Perovskite solar cell and preparation method thereof

Abstract

The invention belongs to the field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof. The perovskite solar cell provided by the invention comprises a perovskite layer; the perovskite layer comprises a perovskite structure substance and a perfluorinated compound. The oxidation and degradation speed of the perovskite material in the perovskite solar cell is slowed down, the stability of the perovskite solar cell is effectively improved, and the service life of the perovskite solar cell is effectively prolonged.

Description

Technical Field

[0001] The present invention belongs to the field of solar cells, and in particular relates to a perovskite solar cell and a preparation method thereof. Background Art

[0002] As the global demand for renewable energy grows, solar cells, as a clean and renewable energy source, have received extensive attention and research. Among them, perovskite solar cells have become a research hotspot in the field of solar cells due to their high efficiency and low cost. However, during the use of perovskite cells, the organic components they contain are easily oxidized and degraded, which affects the stability and life of the battery.

[0003] To solve this problem, existing technologies mainly improve the stability of perovskite solar cells by changing their structure or improving their manufacturing process. For example, stabilizers are added to slow down the oxidation and degradation of perovskite materials, and the packaging technology of the cells is optimized to prevent the intrusion of oxygen and moisture. In addition, some studies have changed the chemical composition of perovskite materials to make them more stable.

[0004] Although existing technologies have improved the stability of perovskite solar cells to a certain extent, there are still some problems and shortcomings. First, existing stabilizers may have a negative impact on the performance of the battery, such as reducing the efficiency of the battery or increasing the resistance of the battery; second, although existing packaging technology can prevent the intrusion of oxygen and moisture, it cannot completely prevent other substances in the air from corroding the battery; finally, changing the chemical composition of perovskite materials may increase the preparation cost of the battery, which is not conducive to large-scale production.

[0005] Therefore, there is an urgent need to develop a perovskite solar cell with low cost, high stability and excellent electrochemical performance. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention adds perfluorinated compounds to the perovskite material to effectively slow down the oxidation and degradation rate of the perovskite material, thereby improving the stability, life and efficiency of the perovskite battery and module.

[0007] Specifically, the present invention provides a perovskite solar cell, which includes a perovskite layer; the perovskite layer includes a perovskite structure material and a perfluorinated compound.

[0008] In one or more embodiments, the perovskite structure material is ABX3, A is selected from methylamine cation, methylamine cation, Cs + , Rb +, butylamine cation, phenethylamine cation, fluorophenethylammonium cation, 4-fluoro-phenethylammonium cation, B is selected from one or more of Pb, Sn and Bi, and X is selected from one or more of Cl, Br, I and SCN-.

[0009] In one or more embodiments, the perfluorinated compound is selected from one or more of perfluorooctanoic acid, perfluorooctane sulfonate and its derivatives, perfluorobutane sulfonamide and its derivatives, and ammonium perfluorooctanoate and its derivatives.

[0010] In one or more embodiments, the molar ratio of the B element to the perfluorinated compound in the perovskite structure material is 100:(0.1-10).

[0011] In one or more embodiments, the perovskite layer has a thickness of 200-1000 nm.

[0012] In one or more embodiments, the perovskite solar cell is a formal perovskite solar cell or an inverted perovskite solar cell.

[0013] In one or more embodiments, the formal perovskite solar cell includes a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode layer in sequence in the thickness direction.

[0014] In one or more embodiments, the inverse perovskite solar cell includes a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer and an electrode layer in sequence in the thickness direction.

[0015] In one or more embodiments, in the formal perovskite solar cell, the transparent glass conductive substrate includes a transparent substrate and a conductive coating, the transparent substrate is a flexible substrate or a rigid substrate, and the material of the conductive coating is selected from one or more of indium tin oxide, fluorine-doped tin oxide and indium zinc oxide.

[0016] In one or more embodiments, in the formal perovskite solar cell, the thickness of the transparent conductive substrate is 100-1000 nm.

[0017] In one or more embodiments, in the formal perovskite solar cell, the electron transport layer is made of SnO2 or TiO2.

[0018] In one or more embodiments, in the formal perovskite solar cell, the thickness of the electron transport layer is 10-50 nm.

[0019] In one or more embodiments, in the formal perovskite solar cell, the thickness of the perovskite layer is 200-1000 nm.

