Perovskite precursor solution, thin film, preparation method of thin film and perovskite battery

Abstract

The invention relates to a perovskite precursor solution, a thin film, a preparation method of the thin film and a perovskite battery. The perovskite precursor solution comprises a perovskite precursor and an organic passivation material, the organic passivation material comprises an annular connector and an active group connected to the annular connector, the active group can be combined with a perovskite site, and the intermolecular distance of the organic passivation material is 3.9-4.1. In the organic passivation material of the perovskite precursor solution, active groups are combined with perovskite sites, and passivation of three defect concentration parts of a perovskite body phase, a grain boundary and an interface can be realized by controlling the intermolecular distance of the organic passivation material and controlling the concentration of the organic passivation material in the perovskite precursor solution. When the material is used for preparing the perovskite cell, the photoelectric conversion efficiency and the stability of the perovskite cell can be effectively improved.

Description

Technical Field

[0001] The present application relates to the field of photovoltaic technology, and in particular to a perovskite precursor solution, a film, a preparation method thereof, and a perovskite cell. Background Art

[0002] Perovskite solar cells are highly efficient third-generation photovoltaic cell technology. Compared with crystalline silicon-based cells, they have attracted widespread attention due to their higher theoretical efficiency limit and lower production cost. However, polycrystalline perovskites inevitably produce various dangling bonds, vacancies, interstitials and antisite defects in their bulk, grain boundaries and interfaces. These defects will increase the non-radiative recombination of the perovskite layer, thereby reducing the photovoltaic performance of the module.

[0003] Therefore, it is necessary to improve the traditional technology. Summary of the invention

[0004] Based on this, the present application provides a perovskite precursor solution, a film and a preparation method thereof, and a perovskite battery with high photoelectric conversion efficiency.

[0005] The technical solution of this application to solve the above technical problems is as follows.

[0006] The first aspect of the present application provides a perovskite precursor solution, comprising a perovskite precursor and an organic passivation material, wherein the organic passivation material comprises a cyclic connector and an active group connected to the cyclic connector, wherein the active group can bind to a perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0007] In some of the embodiments, in the perovskite precursor solution, the active groups include at least one of -NH2, -COOH, -PO3H and -SO3H.

[0008] In some of the embodiments, in the perovskite precursor solution, the cyclic linker includes at least one of a benzene ring, furan, pyridine, thiophene, indane and a combination thereof.

[0009] In some of the embodiments, in the perovskite precursor solution, the organic passivation material includes at least one of 1-carboxy-4-aminoindane, phenbutamine acetic acid, 2,5-thiophenedicarboxylic acid, 3,3′-dibromo-2,2′-bithiophene, 2,5-furandicarboxylic acid and 2-amino-5-fluoropyridine.

[0010] In some of the embodiments, in the perovskite precursor solution, the concentration of the organic passivation material in the perovskite precursor solution is 1 mmol to 3 mmol.

[0011] In some of the embodiments, in the perovskite precursor solution, the molar concentration ratio of the organic passivation material to the perovskite precursor is 1-3:1700.

[0012] In some of the embodiments, in the perovskite precursor solution, the concentration of the organic passivation material in the perovskite precursor solution is 0.5 mmol / L~1.5 mmol / L.

[0013] In some embodiments, in the perovskite precursor solution, the perovskite precursor includes monovalent cations, divalent cations and halogen ions, and the monovalent cations include CH(NH2)2 + 、CH3NH3 + , Cs + and Rb + At least one of the divalent cations, wherein the divalent cations include Pb 2+ Sn 2+ and Sr 2+ At least one of the halogen ions, wherein the halogen ions include Cl - Br - and I - At least one of .

[0014] In some of the embodiments, in the perovskite precursor solution, the solvent in the perovskite precursor solution includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0015] The second aspect of the present application provides a method for preparing a perovskite precursor solution, comprising the following steps:

[0016] A perovskite precursor, an organic passivation material and an organic solvent are mixed to prepare a perovskite precursor solution; the organic passivation material includes a cyclic connector and an active group connected to the cyclic connector, the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0017] A third aspect of the present application provides a perovskite film, which is prepared using the above-mentioned perovskite precursor solution or the perovskite precursor solution prepared by the above-mentioned preparation method.

[0018] The present application also provides a perovskite film, including a perovskite body layer, a first passivation layer and a second passivation layer, wherein the first passivation layer is arranged on at least one surface of the perovskite body layer, and the second passivation layer vertically penetrates the perovskite body layer, and the organic passivation material in the first passivation layer and the second passivation layer includes a cyclic connector and an active group connected to the cyclic connector, wherein the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0019] In some of the embodiments, in the perovskite film, the band gap of the perovskite film is 1.6 eV~2.3 eV.

[0020] A fourth aspect of the present application provides a method for preparing a perovskite film, comprising the following steps:

[0021] The perovskite precursor solution or the perovskite precursor solution prepared by the preparation method is made into a wet film;

[0022] The wet film is subjected to annealing treatment to prepare the perovskite film.

[0023] In some of the embodiments, in the method for preparing a perovskite film, the annealing treatment includes a first annealing treatment and a second annealing treatment, the temperature of the first annealing treatment is 60°C to 80°C, and the temperature of the second annealing treatment is 110°C to 130°C.

