A method for preparing a perovskite battery

Abstract

The present invention provides a method for preparing a perovskite battery, comprising: preparing a precursor solution, wherein the solute of the precursor solution is a quasi-two-dimensional perovskite (RNH3)2A n‑1 M n X 3n+1 , n is an integer greater than or equal to 2; a first electrode layer and a first charge transport layer are sequentially formed on one side of the substrate; a liquid film is formed on the surface of the first charge transport layer away from the substrate using a precursor solution; the liquid film is annealed in a protonic organic atmosphere, and the protonic organic molecules combine with the hydrogen elements in the larger amine ions in the quasi-two-dimensional perovskite, so that the amine ions are converted into neutral organic amines and separated from the quasi-two-dimensional perovskite, thereby gradually converting the quasi-two-dimensional perovskite into a three-dimensional perovskite. The above conversion process makes the crystallization process of the three-dimensional perovskite controllable, slows down the crystallization speed of the three-dimensional perovskite, thereby obtaining three-dimensional perovskite grains with larger sizes, improving the quality of the three-dimensional perovskite layer, and further improving the photoelectric conversion efficiency of the perovskite battery.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite batteries, and in particular to a method for preparing a perovskite battery. Background Art

[0002] As the global ecological environment and energy shortage problems become increasingly severe, solar photovoltaic power generation has received widespread attention. As a third-generation new type of solar cell, perovskite cells have become a rising star in the field of solar cells with their advantages of low cost, simple preparation process, and high efficiency. Perovskite cells include a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode stacked in sequence. Currently, the material of the perovskite layer is mostly three-dimensional perovskite. At present, the steps of forming a three-dimensional perovskite layer include: preparing a precursor solution, the solute of the precursor solution is a three-dimensional perovskite; using the precursor solution to form a liquid film on the surface of the first charge transport layer; annealing the liquid film to evaporate the solvent and crystallize the three-dimensional perovskite, thereby obtaining a three-dimensional perovskite layer.

[0003] However, too fast crystallization during the above annealing process can easily lead to smaller grain size and more grain boundaries, making it impossible to obtain a high-quality three-dimensional perovskite layer, which in turn limits the performance of the perovskite battery. Summary of the invention

[0004] Therefore, the technical problem to be solved by the present invention is how to improve the quality of the three-dimensional perovskite layer, thereby providing a method for preparing a perovskite battery.

[0005] The present invention provides a method for preparing a perovskite battery, comprising: preparing a precursor solution, wherein the solute of the precursor solution is a quasi-two-dimensional perovskite (RNH3)2An-1MnX3n+1, where n is an integer greater than or equal to 2; sequentially forming a first electrode layer and a first charge transport layer on a surface of one side of a substrate; using the precursor solution to form a liquid film on a surface of the first charge transport layer that is away from the substrate; and annealing the liquid film in a protonic organic atmosphere to form a three-dimensional perovskite layer.

[0006] Optionally, the protophilic organic atmosphere is provided by heating the protophilic organic solvent to volatilize the organic molecules.

[0007] Optionally, the liquid film is heated together with the organic solvent so that the liquid film is annealed in a protophilic organic atmosphere.

[0008] Optionally, the step of heating the liquid film together with the organic solvent includes: providing a carrier, wherein the organic solvent is contained in the carrier; placing the substrate having the liquid film together with the carrier on a heating panel, and the carrier is located on the side of the substrate, so that the heating panel heats the substrate and the carrier together.

[0009] Optionally, the organic solvent includes at least one of ethanol, isopropanol, n-butanol, acetone, ethyl acetate, propyl acetate, acetylacetone, butyl acetate, acetypropylamine, picoline, acetyl chloride and acetic anhydride.

[0010] Optionally, after placing the substrate with the liquid film together with the carrier on the heating panel, the method further includes: providing a shielding cover, buckling the shielding cover on the heating panel, forming a accommodating space between the shielding cover and the heating panel, and the substrate and the carrier are both located in the accommodating space; when the heating panel heats the substrate and the carrier together, a proton-philic organic atmosphere is formed in the accommodating space.

[0011] Optionally, the shielding cover includes a top plate and a side plate, the side plate is arranged around the edge of the top plate, one end of the side plate is connected to the top plate, and the other end of the side plate is suitable for contacting the heating panel; the top plate and / or the side plate have through holes, and the through holes constitute the flow opening; and / or a partial area of ​​the side plate has a notch, and the notch constitutes the flow opening.