[0020] In one or more embodiments, in the formal perovskite solar cell, the hole transport layer material is selected from one or more of NiOx, 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene, poly(3-hexylthiophene) and CuSCN, and 1≤x≤2.

[0021] In one or more embodiments, in the formal perovskite solar cell, the thickness of the hole transport layer is 2-100 nm.

[0022] In one or more embodiments, in the formal perovskite solar cell, the electrode layer material is selected from one or more of Cu, Ag, Au, indium zinc oxide, indium tin oxide, tungsten-doped indium oxide and zinc aluminum oxide.

[0023] In one or more embodiments, in the formal perovskite solar cell, the electrode layer is an opaque electrode or a transparent electrode.

[0024] In one or more embodiments, in the formal perovskite solar cell, the thickness of the electrode layer is 30-200 nm.

[0025] In one or more embodiments, in the inverted perovskite solar cell, the transparent glass conductive substrate includes a transparent substrate and a conductive coating, the transparent substrate is a flexible substrate or a rigid substrate, and the material of the conductive coating is selected from one or more of indium tin oxide, fluorine-doped tin oxide and indium zinc oxide.

[0026] In one or more embodiments, in the inverse perovskite solar cell, the thickness of the transparent conductive substrate is 100-1000 nm.

[0027] In one or more embodiments, in the inverted perovskite solar cell, the hole transport layer material is selected from one or more of NiOx, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid and 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 1≤x≤2.

[0028] In one or more embodiments, in the inverse perovskite solar cell, the hole transport layer has a thickness of 5-100 nm.

[0029] In one or more embodiments, in the inverse perovskite solar cell, the thickness of the perovskite layer is 200-1000 nm.

[0030] In one or more embodiments, in the inverse perovskite solar cell, the electron transport layer includes a C60 layer and a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer or a C60 layer and a SnO2 layer; preferably, the thickness of the C60 layer is 10-60nm, the thickness of the 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer is 6-10nm, and the thickness of the SnO2 layer is 5-30nm.

[0031] In one or more embodiments, in the inverse perovskite solar cell, the thickness of the electron transport layer is 25-90 nm.

[0032] In one or more embodiments, in the inverted perovskite solar cell, the material of the electrode layer is selected from one or more of Cu, Ag, Au, indium zinc oxide, indium tin oxide, tungsten-doped indium oxide and zinc aluminum oxide.

[0033] In one or more embodiments, in the inverse perovskite solar cell, the electrode layer is an opaque electrode or a transparent electrode.

[0034] In one or more embodiments, in the inverse perovskite solar cell, the thickness of the electrode layer is 30-200 nm.

[0035] In one or more embodiments, the perovskite solar cell includes an encapsulation structure.

[0036] The present invention provides a method for preparing the perovskite solar cell of the present invention, the preparation method comprising the following steps:

[0037] (1) depositing a hole transport layer on the surface of a transparent glass conductive substrate;

[0038] (2) depositing a perovskite layer on the surface of the hole transport layer;

[0039] (3) depositing an electron transport layer on the surface of the perovskite layer;

[0040] (4) depositing an electrode layer on the surface of the electron transport layer to obtain an inverse perovskite solar cell; or

[0041] (1') depositing an electron transport layer on the surface of a transparent glass conductive substrate;

[0042] (2') depositing a perovskite layer on the surface of the electron transport layer;

[0043] (3') depositing a hole transport layer on the surface of the perovskite layer;

[0044] (4') An electrode layer is deposited on the surface of the hole transport layer to obtain a formal perovskite solar cell.

[0045] In one or more embodiments, in step (1), the hole transport layer is deposited by plasma deposition, slit coating, vacuum evaporation or spin coating.

[0046] In one or more embodiments, in step (2), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, a perfluoro compound and a solvent are added, and dissolved to obtain a perovskite precursor solution modified by a perfluoro compound; the perovskite precursor solution is coated on the surface of the hole transport layer to obtain a perovskite layer.

[0047] In one or more embodiments, in step (2), the concentration of element B in the perovskite precursor solution is 0.2-3 mol / L.

[0048] In one or more embodiments, in step (2), the solvent of the perovskite precursor solution is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and 2-methoxyestradiol.

[0049] In one or more embodiments, in step (2), the perovskite layer is deposited by blade coating, slit coating, evaporation or spin coating.

