Preparation method of perovskite active layer, perovskite battery and perovskite material

Abstract

The invention discloses a preparation method of a perovskite active layer, a perovskite battery and a perovskite material, and belongs to the technical field of perovskite batteries. According to the invention, bisphosphonate is added when the perovskite active layer is prepared, and the bisphosphonate is obtained by carrying out a deprotonation reaction on 1-aminodecane-1, 1-diphosphonic acid and methylamine, formamidine iodine or cesium carbonate. The bisphosphonate can be anchored on the surface of the substrate and form a self-assembled monomolecular structure, a simple and effective coating process is realized, the bisphosphonate structure of the bisphosphonate is beneficial to anchoring on the substrate, the possibility and effectiveness of anchoring the substrate are increased, the combination of the perovskite active layer and the substrate is enhanced, the formation of nano-pores is reduced, and the photoelectric conversion efficiency is improved. In addition, the introduced cations MA < + >, FA < + > and Cs < + > not only can enhance the self-assembly capability of the bisphosphonate, but also can be used as nucleating agents to promote the growth of perovskite crystals and improve the quality of the perovskite crystals.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite cells, and in particular to a method for preparing a perovskite active layer, a perovskite cell and a perovskite material. Background Art

[0002] With the continuous development and progress of perovskite solar cells, self-assembled monolayers (SAMs) have been widely studied and applied to improve the overall photoelectric conversion efficiency (PCE).

[0003] At present, the research on perovskite solar cells (PSCs) based on self-assembled monolayers (SAMs) has made significant progress, and the efficiency of perovskite solar cells has also achieved high laboratory efficiency records. These results show that SAM-based perovskite cells are not only close to the cutting-edge level in efficiency, but also continue to improve in stability and repeatability, demonstrating their potential in commercial applications. However, there is still the problem of nanopores on the surface of the substrate under the perovskite active layer. The appearance of nanopores on the surface of the substrate will limit the improvement of the photoelectric conversion efficiency and stability of perovskite cells. Summary of the invention

[0004] The main purpose of the present invention is to provide a method for preparing a perovskite active layer, a perovskite battery and a perovskite material, so as to solve the technical problem that nanopores exist between the perovskite active layer and the substrate in the perovskite battery.

[0005] To achieve the above object, the present invention provides a method for preparing a perovskite active layer, comprising the following steps:

[0006] A bisphosphonate is added to a perovskite precursor solution and then coated on the surface of a substrate to obtain the perovskite active layer. The bisphosphonate is obtained by a deprotonation reaction between 1-aminodecane-1,1-diphosphonic acid and methylamine, formamidinium iodide or cesium carbonate.

[0007] In some embodiments of the present invention, the method for preparing the bisphosphonate comprises method 1, method 2 or method 3,

[0008] The method 1 comprises the following steps:

[0009] Dispersing the methylamine in a solvent and cooling the solvent and mixing the solvent with the 1-aminodecane-1,1-diphosphonic acid to obtain a mixture, stirring the mixture for reaction, concentrating the mixture to obtain a crude solid, washing and drying the crude solid to obtain the bisphosphonate;

[0010] The second method comprises the following steps:

[0011] Dispersing the formamidine iodine and 1-aminodecane-1,1-diphosphonic acid in a solvent to obtain a mixture, cooling the mixture, stirring the reaction, and concentrating the mixture to obtain a crude solid, and washing and drying the crude solid to obtain the bisphosphonate;

[0012] The method three comprises the following steps:

[0013] The cesium carbonate and 1-aminodecane-1,1-diphosphonic acid are dispersed in a solvent to obtain a mixture, the mixture is stirred and heated until the cesium carbonate is completely dissolved to obtain a mixture, the mixture is stirred and concentrated to obtain a crude solid, and the crude solid is washed and dried to obtain the bisphosphonate.

[0014] In some embodiments of the present invention, in the method 1,

[0015] The molar ratio of the methylamine to the 1-aminodecane-1,1-diphosphonic acid is (1.1:1) to (1.3:1);

[0016] and / or, the solvent comprises ethanol;

[0017] and / or, dispersing the methylamine in a solvent and cooling the solvent to -1°C to 1°C;

[0018] And / or, the stirring reaction time is 1.5 to 3 hours;

[0019] And / or, the concentration method comprises rotary evaporation;

[0020] and / or, the detergent used in the washing step comprises diethyl ether;

[0021] and / or, drying is performed under vacuum conditions at 45°C to 55°C.

[0022] In some embodiments of the present invention, in the second method,

[0023] The molar ratio of the formamidine iodine to the 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1);

[0024] and / or, the solvent comprises ethanol;

[0025] and / or, the mixture is cooled to -1°C to 1°C;

[0026] And / or, the stirring reaction time is 1.5 to 3 hours;

[0027] And / or, the concentration method comprises rotary evaporation;

[0028] and / or, the detergent used in the washing step comprises diethyl ether;

[0029] and / or, drying is performed under vacuum conditions at 45°C to 55°C.