[0012] Optionally, the flow port is located on a side of the substrate facing away from the carrier.

[0013] Optionally, the annealing temperature is 100° C.-150° C., and the annealing time is 20 min-60 min.

[0014] Optionally, in the precursor solution, the concentration of the solute is 1.0 mol / L-1.8 mol / L.

[0015] Optionally, R includes at least one of a straight-chain alkyl group, piperidine, pyridine, a benzene ring, and a thiophene aromatic group.

[0016] Optionally, R includes at least one of benzylamine, phenylethylamine, amphetamine, 1,4-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 2-aminoanthracene, 2-naphthylamine, 3-phenanthrenamine, (6-amino-2-naphthyl)amine, 3-phenanthrenamine, 2,7-naphthalenediamine, 2-aminochrysene, 2,6-diaminoanthracene, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, p-trifluoromethylaniline, 3-methyldiphenylamine, and thiophenemethylamine.

[0017] Optionally, the substrate includes glass, a flexible substrate, a heterojunction cell, a crystalline silicon cell or a thin film solar cell.

[0018] The technical solution of the present invention has the following advantages:

[0019] 1. The preparation method of the perovskite battery provided by the present invention, the liquid film contains a quasi-two-dimensional perovskite (RNH3)2An-1MnX3n+1, and during the annealing process, the protonic organic molecules combine with the hydrogen element in the larger amine ions in the quasi-two-dimensional perovskite, so that the amine ions are converted into neutral organic amines and separated from the quasi-two-dimensional perovskite, thereby gradually converting the quasi-two-dimensional perovskite into a three-dimensional perovskite. The above-mentioned conversion process makes the crystallization process of the three-dimensional perovskite controllable, slows down the crystallization speed of the three-dimensional perovskite, thereby obtaining a three-dimensional perovskite grain with a larger size, reducing the number of grain boundaries in the three-dimensional perovskite layer, improving the quality of the three-dimensional perovskite layer, and thus improving the photoelectric conversion efficiency of the perovskite battery.

[0020] 2. The preparation method of the perovskite battery provided by the present invention, the shielding cover is provided with a flow port, and the neutral organic amine generated in the conversion process can flow out from the flow port, so that the concentration of the neutral organic amine in the shielding cover is not too high, thereby avoiding the inhibition of the conversion process due to the excessive concentration of the neutral organic amine, ensuring the smooth progress of the conversion reaction, thereby ensuring the quality of the three-dimensional perovskite layer.

[0021] 3. The preparation method of the perovskite battery provided by the present invention, wherein the flow port is located on the side of the substrate away from the carrier, and the organic molecules from the carrier diffuse toward the flow port. The substrate is located on the diffusion path of the organic molecules, which is beneficial to the contact between the liquid film on the surface of the substrate and the organic molecules, thereby facilitating the reaction between the quasi-two-dimensional perovskite in the liquid film and the organic molecules, effectively improving the uniformity of the three-dimensional perovskite layer, effectively improving the quality of the three-dimensional perovskite layer, and thereby effectively improving the photoelectric conversion efficiency of the perovskite battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0023] Figure 1 These are the XRD spectra of the quasi-two-dimensional perovskite layer and the three-dimensional perovskite layer of the experimental examples of the present invention. DETAILED DESCRIPTION

[0024] The present embodiment provides a method for preparing a perovskite battery, comprising: preparing a precursor solution, wherein the solute of the precursor solution is a quasi-two-dimensional perovskite (RNH3)2An-1MnX3n+1, where n is an integer greater than or equal to 2; sequentially forming a first electrode layer and a first charge transfer layer on a surface of one side of a substrate; using the precursor solution to form a liquid film on a surface of the first charge transfer layer that is away from the substrate; and annealing the liquid film in a protonic organic atmosphere to form a three-dimensional perovskite layer.