[0024] In a fifth aspect, the present application provides the use of the above-mentioned perovskite precursor solution, the perovskite precursor solution prepared by the above-mentioned preparation method, the above-mentioned perovskite film or the perovskite film prepared by the above-mentioned preparation method in the preparation of perovskite cells.

[0025] A sixth aspect of the present application provides a perovskite cell, comprising the above-mentioned perovskite film or the perovskite film prepared by the above-mentioned preparation method.

[0026] In some of the embodiments, in the perovskite cell, the perovskite cell includes a perovskite crystalline silicon stacked cell, and the perovskite crystalline silicon stacked cell includes a stacked suede crystalline silicon cell, a perovskite film and a first conductive layer.

[0027] The seventh aspect of the present application provides a photovoltaic module, including the above-mentioned perovskite cell.

[0028] Compared with the prior art, the perovskite precursor solution of the present application has the following beneficial effects:

[0029] The perovskite precursor solution of the present application includes a perovskite precursor and an organic passivation material. The active groups in the organic passivation material are combined with the perovskite sites. By controlling the intermolecular distance of the organic passivation material and the concentration of the organic passivation material in the perovskite precursor solution, the three defect concentration sites of the perovskite bulk phase, grain boundary and interface can be passivated. The perovskite precursor solution is used to prepare a perovskite battery, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the specific implementation methods of the present application 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 application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0031] Figure 1 A schematic diagram of the structure of a perovskite film provided in one embodiment;

[0032] Figure 2 A schematic diagram of the structure of a perovskite crystalline silicon tandem cell provided in one embodiment.

[0033] Reference numerals:

[0034] 110: perovskite film; 1100: perovskite bulk layer; 1101: passivation layer; 11011: first passivation layer; 11012: second passivation layer;

[0035] 100: Perovskite crystalline silicon stacked cell; 101: Single crystal silicon substrate; 102: a-Si:H layer; 103: Boron-doped a-Si:H layer; 104: Second conductive transparent layer; 105: Second metal electrode layer; 106: a-Si:H layer; 107: Phosphorus-doped a-Si:H layer; 108: Carrier recombination layer; 109: Hole transport layer; 111: Electron transport layer; 112: Buffer layer; 113: First conductive transparent layer; 114: First metal electrode layer; 115: Anti-reflection layer. DETAILED DESCRIPTION

[0036] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0037] Therefore, it is intended that the present invention covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0039] The term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of more restrictions, the elements defined by the sentence "comprising one..." do not exclude the presence of other identical elements in the process, method, article or equipment including the elements. The indefinite articles "a kind of" and "an" before the elements or components of the present invention are not restrictive to the quantity requirements (i.e., the number of occurrences) of the elements or components. Therefore, "a" or "a kind of" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number clearly refers only to the singular form. The meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0040] The weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also indicate the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0041] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0042] Technicians have found that adding 2-aminoindene monohydrochloride to the perovskite precursor solution can passivate the perovskite bulk phase and interface, but the passivation effect on the grain boundaries between perovskite grains is poor. After analysis, it is believed that this is because the intermolecular distance of 2-aminoindene monohydrochloride is 3.5Å, which cannot form a 2D monolayer, resulting in excessive gaps between grains, and even expanding the gaps, affecting the overall film quality of the perovskite.

[0043] An embodiment of the present application provides a perovskite precursor solution, including a perovskite precursor and an organic passivation material, wherein the organic passivation material includes a cyclic connector and an active group connected to the cyclic connector, wherein the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0044] The perovskite precursor solution of the present application includes a perovskite precursor and an organic passivation material. The active groups in the organic passivation material are combined with the perovskite sites. By controlling the intermolecular distance of the organic passivation material and the concentration of the organic passivation material in the perovskite precursor solution, the three defect concentration sites of the perovskite bulk phase, grain boundary and interface can be passivated. The perovskite precursor solution is used to prepare a perovskite battery, which can effectively improve the photoelectric conversion efficiency and stability of the perovskite battery.

[0045] By controlling the intermolecular distance of the organic passivation material and the concentration of the organic passivation material in the perovskite precursor solution, a 2D perovskite layer (monolayer) can be generated on the grain boundaries in the vertical direction of the perovskite body. While passivating the grain boundaries, it is beneficial to the vertical transport of photogenerated carriers, preventing the lateral diffusion of electron-hole pairs and trapping them in the recombination center for non-radiative recombination, while protecting the grains from the influence of moisture in the air that causes perovskite degradation. If the intermolecular distance is too long or the concentration is too low, it will lead to the inability to form intermolecular connections or the formed 2D layer will be discontinuous, resulting in a loss of open-circuit voltage, filling factor and stability performance. If the distance is too short or the concentration is too high, the molecules will overlap with each other, which is not conducive to growth in the grain boundaries, resulting in a significant reduction in short-circuit current density.

[0046] It can be understood that the intermolecular distance of the organic passivation material can be obtained by DFT (density functional theory) calculation based on the molecular structure; further, the intermolecular distance of the organic passivation material includes but is not limited to 3.9Å, 3.92Å, 3.95Å, 3.98Å, 4Å, 4.02Å, 4.05Å, 4.08Å, and 4.1Å; in some examples, it can be within the range consisting of any two of these point values ​​as end values, the same below.