[0030] In some embodiments of the present invention, in the method three,

[0031] The molar ratio of the cesium carbonate to the 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1);

[0032] and / or, the solvent comprises anhydrous toluene;

[0033] And / or, the stirring and heating temperature is 95°C to 105°C;

[0034] And / or, the mixture is stirred for 11 h to 13 h;

[0035] And / or, the concentration method comprises rotary evaporation;

[0036] and / or, the detergent used in the washing step comprises diethyl ether;

[0037] and / or, drying is performed under vacuum conditions at 45°C to 55°C.

[0038] In some embodiments of the present invention, in the step of adding the bisphosphonate to the perovskite precursor solution, the bisphosphonate is dissolved in an organic solvent to obtain a bisphosphonate solution, and then the bisphosphonate solution is added to the perovskite precursor solution, and the organic solvent includes 2-methoxyestradiol and N-methylpyrrolidone;

[0039] and / or, the bisphosphonate is added to the perovskite precursor solution in an amount of (0.2-0.4) mg / ml;

[0040] and / or, the method of coating the perovskite precursor solution to which the bisphosphonate is added onto the surface of the substrate comprises a slit coating method;

[0041] and / or, after the perovskite precursor solution to which the bisphosphonate is added is coated on the surface of the substrate, an annealing treatment is further performed;

[0042] And / or, the thickness of the perovskite active layer is 400nm to 800nm.

[0043] In some embodiments of the present invention, the substrate includes a transparent electrode, and the perovskite active layer is prepared on the surface of the transparent electrode.

[0044] The present invention also provides a perovskite battery, which comprises a perovskite active layer prepared by the method for preparing a perovskite active layer as described above.

[0045] In some embodiments of the present invention, the perovskite cell comprises a transparent electrode, the perovskite active layer, a transport layer, and a metal electrode stacked in sequence, wherein the transport layer is an electron transport layer or a hole transport layer.

[0046] The present invention also provides a perovskite material for preparing a perovskite active layer of a perovskite battery. The perovskite material includes a bisphosphonate, which is obtained by a deprotonation reaction of 1-aminodecane-1,1-diphosphonic acid with methylamine, formamidinium iodide or cesium carbonate.

[0047] The beneficial effects that can be achieved by the present invention are:

[0048] In the present invention, when preparing the perovskite active layer, bisphosphonate is added to the perovskite precursor solution. The bisphosphonate is obtained by deprotonating 1-aminodecane-1,1-diphosphonic acid with methylamine, formamidine iodide or cesium carbonate, and MA is introduced into the 1-aminodecane-1,1-diphosphonic acid molecule. + , FA + , Cs + Isocations.

[0049] The bisphosphonates in the perovskite precursor solution can react with substrates such as ITO substrates, anchor on the surface of the substrate and form a self-assembled single molecule structure, realizing a simple and effective coating process. The bisphosphonic acid structure of the bisphosphonates is also conducive to anchoring on the substrate, increasing the possibility and effectiveness of anchoring the substrate, strengthening the combination of the perovskite active layer and the substrate, and effectively reducing the formation of nanopores, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery. In addition, the MA introduced above + , FA + , Cs + Isocations can not only enhance the self-assembly ability of bisphosphonates, but also act as nucleating agents to promote the growth of perovskite crystals, ensure the contact between perovskite and self-assembled single molecules, and improve the quality of perovskite crystallization.

[0050] The method of the present invention is used to prepare the perovskite active layer, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite component, and is conducive to the industrialization of the perovskite battery technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0052] Figure 1Schematic diagram of the structure of a perovskite battery according to an embodiment of the present invention.

[0053] Figure 2 It is a JV performance curve diagram of the perovskite battery obtained in the embodiment of the present invention and the comparative example.

[0054] Figure 3 It is the maximum power point (MPPT) output curve of the perovskite battery of the embodiment of the present invention and the comparative example.

[0055] The figures are as follows:

[0056] 1. Transparent electrode; 2. Perovskite active layer; 3. Post-processing interface layer; 4. Transport layer; 5. Hole blocking layer; 6. Metal electrode.

[0057] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0058] It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0059] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0060] In the present invention, descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0061] The invention provides a method for preparing a perovskite active layer, comprising the following steps: adding bisphosphonate to a perovskite precursor solution, and then coating the perovskite precursor solution with the bisphosphonate added on the surface of a substrate to prepare the perovskite active layer.

[0062] 1-aminodecane-1,1-diphosphonic acid is abbreviated as C10, which has a diphosphonic acid structure. Methylamine is abbreviated as MA, with a chemical formula of CH3NH2, containing MA +, the abbreviation of formamidinium iodine is FAI, which contains FA + The chemical formula of cesium carbonate is Cs2CO3, which contains Cs + , 1-aminodecane-1,1-diphosphonic acid and the above methylamine, formamidine iodide or cesium carbonate undergo deprotonation reaction to obtain bisphosphonate, which can be expressed as bisphosphonate [C10] - [A] + , [A] + It varies depending on the reactants. For example, when 1-aminodecane-1,1-diphosphonic acid and methylamine undergo a deprotonation reaction, MA is introduced. + , bisphosphonates can be expressed as bisphosphonates [C10] - [MA] + When 1-aminodecane-1,1-diphosphonic acid and formamidine iodide undergo a deprotonation reaction, FA is introduced. + , bisphosphonates can be expressed as bisphosphonates [C10] - [FA] + When 1-aminodecane-1,1-diphosphonic acid and cesium carbonate undergo a deprotonation reaction, Cs + , bisphosphonates can be expressed as bisphosphonates [C10] - [Cs] + .

