, 4, and 5 are listed as maximum range values, the ranges 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all contemplated. In this application, unless otherwise specified, a numerical range "a to b" is a shorthand representation of any combination of real numbers a to b, where a and b are both real numbers. For example, the numerical range "0-5" represents that the present specification has already listed all real numbers between "0-5," and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0035] Unless otherwise stated, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0036] Unless otherwise stated, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0037] Unless otherwise specified, all steps in this application may be performed in order or randomly, and are preferably performed in order. For example, when the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed in order, or steps (b) and (a) performed in order. For example, when the method mentioned above may further include step (c), it means that step (c) may be added to the method in any order, and for example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.

[0038] Unless otherwise specified, the terms "comprise" and "include" used in this application may be open-ended or closed-ended. For example, the terms "comprise" and "include" may further include or include other components not listed, or may include or include only the listed components.

[0039] Unless otherwise stated, the terms "first," "second," "third," "fourth," etc. in the "first aspect," "second aspect," "third aspect," "fourth aspect," etc. referred to in this application are used for descriptive purposes only and should not be understood to indicate or imply relative importance or number, nor should they be understood to suggest the importance or number of the technical features indicated. Furthermore, "first," "second," "third," "fourth," etc. should be understood to be for non-exhaustive listing and description purposes only, and not to constitute restrictive limitations on quantity.

[0040] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) but B is true (or exists), or when both A and B are true (or exist).

[0041] Currently, in perovskite batteries, the crystalline quality of the perovskite layer is crucial to the performance of the perovskite battery. Grain boundary defects provide recombination sites, reduce carrier lifetimes, and severely affect the performance of the perovskite battery. To this end, the present application provides an organic compound, which is added as an additive (passivator) to the perovskite precursor solution. By adopting an in situ passivation method, the nucleation crystallization process of the perovskite layer can be controlled, and the defects at the grain boundaries can be passivated in situ, thereby improving the long-term stability of the perovskite battery.

[0042] organic compound A first aspect of the present application proposes an organic compound MQ, which comprises a cation, M, and an anion, Q, associated with the cation M, wherein M is CH3NH3 + [MA + ], CH5N2 + [FA + ], Cs + and C2H5NH3 + wherein Q is HPO x - and H2NO y - wherein x and y are each independently an integer of 2 to 4.

[0043] As can be appreciated, M may be only one of the above cations or may include multiple of the above cations, in which case the total number of atoms of the various cations in each MQ molecule is 1.

[0044] As a non-limiting example, M may be CH3NH3 + [MA + ] and CH5N2 + [FA + ], these two cations [MA + ] and [FA + ] The sum of the number of atoms is 1.

[0045] Without intending to be limited by any theory, the organic compound according to the present application contains a cation M and an anion Q, and when used as an additive (passivator) in a perovskite cell, particularly when used in the production of a perovskite layer, the cation M can provide the perovskite layer with cations necessary for photoelectric conversion. The anion Q can interact with the perovskite mesophase (e.g., MAI-PbI-DMSO phase) formed in the perovskite precursor solution (typically containing an organic halide ABX3 and an organic solvent) before annealing the perovskite layer. This interaction with the cations in the perovskite mesophase can slow the volatilization of the cations in the subsequent crystallization process, thereby suppressing nucleation, slowing the crystallization rate, reducing grain boundary defects, and achieving in situ passivation of the grain boundary defects, reducing the generation of grain boundary recombination sites, extending the carrier lifetime, and improving the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0046] In some embodiments, the organic compound may include one or more of MAH2PO2, FAH2PO2, CsH2PO2, C2H5NH3H2PO2, MAH2PO3, FAH2PO3, CsH2PO3, C2H5NH3H2PO3, MAH2PO4, FAH2PO4, CsH2PO4, C2H5NH3H2PO4, MAH2NO2, FAH2NO2, CsH2NO2, C2H5NH3H2NO2, MAH2NO3, FAH2NO3, CsH2NO3, C2H5NH3H2NO3, MAH2NO4, FAH2NO4, CsH2NO4, C2H5NH3H2NO4.

[0047] In some embodiments, the organic compound includes one or more of CH3NH3H2PO4, CH5N2H2PO4, CsH2PO4, C2H5NH3H2PO4, CH3NH3H2PO3, CH3NH3H2PO2.