[0047] In some of the examples, in the perovskite precursor solution, the active groups include at least one of -NH2, -COOH, -PO3H and -SO3H.

[0048] In some of the examples, in the perovskite precursor solution, the cyclic linker includes at least one of a benzene ring, furan, pyridine, thiophene, indane, and a combination thereof.

[0049] Wherein, the structural formula of indane is shown in formula (I):

[0050]

[0051] (I).

[0052] It can be understood that the combination refers to a combination of at least two of benzene ring, furan, pyridine, thiophene and indane, for example, the combination of benzene ring and furan, pyridine and thiophene is benzofuran, benzopyridine and benzothiophene respectively.

[0053] It is understood that both the linker and the active group will affect the molecular distance of the final passivation material. At the same time, the same active group at different positions on the same linker will also affect the molecular distance of the final passivation material. By connecting the above-mentioned specific type of active group to a specific site of the linker, the molecular distance of the final passivation material meets a specific range.

[0054] In some of the examples, in the perovskite precursor solution, the organic passivation material includes at least one of 1-carboxy-4-aminoindan, phenbutamine acetic acid, 2,5-thiophenedicarboxylic acid, 3,3′-dibromo-2,2′-bithiophene, 2,5-furandicarboxylic acid and 2-amino-5-fluoropyridine.

[0055] The structural formula of 1-carboxy-4-aminoindan is shown in formula (I-1):

[0056]

[0057] (I-1).

[0058] The structural formula of 2,5-thiophenedicarboxylic acid is shown in formula (I-2):

[0059]

[0060] (I-2).

[0061] The structural formula of 3,3′-dibromo-2,2′-bithiophene is shown in formula (I-3):

[0062]

[0063] (I-3).

[0064] The structural formula of 2,5-furandicarboxylic acid is shown in formula (I-4):

[0065]

[0066] (I-4).

[0067] The structural formula of 2-amino-5-fluoropyridine is shown in formula (I-5):

[0068]

[0069] (I-5).

[0070] Among them, the intermolecular distance of 1-carboxy-4-aminoindan is 4Å, the intermolecular distance of 2,5-thiophenedicarboxylic acid is 4.03Å, the intermolecular distance of 3,3′-dibromo-2,2′-bithiophene is 3.96Å, the intermolecular distance of 2,5-furandicarboxylic acid is 4.06Å, and the intermolecular distance of 2-amino-5-fluoropyridine is 4.07Å.

[0071] In some of these examples, the concentration of the organic passivation material in the perovskite precursor solution is 0.5 mmol~1.5 mmol.

[0072] It is understood that the concentration of the organic passivation material in the perovskite precursor solution includes but is not limited to 0.5 mmol, 0.6 mmol, 0.7 mmol, 0.8 mmol, 0.9 mmol, 1 mmol, 1.1 mmol, 1.2 mmol, 1.3 mmol, 1.4 mmol, and 1.5 mmol.

[0073] In some of these examples, the concentration of the organic passivation material in the perovskite precursor solution is 0.8 mmol~1.2 mmol.

[0074] In some of these examples, the concentration of the organic passivation material in the perovskite precursor solution is 0.9 mmol~1.1 mmol.

[0075] In some of the examples, in the perovskite precursor solution, the molar concentration ratio of the organic passivation material to the perovskite precursor is 1 to 3: 1700. It is understood that the molar concentration ratio of the organic passivation material to the perovskite precursor includes but is not limited to 1: 1700, 2: 1700, and 3: 1700.

[0076] In some of these examples, in the perovskite precursor solution, the perovskite precursor includes monovalent cations, divalent cations, and halide ions.

[0077] It is understood that the monovalent cations include but are not limited to at least one of nitrogen-containing monovalent cations and monovalent metal cations. Further, the nitrogen-containing monovalent cations include but are not limited to at least one of amine monovalent cations, diamine monovalent cations and guanidine monovalent cations; amine monovalent cations include but are not limited to at least one of methylamine ion, methylenediamine ion, dimethylamine ion, ethylamine ion, n-octylamine ion, butylamine ion, dodecane ion, propylamine ion, ethylenediamine ion, phenylethylamine ion, 1-pyreneamine ion, 1-pyreneamine ion, 1-pyreneethylamine ion and 2-(4-fluorophenyl)ethylamine ion; diamine monovalent cations include but are not limited to at least one of formamidine ion and acetamidine ion; guanidine monovalent cations include but are not limited to guanidine ion (GA + ); monovalent metal cations include but are not limited to Cs + and Rb + At least one of the above.

[0078] In some of these examples, the monovalent cations in the perovskite precursor solution include CH(NH2)2 + (Methylamine ion, FA + )、CH3NH3 + (Methylamine ion, MA + )、Cs + (cesium ion) and Rb + At least one of (rubidium ions).

[0079] In some of these examples, the divalent cations in the perovskite precursor solution include lead (Pb 2+ ), tin (Sn 2+ ) and strontium (Sr 2+ ) at least one of the following.

[0080] In some of these examples, the halide ions in the perovskite precursor solution include Cl - Br - and I - At least one of .