[0025] In the preparation method of the above perovskite battery, during the annealing process, the protonic organic molecules combine with the hydrogen elements in the larger amine ions in the quasi-two-dimensional perovskite, so that the amine ions are converted into neutral organic amines and separated from the quasi-two-dimensional perovskite, thereby gradually converting the quasi-two-dimensional perovskite into a three-dimensional perovskite. The above conversion process makes the crystallization process of the three-dimensional perovskite controllable, slows down the crystallization speed of the three-dimensional perovskite, thereby obtaining three-dimensional perovskite grains with larger sizes, reducing the number of grain boundaries in the three-dimensional perovskite layer, improving the quality of the three-dimensional perovskite layer, and thus improving the photoelectric conversion efficiency of the perovskite battery.

[0026] The following is a clear and complete description of the preparation method of perovskite cells.

[0027] Step S1, prepare a precursor solution, the solute of the precursor solution is a quasi-two-dimensional perovskite (RNH3)2An-1MnX3n+1, where n is an integer greater than or equal to 2. Wherein, R includes at least one of a straight-chain alkyl group, piperidine, pyridine, a benzene ring, and a thiophene aromatic group; specifically, R includes but is not limited to benzylamine, phenylethylamine, amphetamine, 1,4-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 2-aminoanthracene, 2-naphthylamine, 3-phenanthrenylamine, (6-amino-2-naphthyl)amine, 3-phenanthrenylamine, 2,7-naphthalenediamine, 2-aminochrysene, 2,6-diaminoanthracene, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, p-trifluoromethylaniline, 3-methyldiphenylamine, and thiophenemethylamine; A is a monovalent cation, including but not limited to methylamine ion (MA+), formamidine ion (FA+), and cesium ion (Cs+); M is a divalent metal ion, including but not limited to Pb2+ and Sn2+; X is a halogen ion, including I-, Br-, and Cl-.

[0028] Specifically, the solvent of the precursor solution is a DMF:DMSO mixed solvent, and the volume ratio of DMF (dimethylformamide) and DMSO (dimethyl sulfoxide) is (3-10):1; illustratively, the volume ratio of DMF and DMSO can be 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0029] Specifically, in the precursor solution, the concentration of the solute is 1.0 mol / L-1.8 mol / L; illustratively, the concentration of the solute can be 1.0 mol / L, 1.2 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, or 1.8 mol / L.

[0030] Step S2: providing a substrate.

[0031] Specifically, the substrate includes but is not limited to glass, flexible substrate, heterojunction cell, crystalline silicon cell or thin film solar cell; flexible substrate includes but is not limited to polyethylene naphthalate (PEN), polyethylene terephthalate (PET); thin film solar cell includes but is not limited to copper indium gallium selenide thin film solar cell, cadmium telluride thin film solar cell, gallium arsenide thin film solar cell, perovskite solar cell; crystalline silicon cell includes but is not limited to N-type single crystal passivated contact cell (TopCon cell). When the substrate is glass or flexible substrate, the final cell prepared is a single junction perovskite cell; when the substrate is a heterojunction cell, crystalline silicon cell or thin film solar cell, the final cell prepared is a stacked cell.

[0032] Step S3: forming a first electrode layer on one surface of the substrate.

[0033] Specifically, the process of forming the first electrode layer on one side of the substrate includes but is not limited to a magnetic sputtering process or a chemical vapor deposition process; the material of the first electrode layer includes but is not limited to fluorine-doped tin oxide (FTO) or indium tin oxide (ITO). It should be understood that when the substrate is made of glass or PEN, and the material of the first electrode layer is FTO or ITO, commercial FTO conductive glass, ITO conductive glass, PEN / ITO can be directly used.

[0034] Step S4, forming a first charge transport layer on a surface of the first electrode layer that is away from the substrate.

[0035] Specifically, the method for forming the first charge transport layer includes, but is not limited to, spin coating, coating, vacuum evaporation, and magnetron sputtering. The preparation method can be selected according to the material of the first charge transport layer.

[0036] Step S5, forming a three-dimensional perovskite layer on the surface of the first charge transport layer facing away from the substrate.

[0037] Specifically, the steps of forming a three-dimensional perovskite layer include:

[0038] Step S51, using the precursor solution to form a liquid film on the surface of the first charge transport layer on the side away from the substrate; methods for forming the liquid film include but are not limited to spin coating and scraping.

[0039] Step S52, annealing the liquid film in a protophilic organic atmosphere to form a three-dimensional perovskite layer; wherein the protophilic organic solvent is heated to volatilize organic molecules to provide the protophilic organic atmosphere.