[0048] The present application selects the above-mentioned organic compounds, where the cations in each organic compound are selected from cation types commonly contained in the perovskite layer of a perovskite battery, to provide more cations for the photoelectric conversion of the perovskite layer, and the selected anions in each organic compound can interact with the perovskite layer intermediate phase (e.g., MAI-PbI2-DMSO phase) before annealing the perovskite layer, thereby further improving the photoelectric conversion efficiency and long-term stability of the perovskite battery.

[0049] As a non-limiting example, the above organic compounds can be produced by the following method.

[0050] Take a dried crystal round-bottom flask, add methylamine ethanol solution and ethanol, and stir in an ice-water bath until the solution cools to 0-5°C. Take phosphoric acid and add it dropwise to the round-bottom flask. Allow to react in an ice-water bath, then slowly warm it to room temperature. Remove the solvent by spin-drying, then disperse it in ethanol and wash it repeatedly with ethyl ether to obtain the organic compound methylamine phosphate (MAH2PO4).

[0051] A second aspect of the present application provides a perovskite precursor solution, the solution comprising the organic compound of the first aspect of the present application and a perovskite precursor material.

[0052] The perovskite precursor solution according to the present application comprises the organic compound of the first aspect of the present application, i.e., the organic compound is added to the perovskite precursor solution as an additive (passivator). When the perovskite precursor solution is used to produce a perovskite material, the cation M in the organic compound can provide the cations necessary for photoelectric conversion in the light-absorbing layer containing the perovskite material. The anion Q can interact with the intermediate phase (e.g., MAI-PbI-DMSO phase) formed in the perovskite precursor material, i.e., slow down the volatilization of the cations in the subsequent crystallization process by interacting with the cations in the perovskite intermediate phase, thereby suppressing nucleation, slowing down the crystallization rate, reducing grain boundary defects, and achieving in situ passivation of the grain boundary defects, reducing the generation of grain boundary recombination sites, extending carrier lifetime, and improving the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0053] In some embodiments, the molar concentration of the organic compound in the perovskite precursor solution is 0.0008×10 -2 mol / L~0.18mol / L.

[0054] In some embodiments, the molar concentration of the organic compound in the perovskite precursor solution is 0.003×10 -2 mol / L~0.1 mol / L.

[0055] In some embodiments, the molar concentration of the organic compound in the perovskite precursor solution is 0.01×10 -2 mol / L~0.01mol / L.

[0056] In some embodiments, the molar ratio of the organic halide to the organic compound in the perovskite precursor solution is 100:(0.0008-12). For example, the molar ratio may be 100:0.0008, 100:0.001, 100:0.003, 100:0.005, 100:0.007, 100:0.01, 100:0.03, 100:0.05, 100:0.07, 100:0.1, 100:0.3, 100:0.5, 100:0.7, 100:1, 100:3, 100:5, 100:7, 100:10, 100:12, or any range therein.

[0057] In some embodiments, the ratio of the molar concentration of the organic halide to the molar concentration of the organic compound in the perovskite precursor solution is 100:(0.001-10).

[0058] In some embodiments, the molar concentration ratio is 100:(0.003-5).

[0059] The molar concentration of the organic compound in the perovskite precursor solution and the ratio of its molar concentration to that of the organic halide within the above range are advantageous for further promoting the interaction of the anion Q in the organic compound with the perovskite mesophase (e.g., MAI-PbI2-DMSO phase) before annealing the perovskite layer. This further promotes the interaction of the anion Q with the cation in the perovskite mesophase, thereby slowing down the volatilization of the cation in the subsequent crystallization process, thereby suppressing nucleation, slowing down the crystallization rate, reducing grain boundary defects, achieving in situ passivation of the grain boundary defects, reducing the generation of grain boundary recombination sites, extending carrier lifetime, and improving the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0060] In some embodiments, the perovskite precursor material comprises an organic halide ABX3, where A is CH3NH3 + , CH5N2 + , Cs+ and C2H5NH3 + B includes one or more of Pb, Sn, and Ge; and X includes F. - , Cl - , Br - and I - It includes one or more of the following.

[0061] In some embodiments, A is CH5N2 + , C2H5NH3 + , Cs + It includes one or more of the following.

[0062] In some embodiments, B comprises Pb.

[0063] In some embodiments, X is Br - and I - Includes.