[0063] In the present invention, bisphosphonates are used to prepare the perovskite active layer. The bisphosphonates can react with substrates such as ITO substrates and anchor on the surface of the substrate to achieve a simple and effective coating process. The bisphosphonic acid structure of the bisphosphonates is also conducive to anchoring on the substrate, increasing the possibility and effectiveness of anchoring the substrate, strengthening the combination of the perovskite active layer and the substrate, and reducing the formation of nanopores, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery. In addition, the MA introduced above + , FA + , Cs + The cations can not only enhance the self-assembly ability of bisphosphonates, but also act as nucleating agents to promote the growth of perovskite crystals, ensure the contact between perovskite and self-assembled single molecules, and improve the quality of perovskite crystallization. The method of the present invention is used to prepare the perovskite active layer, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite component, and is conducive to the industrialization of perovskite battery technology. In addition, the perovskite active layer prepared by the present invention can also play a role in transporting carriers. Therefore, the perovskite active layer of the present invention can be directly prepared on the surface of the transparent electrode without preparing a transmission layer between the transparent electrode and the perovskite active layer, which simplifies the process and saves energy.

[0064] The bisphosphonate of the present invention can be prepared by method one, method two or method three.

[0065] Method 1 comprises the following steps: dispersing methylamine in a solvent and mixing it with 1-aminodecane-1,1-diphosphonic acid to obtain a mixture, stirring the mixture for reaction, concentrating the mixture to obtain a crude solid, washing and drying the crude solid to obtain a bisphosphonate [C10] - [MA] + .

[0066] In some embodiments of method 1, the molar ratio of methylamine to 1-aminodecane-1,1-diphosphonic acid is (1.1:1) to (1.3:1), and may be 1.2:1.

[0067] In some embodiments of method 1, the solvent for dispersing methylamine includes ethanol, and the amount of ethanol used is preferably sufficient to disperse and dissolve the methylamine.

[0068] In some embodiments of method 1, methylamine is dispersed in a solvent and cooled to -1°C to 1°C, which may be 0°C.

[0069] In some embodiments of method 1, the stirring reaction time is 1.5 h to 3 h, which can be 1.5 h, 2 h, 2.5 h, 3 h, etc. This is beneficial to promote the complete reaction of methylamine and 1-aminodecane-1,1-diphosphonic acid and increase the yield of bisphosphonate.

[0070] In the present invention, in method 1, stirring is performed during the reaction process, which is beneficial to promoting the reaction, while the volatile substances in the mixture are mainly removed during the concentration process to improve the purity of the product.

[0071] In some embodiments of method one, the concentration comprises rotary evaporation, which can easily remove volatile substances in the mixture and improve the purity of the product.

[0072] In some embodiments, concentration is performed under negative pressure to rapidly remove volatile substances.

[0073] In some embodiments of method 1, the washing agent used in the washing step includes diethyl ether, which can effectively wash away impurities in the crude solid, retain the product bisphosphonate, and improve the purity of the product.

[0074] In some embodiments of method 1, drying is performed under vacuum conditions at 45°C to 55°C, and may be 50°C.

[0075] Method 2 comprises the following steps: dispersing formamidine iodine and 1-aminodecane-1,1-diphosphonic acid in a solvent to obtain a mixture, cooling the mixture, stirring the mixture for reaction, and concentrating the mixture to obtain a crude solid, and washing and drying the crude solid to obtain a bisphosphonate [C10] - [FA] + .

[0076] In some embodiments of method 2, the molar ratio of formamidine iodide to 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1), and can be 1:1.

[0077] In some embodiments of method 2, the solvent includes ethanol, and ethanol can better disperse formamidine iodine and 1-aminodecane-1,1-diphosphonic acid evenly.

[0078] In some embodiments of method 2, formamidine iodine and 1-aminodecane-1,1-diphosphonic acid are dispersed in a solvent to obtain a mixture, and the mixture is cooled to -1°C to 1°C, which may be 0°C.

[0079] In some embodiments of method 2, the stirring reaction time is 1.5 h to 3 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, etc., which is conducive to promoting the complete reaction of formamidinium iodine and 1-aminodecane-1,1-diphosphonic acid and increasing the yield of bisphosphonate.

[0080] In the present invention, in method 2, stirring is performed during the reaction process, which is beneficial to promoting the reaction, while the concentration process mainly removes volatile substances in the mixture to improve the purity of the product.

[0081] In some embodiments of method 2, the concentration includes rotary evaporation, which can easily remove volatile substances in the mixture and improve the purity of the product.

