Perovskite passivation film layer, preparation method thereof and perovskite battery

Abstract

The application relates to the technical field of photovoltaic cells, in particular to a perovskite passivation film layer, a preparation method thereof and a perovskite cell. The perovskite passivation film layer comprises a first passivation material and / or a second passivation material, the first passivation material is a compound containing a thiazole ring and an amine group, and the second passivation material is a compound containing a sulfoxide group. The passivation film layer can effectively improve the performance of the perovskite film layer, and improve the device efficiency and long-term stability.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic cell technology, and more specifically, to a perovskite passivation film, its preparation method, and a perovskite cell. Background Technology

[0002] Perovskite solar cells (PSCs) possess many attractive properties, including solution processability, low manufacturing costs, and high power conversion efficiency (PCE). This has garnered significant attention over the past decade and driven their commercialization. To date, the best certified PCE for PSCs has reached over 26%. Inverted-structure (pin) perovskite cells have attracted considerable attention due to their low-temperature fabrication process and good stability. Their core structure consists of: ITO (indium tin oxide) / hole transport layer (HTL) / perovskite light-absorbing layer / electron transport layer (ETL, such as tin oxide SnO2) / metal electrode. However, interfacial defects between the electron transport layer (ETL) and the perovskite light-absorbing layer in perovskite solar cells (PSCs), such as uncoordinated Pb... 2 +Oxygen vacancies and halogen vacancies are key factors limiting device efficiency and stability. Common passivation methods in the prior art include: single passivation agent modification (such as PEAI, PMMA): targeting only Pb. 2 Partial passivation using positive or negative oxygen vacancies cannot synergistically suppress multiple types of defects; vacuum deposition processes (such as ALD passivation layers) are complex and costly, making large-scale application difficult; solvent additive methods can easily cause perovskite decomposition due to additive residues, resulting in poor long-term stability. The above methods suffer from incomplete passivation effects, poor process compatibility, and high costs, necessitating the development of novel passivation strategies.

[0003] Currently, interface passivation technology is a key means to solve the above problems. Commonly used passivation materials in existing technologies include: 1) small molecule amine compounds (such as phenylethyl ammonium iodide, PEAI): through the interaction of the amine group with Pb. 2 + Coordination passivates interfacial defects, but has poor thermal stability (easily decomposes at >80℃); 2) Polymer materials (such as PMMA): form a physical passivation film, but reduce interfacial conductivity; 3) Bifunctional passivators (such as sulfur-containing compounds): partially and simultaneously passivate Pb. 2 + and oxygen vacancies, but the synthesis process is complex (requiring multiple steps) and costly (e.g., containing noble metal ligands).

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] One objective of this invention is to provide a perovskite passivation film that can effectively passivate perovskite films, improve the quality and performance of perovskite films, and enhance device efficiency and long-term stability.

[0006] Another object of the present invention is to provide a method for preparing a perovskite passivation film.

[0007] Another object of the present invention is to provide a perovskite battery.

[0008] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0009] A perovskite passivation film includes a first passivation material and / or a second passivation material, wherein the first passivation material is a compound containing a thiazole ring and an amino group, and the second passivation material is a compound containing a sulfoxide group.

[0010] In some embodiments, the first passivating material includes at least one of thiazole-2,4-diamine, thiazole-2,5-diamine, 5-fluoro-2-aminothiazole, and 5-amino-1,3,4-thiadiazole-2-thiol.

[0011] In some embodiments, the passivating material includes at least one of tetramethylene sulfoxide, cyclobutyl sulfoxide, diphenyl sulfoxide, and bis(ethylene sulfone)ethane.

[0012] In some embodiments, the molar ratio of the first passivating material to the second passivating material is (1.1 to 3.3):1.

[0013] In some embodiments, the perovskite passivation film is also doped with quantum dots.

[0014] In some embodiments, a polymer layer is further disposed on the surface of the perovskite passivation film, the polymer layer having a thickness of 1 to 4 nm.

[0015] In some embodiments, the thickness of the perovskite passivation film is 2–5 nm.