[0064] It should be explained that in the organic compounds according to the present application, the cation M comprises a cation type A in the organic halide ABX3.

[0065] In some embodiments, the organic halide is FA 1-x’ Cs x’ Pb(I 1-y’ Br y’ )3, including 0 <x’<1、0<y’<1である。

[0066] In some embodiments, the molar concentration of the organic halide in the perovskite precursor solution is between 0.5 mol / L and 3 mol / L. For example, the molar concentration of the organic halide in the perovskite precursor solution can be 0.5 mol / L, 0.7 mol / L, 0.9 mol / L, 1.1 mol / L, 1.3 mol / L, 1.5 mol / L, 1.7 mol / L, 1.9 mol / L, 2.1 mol / L, 2.3 mol / L, 2.5 mol / L, 2.7 mol / L, 2.9 mol / L, 3 mol / L, or any range therein.

[0067] In some embodiments, the molar concentration of the organic halide in the perovskite precursor solution is between 0.8 mol / L and 1.5 mol / L.

[0068] The molar concentration of the organic halide in the perovskite precursor solution is within the above range, and can provide a sufficient amount of organic light-emitting material in the perovskite layer of the perovskite cell, thereby providing sufficient photoelectrons and keeping the luminous efficiency (photoelectric conversion efficiency) of the perovskite cell at a relatively high level.

[0069] In some embodiments, the perovskite precursor solution further comprises an organic solvent, the organic solvent comprising one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, 2-mercaptoethanol, and 1-methyl-2-pyrrolidone.

[0070] The perovskite precursor solution contains the above-mentioned organic solvent, where the organic solvent can form a mesophase complex with the organic halide component in the perovskite precursor solution, for example, when the organic solvent is dimethyl sulfoxide and the organic halide is MAPbI3, a MAI-PbI2-DMSO mesophase complex can be formed. The cation in this mesophase complex can interact with the anion Q in the organic compound, for example, Pb 2+ can interact with the anion Q in the organic compound to form a coordinate bond, which can slow down the volatilization of the cation in the organic halide in the subsequent crystallization process, thereby suppressing nucleation, slowing down the crystallization rate, reducing grain boundary defects, and achieving in-situ passivation of grain boundary defects, reducing the generation of grain boundary recombination sites, extending carrier lifetime, and further improving the photoelectric conversion efficiency and long-term stability of perovskite cells.

[0071] As can be understood, the organic solvents may be used singly or in combination, and when a mixture of solvents is used, the volume ratio between the solvents may be adjusted depending on the different components, molar concentrations, etc.

[0072] A third aspect of the present application provides a perovskite film, formed by fabrication from a precursor solution as described in the second aspect of the present application.

[0073] The perovskite film according to the present application is prepared using a perovskite precursor solution containing the aforementioned organic compound and perovskite precursor material, and therefore has similar effects to the aforementioned perovskite precursor solution when used in a perovskite battery, and will not be further described here.

[0074] A fourth aspect of the present application further provides a method for producing a perovskite film, the method may comprise the steps of:

[0075] S10. Supporting the perovskite precursor solution according to the second aspect of the present application on a substrate; S20: annealing the perovskite precursor solution to obtain the perovskite film.

[0076] By supporting the perovskite precursor solution on a substrate and subjecting it to an annealing treatment, the organic solvent in the perovskite precursor solution can be removed, and nucleation and crystal growth of the organic halide can be achieved.

[0077] In some embodiments, the annealing comprises heating the perovskite precursor solution at a temperature between 70 degrees Celsius (°C) and 200°C for a period between 3 minutes (min) and 60 minutes.

[0078] In some embodiments, the annealing temperature may be 70°C, 90°C, 110°C, 130°C, 150°C, 170°C, 190°C, 200°C, or any value within the range above.

[0079] In some embodiments, the annealing time may be 3 minutes, 6 minutes, 9 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, or any number in the range above.

[0080] The annealing temperature and time within the above ranges can remove the organic solvent in the perovskite precursor solution and allow the organic halide to undergo a relatively good nucleation and crystal growth process, reduce grain boundary defects, reduce the occurrence of grain boundary recombination sites, extend the carrier lifetime, and further improve the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0081] In some embodiments, the type of substrate used in step S10 is not particularly limited and can be selected according to actual needs, for example, the substrate may be one or more of transparent glass, polyethylene terephthalate (PET), polyimide substrate, etc.