[0082] In some embodiments, concentration is performed under negative pressure to accelerate the removal of volatile substances.

[0083] In some embodiments of method 2, the washing agent used in the washing step includes diethyl ether, which can effectively wash away impurities in the crude solid, retain the product bisphosphonate, and improve the purity of the product.

[0084] In some embodiments of method 2, drying is performed under vacuum conditions at 45°C to 55°C, and may be 50°C.

[0085] Method 3 comprises the following steps: dispersing cesium carbonate and 1-aminodecane-1,1-diphosphonic acid in a solvent to obtain a mixture, stirring and heating the mixture until the cesium carbonate is completely dissolved to obtain a mixture, stirring and concentrating the mixture to obtain a crude solid, washing and drying the crude solid to obtain the bisphosphonate [C10] - [Cs] + .

[0086] In some embodiments of method three, the molar ratio of cesium carbonate to 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1), and may be 1:1.

[0087] In some embodiments of method three, the solvent for dispersing cesium carbonate and 1-aminodecane-1,1-diphosphonic acid includes anhydrous toluene.

[0088] In method three, the amount of solvent used is not limited, as long as it can completely disperse and dissolve cesium carbonate and 1-aminodecane-1,1-diphosphonic acid.

[0089] In some embodiments of method three, the mixture is heated to 95° C. to 105° C., and may be 100° C., after stirring, which is conducive to promoting the complete dissolution of cesium carbonate.

[0090] In some embodiments of method three, after cesium carbonate is completely dissolved to obtain a mixture, the mixture is stirred for 11 h to 13 h, which may be 11 h, 12 h, 13 h, etc.

[0091] In the present invention, the volatile substances in the mixture are mainly removed during the concentration process to improve the purity of the product.

[0092] In some embodiments of method three, the concentration includes rotary evaporation, which can easily remove volatile substances in the mixture and improve the purity of the product.

[0093] In some embodiments, concentration is performed under negative pressure conditions to facilitate rapid removal of volatile substances.

[0094] In some embodiments of method three, the washing agent used in the washing step includes diethyl ether, which can effectively wash away impurities in the crude solid, retain the product bisphosphonate, and improve the purity of the product.

[0095] In some embodiments of method three, drying is performed under vacuum conditions at 45°C to 55°C, and may be 50°C.

[0096] In the present invention, the perovskite precursor solution can be understood as a solution prepared by dissolving a perovskite material known in the art into a solvent when preparing a perovskite active layer in the art.

[0097] Perovskite materials known in the art include the structural formula ABX3, wherein A includes organic cations or inorganic cations, such as MA + , FA + , Cs + At least one of the above, the B position includes a metal cation, such as Pb 2+ Sn 2+ At least one of the following, the X position includes a halogen anion, for example, Br - ,I - , Cl - The commonly used solvents in the art include, but are not limited to, at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0098] In the present invention, the bisphosphonate can be directly added to the perovskite precursor solution, or the bisphosphonate and the perovskite material known in the art can be dissolved separately to obtain a bisphosphonate solution and a perovskite precursor solution, and then the bisphosphonate solution and the perovskite precursor solution are mixed, and then the mixed solution is used to prepare the perovskite active layer.

[0099] In some embodiments, the bisphosphonate may be dissolved in an organic solvent, which includes a mixed solution of 2-methoxyestradiol (2ME) and N-methylpyrrolidone (NMP).

[0100] In some embodiments, the volume ratio of 2-methoxyestradiol (2ME) and N-methylpyrrolidone (NMP) is 9:1.

[0101] In some embodiments, the amount of bisphosphonate added to the perovskite precursor solution is (0.2-0.4) mg / ml, and may be 0.3 mg / ml.

[0102] In the present invention, after adding bisphosphonate to the perovskite precursor solution, the method of coating it on the surface of the substrate can refer to the method known in the art for preparing perovskite active layer. In some embodiments, the method for preparing the perovskite active layer includes a slit coating method.

[0103] In some embodiments, after the perovskite precursor solution to which bisphosphonate is added is coated on the surface of the substrate, an annealing treatment is performed, and the annealing temperature is 145°C to 155°C, for example, it can be 145°C, 150°C, 155°C, etc., and the annealing time is 28min to 32min, for example, it can be 28min, 29min, 30min, 31min, 32min, etc.

[0104] In some embodiments, a perovskite precursor solution containing a bisphosphonate is coated onto the surface of a substrate by a slit coating method using a slit coating device. Specifically, the blade of the slit coating device is deposited onto the surface of the substrate, and a semi-dry film is formed by an air knife, and then annealing is performed to obtain a perovskite film, i.e., a perovskite active layer.

[0105] In some embodiments, a perovskite precursor solution containing a bisphosphonate is coated onto the surface of a substrate using a slit coating method, and an anti-solvent is added during the spin coating process to promote the crystallization of the perovskite, and the anti-solvent includes at least one of chlorobenzene (CB), ethylmethyl carbonate (EMC), ethyl acetate (EA) and m-chloroaniline.