[0040] Furthermore, the organic solvent includes but is not limited to at least one of ethanol, isopropanol, n-butanol, acetone, ethyl acetate, propyl acetate, butyl acetate, acetylopyramide, acetylacetone, picoline, acetyl chloride and acetic anhydride.

[0041] In one embodiment, the liquid film is heated together with the organic solvent so that the liquid film is annealed in a protonic organic atmosphere. Here, heating together means that the liquid film and the organic solvent are in the same heating environment. Exemplarily, the step of heating the liquid film together with the organic solvent includes: providing a carrier, the carrier containing the organic solvent, the carrier including but not limited to a beaker; placing the substrate with the liquid film together with the carrier on a heating panel, and the carrier is located on the side of the substrate, so that the heating panel heats the substrate and the carrier together.

[0042] Furthermore, after placing the substrate with the liquid film together with the carrier on the heating panel, it also includes: providing a shielding cover, buckling the shielding cover on the heating panel, forming a containing space between the shielding cover and the heating panel, and the substrate and the carrier are both located in the containing space; when the heating panel heats the substrate and the carrier together, a proton-philic organic atmosphere is formed in the containing space. Specifically, the shielding cover includes a top plate and a side plate, the side plate is arranged around the edge of the top plate, one end of the side plate is connected to the top plate, and the other end of the side plate is suitable for contacting the heating panel. The material of the shielding cover is a high temperature resistant material. The material of the shielding cover includes but is not limited to tin foil.

[0043] Furthermore, the top plate and / or the side plate have through holes, which constitute the flow openings; and / or, a part of the side plate has notches, which constitute the flow openings. The neutral organic amines generated during the conversion process can flow out from the flow openings, so that the concentration of the neutral organic amines in the shielding cover is not too high, thus avoiding the inhibition of the conversion process due to the excessive concentration of the neutral organic amines, ensuring the smooth progress of the conversion reaction, and thus ensuring the quality of the three-dimensional perovskite layer.

[0044] Preferably, the flow port is located on the side of the substrate away from the carrier. The organic molecules from the carrier diffuse toward the flow port, and the substrate is located on the diffusion path of the organic molecules, which is conducive to the contact between the liquid film on the surface of the substrate and the organic molecules, thereby facilitating the reaction between the quasi-two-dimensional perovskite in the liquid film and the organic molecules, effectively improving the uniformity of the three-dimensional perovskite layer, effectively improving the quality of the three-dimensional perovskite layer, and thus effectively improving the photoelectric conversion efficiency of the perovskite cell.

[0045] Further, the shape of the flow opening includes but is not limited to a rectangle, a circle, or a trapezoid; preferably, the shape of the flow opening is a rectangle, and the length direction of the flow opening is parallel to the substrate during the annealing process, the length of the flow opening is greater than or equal to the length of the edge of the substrate close to the flow opening, and the width of the flow opening is 5 cm-50 cm. Exemplarily, the width of the flow opening is 5 cm, 10 cm, 15 cm, 20 cm, 25 cm, 30 cm, 35 cm, 40 cm, 45 cm, or 50 cm.

[0046] Further, the annealing temperature is 100°C-150°C, and the annealing time is 20min-60min; for example, the annealing temperature can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and the annealing time can be 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min. The higher the annealing temperature, the shorter the annealing time.

[0047] Step S6, forming a second charge transport layer on a surface of the three-dimensional perovskite layer facing away from the substrate;

[0048] Specifically, the method for forming the second charge transport layer includes, but is not limited to, spin coating, coating, vacuum evaporation, and magnetron sputtering. The preparation method can be selected according to the material of the second charge transport layer.

[0049] It should be understood that one of the first charge transport layer and the second charge transport layer is a hole transport layer, and the other is an electron transport layer; when the first charge transport layer is a hole transport layer and the second charge transport layer is an electron transport layer, the perovskite cell is an inverse perovskite cell; when the first charge transport layer is an electron transport layer and the second charge transport layer is a hole transport layer, the perovskite cell is a formal perovskite cell.

[0050] Step S7, forming a second electrode layer on the surface of the second charge transport layer facing away from the substrate to obtain a perovskite cell.