[0082] In some embodiments, in the above step S10, a method such as vacuum evacuation can be adopted to deposit the perovskite precursor solution onto a substrate, and then the perovskite film is formed.

[0083] Alternatively, when using a vacuum evacuation method, the evacuation time is controlled to 0.5 to 10 minutes, for example, 0.5 minutes, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, or any number within the range.

[0084] Perovskite Battery A fifth aspect of the present application provides a perovskite battery, as shown in Figure 1, the battery comprising a perovskite layer 14, said perovskite layer 14 comprising the perovskite film of the fourth aspect of the present application.

[0085] In some embodiments, the perovskite layer has a thickness of 150 nm to 600 nm. For example, the perovskite layer may have a thickness of 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, or any range therein.

[0086] The perovskite layer is the light-absorbing layer, i.e., the active layer of the perovskite battery, and this layer is the core position of the entire battery structure. The thickness of the perovskite layer within this range can further improve the photoelectric conversion efficiency and long-term stability of the perovskite battery.

[0087] In some embodiments, the perovskite cell may be a cis-perovskite cell or a trans-perovskite cell.

[0088] In some embodiments, the perovskite cell further comprises a transparent substrate layer 11, a transparent conductive layer 12, a first charge transport layer 13, a second charge transport layer 15 and a back electrode layer 16, stacked one on top of the other, as shown in FIG.

[0089] In some embodiments, the transparent substrate layer 11 serves as a support for the cell, and its light transmittance and strength must both meet the requirements of perovskite cells. It may comprise at least one of a transparent glass, polyethylene terephthalate (PET), or polyimide (PI) substrate. The transparent substrate layer 11 has a thickness of 0.5 millimeters (mm) to 5 mm. For example, the thickness of the transparent substrate layer may be 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, or any range of values ​​above.

[0090] In some embodiments, the transparent conductive layer 12 is an anode layer, acts as a hole collector, can extract photo-induced carriers, is electrically conductive, and can filter out ultraviolet light that is destructive to perovskite layers.

[0091] In some embodiments, the transparent conductive layer may comprise at least one of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO).

[0092] In some embodiments, the transparent conductive layer 12 has a thickness of 200 nm to 1000 nm. For example, the thickness of the transparent conductive layer may be 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range therein.

[0093] In some embodiments, the first charge transport layer 13 may be a hole transport layer or an electron transport layer, and the second charge transport layer 15 may be a hole transport layer or an electron transport layer. An electron transport layer acts to extract electrons and block holes, and a hole transport layer acts to transport holes and block electrons.

[0094] In some embodiments, the thickness of the first charge transport layer is between 10 nm and 100 nm. For example, the thickness of the first charge transport layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or any value in the range above.

[0095] In some embodiments, the thickness of the second charge transport layer is between 10 nm and 100 nm. For example, the thickness of the second charge transport layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or any value in the range above.

[0096] As can be seen, the first charge transport layer 13 and the second charge transport layer 15 are generally arranged differently. That is, when the first charge transport layer 13 is an electron transport layer and the second charge transport layer 15 is a hole transport layer, the perovskite battery corresponds to a cis-type perovskite battery. When the first charge transport layer 13 is a hole transport layer and the second charge transport layer 15 is an electron transport layer, the perovskite battery corresponds to a trans-type perovskite battery.

[0097] In some embodiments, the material of the electron transport layer is selected from the group consisting of imide compounds, quinone-based compounds, fullerenes and their derivatives, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), calcium titanate (CaTiO), lithium fluoride (LiF), calcium fluoride (CaF), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly-3-hexylthiophene (P3HT), triptycene-based triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeT The material may include one or more of materials such as N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), polythiophene, metal oxides, silicon oxide (SiO2), tin oxide (SnO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), and derivatives thereof, wherein the metal element may 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.

[0098] In some embodiments, the material of the hole transport layer may include at least one of materials such as 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), NiOx, poly3,4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS), Me-4PACz, MeO-2PACz, WO3, and derivatives thereof.

[0099] In some embodiments, the back electrode layer is a cathode layer, which acts to collect free electrons.

[0100] In some embodiments, the back electrode layer is generally an organic, inorganic, or mixed organic-inorganic conductive material, including at least one of indium tin oxide (ITO), lanthanide-doped indium oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof, graphite, graphene, carbon nanotubes, and optionally Ag, Cu, C, Au, Al, ITO, AZO, BZO, or IZO, and further optionally Cu, Ag, Au, or combinations thereof.