[0081] In some of the examples, in the perovskite precursor solution, the solvent in the perovskite precursor solution includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0082] In some examples, in the perovskite precursor solution, the solvent in the perovskite precursor solution includes N,N-dimethylformamide and dimethyl sulfoxide. Further, the volume ratio of N,N-dimethylformamide to dimethyl sulfoxide is 2 to 6:1. Optionally, the volume ratio of N,N-dimethylformamide to dimethyl sulfoxide is 4:1.

[0083] An embodiment of the present application provides a method for preparing a perovskite precursor solution, comprising the following steps:

[0084] A perovskite precursor, an organic passivation material and an organic solvent are mixed to prepare a perovskite precursor solution; the organic passivation material includes a cyclic linker and an active group connected to the cyclic linker, the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0085] One embodiment of the present application provides a perovskite film, which is prepared using the above-mentioned perovskite precursor solution or the perovskite precursor solution prepared by the above-mentioned preparation method.

[0086] The perovskite film provided in the present application has high photoelectric conversion efficiency and good stability.

[0087] See also Figure 1 In one embodiment of the present application, a perovskite film 110 is provided, comprising a perovskite body layer 1100 and a passivation layer, wherein the passivation layer 1101 is disposed on at least one surface of the perovskite body layer 1100 and vertically penetrates the perovskite body layer 1100, and an organic passivation material in the passivation layer 1101 comprises a cyclic connector and an active group connected to the cyclic connector, wherein the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

[0088] It can be understood that the passivation layer 1101 includes a first passivation layer 11011 and a second passivation layer 11012 , the first passivation layer 11011 is disposed on at least one surface of the perovskite body layer 1100 , and the second passivation layer 11012 vertically penetrates the perovskite body layer 1100 .

[0089] It can be understood that the first passivation layer 11011 may exist on both surfaces of the perovskite body layer 1100 at the same time.

[0090] The first passivation layer enriched at the interface of the perovskite body plays an interface passivation role, and the second passivation layer vertically penetrating the perovskite body is conducive to the vertical transport of photogenerated carriers, preventing the lateral diffusion of electron-hole pairs and trapping them in the recombination center for non-radiative recombination.

[0091] In some of these examples, the thickness of the perovskite film ranges from 1 nm to 2000 nm.

[0092] Optionally, the thickness of the perovskite film is 400 nm~600 nm.

[0093] It is understood that the thickness of the perovskite film includes but is not limited to 400 nm, 450 nm, 500 nm, 550 nm, and 600 nm.

[0094] In some of these examples, perovskite films have a band gap of 1.6 eV to 2.3 eV.

[0095] It is understood that the band gap of the perovskite film includes but is not limited to 1.6 eV, 1.65 eV, 1.68 eV, 1.7 eV, 1.75 eV, 1.8 eV, 1.85 eV, 1.9 eV, 1.95 eV, 2 eV, 2.1 eV, 2.2 eV, and 2.3 eV.

[0096] It is understood that the perovskite film can be an intrinsic perovskite layer or a doped perovskite layer.

[0097] An embodiment of the present application provides a method for preparing a perovskite film, comprising the following steps:

[0098] The perovskite precursor solution or the perovskite precursor solution prepared by the preparation method is made into a wet film;

[0099] The wet film is annealed to prepare a perovskite film.

[0100] After the above-mentioned perovskite precursor solution or the perovskite precursor solution prepared by the above-mentioned preparation method is made into a wet film and annealed, the generated perovskite grains are relatively large and have no grain boundaries in the horizontal direction. The organic passivation material in the perovskite precursor solution adheres to the grain boundaries in the vertical direction to generate a 2D perovskite layer. While passivating the grain boundaries, it is beneficial to the vertical transport of photogenerated carriers and prevents the lateral diffusion of electron-hole pairs from being trapped in the recombination center and causing non-radiative recombination.

[0101] It can be understood that the annealing treatment evaporates the solvent and promotes the formation of a 2D perovskite layer; since the main part of the organic passivation material is a ring connector, the molecules of this structure are generally aggregated in a horizontal plane that is horizontal to the ring structure, so it can form a 2D structure.

[0102] In some of the examples, in the method for preparing a perovskite film, the annealing treatment includes a first annealing treatment and a second annealing treatment, the temperature of the first annealing treatment is 60°C to 80°C, and the temperature of the second annealing treatment is 110°C to 130°C.

[0103] Compared with not performing the first annealing treatment and directly performing the second annealing treatment (the organic passivation molecules are not fully anchored on the grains and are squeezed out of the perovskite layer by the overly fast growing grains into the upper and lower interfaces), the two-stage annealing method of bulk doping can effectively passivate the three defect concentration sites of the perovskite bulk phase, grain boundary and interface; wherein, during the first annealing treatment, part of the organic passivation material is anchored on the perovskite grains, and under the influence of the intermolecular interaction force, it is orderly arranged on the vertical grain boundary of the perovskite to form a continuous organic molecule layer, and with the second annealing treatment, a continuous 2D perovskite layer is formed from bottom to top and through the perovskite layer; the passivation material that is not anchored to the perovskite is squeezed out during the second annealing treatment, enriched at the interface of the perovskite, and plays an interface passivation role.