[0050] In one or more embodiments, in step (3), the electron transport layer is deposited by vacuum evaporation, spin coating, blade coating, slit coating, atomic layer deposition or plasma deposition.

[0051] In one or more embodiments, in step (4), the electrode layer is deposited by vacuum evaporation or magnetron sputtering.

[0052] In one or more embodiments, in step (1'), the electron transport layer is deposited by blade coating, atomic layer deposition, slit coating or chemical bath deposition.

[0053] In one or more embodiments, in step (2'), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, a perfluorinated compound and a solvent are added, and dissolved to obtain a perovskite precursor solution modified by a perfluorinated compound; the perovskite precursor solution is coated on the surface of the electron transport layer to obtain a perovskite layer.

[0054] In one or more embodiments, in step (2'), the concentration of element B in the perovskite precursor solution is 0.2-3 mol / L.

[0055] In one or more embodiments, in step (2'), the solvent of the perovskite precursor solution is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and 2-methoxyestradiol.

[0056] In one or more embodiments, in step (2'), the perovskite layer is deposited by blade coating, slit coating, vacuum evaporation or spin coating.

[0057] In one or more embodiments, in step (3'), the hole transport layer is deposited by blade coating, slit coating, vacuum evaporation, spin coating or chemical bath deposition.

[0058] In one or more embodiments, in step (4'), the electrode layer is deposited by vacuum evaporation or magnetron sputtering. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 Schematic diagram of the structure of an inverted perovskite solar cell according to some embodiments of the present invention.

[0060] Figure 2 Figure 2 is a structural diagram of a formal perovskite solar cell according to some embodiments of the present invention. DETAILED DESCRIPTION

[0061] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0062] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0063] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0064] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0065] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0066] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0067] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0068] The present invention provides a perovskite solar cell, which may include a perovskite layer, and the perovskite layer may include a perovskite structure material and a perfluorinated compound. In the present invention, adding a perfluorinated compound can effectively slow down the oxidation rate of an organic layer in the perovskite solar cell, thereby improving the stability and durability of the perovskite solar cell.

[0069] In the present invention, the perovskite structure material is ABX3, and A can be selected from methylamine cation (MA + ), FA + ), Cs + , Rb + , butylamine cation (BA + ), phenylethylamine cation (PEA + ), fluorophenethylammonium cation (F-PEA + ), 4-fluoro-phenylethylammonium cation (4F-PEA + ), B may be one or more selected from Pb, Sn and Bi, and X may be one or more selected from Cl, Br, I and SCN-.

[0070] In the present invention, the perfluorinated compound may be one or more selected from perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), perfluorobutane sulfonamide (FTSA) and perfluorooctanoic acid ammonium (PFOA).

[0071] In the present invention, the molar ratio of the B element to the perfluorinated compound in the perovskite structure material can be 100:(0.1-10), for example, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10.

[0072] In the present invention, the thickness of the perovskite layer may be 200-1000 nm, for example, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm.

[0073] In the present invention, the perovskite solar cell may be a regular perovskite solar cell or an inverted perovskite solar cell.

[0074] In the present invention, the formal perovskite solar cell may include a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode layer in sequence in the thickness direction.

[0075] In the present invention, the inverse perovskite solar cell may include a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer and an electrode layer in sequence in the thickness direction.

[0076] In the present invention, the perovskite solar cell may further include a modification layer.

[0077] In the present invention, the formal perovskite solar cell may include a transparent glass conductive substrate, an electron transport layer, a modification layer, a perovskite layer, a hole transport layer and an electrode layer in sequence in the thickness direction.

[0078] In the present invention, the inverse perovskite solar cell may include a transparent glass conductive substrate, a hole transport layer, a modification layer, a perovskite layer, an electron transport layer and an electrode layer in sequence in the thickness direction.

[0079] In the perovskite solar cell of the present invention, the transparent glass conductive substrate includes a transparent substrate and a conductive coating, the transparent substrate can be a flexible substrate or a rigid substrate, in some embodiments, the flexible substrate can be a flexible polyimide, and in some embodiments, the rigid substrate can be a glass substrate. The material of the conductive coating can be one or more selected from indium tin oxide (ITO), fluorine-doped tin oxide (FTO) and indium zinc oxide (IZO).

[0080] In the perovskite solar cell of the present invention, the thickness of the transparent conductive substrate can be 100-1000nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm.