[0101] In some embodiments, the thickness of the back electrode layer is 20 nm to 200 nm, for example, the thickness of the back electrode layer may be 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, or any number in the range above.

[0102] A sixth aspect of the present application further provides a method for manufacturing a perovskite battery, which may include the steps of:

[0103] S10'. Provide a substrate for a perovskite cell, the substrate including a transparent conductive glass and a first charge transport layer disposed on the transparent conductive glass; S20′, preparing a perovskite precursor solution according to the second aspect of the present application; S30': supporting the precursor solution on the substrate and removing the organic solvent in the precursor solution to obtain a perovskite layer; S40': A second charge transport layer and a back electrode layer are sequentially formed on the perovskite layer to obtain a perovskite battery.

[0104] As can be understood, the above step numbers are merely an exemplary description of the method for fabricating a perovskite battery, and do not necessarily constitute a limitation on the order of the steps.

[0105] In some embodiments, the first charge transport layer, the perovskite layer, and the second charge transport layer may be fabricated by spin coating.

[0106] A seventh aspect of the present application further provides a power consuming device, the power consuming device comprising a perovskite battery according to the present application. The perovskite battery serves as a power source for the power consuming device. The power consuming device may include, but is not limited to, mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships, satellites, power generation systems, etc.

[0107] FIG. 2 shows an example of a power-consuming device. The power-consuming device may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. Other examples of the device may include a mobile phone, a tablet computer, or a laptop computer. These devices generally require a thin design and may employ perovskite batteries as their power source.

[0108] Example The following describes examples of the present application. The examples described below are illustrative and are intended to interpret the present application, but should not be understood as limitations on the present application. If no specific techniques or conditions are described in the examples, they are carried out according to the techniques, conditions, or product specifications described in documents within the field. If no manufacturer is specified for the reagents or equipment used, they are all ordinary products that are commercially available.

[0109] Example 1 Production of organic compounds: A dried crystallized round-bottom flask was taken, and 9.5 g of methylamine ethanol solution (0.096 mol, the concentration of the methylamine ethanol solution is 30 wt%-33 wt%) and 100 mL of ethanol were added. The mixture was stirred in an ice-water bath for 10 minutes until the solution cooled to 0-5°C. 9.8 g (0.1 mol) of phosphoric acid was added dropwise to the round-bottom flask, and the mixture was allowed to react in an ice-water bath for 3 hours. The mixture was then slowly warmed to room temperature (25°C). The solvent was removed by spin-drying, and the mixture was then dispersed in ethanol and repeatedly washed with ethyl ether to obtain white particles of methylamine phosphate (MAH2PO4).

[0110] Perovskite battery manufacturing: (a) A 5cm x 5cm FTO conductive glass was taken and etched with a laser, leaving an insulating area. After ultrasonic cleaning for 20 minutes in deionized water, detergent, ethanol, isopropyl alcohol, acetone, ethanol, and deionized water, it was blown dry with N2 in preparation for use as a transparent conductive layer. (b) The NiOx nanoparticle solution was spin-coated onto the transparent conductive layer at a speed of 3000 rpm, annealed at 200°C for 15 minutes, and then naturally cooled to obtain an electron transport layer with a thickness of 10 nm. (c) FA with a molar concentration of 1 mol / L 0.9 Cs 0.1 The PbI3 perovskite precursor solution was mixed with methylamine phosphate (molarity 0.01 mol / L) and FA 0.9 Cs 0.1The ratio of Pb to PbI3 is 1:100) and stirred to prepare a perovskite precursor solution, which is then sealed and ready for use. (d) After 15 minutes of UV ozone treatment, the NiOx substrate surface was cleaned, and an appropriate amount of perovskite precursor solution was taken and spin-coated at a rotation speed of 4000 rpm for 20 seconds to produce a wet film. The film was then evacuated for 30 seconds, annealed on a heating table at 120°C for 45 minutes, and naturally cooled to obtain a perovskite layer with a thickness of 500 nm. (e) Spin-coating the PCBM solution onto the perovskite layer at a rotation speed of 3000 rpm to form a hole transport layer with a thickness of 80 nm; (f) Using thermal evaporation, a Cu counter electrode was deposited on the hole transport layer using a specific patterned reticle to form a back electrode layer with a thickness of 100 nm, and a perovskite cell was obtained.