[0104] It can be understood that the temperature of the first annealing treatment includes but is not limited to 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, and 80°C; the temperature of the second annealing treatment includes but is not limited to 110°C, 112°C, 115°C, 118°C, 120°C, 122°C, 125°C, 128°C, and 130°C.

[0105] In some of the examples, in the method for preparing the perovskite film, the time of the first annealing treatment is 1 min to 10 min, and the time of the second annealing treatment is 10 min to 30 min.

[0106] It can be understood that the time for the first annealing treatment includes but is not limited to 1 min, 2 min, 5 min, 8 min, and 10 min; the time for the second annealing treatment includes but is not limited to 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min, 28 min, and 30 min.

[0107] It can be understood that the present application does not limit the method of forming the wet film, including but not limited to wet processes such as spin coating, spray coating, blade coating, and slit coating.

[0108] One embodiment of the present application provides the use of the above-mentioned perovskite precursor solution or the perovskite precursor solution prepared by the above-mentioned preparation method in the preparation of a perovskite battery.

[0109] One embodiment of the present application provides a perovskite cell, comprising the above-mentioned perovskite film or the perovskite film prepared by the above-mentioned preparation method.

[0110] Using the above perovskite film in perovskite cells can give the perovskite cells better stability and higher conversion efficiency.

[0111] It can be understood that the perovskite cell can be a single-layer cell or a stacked cell.

[0112] In some of these examples, the perovskite cell is a perovskite-crystalline silicon tandem cell.

[0113] In some of the examples, the perovskite crystalline silicon stacked cell includes a stacked suede crystalline silicon cell, the above-mentioned perovskite film and a first conductive layer.

[0114] In some of the examples, in the perovskite crystalline silicon tandem cell, the first passivation layer in the perovskite film is disposed between the perovskite body layer and the first conductive layer.

[0115] In some of these examples, in perovskite crystalline silicon tandem cells, the crystalline silicon bottom cell has a 1 μm~5 μm velvet structure.

[0116] In some of the examples, in the perovskite crystalline silicon tandem cell, the first conductive layer includes a first conductive transparent layer and a first metal electrode layer, and the first conductive transparent layer is disposed between the perovskite film and the first metal electrode layer.

[0117] Optionally, the first conductive transparent layer includes at least one of indium tin oxide (ITO), indium zinc oxide (IZO) and aluminum zinc oxide (AZO).

[0118] Optionally, the first metal electrode layer includes at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al) and carbon (C).

[0119] In some of the examples, in the perovskite crystalline silicon stacked cell, the textured crystalline silicon cell includes a stacked single crystal silicon substrate, an a-Si:H layer, a boron-doped a-Si:H layer, a second conductive transparent layer, and a second metal electrode layer.

[0120] Optionally, the second conductive transparent layer includes at least one of indium tin oxide (ITO), indium zinc oxide (IZO) and aluminum zinc oxide (AZO).

[0121] Optionally, the second metal electrode layer includes at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al) and carbon (C).

[0122] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a hole transport layer and an electron transport layer, the hole transport layer is arranged between the suede crystalline silicon cell and the perovskite light absorbing layer, and the electron transport layer is arranged between the perovskite light absorbing layer and the first conductive layer.

[0123] In some of the examples, in the perovskite crystalline silicon tandem cell, the hole transport layer includes but is not limited to at least one of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) and [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB).

[0124] In some of these examples, in the perovskite silicon tandem cell, the electron transport layer includes at least one of fullerene and its derivatives.

[0125] It can be understood that fullerene and its derivatives include but are not limited to at least one of C60, C70 and PCBM.

[0126] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a carrier recombination layer, and the carrier recombination layer is arranged between the suede crystalline silicon cell and the hole transport layer.

[0127] In some of the examples, in the perovskite crystalline silicon tandem cell, the carrier recombination layer includes at least one of an ITO composite layer and an IZO composite layer.

[0128] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a buffer layer, and the buffer layer is disposed between the electron transport layer and the first conductive layer.

[0129] In some of these examples, in the perovskite crystalline silicon tandem cell, the buffer layer includes at least one of bathocuproine (BCP) and tin dioxide (SnO2).

[0130] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes an anti-reflection layer, and the anti-reflection layer is disposed between the first conductive transparent layer and the first metal electrode layer.

[0131] In some of the examples, in the perovskite crystalline silicon tandem cell, the anti-reflection layer includes at least one of magnesium fluoride (MgFx), lithium fluoride (LiF), sodium fluoride (NaF), and silicon oxide (SiO2).

[0132] See also Figure 1In some examples, a perovskite crystalline silicon stacked cell 100 is provided, including a single crystal silicon substrate 101, an a-Si:H layer 102, a boron-doped a-Si:H layer 103, a second conductive transparent layer 104, a second metal electrode layer 105, and an a-Si:H layer 106, a phosphorus-doped a-Si:H layer 107, a carrier recombination layer 108, a hole transport layer 109, a perovskite film 110, an electron transport layer 111, a buffer layer 112, a first conductive transparent layer 113, a first metal electrode layer 114, and an anti-reflection layer 115, which are sequentially arranged on the front side of the single crystal silicon substrate 101.