[0081] In the perovskite solar cell of the present invention, the electron transport layer may be made of SnO2 or TiO2.

[0082] In the perovskite solar cell of the present invention, the thickness of the electron transport layer can be 10-50 nm, for example, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm.

[0083] In the perovskite solar cell of the present invention, the thickness of the perovskite layer can be 200-1000nm, for example, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm.

[0084] In the perovskite solar cell of the present invention, the hole transport layer material can be one or more selected from NiOx, 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), poly(3-hexylthiophene) (P3HT) and CuSCN, 1≤x≤2.

[0085] In the perovskite solar cell of the present invention, the thickness of the hole transport layer can be 2-100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm.

[0086] In the perovskite solar cell of the present invention, the material of the electrode layer can be one or more selected from Cu, Ag, Au, indium zinc oxide (IZO), indium tin oxide (ITO), tungsten-doped indium oxide (IWO) and aluminum zinc oxide (AZO).

[0087] In the perovskite solar cell of the present invention, the electrode layer can be an opaque electrode or a transparent electrode.

[0088] In the perovskite solar cell of the present invention, the thickness of the electrode layer can be 30-200 nm, for example, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, and 200 nm.

[0089] In the inverted perovskite solar cell of the present invention, the transparent glass conductive substrate may include a transparent substrate and a conductive coating, the transparent substrate may be a flexible substrate or a rigid substrate, in some embodiments, the flexible substrate may be a flexible polyimide, and in some embodiments, the rigid substrate may be a glass substrate. The material of the conductive coating may be one or more selected from indium tin oxide (ITO), fluorine-doped tin oxide (FTO) and indium zinc oxide (IZO).

[0090] In the inverted perovskite solar cell of the present invention, the thickness of the transparent conductive substrate can be 100-1000nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm.

[0091] In the inverted perovskite solar cell of the present invention, the hole transport layer material can be one or more selected from NiOx, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2-PACz), [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid and 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 1≤x≤2.

[0092] In the inverse perovskite solar cell of the present invention, the thickness of the hole transport layer can be 5-100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm.

[0093] In the inverse perovskite solar cell of the present invention, the thickness of the perovskite layer can be 200-1000nm, for example, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm.

[0094] In the inverse perovskite solar cell of the present invention, the electron transport layer may include a C60 layer and a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) layer or a C60 layer and a SnO2 layer; preferably, the thickness of the C60 layer may be 10-60nm, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm. The thickness of the 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer may be 6-10nm, for example, 6nm, 7nm, 8nm, 9nm, 10nm. The thickness of the SnO2 layer may be 5-30nm, for example, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm.

[0095] In the inverted perovskite solar cell of the present invention, the thickness of the electron transport layer can be 25-90 nm, for example, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm.

[0096] In the inverted perovskite solar cell of the present invention, the material of the electrode layer can be one or more selected from Cu, Ag, Au, indium zinc oxide (IZO), indium tin oxide (ITO), tungsten-doped indium oxide (IWO) and aluminum zinc oxide (AZO).

[0097] In the inverse perovskite solar cell of the present invention, the electrode layer can be an opaque electrode or a transparent electrode.

[0098] In the inverted perovskite solar cell of the present invention, the thickness of the electrode layer can be 30-200 nm, for example, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, or 200 nm.

[0099] The perovskite solar cell of the present invention comprises a packaging structure.

[0100] The present invention provides a method for preparing a perovskite solar cell, the preparation method comprising the following steps:

[0101] (1) depositing a hole transport layer on the surface of a transparent glass conductive substrate;

[0102] (2) depositing a perovskite layer on the surface of the hole transport layer;

[0103] (3) depositing an electron transport layer on the surface of the perovskite layer;

[0104] (4) depositing an electrode layer on the surface of the electron transport layer to obtain an inverse perovskite solar cell; or

[0105] (1') depositing an electron transport layer on the surface of a transparent glass conductive substrate;

[0106] (2') depositing a perovskite layer on the surface of the electron transport layer;

[0107] (3') depositing a hole transport layer on the surface of the perovskite layer;

[0108] (4') An electrode layer is deposited on the surface of the hole transport layer to obtain a formal perovskite solar cell.

[0109] In step (1), the hole transport layer can be deposited by plasma deposition, slit coating, vacuum evaporation or spin coating.