[0051] Specifically, the method for forming the second electrode layer includes but is not limited to vacuum evaporation; the material of the second electrode layer includes but is not limited to gold, silver, and aluminum.

[0052] The following specific embodiments are provided to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than 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.

[0053] Example 1

[0054] This embodiment provides a method for preparing a perovskite battery, comprising:

[0055] A precursor solution is prepared, wherein the solvent of the precursor solution is a DMF:DMSO mixed solvent, the volume ratio of DMF to DMSO is 3:1, the solute of the precursor solution is MA3(PEA)2Pb4I13, and the concentration of the solute is 1.6 mol / L;

[0056] Providing FTO conductive glass, the size of which is 2 cm×2.5 cm;

[0057] The electron transport layer is formed on the surface of the FTO layer of the FTO conductive glass by spin coating. The material of the electron transport layer is TiO2 and the thickness is 10nm.

[0058] The precursor solution is spin-coated to form a liquid film on the surface of the electron transport layer, a beaker carrying acetylacetone and the liquid film are placed on the same heating table, and the beaker and the liquid film are covered with a shielding cover made of tin foil, the side of the shielding cover has a notch, the notch is located on the side of the substrate away from the carrier, the size of the notch is 2.5 cm × 8 cm, annealed at 100 ° C for 60 min, and a three-dimensional perovskite MAPbI3 with a thickness of 600 nm is obtained;

[0059] A hole transport layer is formed on the surface of the three-dimensional perovskite layer by spin coating. The material of the hole transport layer is CuSCN with a thickness of 15 nm.

[0060] A second electrode layer is formed on the surface of the hole transport layer by a vacuum evaporation process. The material of the second electrode layer is silver and has a thickness of 100 nm, thereby obtaining a perovskite battery.

[0061] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 21.4%.

[0062] Example 2

[0063] This embodiment provides a method for preparing a perovskite battery, comprising:

[0064] A precursor solution is prepared, wherein the solvent of the precursor solution is a DMF:DMSO mixed solvent, the volume ratio of DMF to DMSO is 5:1, the solute of the precursor solution is MA4(CH3CH2CH2CH2NH3)2Pb5I16, and the concentration of the solute is 1.6 mol / L;

[0065] Providing ITO conductive glass, the size of which is 2 cm×2.5 cm;

[0066] A hole transport layer is formed on the surface of the ITO layer of the ITO conductive glass by spin coating, the material of the hole transport layer is NiOx, and the thickness of the hole transport layer is 10 nm;

[0067] The precursor solution is spin-coated to form a liquid film on the surface of the hole transport layer, and a beaker containing acetone and the liquid film are placed on the same heating table. The beaker and the liquid film are covered with a shielding cover made of tin foil. The side of the shielding cover has a notch, which is located on the side of the substrate away from the carrier. The size of the notch is 2.5 cm × 8 cm. Annealing at 120 ° C for 40 min to obtain a three-dimensional perovskite MAPbI3 with a thickness of 680 nm.

[0068] A 20nm thick PCBM layer and a 10nm thick BCP layer were formed on the surface of the three-dimensional perovskite layer by spin coating;

[0069] A second electrode layer is formed on the surface of the BCP layer by a vacuum evaporation process. The material of the second electrode layer is silver and has a thickness of 120 nm, thereby obtaining a perovskite cell.

[0070] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 22.1%.

[0071] Example 3

[0072] This embodiment provides a method for preparing a perovskite battery, comprising:

[0073] A precursor solution was prepared, wherein the solvent of the precursor solution was a DMF:DMSO mixed solvent, the volume ratio of DMF to DMSO was 8:1, the solute of the precursor solution was FA2(CH3CH2CH2CH2CH2NH3)2Pb3I10, and the concentration of the solute was 1.4 mol / L;

[0074] Provide copper indium gallium selenide thin film solar cells with a size of 4cm×4cm;

[0075] A first electrode layer is formed on the electrode surface of the copper indium gallium selenide thin film solar cell by a physical vapor deposition process (PVD), wherein the material of the first electrode layer is ITO and the thickness is 100 nm;

[0076] A hole transport layer is formed on the surface of the first electrode layer by spin coating. The material of the hole transport layer is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) with a thickness of 15 nm.