[0106] In some embodiments, the coating speed of the perovskite active layer prepared by the slit coating method is 10 mm / s to 11 mm / s, the injection speed is 0.3 ml / min to 0.5 ml / min, and the air knife pressure is 0.85 bar to 0.9 bar, which is conducive to controlling the thickness of the perovskite active layer to 400 nm to 800 nm.

[0107] In some embodiments, the thickness of the perovskite active layer is 400 nm to 800 nm, and can be 400 nm, 500 nm, 600 nm, 700 nm, or 800 nm.

[0108] In some embodiments, the substrate includes a transparent electrode, the transparent electrode includes at least one of indium tin oxide (ITO) and fluorine-doped tin oxide (FTO), a perovskite active layer is prepared on the surface of the transparent electrode, the bisphosphonate can react with the substrate of the transparent electrode, and anchored on the surface of the transparent electrode to achieve a simple and effective coating process, and the bisphosphonic acid structure of the bisphosphonate is also conducive to anchoring on the transparent electrode, increasing the possibility and effectiveness of anchoring the substrate, strengthening the combination of the perovskite active layer and the transparent electrode, and reducing the formation of nanopores, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery. In addition, the MA introduced into the bisphosphonate + , FA + , Cs + The isocations can not only enhance the self-assembly ability of bisphosphonates, but also act as nucleating agents to promote the growth of perovskite crystals, ensure the contact between perovskite and self-assembled single molecules, and improve the quality of perovskite crystals. The method of the present invention is used to prepare the perovskite active layer, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite component, and is conducive to the industrialization of perovskite battery technology.

[0109] The present invention now provides an embodiment of a method for preparing a perovskite active layer, comprising the following steps: dissolving a perovskite material known in the art into an organic solvent to obtain a perovskite precursor solution, dissolving a bisphosphonate into a mixed solution of 2-methoxyestradiol (2ME) and N-methylpyrrolidone (NMP) to obtain a bisphosphonate solution, mixing the perovskite precursor solution and the bisphosphonate solution, and coating the mixture on the surface of a substrate by a slit coating method, wherein the coating speed is 10 mm / s to 11 mm / s, the injection speed is 0.3 ml / min to 0.5 ml / min, and the air knife pressure is 0.85 bar to 0.9 bar. After coating, annealing is performed at 145° C. to 155° C. for 28 min to 30 min to obtain a perovskite active layer with a thickness of 400 nm to 800 nm.

[0110] In some embodiments, the perovskite active layer is also post-treated, and the post-treatment solution is coated on the surface of the perovskite active layer, and then annealing is performed. The coating method includes spin coating, the spin coating speed is 3000rpm~3500rpm, the spin coating time is 30s~35s, the annealing temperature is 90℃~110℃, which can be 100℃, and the annealing time is 8min~11min, which can be 10min.

[0111] In some embodiments, the post-treatment solution includes formamidine hydrochloride, phenethylamine hydroiodide and piperazine hydroiodide. Exemplarily, formamidine hydrochloride, phenethylamine hydroiodide and piperazine hydroiodide can be dissolved in isopropanol to obtain formamidine hydrochloride solution, phenethylamine hydroiodide solution and piperazine hydroiodide solution, respectively, and then the above three solutions are mixed to obtain a post-treatment solution. In this embodiment, the perovskite active layer is treated with the post-treatment solution to passivate the defects of the perovskite active layer, reduce non-radiative recombination losses, and promote the perovskite active layer to obtain a smoother morphology, thereby improving the photoelectric conversion efficiency of the perovskite cell.

[0112] The present invention also provides a perovskite battery, wherein the perovskite active layer in the perovskite battery is prepared by the above-mentioned preparation method, and comprises a bisphosphonate, which can react with a substrate such as an ITO substrate, anchored on the surface of the substrate and forming a self-assembled monomolecular structure, realizing a simple and effective coating process, and the bisphosphonic acid structure of the bisphosphonate is conducive to anchoring on the substrate, increasing the possibility and effectiveness of anchoring the substrate, strengthening the combination of the perovskite active layer and the substrate, reducing the formation of nanopores, and improving the photoelectric conversion efficiency of the perovskite battery. In addition, the cations introduced above can not only enhance the self-assembly ability of the bisphosphonate, but also act as a nucleating agent to promote the growth of perovskite crystals, ensure the contact between the perovskite and the self-assembled monomolecule, and improve the quality of the perovskite crystal. The perovskite battery containing the perovskite active layer can effectively improve the photoelectric conversion efficiency and stability, and is conducive to the industrialization of the perovskite battery technology.

[0113] In some embodiments, reference Figure 1 The perovskite battery of the present invention comprises a transparent electrode 1, a perovskite active layer 2, a transport layer 4, and a metal electrode 6 which are stacked in sequence, and the transport layer 4 comprises an electron transport layer or a hole transport layer.

[0114] In some embodiments, some functional layers commonly used in the art may be disposed between the perovskite active layer 2 and the transport layer 4, and between the transport layer 4 and the metal electrode 6. Figure 1 After the perovskite active layer 2 is treated with a post-treatment solution, a post-treatment interface layer 3 can be formed. A hole blocking layer 5 can be arranged between the transport layer 4 and the metal electrode 6. The hole blocking layer 5 includes a bathocuproin blocking layer.