[0110] In step (2), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, and a perfluorinated compound and a solvent are added to dissolve to obtain a perovskite precursor solution modified by a perfluorinated compound; the perovskite precursor solution is deposited on the surface of the hole transport layer to obtain a perovskite layer.

[0111] In step (2), the concentration of element B in the perovskite precursor solution can be 0.2-3 mol / mL, for example, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L.

[0112] In step (2), the solvent of the perovskite precursor solution may be one or more selected from N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile and 2-methoxyestradiol (2-Me).

[0113] In step (2), the perovskite layer can be deposited by blade coating, slit coating, evaporation or spin coating.

[0114] In step (3), the electron transport layer can be deposited by vacuum evaporation, spin coating, blade coating, slit coating, atomic layer deposition or plasma deposition.

[0115] In step (4), the electrode layer can be deposited by vacuum evaporation or magnetron sputtering.

[0116] In step (1'), the electron transport layer can be deposited by blade coating, atomic layer deposition, slit coating or chemical bath deposition.

[0117] In step (2'), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, and a perfluorinated compound and a solvent are added to dissolve to obtain a perovskite precursor solution modified by a perfluorinated compound; the perovskite precursor solution is deposited on the surface of the electron transport layer to obtain a perovskite layer.

[0118] In step (2'), the perovskite layer may be deposited by blade coating, slit coating, vacuum evaporation or spin coating.

[0119] In step (3'), the hole transport layer can be deposited by blade coating, slit coating, vacuum evaporation, spin coating or chemical bath deposition.

[0120] In step (4'), the electrode layer may be deposited by vacuum evaporation or magnetron sputtering.

[0121] Compared with the prior art, the present invention has the following beneficial effects:

[0122] (1) The present invention can effectively slow down the oxidation and degradation rate of perovskite materials by adding perfluorinated compounds with antioxidant properties to perovskite cells, thereby improving the stability and life of the cells. This method does not require changing the structure and manufacturing process of the cells, and therefore will not have a negative impact on the performance of the cells.

[0123] (2) The perfluorinated compound of the present invention can form a protective layer to prevent other substances in the air from corroding the battery, thereby further improving the stability of the battery. This method is more effective than the existing packaging technology and can completely prevent substances in the air from corroding the battery;

[0124] (3) The perfluorinated compound of the present invention is an organic chemical synthetic material with a relatively low preparation cost, which is conducive to large-scale production.

[0125] The present invention will be described below in the form of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise stated, conventional methods, reagents and materials in the art. The raw material compounds in the examples can all be purchased through commercial routes.

[0126] The NiOx in the examples and comparative examples of the present invention was purchased from Zhongchengda.

[0127] Example 1

[0128] This example was prepared according to the following steps Figure 1 An inverted perovskite solar cell shown:

[0129] (1) NiOx was deposited on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate was a glass substrate and the conductive coating was ITO) by plasma deposition to obtain a hole transport layer with a thickness of 30 nm;

[0130] (2) A perovskite precursor solution was deposited on the surface of the hole transport layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein 4FPEAI, FAI, MAI and PbI2 were weighed in a molar ratio of 2:1.2:2.8:5, and ammonium perfluorooctanoate was added thereto in a molar ratio of Pb ion to ammonium perfluorooctanoate of 24:1, and then DMF was added thereto and shaken for 2 hours until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated (4FPEA)2(FA 0.3 MA 0.7 )4Pb5I 16 and ammonium perfluorooctanoate, the solvent is DMF, (4FPEA)2(FA 0.3 MA 0.7 )4Pb5I 16 The concentration of Pb ions in the solution is 1.2 mol / L, and the concentration of ammonium perfluorooctanoate is 0.05 mol / L;

[0131] (3) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0132] (4) Cu is deposited on the surface of the electron transport layer by vacuum evaporation to obtain an electrode layer with a thickness of 100 nm, and an inverse perovskite solar cell is obtained at the same time.