[0077] The precursor solution is spin-coated to form a liquid film on the surface of the hole transport layer, a beaker containing ethanol and the liquid film are placed on the same heating table, and the beaker and the liquid film are covered with a shielding cover made of tin foil. The side of the shielding cover has a notch, which is located on the side of the substrate away from the carrier. The size of the notch is 4cm×6cm. Annealing at 110°C for 50min to obtain a three-dimensional perovskite FAPbI3 with a thickness of 650nm.

[0078] A 30nm thick C60 layer is deposited on the surface of the three-dimensional perovskite layer by vacuum evaporation process, and an electron transport layer is deposited on the surface of the C60 layer by atomic sputtering deposition process. The material of the electron transport layer is SnO2 with a thickness of 15nm.

[0079] A second electrode layer is formed on the surface of the electron transport layer by a vacuum evaporation process. The material of the second electrode layer is silver with a thickness of 100 nm, thereby obtaining a perovskite / copper indium gallium selenide stacked cell.

[0080] The photoelectric conversion efficiency of the prepared perovskite / copper indium gallium selenide stacked cell was tested, and the initial efficiency was 20.4%.

[0081] Example 4

[0082] This embodiment provides a method for preparing a perovskite battery, comprising:

[0083] A precursor solution is prepared, wherein the solvent of the precursor solution is a DMF:DMSO mixed solvent, the volume ratio of DMF to DMSO is 10:1, the solute of the precursor solution is MA3Tu2Pb4I13, and the concentration of the solute is 1.4 mol / L;

[0084] A heterojunction cell is provided, the size of which is 4 cm×4 cm;

[0085] A first electrode layer is formed on the electrode surface of the heterojunction battery by a physical vapor deposition (PVD) process, wherein the material of the first electrode layer is ITO and has a thickness of 100 nm;

[0086] A hole transport layer is formed on the surface of the first electrode layer by spin coating. The material of the hole transport layer is [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACZ) with a thickness of 10 nm.

[0087] The precursor solution is spin-coated to form a liquid film on the surface of the hole transport layer, a beaker containing ethyl acetate and the liquid film are placed on the same heating table, and the beaker and the liquid film are covered with a shielding cover made of tin foil, the side of the shielding cover has a notch, the notch is located on the side of the substrate away from the carrier, the size of the notch is 4cm×6cm, annealed at 100°C for 60min, and a three-dimensional perovskite MAPbI3 with a thickness of 680nm is obtained;

[0088] A 20nm thick PCBM layer, a 10nm thick BCP layer and a 120nm thick second electrode layer are sequentially deposited on the three-dimensional perovskite layer using a vacuum evaporation process. The material of the second electrode layer is silver, thereby obtaining a perovskite / heterojunction stacked cell.

[0089] The photoelectric conversion efficiency of the prepared perovskite / heterojunction stacked cell was tested, and the initial efficiency was 26.4%.

[0090] Example 5

[0091] This embodiment provides a method for preparing a perovskite battery, comprising:

[0092] A precursor solution is prepared, wherein the solvent of the precursor solution is a DMF:DMSO mixed solvent, the volume ratio of DMF to DMSO is 6:1, the solute of the precursor solution is FA3(2-naphthylamine)2Pb4I13, and the concentration of the solute is 1.6 mol / L;

[0093] Provide a gallium arsenide thin film solar cell with a size of 4cm×4cm;

[0094] A first electrode layer is formed on the electrode surface of the gallium arsenide thin film solar cell by using a physical vapor deposition process (PVD), wherein the material of the first electrode layer is ITO and the thickness is 100 nm;

[0095] A hole transport layer is formed on the surface of the first electrode layer by spin coating. The material of the hole transport layer is [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACZ) with a thickness of 10 nm.

[0096] The precursor solution is spin-coated to form a liquid film on the surface of the hole transport layer. A beaker containing ethyl acetate and the liquid film are placed on the same heating table. The beaker and the liquid film are covered with a shielding cover made of tin foil. The side of the shielding cover has a notch, which is located on the side of the substrate away from the carrier. The size of the notch is 4 cm × 6 cm. Annealing is performed at 100°C for 60 min to obtain a three-dimensional perovskite FAPbI3 with a thickness of 660 nm.