[0133] An embodiment of the present application provides a method for preparing a perovskite crystalline silicon stacked cell, comprising the following steps:

[0134] Provide velvet crystalline silicon cells;

[0135] The perovskite precursor solution or the perovskite precursor solution prepared by the preparation method is placed on one surface of the textured crystalline silicon cell, and subjected to annealing treatment to prepare a perovskite film;

[0136] A first conductive layer is prepared on the surface of the perovskite film away from the textured silicon cell.

[0137] In some of the examples, the method for preparing the perovskite crystalline silicon tandem cell includes the following steps:

[0138] Step S200: providing a textured silicon substrate 101;

[0139] Step S210: depositing an a-Si:H layer 106 and an a-Si:H layer 102 on the front side and the back side of the textured silicon substrate respectively;

[0140] Step S220: depositing a boron-doped a-Si:H layer 103 (constituting a back full-area hole transport layer) on the surface of the a-Si:H layer 102 away from the textured silicon substrate;

[0141] Step S230 : depositing a phosphorus-doped a-Si:H layer 107 (constituting a front full-area electron transport layer) on the surface of the a-Si:H layer 102 away from the textured silicon substrate.

[0142] Optionally, in step S210 to step S230, the deposition temperature is independently 100° C. to 300° C.; optionally, the deposition method is independently including but not limited to PECVD.

[0143] Step S240 : depositing a second transparent conductive layer 104 and a second metal electrode 105 in sequence on a surface of the boron-doped a-Si:H layer 103 away from the a-Si:H layer 102 .

[0144] Optionally, in step S240, a method of depositing the second transparent conductive layer includes but is not limited to a magnetron sputtering method.

[0145] Step S240 : depositing a carrier recombination layer 108 on a surface of the phosphorus-doped a-Si:H layer 107 away from the a-Si:H layer 106 .

[0146] Optionally, in step S240, a method of depositing the carrier recombination layer includes but is not limited to magnetron sputtering.

[0147] Step S250 : depositing a hole transport layer 109 on the surface of the carrier recombination layer 108 prepared in step S240 away from the phosphorus-doped a-Si:H layer 107 .

[0148] Optionally, in step S250, the method of depositing the hole transport layer includes but is not limited to spin coating.

[0149] Step S260: placing the above perovskite precursor solution or the perovskite precursor solution prepared by the above preparation method on the surface of the hole transport layer 109 away from the carrier recombination layer 108, and performing annealing treatment to prepare the perovskite film 110;

[0150] Step S270: On the surface of the perovskite film 110 away from the hole transport layer 109 , an electron transport layer 111 , a buffer layer 112 , a first conductive transparent layer 113 , a first metal electrode layer 114 , and an anti-reflection layer 115 are sequentially prepared.

[0151] Optionally, in step S270, the method of preparing the electron transport layer includes but is not limited to thermal evaporation.

[0152] Optionally, in step S270, the method of preparing the buffer layer includes but is not limited to ALD deposition method.

[0153] Optionally, in step S270, the method of preparing the first conductive transparent layer includes but is not limited to magnetron sputtering.

[0154] Optionally, in step S270, the method of preparing the anti-reflection layer includes but is not limited to a thermal evaporation method.

[0155] Optionally, in step S270, the method of preparing the first metal electrode layer includes but is not limited to thermal evaporation.

[0156] One embodiment of the present application provides a photovoltaic module, including the above-mentioned perovskite cell or the perovskite cell prepared by the above-mentioned preparation method.

[0157] It can be understood that photovoltaic modules can be used in photovoltaic power stations, such as ground power stations, rooftop power stations, water power stations, etc., and can also be used in equipment or devices that use solar energy to generate electricity, such as user solar power supplies, solar street lights, solar cars, solar buildings, etc. It can also be understood that the application scenarios of photovoltaic systems include but are not limited to this, that is, photovoltaic systems can be used in all fields that require solar energy to generate electricity. Taking the photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a junction box and an inverter. The photovoltaic array can be an array combination of multiple photovoltaic modules. For example, multiple photovoltaic modules can form multiple photovoltaic arrays. The photovoltaic array is connected to the junction box. The junction box can converge the current generated by the photovoltaic array. The converged current flows through the inverter and is converted into the alternating current required by the mains power grid, and then connected to the mains network to achieve solar power supply.

[0158] The photovoltaic module provided in the present application can be used in, but is not limited to, electrical devices such as vehicles, ships or aircraft.

[0159] The embodiments of the present application provide an electric device, which may be, but is not limited to, a mobile phone, a tablet, a laptop, an electric toy, an electric tool, a battery car, an electric car, a ship, a spacecraft, etc. Among them, the electric toy may include a fixed or mobile electric toy, such as a game console, an electric car toy, an electric ship toy, and an electric airplane toy, etc., and the spacecraft may include an airplane, a rocket, a space shuttle, and a spacecraft, etc.