[0115] In some embodiments, the perovskite cell of the present invention includes a transparent electrode 1, a perovskite active layer 2, a transport layer 4, a hole blocking layer 5, and a metal electrode 6 stacked in sequence, and the transport layer 4 is an electron transport layer.

[0116] In the present invention, the preparation of the transparent electrode, the electron transport layer, the hole transport layer and some common functional layers such as the hole blocking layer can be prepared by referring to conventional technical means in the art.

[0117] The present invention also provides a perovskite material for preparing a perovskite active layer of a perovskite battery. The perovskite material includes a bisphosphonate, which is obtained by a deprotonation reaction of 1-aminodecane-1,1-diphosphonic acid with methylamine, formamidinium iodide or cesium carbonate.

[0118] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention, and are not used to limit the present invention.

[0119] Preparation of bisphosphonates [C10] - [MA] +

[0120] Preparation of bisphosphonate [C10] by method 1 - [MA] + :Methylamine was dissolved in a round-bottom flask containing ethanol, cooled to 0°C, and then 1-aminodecane-1,1-diphosphonic acid was added and mixed to obtain a mixture, wherein the molar ratio of methylamine to 1-aminodecane-1,1-diphosphonic acid was 1.2:1.0. After the mixture was stirred and reacted for 2 hours, volatile substances were removed by rotary evaporator under reduced pressure to obtain a crude solid. The crude solid was washed with diethyl ether and dried in a vacuum environment at 50°C to obtain a white powder, i.e., bisphosphonate [C10] - [MA] + .

[0121] Preparation of bisphosphonates [C10] - [FA] +

[0122] Preparation of bisphosphonate [C10] by method 2 - [FA] + :Formamidine iodine and 1-aminodecane-1,1-diphosphonic acid are dispersed in a round-bottom flask filled with an ethanol solution to obtain a mixture, wherein the molar ratio of formamidine iodine to 1-aminodecane-1,1-diphosphonic acid is 1.0:1.0, the mixture is cooled to 0°C, stirred for reaction for 2 hours, and then volatile substances are removed by rotary evaporator under reduced pressure to obtain a crude solid, which is washed with diethyl ether and dried in a vacuum environment at 50°C to obtain a white powder, i.e., bisphosphonate [C10]- [FA] + .

[0123] Preparation of bisphosphonates [C10] - [Cs] +

[0124] Preparation of bisphosphonates [C10] by method 3 - [Cs] + :Cesium carbonate and 1-aminodecane-1,1-diphosphonic acid are dissolved in a round-bottom flask filled with anhydrous toluene at a molar ratio of 1.0:1.0 to obtain a mixture, the mixture is placed in an oil bath, stirred and heated to 100°C until the cesium carbonate is completely dissolved, and the stirring is continued for 12 hours. The volatile matter is removed by a rotary evaporator under reduced pressure to obtain a crude solid, the crude solid is washed with diethyl ether, and dried in a vacuum environment at 50°C to obtain a white powder, i.e., bisphosphonate [C10] - [Cs] + .

[0125] Example 1

[0126] S10: After P1 is scribed on the ITO transparent electrode, the ITO transparent electrode is cleaned with a cleaning agent, deionized water, acetone, and isopropyl alcohol in sequence, and then placed in a UV ozone treatment machine for 20 minutes to remove organic residues on the surface.

[0127] S20: Prepare a 1.2M FAPbI3 perovskite precursor solution, and then add an additional 0.3 mg of bisphosphonate [C10] per ml of perovskite precursor solution. - [MA] + and 10 mg of MACl, bisphosphonate [C10] - [MA] + The perovskite precursor solution dissolved in 2-methoxyestradiol (2ME) and N-methylpyrrolidone (NMP) (the volume ratio of 2ME to NMP is 9:1) is added, and the perovskite precursor solution to which the bisphosphonate is added is stirred at room temperature for 18 hours and then filtered, and deposited on the surface of the ITO transparent electrode by a slit coating method, with a coating speed of 10 mm / s, a liquid injection speed of 0.3 ml / min, and a wind knife pressure of 0.85 bar. After the coating is completed, the perovskite active layer is annealed at 150° C. for 30 minutes.

[0128] S30: Post-treating the perovskite active layer, specifically, dissolving 1 mg of formamidine hydrochloride in 1 ml of isopropanol solvent, dissolving 1 mg of phenylethylamine hydroiodide in 1 ml of isopropanol solvent, and dissolving piperazine hydroiodide in 1 ml of isopropanol solvent, and after sufficient stirring, filtering them separately, and then mixing the three solutions in a volume ratio of 1:1:0.1 to obtain an isopropanol solution, and spin-coating the above isopropanol solution on the surface of the perovskite active layer by spin coating at a rotation speed of 3000 rpm for 30 seconds, and then annealing at 100°C for 10 minutes to complete the post-treatment of the perovskite active layer.