[0097] A 30nm thick C60 layer, a 10nm thick BCP layer and a 120nm thick second electrode layer are sequentially deposited on the three-dimensional perovskite layer using a vacuum evaporation process. The material of the second electrode layer is silver, thereby obtaining a perovskite / heterojunction stacked cell.

[0098] The photoelectric conversion efficiency of the prepared perovskite / gallium arsenide stacked cell was tested, and the initial efficiency was 18.7%.

[0099] Example 6

[0100] This embodiment provides a method for preparing a perovskite battery, which differs from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses isopropanol to provide a protonic organic atmosphere during the annealing of the liquid film.

[0101] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 20.8%.

[0102] Example 7

[0103] This embodiment provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses n-butanol to provide a protonic organic atmosphere during the annealing of the liquid film.

[0104] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 22.3%.

[0105] Example 8

[0106] This embodiment provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses propyl acetate to provide a protonic organic atmosphere during the annealing of the liquid film.

[0107] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 21.7%.

[0108] Example 9

[0109] This embodiment provides a method for preparing a perovskite battery, which differs from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses butyl acetate to provide a protonic organic atmosphere during the annealing of the liquid film.

[0110] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 21.1%.

[0111] Example 10

[0112] This embodiment provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses acetylpropylamine to provide a protonic organic atmosphere during the annealing of the liquid film.

[0113] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 20.9%.

[0114] Embodiment 11

[0115] This embodiment provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses methylpyridine to provide a protonic organic atmosphere during the annealing of the liquid film.

[0116] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 21.8%.

[0117] Example 12

[0118] This embodiment provides a method for preparing a perovskite battery, which differs from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses acetyl chloride to provide a protonic organic atmosphere during the annealing of the liquid film.

[0119] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 22.0%.

[0120] Embodiment 13

[0121] This embodiment provides a method for preparing a perovskite battery, which differs from the method for preparing a perovskite battery provided in Example 1 in that this embodiment uses acetic anhydride to provide a protonic organic atmosphere during the annealing of the liquid film.

[0122] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 20.7%.

[0123] Comparative Example 1

[0124] This comparative example provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 1 in that: in this comparative example, the liquid film is directly annealed instead of being annealed in a protonic organic atmosphere.

[0125] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 18.7%.

[0126] Comparative Example 2

[0127] This comparative example provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 2 in that: this comparative example directly anneals the liquid film instead of performing the annealing in a protonic organic atmosphere.

[0128] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 18.2%.

[0129] Comparative Example 3

[0130] This comparative example provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 3 in that: this comparative example directly anneals the liquid film instead of performing the annealing in a protonic organic atmosphere.

[0131] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 19.4%.

[0132] Comparative Example 4

[0133] This comparative example provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 4 in that: this comparative example directly anneals the liquid film instead of performing the annealing in a protonic organic atmosphere.

[0134] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 23.2%.

[0135] Comparative Example 5

[0136] This comparative example provides a method for preparing a perovskite battery, which is different from the method for preparing a perovskite battery provided in Example 5 in that: this comparative example directly anneals the liquid film instead of performing the annealing in a protonic organic atmosphere.

[0137] The photoelectric conversion efficiency of the prepared perovskite cell was tested, and the initial efficiency was 17.1%.

[0138] Test Example 5

[0139] In order to verify that the quasi-two-dimensional perovskite material can be converted into a three-dimensional perovskite by annealing in a protonic organic atmosphere, XRD tests were performed on the quasi-two-dimensional perovskite layer and the three-dimensional perovskite layer in this experimental example.

[0140] Among them, the preparation method of the test sample of the three-dimensional perovskite layer is: using the precursor solution prepared in Example 1, the preparation method of the three-dimensional perovskite layer provided in Example 1 is used to directly form a three-dimensional perovskite layer on the surface of the FTO layer of the FTO conductive glass, that is, the quasi-two-dimensional perovskite precursor solution forms a liquid film on the surface of the FTO conductive glass, and then annealing is performed in an acetylacetone atmosphere.

[0141] The difference between the preparation method of the control sample of the quasi-two-dimensional perovskite layer and the preparation method of the test sample of the three-dimensional perovskite layer is that the liquid film is annealed directly instead of in the protophilic organic atmosphere of acetylacetone.