[0160] The present application is further described in detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0161] Example 1

[0162] An inverted wide bandgap perovskite / inverted pyramid velvet heterojunction silicon tandem solar cell

[0163] (1) Select n-type single crystal silicon 101, perform RCA standard cleaning process, and use KOH aqueous solution to etch the silicon wafer to prepare a double-sided positive pyramid velvet surface with a thickness of 1 μm and a positive pyramid sidewall at an angle of 35° to the horizontal direction of the silicon wafer;

[0164] (2) using a PECVD process to deposit an a-Si:H passivation layer 106 and an a-Si:H layer 102 on the front and back sides of the silicon substrate, respectively, with a thickness of about 5 nm and a deposition temperature of 200°C;

[0165] (3) A boron-doped a-Si:H layer 103 (12 nm) is deposited on the back side by PECVD process at a deposition temperature of 200°C to form a full-area hole transport layer on the back side;

[0166] (4) A phosphorus-doped a-Si:H layer 107 (6 nm) was deposited on the front side using a PECVD process at a deposition temperature of 200°C to form a full-area electron transport layer on the front side;

[0167] (5) Using magnetron sputtering to deposit an ITO transparent electrode 104 (110 nm) on the back, the square resistance is about 120Ω / sq; then, a gate line silver electrode 105 is deposited at low temperature;

[0168] (6) depositing an IZO composite layer 108 on the front side by magnetron sputtering with a thickness of 15 nm;

[0169] (7) The Me-4PACz hole transport layer 109 is prepared by spin coating, and the thickness is about 1 nm to 2 nm;

[0170] (8) mixing a perovskite precursor, an organic passivation material (1-carboxy-4-aminoindan, with an intermolecular distance of 4.0 Å) and an organic solvent (DMF and DMSO in a volume ratio of 4:1) to prepare a perovskite precursor solution, wherein the concentration of the organic passivation material is 1 mmol / L and the concentration of the perovskite precursor is 1.7 mol / L;

[0171] (9) The perovskite precursor solution is placed on the surface of the hole transport layer 109 by spin coating, annealed at 70°C for 3 min, and then annealed at 120°C for 20 min to prepare the perovskite film 110 (Cs 0.05 MA 0.15 FA 0.8 PbI 2.25 Br 0.75 ), with a band gap of about 1.68 eV and a thickness of about 500 nm. The perovskite film includes a perovskite body 1100, a 2D passivation layer 1101 existing at the buried interface of the perovskite body, and a 2D passivation layer 1102 vertically penetrating the perovskite body;

[0172] (10) A C60 electron transport layer 111 with a thickness of 20 nm was prepared by thermal evaporation;

[0173] (11) The cell was taken out and annealed at 100°C for 15 min, and then an SnO2 buffer layer 112 was prepared by ALD with a thickness of 20 nm.

[0174] (12) depositing an IZO transparent electrode 113 on the SnO2 buffer layer by magnetron sputtering, with a thickness of 100 nm;

[0175] (13) A silver electrode 114 with a thickness of 400 nm is prepared through a mask by thermal evaporation, and a MgFx anti-reflection layer 115 with a thickness of 100 nm is prepared in the effective area by thermal evaporation.

[0176] Example 2

[0177] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by an equal concentration of 2,5-thiophenedicarboxylic acid, and the intermolecular distance is 4.03 Å.

[0178] Example 3

[0179] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by an equal concentration of phenbutamol acetate, and the intermolecular distance is 4.04 Å.

[0180] Example 4

[0181] The method is basically the same as Example 1, except that in step (9), annealing is not performed at 70°C, but directly performed at 120°C for 23 min. Step (10) is specifically as follows:

[0182] The perovskite precursor solution was placed on the surface of the hole transport layer 109 by spin coating and annealed at 120°C for 23 min to prepare the perovskite film 110 (Cs 0.05 MA 0.15 FA 0.8 PbI 2.25 Br 0.75 ), with a band gap of about 1.68 eV and a thickness of about 500 nm.

[0183] Example 5

[0184] The method is basically the same as Example 1, except that in step (8), the concentration of the organic passivation material in the perovskite precursor solution is 2 mmol / L.

[0185] Example 6

[0186] The method is basically the same as Example 1, except that in step (8), the concentration of the organic passivation material in the perovskite precursor solution is 3 mmol / L.

[0187] Comparative Example 1

[0188] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by an equal concentration of 2-aminoindene, the intermolecular distance is 3.6 Å, and the structural formula is shown in formula (II):

[0189]

[0190] (II).

[0191] Comparative Example 2

[0192] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by 4-aminobenzoic acid of equal concentration, the intermolecular distance is 3.6 Å, and the structural formula is shown in formula (III):

[0193]

[0194] (III).

[0195] Comparative Example 3

[0196] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by 3-amino-2-thiophenecarboxylic acid methyl ester of equal concentration, the intermolecular distance is 4.6 Å, and the structural formula is shown in formula (IV):

[0197]

[0198] (IV).

[0199] Comparative Example 4

[0200] The method is basically the same as Example 1, except that in step (8), the organic passivation material is replaced by an equal concentration of amylamine iodine.

[0201] The perovskite solar cells prepared in each embodiment and comparative example were subjected to performance tests of open circuit voltage, short circuit current density, fill factor and energy conversion efficiency. The IV curve was used for the test. The test conditions were: AM 1.5G standard solar spectrum, irradiance of 1000W / m 2 The experimental test results are shown in Table 1. PCE represents the energy conversion efficiency in %, Voc represents the open circuit voltage in V, and Jsc represents the short circuit current density in mA / cm 2 , FF stands for fill factor, the unit is %.