[0111] Example 2 The same technical solution as in Example 1 is basically adopted, except that in step (c), the molar concentration of methylamine phosphate (MAH2PO4) is 0.01 × 10 -2 The concentration was mol / L.

[0112] Example 3 The same technical solution as in Example 1 is basically adopted, except that in step (c), the molar concentration of methylamine phosphate (MAH2PO4) is 0.003 × 10 -2 The concentration was mol / L.

[0113] Example 4 The technical solution used was basically the same as in Example 1, except that in step (c), the molar concentration of methylamine phosphate (MAH2PO4) was 0.05 mol / L.

[0114] Example 5 The technical solution used was basically the same as in Example 1, except that in step (c), the molar concentration of methylamine phosphate (MAH2PO4) was 0.1 mol / L.

[0115] Example 6 The same technical solution as in Example 1 is basically adopted, except that in the organic compound production process, hypophosphorous acid is used to replace phosphoric acid, and the molar ratio of hypophosphorous acid to methylamine in the methylamine ethanol solution is 1:1.1 to obtain methylamine hypophosphite (MAH2PO2), and in step (c), the molar concentration of methylamine hypophosphite is 0.003×10 -2 The concentration was mol / L.

[0116] Example 7 The same technical solution as in Example 1 is basically adopted, except that in the organic compound production process, the same mass of phosphorous acid is used to replace phosphoric acid to obtain methylamine phosphite (MAH2PO3), and in step (c), the molar concentration of methylamine phosphite is 0.003 × 10 -2 The concentration was mol / L.

[0117] Example 8 The same technical solution as in Example 1 is basically adopted, except that in the organic compound preparation process, the same mass of formamidine acetate is used to replace the methylamine ethanol solution to obtain formamidine phosphate (FAH2PO4), and in step (c), the molar concentration of formamidine phosphate is 0.003×10 -2 The concentration was mol / L.

[0118] Example 9 The same technical solution as in Example 1 is basically adopted, except that in the organic compound production process, the same mass of cesium carbonate is used to replace the methylamine ethanol solution to obtain cesium phosphate (CsH2PO4), and in step (c), the molar concentration of cesium phosphate is 0.003 × 10 -2 The concentration was mol / L.

[0119] Example 10 The same technical solution as in Example 1 is basically adopted, except that in the organic compound preparation process, the same mass of ethylamine is used to replace the methylamine ethanol solution to obtain C2H5NH3H2PO4, and in step (c), the molar concentration of C2H5NH3H2PO4 is 0.003×10 -2 The concentration was mol / L.

[0120] Example 11 The same technical solution as in Example 1 is basically adopted, except that in step (c), the molar concentration of methylamine phosphate (MAH2PO4) is 0.001 × 10 -2 The concentration was mol / L.

[0121] Example 12 The same technical solution as in Example 1 is basically adopted, with the difference being that in step (c), FA 0.9 Cs 0.1 The molar concentration of PbI3 was 0.5 mol / L.

[0122] Example 13 The same technical solution as in Example 1 is basically adopted, with the difference being that in step (c), FA 0.9 Cs 0.1 The molar concentration of PbI3 was 3 mol / L.

[0123] Example 14 The same technical solution as in Example 1 is basically adopted, with the difference being that in step (c), FA 0.9 Cs 0.1 The molar concentration of PbI3 is 0.8 mol / L, and the molar concentration of methylamine phosphate (MAH2PO4) is 0.0008 × 10 -2 The concentration was mol / L.

[0124] Example 15 The same technical solution as in Example 1 is basically adopted, with the difference being that in step (c), FA 0.9 Cs 0.1The molar concentration of PbI3 was 1.5 mol / L and the molar concentration of methylamine phosphate (MAH2PO4) was 0.18 mol / L.

[0125] Example 16 The same technical solution as in Example 1 is adopted, with the difference being that in step (c), the same mass of (C2H5NH3) 0.9 Cs 0.1 FA with PbI3 0.9 Cs 0.1 The aim was to replace PbI3.

[0126] Example 17 The same technical solution as in Example 1 is basically adopted, with the difference being that in step (c), MA of the same mass is used. 0.8 Cs 0.2 FA with PbI3 0.9 Cs 0.1 The aim was to replace PbI3.