[0133] Example 2

[0134] This example was prepared according to the following steps Figure 1 An inverted perovskite solar cell shown:

[0135] (1) 2-PACz was deposited on the surface of a transparent FTO conductive substrate with a thickness of 500 nm (wherein the transparent substrate was a glass substrate and the conductive coating was FTO) by slit coating to obtain a hole transport layer with a thickness of 10 nm;

[0136] (2) A perovskite precursor solution was deposited on the surface of the hole transport layer by slit coating to obtain a perovskite layer with a thickness of 700 nm, wherein FAI, MAI and PbI2 were weighed at a molar ratio of 0.9:0.1:1, perfluorobutane sulfonamide was added thereto at a molar ratio of Pb ion to perfluorobutane sulfonamide of 100:1, and then a mixed solution of DMF and NMP at a volume ratio of 4:1 was added thereto, and the mixture was shaken for 2 hours until the solute was completely dissolved to obtain a perovskite precursor solution, wherein the solute of the perovskite precursor solution was the theoretically generated FA 0.9 MA 0.1 PbI3 and perfluorobutanesulfonamide, the solvent is a mixture of DMF and NMP with a volume ratio of 4:1, FA 0.9 MA 0.1 The concentration of Pb ions in PbI3 is 1.0 mol / L, and the concentration of perfluorobutanesulfonamide is 0.01 mol / L;

[0137] (3) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0138] (4) Cu is deposited on the surface of the electron transport layer by vacuum evaporation to obtain an electrode layer with a thickness of 100 nm, and an inverse perovskite solar cell is obtained at the same time.

[0139] Example 3

[0140] This example was prepared according to the following steps Figure 2 A formal perovskite solar cell shown:

[0141] (1) SnO2 was deposited on the surface of a transparent FTO conductive substrate with a thickness of 700 nm (wherein the transparent substrate was flexible polyimide and the conductive coating was FTO) by scraping to obtain an electron transport layer with a thickness of 30 nm;

[0142] (2) depositing a perovskite precursor solution on the surface of the electron transport layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein MAI and PbI2 are weighed at a molar ratio of 1:1, perfluorooctane sulfonate is added thereto at a molar ratio of Pb ions to perfluorooctane sulfonate of 15:1, and then a mixed solution of DMF and DMSO in a volume ratio of 6:1 is added thereto, and the mixture is shaken for 2 hours until the solute is completely dissolved to obtain a perovskite precursor solution, wherein the solute of the perovskite precursor solution is the theoretically generated MAPbI3 and perfluorooctane sulfonate, the solvent DMF and DMSO are a mixed solution in a volume ratio of 6:1, the concentration of Pb ions in MAPbI3 is 1.5 mol / L, and the concentration of perfluorooctane sulfonate is 0.1 mol / L;

[0143] (3) depositing Spiro-OMeTAD on the surface of the perovskite layer by blade coating to obtain a hole transport layer with a thickness of 30 nm;

[0144] (4) Au is deposited on the surface of the hole transport layer by thermal evaporation to obtain an electrode layer with a thickness of 100 nm, and a formal perovskite solar cell is obtained.

[0145] Comparative Example 1

[0146] This example was prepared according to the following steps Figure 1 An inverted perovskite solar cell shown:

[0147] (1) NiOx was deposited on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate was a glass substrate and the conductive coating was ITO) by plasma deposition to obtain a hole transport layer with a thickness of 30 nm;

[0148] (2) A perovskite precursor solution was deposited on the surface of the hole transport layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein 4FPEAI, FAI, MAI and PbI2 were weighed in a molar ratio of 2:1.2:2.8:5, DMF was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated (4FPEA)2(FA 0.3 MA 0.7 )4Pb5I 16 , solvent is DMF, (4FPEA)2(FA 0.3 MA 0.7 )4Pb5I 16 The concentration of Pb ions in the solution is 1.2 mol / L;

[0149] (3) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0150] (4) Cu is deposited on the surface of the electron transport layer by vacuum evaporation to obtain an electrode layer with a thickness of 100 nm, and an inverse perovskite solar cell is obtained at the same time.