[0202] The perovskite solar cells prepared in each embodiment and comparative example were subjected to a 1000H stability test MPP (maximum power point tracking), and the results are shown in Table 1.

[0203] Table 1

[0204]

[0205] As can be seen from Table 1, compared with the comparative example, the energy conversion efficiency, open circuit voltage, short circuit current density and filling factor of the perovskite solar cell prepared in the embodiment are higher, and the cycle performance is better; while the intermolecular distance of the organic passivation material in Comparative Example 1 and Comparative Example 2 is too short, and the 2-aminoindene in Comparative Example 1 has only one functional group, which cannot fix the direction of the ring structure and cannot form a 2D monolayer, resulting in a significant decrease in the short circuit current density; the intermolecular distance of the organic passivation material in Comparative Example 3 is too long, and the open circuit voltage, filling factor and stability performance are lost; although the intermolecular distance of the organic passivation material in Comparative Example 4 is in the range of 3.9Å~4.1Å, amylamine iodine does not have a cyclic connector, and cannot form a 2D monolayer between grains and grain boundaries, and the MPP is reduced.

[0206] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0207] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A perovskite precursor solution, characterized in that: It includes a perovskite precursor and an organic passivation material, wherein the organic passivation material includes a cyclic connector and at least two active groups connected to the cyclic connector, wherein the active groups can be combined with the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

2. The perovskite precursor solution according to claim 1, characterized in that The active groups include at least one of -NH2, -COOH, -PO3H and -SO3H.

3. The perovskite precursor solution according to claim 1, characterized in that The cyclic connector includes at least one of a benzene ring, furan, pyridine, thiophene, indane and a combination thereof.

4. The perovskite precursor solution according to claim 1, characterized in that The organic passivation material includes at least one of 1-carboxy-4-aminoindane, phenbutamine acetic acid, 2,5-thiophene dicarboxylic acid, 3,3′-dibromo-2,2′-bithiophene, 2,5-furandicarboxylic acid and 2-amino-5-fluoropyridine.

5. The perovskite precursor solution according to claim 1, characterized in that The molar concentration ratio of the organic passivation material to the perovskite precursor is 1-3:1700.

6. The perovskite precursor solution according to claim 1, characterized in that The concentration of the organic passivation material in the perovskite precursor solution is 0.5 mmol / L to 1.5 mmol / L.

7. The perovskite precursor solution according to any one of claims 1 to 6, characterized in that: The perovskite precursor includes monovalent cations, divalent cations and halogen ions, wherein the monovalent cations include CH(NH2)2 + 、CH3NH3 + , Cs + and Rb + At least one of the divalent cations, wherein the divalent cations include Pb 2+ Sn 2+ and Sr 2+ At least one of the halogen ions, wherein the halogen ions include Cl - Br - and I - At least one of; and / or The solvent in the perovskite precursor solution includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

8. A method for preparing a perovskite precursor solution, characterized in that: The following steps are involved: A perovskite precursor, an organic passivation material and an organic solvent are mixed to prepare a perovskite precursor solution; the organic passivation material includes a cyclic connector and an active group connected to the cyclic connector, the active group can bind to the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

9. A perovskite film, characterized in that: It is prepared by using the perovskite precursor solution according to any one of claims 1 to 7 or the perovskite precursor solution prepared by the preparation method according to claim 8.

10. A perovskite film, characterized in that: It includes a perovskite body layer and a passivation layer, wherein the passivation layer is arranged on at least one surface of the perovskite body layer and vertically penetrates the perovskite body layer, the organic passivation material in the passivation layer includes a cyclic connector and an active group connected to the cyclic connector, the active group can be combined with the perovskite site, and the intermolecular distance of the organic passivation material is 3.9Å~4.1Å.

11. The perovskite film according to claim 10, characterized in that The band gap of the perovskite film is 1.6 eV~2.3 eV.

12. A method for preparing a perovskite film, characterized in that: The following steps are involved: Forming a wet film from the perovskite precursor solution according to any one of claims 1 to 7 or the perovskite precursor solution prepared by the preparation method according to claim 8; The wet film is subjected to annealing treatment to prepare the perovskite film.

13. The preparation method according to claim 12, characterized in that: The annealing treatment includes a first annealing treatment and a second annealing treatment, the temperature of the first annealing treatment is 60°C to 80°C, and the temperature of the second annealing treatment is 110°C to 130°C.

14. Use of the perovskite precursor solution according to any one of claims 1 to 7, the perovskite precursor solution prepared by the preparation method according to claim 8, the perovskite film according to any one of claims 9 to 11, or the perovskite film prepared by the preparation method according to any one of claims 12 to 13 in the preparation of perovskite cells.

15. A perovskite battery, characterized in that: It includes the perovskite film as described in any one of claims 9 to 11 or the perovskite film prepared by the preparation method as described in any one of claims 12 to 13.

16. The perovskite cell according to claim 15, characterized in that The perovskite cell comprises a perovskite crystalline silicon stacked cell, and the perovskite crystalline silicon stacked cell comprises a stacked suede crystalline silicon cell, the perovskite film and a first conductive layer.

17. A photovoltaic module, characterized in that: Comprising the perovskite cell as claimed in claim 15 or 16.

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