[0127] Example 18 The same technical solution as in Example 1 was basically adopted, except that in step (c), MAH2PO4 was replaced with the same mass of MAH2NO4.

[0128] Example 19 The same technical solution as in Example 1 was basically adopted, except that in step (c), MAH2PO4 was replaced with the same mass of MAH2NO3.

[0129] Example 20 The same technical solution as in Example 1 was basically adopted, except that in step (c), MAH2PO4 was replaced with the same mass of MAH2NO2.

[0130] Example 21 The same technical solution as in Example 1 was basically adopted, with the difference being that in step (d), the thickness of the perovskite layer was 160 nm.

[0131] Example 22 The same technical solution as in Example 1 was basically adopted, except that in step (d), the thickness of the perovskite layer was 600 nm.

[0132] Comparative Example 1 The same technical solution as in Example 1 was basically adopted, except that no organic compound was added in step (c).

[0133] Comparative Example 2 The same technical solution as in Example 1 was basically adopted, except that in step (c), MAH2NO4 was replaced with the same mass of MAI.

[0134] The relevant parameters of the organic compounds, perovskite precursor solutions, and perovskite batteries of Examples 1 to 22 and Comparative Examples 1 and 2 are shown in Table 1 below.

[0135] [Table 1]

[0136] In addition, the perovskite batteries obtained in Examples 1 to 22 and Comparative Examples 1 and 2 above were subjected to relevant performance tests, and the test results are shown in Tables 2 and 3 below.

[0137] Test part (1) Photoelectric conversion efficiency test At room temperature and pressure, sunlight was used to simulate a standard AM1.5G light source (AM 1.5G, 100 mW / cm2), and a 4-channel digital source table (Keithley 2440) was used to measure the volt-ampere characteristic curve of the assembly irradiated by the light source. The open-circuit voltage Voc, short-circuit current density Jsc, and fill factor FF of the assembly were obtained, thereby obtaining the photoelectric conversion efficiency PCE (efficiency) of the assembly.

[0138] Regarding "normal temperature and normal pressure," normal pressure means that the temperature is 25°C and the pressure is atmospheric pressure, and normal temperature refers to 20°C to 30°C, and may further be 25°C.

[0139] (2) Stability test After the test was completed, the battery was placed in an air environment (relative humidity 85%, ambient temperature approximately 15-40°C) and left in the light for at least 200 hours, after which the photoelectric conversion efficiency was tested again. The difference between the assembly efficiency after 200 hours in the air and the initial efficiency was calculated, and the decrease in photoelectric conversion efficiency was the ratio of this difference to the initial efficiency, which was used as a performance parameter for assembly stability.

[0140] [Table 2]

[0141] [Table 3]

[0142] As can be seen by comparing the Examples and Comparative Example 1 in Tables 1 to 3 above, when the organic compound according to the present application is not added to the perovskite layer, the degree of decrease in the photoelectric conversion efficiency of the perovskite cell after it is left standing for 200 hours is significantly higher than in the Examples. This demonstrates that adding the organic compound according to the present application to the perovskite precursor solution to manufacture a perovskite cell can improve the photoelectric conversion efficiency and long-term stability of the perovskite cell. As can be seen by comparing the Examples and Comparative Example 2, the addition of other types of anions (for example, I in Comparative Example 2) can improve the photoelectric conversion efficiency and long-term stability of the perovskite cell. - After replacing the anion Q in the organic compound of the present application with , the decrease in the photoelectric conversion efficiency of the perovskite cell was also significantly higher, which shows that the anion in the organic compound of the present application can certainly play a better role in improving the photoelectric conversion efficiency and long-term stability of the perovskite cell.

[0143] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea and achieves the same effects within the scope of the technical solution of the present application is included within the technical scope of the present application. In addition, various modifications that a person skilled in the art can make to the embodiments without departing from the spirit of the present application, and other methods configured by combining some of the components of the embodiments, are also included within the scope of the present application. [Explanation of symbols]

[0144] 11 transparent substrate layer, 12 transparent conductive layer, 13 first charge transport layer, 14 perovskite layer, 15 second charge transport layer, 16 back electrode layer.