[0151] Comparative Example 2

[0152] This example was prepared according to the following steps Figure 1 An inverted perovskite solar cell shown:

[0153] (1) 2-PACz was deposited on the surface of a transparent FTO conductive substrate with a thickness of 500 nm (wherein the transparent substrate was a glass substrate and the conductive coating was FTO) by slit coating to obtain a hole transport layer with a thickness of 10 nm;

[0154] (2) A perovskite precursor solution was deposited on the surface of the hole transport layer by slit coating to obtain a perovskite layer with a thickness of 700 nm, wherein FAI, MAI and PbI2 were weighed in a molar ratio of 0.9:0.1:1, and a mixed solution of DMF and NMP in a volume ratio of 4:1 was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated FA 0.9 MA 0.1 PbI3, solvent is a mixture of DMF and NMP with a volume ratio of 4:1, FA 0.9 MA 0.1 The concentration of Pb ions in PbI3 is 1.0 mol / L;

[0155] (3) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0156] (4) Cu is deposited on the surface of the electron transport layer by vacuum evaporation to obtain an electrode layer with a thickness of 100 nm, and an inverse perovskite solar cell is obtained at the same time;

[0157] Comparative Example 3

[0158] This example was prepared according to the following steps Figure 2 A formal perovskite solar cell shown:

[0159] (1) SnO2 was deposited on the surface of a transparent FTO conductive substrate with a thickness of 700 nm (wherein the transparent substrate was flexible polyimide and the conductive coating was ITO) by scraping to obtain an electron transport layer with a thickness of 30 nm;

[0160] (2) depositing a perovskite precursor solution on the surface of the electron transport layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein MAI and PbI2 are weighed in a molar ratio of 1:1, and a mixture of DMF and DMSO in a volume ratio of 6:1 is added thereto, and the mixture is shaken for 2 hours until the solute is completely dissolved to obtain a perovskite precursor solution, wherein the solute of the perovskite precursor solution is the theoretically generated MAPbI3, the solvent is a mixture of DMF and DMSO in a volume ratio of 6:1, and the concentration of Pb ions in MAPbI3 is 1.5 mol / L;

[0161] (3) depositing Spiro-OMeTAD on the surface of the perovskite layer by blade coating to obtain a hole transport layer with a thickness of 30 nm;

[0162] (4) Au is deposited on the surface of the hole transport layer by thermal evaporation to obtain an electrode layer with a thickness of 100 nm, and a formal perovskite solar cell is obtained.

[0163] Test Case

[0164] Perovskite solar cell performance test: at 25°C, AM 1.5G standard solar spectrum, irradiance of 1000W / m 2 Under the condition of , using a solar simulator, the voltage range is set to -0.2V-1.25V, the current output of the perovskite solar cells prepared in Examples 1-3 and Comparative Examples 1-3 at different voltages is tested, and the corresponding current-voltage (IV) characteristic curves are plotted, wherein the cell surface area is 0.1cm 2 , the incident light power (Pin) is 100mW / cm 2 .

[0165] (1) Open circuit voltage (Voc): The voltage value corresponding to when the current is equal to zero.

[0166] (2) Short-circuit current density (Jsc): The current value when the voltage is zero is the short-circuit current (Isc), and the current per unit battery surface area is the short-circuit current density.

[0167] (3) Fill factor (FF): The ratio of the maximum output power (Pmax) of the battery to the product of the open circuit voltage and the short circuit current. The calculation formula is (Pmax / Voc*Isc), where the maximum power point is the point where the battery output power reaches its maximum value.

[0168] (4) Photoelectric conversion efficiency (PCE): Photoelectric conversion efficiency refers to the ratio of maximum output power to incident light power (Pin), and the calculation formula is (Pmax / Pin)*100%.

[0169] The open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the perovskite solar cells prepared in Examples 1-3 and Comparative Examples 1-3 were obtained according to the IV curves.

[0170] Table 1: Open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of perovskite solar cells prepared in Examples 1-3 and Comparative Examples 1-3

[0171] Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Example 1 1.18 22.92 84.7 23.97 Example 2 1.17 24.83 85.0 24.69 Example 3 1.19 24.25 84.3 24.33 Comparative Example 1 1.16 22.54 83.9 21.94 Comparative Example 2 1.15 24.32 83.4 23.33 Comparative Example 3 1.17 24.22 83.8 23.75

[0172] As can be seen from Table 1, the open circuit voltage, short circuit current density, filling factor and photoelectric conversion efficiency of the inverted perovskite solar cell prepared in Example 1 are 1.72%, 1.69%, 0.95% and 9.25% higher than those of the inverted perovskite solar cell prepared in Comparative Example 1, respectively; the open circuit voltage, short circuit current density, filling factor and photoelectric conversion efficiency of the inverted perovskite solar cell prepared in Example 2 are 1.74%, 2.10%, 1.92% and 5.83% higher than those of the inverted perovskite solar cell prepared in Comparative Example 2, respectively. This shows that the inverted perovskite solar cell prepared in the present invention has excellent performance.