[0129] S40, C was prepared on the surface of the post-treated perovskite active layer by thermal evaporation. 60 Electron transport layer, thickness is 25nm.

[0130] S50, using thermal evaporation method at C 60 A bathocuproin hole blocking layer with a thickness of 7 nm was prepared on the surface of the electron transport layer.

[0131] S60, a silver metal electrode with a thickness of 120 nm is prepared on the surface of the copper bath hole blocking layer by a thermal evaporation method.

[0132] Example 2

[0133] Example 2 A perovskite battery was prepared according to the preparation method of Example 1, except that in the step of preparing the perovskite active layer, a bisphosphonate [C10] obtained by deprotonating 1-aminodecane-1,1-diphosphonic acid and formamidine iodide was used. - [FA] + Substituting the bisphosphonate [C10] of Example 1 - [MA] + .

[0134] Example 3

[0135] Example 2 A perovskite battery was prepared by referring to the preparation method of Example 1, except that in the step of preparing the perovskite active layer, a bisphosphonate [C10] obtained by deprotonating 1-aminodecane-1,1-diphosphonic acid and cesium carbonate was used. - [Cs] + Substituting the bisphosphonate [C10] of Example 1 - [MA] + .

[0136] Comparative Example 1

[0137] Comparative Example 1 A perovskite battery was prepared according to the preparation method of Example 1, except that in the step of preparing the perovskite active layer, no bisphosphonate [C10] was added. - [MA] +.

[0138] Comparative Example 2

[0139] Comparative Example 2 A perovskite battery was prepared according to the preparation method of Example 1, except that in the step of preparing the perovskite active layer, 1-aminodecane-1,1-diphosphonic acid was used instead of bisphosphonate [C10] - [MA] + .

[0140] Performance Testing

[0141] The perovskite cells prepared in the above examples and comparative examples were placed under a xenon lamp solar simulator (100 mW cm -2 ), the short-circuit current density-voltage (JV) curve performance of the perovskite battery was tested, and the results are shown in Table 1 and Figure 2 , Figure 3 .

[0142] Figure 2 It is the JV performance curve diagram of comparative example 1, comparative example 2 and embodiment 1 to embodiment 3, Figure 3 These are the maximum power point (MPPT) output curves of Comparative Example 1, Comparative Example 2, and Examples 1 to 3.

[0143] Table 1 JV performance test parameters of perovskite cells of embodiments and comparative examples.

[0144]

[0145] It can be seen from Table 1 that no bisphosphonate is added to the perovskite precursor solution of Comparative Example 1, and the photoelectric conversion efficiency of its perovskite cell is only 11.07%. Although 1-aminodecane-1,1-diphosphonic acid is added to Comparative Example 2, it has not undergone a protonation reaction, and the photoelectric conversion efficiency of its perovskite cell is 15.8%. The photoelectric conversion efficiency of the perovskite cells prepared by the bisphosphonate-doped perovskite precursor solution in Examples 1 to 3 reached 16.56%, 17.07%, and 17.98%, respectively, which are better than Comparative Examples 1 and 2.

[0146] Combining Table 1 and Figure 2 It can be seen that the efficiency improvement of the perovskite cells of Examples 1 to 3 mainly comes from the improvement of the open circuit voltage (VOC) and the fill factor (FF): bisphosphonate [C10] - [MA] + The doped perovskite cell has an open circuit voltage of 1.04 V and a short circuit current of 22.82 mA cm -2 , filling factor is 70.01%; bisphosphonate [C10] - [FA] +The open circuit voltage of the doped perovskite cell is 1.03 V and the short circuit current is 23.03 mA cm -2 , filling factor is 71.83%; bisphosphonate [C10] - [Cs] + The doped perovskite cell has an open circuit voltage of 1.07 V and a short circuit current of 22.82 mA cm -2 , the fill factor is 73.65%; the open circuit voltage of the component of comparative example 1 is 0.89V, and the short circuit current is 22.27mA cm -2 , the fill factor is 55.68%, the open circuit voltage of the component of comparative example 2 is 0.99V, and the short circuit current is 22.34mAcm -2 , the filling factor is 70.73%. This indicates that doping the bisphosphonate obtained by deprotonation reaction in the perovskite precursor solution helps to modify the ITO surface, form more effective carrier extraction, and reduce non-radiative recombination at the interface, proving the effect of bisphosphonate doping in preparing the perovskite active layer on the perovskite crystal quality and substrate anchoring and the efficiency improvement it brings.

[0147] Combining Table 1 and Figure 3 It can be seen that in Comparative Example 2, only 1-aminodecane-1,1-diphosphonic acid C10 was added, and no deprotonation reaction was performed on C10 to introduce MA. + , FA + , Cs + , while in Examples 1 to 3, C10 is deprotonated to introduce MA + , FA + , Cs + The photoelectric conversion efficiency of the prepared perovskite battery is better than that of the comparative example 2 without protonation reaction. This also proves the importance of 1-aminodecane-1,1-diphosphonic acid through deprotonation reaction and introduction of cations, which can give stronger anchoring effect and better stability. In addition, Figure 3 It shows that the stability of bisphosphonate-doped perovskite cells is better than that of undoped perovskite cells, indicating that the improvement of carrier extraction ability can make perovskite cells more stable and can reduce the problems of perovskite and interface degradation caused by carrier accumulation.