Claims

1. An organic compound, a cation M; an anion Q associated with the cation M; Here, M is CH ３ NH ３ ＋ , C.H. ５ N ２ ＋ , Cs ＋ and C ２ H ５ NH ３ ＋ wherein Q is H ２ P.O. ｘ － and H ２ NO ｙ － wherein x and y are each independently an integer from 2 to 4.

2. The organic compound is MAH ２ P.O. ２ , F.A.H. ２ P.O. ２ , CsH ２ P.O. ２ , C ２ H ５ NH ３ H ２ P.O. ２ , M.A.H. ２ P.O. ３ , F.A.H. ２ P.O. ３ , CsH ２ P.O. ３ , C ２ H ５ NH ３ H ２ P.O. ３ , M.A.H. ２ P.O. ４ , F.A.H. ２ P.O. ４ , CsH ２ P.O. ４ , C ２ H ５ NH ３ H ２ P.O. ４ , M.A.H. ２ NO ２ , F.A.H. ２ NO ２ , CsH ２ NO ２ , C ２ H ５ NH ３ H ２ NO ２ , M.A.H. ２ NO ３ , F.A.H. ２ NO ３ , CsH ２ NO ３ , C ２ H ５ NH ３ H ２ NO ３ , M.A.H. ２ NO ４ , F.A.H. ２ NO ４ , CsH ２ NO ４ , C ２ H ５ NH ３ H ２ NO ４ 10. The organic compound of claim 1, comprising one or more of:

3. The organic compound is CH ３ NH ３ H ２ P.O. ４ , C.H. ５ N ２ H ２ P.O. ４ , CsH ２ P.O. ４ , C ２ H ５ NH ３ H ２ P.O. ４ , C.H. ３ NH ３ H ２ P.O. ３ , C.H. ３ NH ３ H ２ P.O. ２ 3. The organic compound according to claim 1, wherein the organic compound is one or more of:

4. 4. A perovskite precursor solution comprising the organic compound of claim 1 and a perovskite precursor material.

5. The perovskite precursor material is an organic halide ABX ３ Including, where A is CH ３ NH ３ ＋ , C.H. ５ N ２ ＋ , Cs ＋ and C ２ H ５ NH ３ ＋ and B includes one or more of Pb, Sn, and Ge; X is F － , Cl － ,Br － and I － 5. The perovskite precursor solution of claim 4, comprising one or more of:

6. The organic halide is FA １－ｘ’ Cs ｘ’ Pb(I １－ｙ’ Br ｙ’ ) ３ 6. The perovskite precursor solution of claim 5, comprising:

7. the molar concentration of the organic halide in the perovskite precursor solution is 0.5 mol / L to 3 mol / L; The molar concentration of the organic compound in the perovskite precursor solution is 0.0008×10 －２ 7. The perovskite precursor solution according to claim 5, wherein the concentration of the perovskite precursor solution is 0.18 mol / L to 0.18 mol / L.

8. 8. The perovskite precursor solution according to claim 5, wherein the organic halide has a molar concentration of 0.8 mol / L to 1.5 mol / L in the perovskite precursor solution.

9. The molar concentration of the organic compound in the perovskite precursor solution is 0.003 × 10 －２ 9. The perovskite precursor solution according to claim 4, wherein the concentration of the perovskite precursor solution is 0.1 mol / L to 0.1 mol / L.

10. The molar concentration of the organic compound in the perovskite precursor solution is 0.01×10 －２ 10. The perovskite precursor solution according to any one of claims 4 to 9, wherein the concentration of the perovskite precursor solution is 0.01 mol / L to 0.01 mol / L.

11. 11. The perovskite precursor solution according to claim 5, wherein in the perovskite precursor solution, a ratio of a molar concentration of the organic halide to a molar concentration of the organic compound is 100:(0.0008 to 12).

12. the perovskite precursor solution further comprises an organic solvent; 12. The perovskite precursor solution of any one of claims 4 to 11, wherein the organic solvent comprises one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, 2-mercaptoethanol, and 1-methyl-2-pyrrolidone.

13. 13. A perovskite film formed by fabrication with a precursor solution according to any one of claims 4 to 12.

14. 14. A perovskite battery comprising a perovskite layer comprising the perovskite film of claim 13.

15. The perovskite battery of claim 14, wherein the perovskite layer has a thickness of 150 nm to 600 nm.

16. 16. An electrical power consuming device comprising a perovskite cell according to claim 14 or 15.

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