[0173] The open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the formal perovskite solar cell prepared in Example 3 are 1.71%, 0.12%, 0.60% and 2.44% higher than those of the formal perovskite solar cell prepared in Comparative Example 3, respectively. This shows that the formal perovskite solar cell prepared in the present invention has excellent performance.

[0174] The increase in open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the inverted perovskite solar cell prepared in the embodiment relative to the open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the inverted perovskite solar cell prepared in the comparative example is greater than the increase in open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the formal perovskite solar cell prepared in the embodiment relative to the open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the formal perovskite solar cell prepared in the comparative example. Therefore, it can be seen that the addition of perfluorinated compounds has a better effect on improving the performance of inverted perovskite solar cells.

Claims

1. A perovskite solar cell, characterized in that: The perovskite solar cell comprises a perovskite layer; the perovskite layer comprises a perovskite structural material and a perfluorinated compound.

2. The perovskite solar cell according to claim 1, characterized in that The perovskite structure material is ABX3, A is selected from methylamine cation, methylamine cation, Cs + , Rb + , butylamine cation, phenethylamine cation, fluorophenethylammonium cation, 4-fluoro-phenethylammonium cation, B is selected from one or more of Pb, Sn and Bi, and X is selected from one or more of Cl, Br, I and SCN-.

3. The perovskite solar cell according to claim 1, characterized in that The perfluoro compound is selected from one or more of perfluorooctanoic acid, perfluorooctane sulfonate, perfluorobutane sulfonamide and ammonium perfluorooctanoate.

4. The perovskite solar cell according to claim 1, characterized in that The molar ratio of the B element to the perfluorinated compound in the perovskite structure material is 100:(0.1-10).

5. The perovskite solar cell according to claim 1, characterized in that The thickness of the perovskite layer is 200-1000 nm.

6. The perovskite solar cell according to claim 1, characterized in that The perovskite solar cell is a formal perovskite solar cell or an inverted perovskite solar cell.

7. The perovskite solar cell according to claim 6, characterized in that The formal perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode layer in sequence in the thickness direction; or The inverse perovskite solar cell comprises a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer and an electrode layer in sequence in the thickness direction.

8. A method for preparing a perovskite solar cell according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) depositing a hole transport layer on the surface of a transparent glass conductive substrate; (2) depositing a perovskite layer on the surface of the hole transport layer; (3) depositing an electron transport layer on the surface of the perovskite layer; (4) depositing an electrode layer on the surface of the electron transport layer to obtain an inverse perovskite solar cell; or (1') depositing an electron transport layer on the surface of a transparent glass conductive substrate; (2') depositing a perovskite layer on the surface of the electron transport layer; (3') depositing a hole transport layer on the surface of the perovskite layer; (4') An electrode layer is deposited on the surface of the hole transport layer to obtain a formal perovskite solar cell.

9. The preparation method according to claim 7, characterized in that: In step (2), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, a perfluorinated compound and a solvent are added, and dissolved to obtain a perovskite precursor solution modified by the perfluorinated compound; the perovskite precursor solution is deposited on the surface of the hole transport layer to obtain a perovskite layer; In step (2'), the raw material of the perovskite structure material is weighed according to the molar ratio of each element of the perovskite structure material, and a perfluorinated compound and a solvent are added to dissolve to obtain a perovskite precursor solution modified by a perfluorinated compound; the perovskite precursor solution is deposited on the surface of the electron transport layer to obtain a perovskite layer.

10. The preparation method according to claim 9, characterized in that: The preparation method has one or more of the following characteristics: In step (2), the concentration of element B in the perovskite precursor solution is 0.2-3 mol / L; In step (2), the solvent of the perovskite precursor solution is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and 2-methoxyestradiol; In step (2), the perovskite layer is deposited by blade coating, slit coating, vacuum evaporation or spin coating; In step (2'), the concentration of element B in the perovskite precursor solution is 0.2-3 mol / L; In step (2'), the solvent of the perovskite precursor solution is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and 2-methoxyestradiol; In step (2'), the perovskite layer is deposited by blade coating, slit coating, vacuum evaporation or spin coating.

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