[0148] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a perovskite active layer, characterized in that: The following steps are involved: A bisphosphonate is added to a perovskite precursor solution and then coated on the surface of a substrate to obtain the perovskite active layer. The bisphosphonate is obtained by a deprotonation reaction between 1-aminodecane-1,1-diphosphonic acid and methylamine, formamidinium iodide or cesium carbonate.

2. The method for preparing the perovskite active layer according to claim 1, characterized in that: The preparation method of the bisphosphonate includes method 1, method 2 or method 3, The method 1 comprises the following steps: Dispersing the methylamine in a solvent and cooling the solvent and mixing the solvent with the 1-aminodecane-1,1-diphosphonic acid to obtain a mixture, stirring the mixture for reaction, concentrating the mixture to obtain a crude solid, washing and drying the crude solid to obtain the bisphosphonate; The second method comprises the following steps: Dispersing the formamidine iodine and 1-aminodecane-1,1-diphosphonic acid in a solvent to obtain a mixture, cooling the mixture, stirring the reaction, and concentrating the mixture to obtain a crude solid, and washing and drying the crude solid to obtain the bisphosphonate; The method three comprises the following steps: The cesium carbonate and 1-aminodecane-1,1-diphosphonic acid are dispersed in a solvent to obtain a mixture, the mixture is stirred and heated until the cesium carbonate is completely dissolved to obtain a mixture, the mixture is stirred and concentrated to obtain a crude solid, and the crude solid is washed and dried to obtain the bisphosphonate.

3. The method for preparing the perovskite active layer according to claim 2, characterized in that: In the first method, The molar ratio of the methylamine to the 1-aminodecane-1,1-diphosphonic acid is (1.1:1) to (1.3:1); and / or, the solvent comprises ethanol; and / or, dispersing the methylamine in a solvent and cooling the solvent to -1°C to 1°C; And / or, the stirring reaction time is 1.5 to 3 hours; And / or, the concentration method comprises rotary evaporation; and / or, the detergent used in the washing step comprises diethyl ether; and / or, drying is performed under vacuum conditions at 45°C to 55°C.

4. The method for preparing the perovskite active layer according to claim 2, characterized in that: In the second method, The molar ratio of the formamidine iodine to the 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1); and / or, the solvent comprises ethanol; and / or, the mixture is cooled to -1°C to 1°C; And / or, the stirring reaction time is 1.5 to 3 hours; And / or, the concentration method comprises rotary evaporation; and / or, the detergent used in the washing step comprises diethyl ether; and / or, drying is performed under vacuum conditions at 45°C to 55°C.

5. The method for preparing the perovskite active layer according to claim 2, characterized in that: In the third method, The molar ratio of the cesium carbonate to the 1-aminodecane-1,1-diphosphonic acid is (1:1) to (1.3:1); and / or, the solvent comprises anhydrous toluene; And / or, the stirring and heating temperature is 95°C to 105°C; And / or, the mixture is stirred for 11 h to 13 h; And / or, the concentration method comprises rotary evaporation; and / or, the detergent used in the washing step comprises diethyl ether; and / or, drying is performed under vacuum conditions at 45°C to 55°C.

6. The method for preparing a perovskite active layer according to claim 1, characterized in that: In the step of adding the bisphosphonate to the perovskite precursor solution, the bisphosphonate is dissolved in an organic solvent to obtain a bisphosphonate solution, and then the bisphosphonate solution is added to the perovskite precursor solution, wherein the organic solvent comprises 2-methoxyestradiol and N-methylpyrrolidone; and / or, the bisphosphonate is added to the perovskite precursor solution in an amount of (0.2-0.4) mg / ml; and / or, the method of coating the perovskite precursor solution to which the bisphosphonate is added onto the surface of the substrate comprises a slit coating method; and / or, after the perovskite precursor solution to which the bisphosphonate is added is coated on the surface of the substrate, an annealing treatment is further performed; And / or, the thickness of the perovskite active layer is 400nm to 800nm.

7. The method for preparing a perovskite active layer according to claim 1, characterized in that: The substrate comprises a transparent electrode, and the perovskite active layer is prepared on the surface of the transparent electrode.

8. A perovskite battery, characterized in that: The perovskite battery comprises a perovskite active layer prepared by the method for preparing a perovskite active layer according to any one of claims 1 to 7.

9. The perovskite cell according to claim 8, characterized in that: The perovskite battery comprises a transparent electrode, the perovskite active layer, a transport layer, and a metal electrode stacked in sequence, wherein the transport layer is an electron transport layer or a hole transport layer.

10. A perovskite material used for preparing a perovskite active layer of a perovskite battery, characterized in that: The perovskite material includes bisphosphonate, which is obtained by deprotonating 1-aminodecane-1,1-diphosphonic acid with methylamine, formamidine iodide or cesium carbonate.

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