[0142] Depend on Figure 1 The XRD spectrum shown shows that the quasi-two-dimensional perovskite includes a small part of the two-dimensional structure and a large part of the three-dimensional structure, in which the left (001) crystal plane corresponds to the diffraction peak of the two-dimensional structure. The three-dimensional perovskite test sample does not include the diffraction peak of the two-dimensional structure, and the other diffraction peaks are at the same position or only slightly offset with the diffraction peaks of the three-dimensional structure of the control sample of the quasi-two-dimensional perovskite layer, which shows that the quasi-two-dimensional perovskite material is converted into a three-dimensional perovskite by annealing in a proton-philic organic atmosphere.

[0143] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A method for preparing a perovskite battery, characterized in that: include: Prepare a precursor solution, wherein the solute of the precursor solution is a quasi-two-dimensional perovskite (RNH3)2An-1MnX3n+1, where n is an integer greater than or equal to 2; A first electrode layer and a first charge transport layer are sequentially formed on a surface of one side of the substrate; Using the precursor solution to form a liquid film on a surface of the first charge transport layer that is away from the substrate; The liquid film is annealed in a protophilic organic atmosphere to form a three-dimensional perovskite layer.

2. The method for preparing a perovskite battery according to claim 1, characterized in that: The protophilic organic atmosphere is provided by heating the protophilic organic solvent to volatilize the organic molecules.

3. The method for preparing a perovskite battery according to claim 2, characterized in that: The liquid film is heated together with the organic solvent so as to anneal the liquid film in a protonic organic atmosphere.

4. The method for preparing a perovskite battery according to claim 3, characterized in that: The step of heating the liquid film and the organic solvent together includes: providing a carrier, wherein the organic solvent is contained in the carrier; placing the substrate having the liquid film and the carrier together on a heating panel, and the carrier is located on the side of the substrate, so that the heating panel heats the substrate and the carrier together.

5. The method for preparing a perovskite battery according to any one of claims 2 to 4, characterized in that: The organic solvent includes at least one of ethanol, isopropanol, n-butanol, acetone, ethyl acetate, propyl acetate, acetylacetone, butyl acetate, acetylacetone, picoline, acetyl chloride and acetic anhydride.

6. The method for preparing a perovskite battery according to claim 4, characterized in that: After placing the substrate with the liquid film and the carrier together on the heating panel, the method also includes: providing a shielding cover, buckling the shielding cover on the heating panel, forming a containing space between the shielding cover and the heating panel, and the substrate and the carrier are both located in the containing space; when the heating panel heats the substrate and the carrier together, a proton-philic organic atmosphere is formed in the containing space.

7. The method for preparing a perovskite battery according to claim 6, characterized in that: The shielding cover comprises a top plate and a side plate, wherein the side plate is arranged around the edge of the top plate, one end of the side plate is connected to the top plate, and the other end of the side plate is suitable for contacting the heating panel; The top plate and / or the side plate have through holes, which constitute flow openings; and / or a partial area of ​​the side plate has a notch, which constitutes the flow opening.

8. The method for preparing a perovskite battery according to claim 7, characterized in that: The flow port is located at a side of the substrate facing away from the carrier.

9. The method for preparing a perovskite battery according to claim 1, characterized in that: The annealing temperature is 100° C.-150° C., and the annealing time is 20 min-60 min.

10. The method for preparing a perovskite battery according to claim 1, characterized in that: In the precursor solution, the concentration of the solute is 1.0 mol / L-1.8 mol / L.

11. The method for preparing a perovskite battery according to claim 1, characterized in that: R includes at least one of a straight-chain alkyl group, piperidine, pyridine, a benzene ring, and a thiophene aromatic group.

12. The method for preparing a perovskite battery according to claim 11, characterized in that: R includes at least one of benzylamine, phenylethylamine, amphetamine, 1,4-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 2-aminoanthracene, 2-naphthylamine, 3-phenanthrenylamine, (6-amino-2-naphthyl)amine, 3-phenanthrenylamine, 2,7-naphthalenediamine, 2-aminochrysene, 2,6-diaminoanthracene, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, p-trifluoromethylaniline, 3-methyldiphenylamine, and thiophenemethylamine.

13. The method for preparing a perovskite battery according to claim 1, characterized in that: The substrate includes glass, a flexible substrate, a heterojunction cell, a crystalline silicon cell or a thin film solar cell.

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