[0016] The method for preparing the perovskite passivation film as described above includes the following steps:

[0017] A first passivation liquid containing a first passivation material and / or a second passivation liquid containing a second passivation material are coated onto the surface of the perovskite film to obtain a coating layer; the coating layer is then annealed.

[0018] In some embodiments, the concentration of the first passivation solution is 0.1–2.0 mg / mL; the concentration of the second passivation solution is 0.05–1.5 μL / mL; and the volume ratio of the first passivation solution to the second passivation solution is 1:(1–5).

[0019] In some embodiments, the first passivating solution and the second passivating solution also each independently include a solvent, said solvent including at least one of isopropanol, acetonitrile, ethanol and 1-ethyl-3-methylimidazolium tetrafluoroborate.

[0020] In some embodiments, the first passivating liquid and the second passivating liquid are coated in the form of a mixture, or are coated sequentially in their respective independent forms.

[0021] In some embodiments, the mixing time of the first passivating solution and the second passivating solution in the form of a mixture is 1 to 3 hours.

[0022] In some embodiments, quantum dots are also incorporated into the first passivation solution and / or the second passivation solution.

[0023] In some embodiments, the method further includes coating the surface of the perovskite passivation film with a polymer to form a polymer layer.

[0024] In some embodiments, the coating includes scraping or spraying, wherein the scraping speed is 3 to 15 mm / s, and the spraying controls the droplet size to be less than 10 μm.

[0025] In some implementations, the coating is replaced by immersion or inkjet printing.

[0026] In some embodiments, the annealing temperature is 70–130°C, and the annealing time is 5–15 minutes.

[0027] A perovskite solar cell includes a perovskite film and a perovskite passivation film located on the surface of the perovskite film.

[0028] In some embodiments, the perovskite solar cell further includes a substrate layer, a first charge transport layer, a second charge transport layer, and an electrode layer; the first charge transport layer is located on the surface of the substrate layer, the perovskite film layer is located on the surface of the first charge transport layer, the second charge transport layer is located on the surface of the perovskite passivation film layer, and the electrode layer is located on the surface of the second charge transport layer.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] (1) In the perovskite passivation film of the present invention, the -NH2 of the first passivation material is associated with uncoordinated Pb on the perovskite surface. 2+ A bidentate coordination bond is formed, with the sulfur atom in the thiazole ring interacting with the oxygen vacancy in SnO2 (Vo 2+The first and second passivation materials suppress deep-level defect states through Lewis acid-base interaction. The sulfoxide groups (dipole moment 4.1D) of the second passivation material (tetramethylene sulfoxide) form hydrogen bonds (O···HI bonds) with the I- on the perovskite surface, reducing surface energy and inducing uniform film formation. Its small molecular size allows it to diffuse into the SnO2 grain boundary gaps, reducing interface defects through physical filling, suppressing electron scattering, and thus improving electron mobility. The first and second passivation materials of this invention can function independently or synergistically. The first and second passivation materials may form a relatively stable chemical interaction, which is beneficial for the effective combination and repair of defects on the perovskite surface by the passivation material. The combination of chemical coordination and physical filling can effectively improve the quality and performance of the perovskite film, and enhance device efficiency and long-term stability.

[0031] (2) The method for preparing the perovskite passivation film of the present invention is simple and easy to implement. The passivation film obtained by this method can effectively passivate defects, isolate the environment, and optimize the interface, thereby improving the efficiency and stability of perovskite solar cells.

[0032] (3) The perovskite battery of the present invention has high efficiency and long-term stability, reduced energy consumption and reduced cost. Attached Figure Description

[0033] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0034] Figure 1 This is a schematic diagram of the perovskite solar cell of the present invention.

[0035] Figure label:

[0036] 1-Base layer, 2-Hole transport layer, 3-Perovskite film layer, 4-Passivation film layer, 5-Electron transport layer, 6-Electrode layer. Detailed Implementation

[0037] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0038] According to one aspect of the present invention, the present invention relates to a perovskite passivation film, comprising a first passivation material and / or a second passivation material, wherein the first passivation material is a compound comprising a thiazole ring and an amino group, and the second passivation material is a compound containing a sulfoxide group.

[0039] In the perovskite film passivation solution of the present invention, the -NH2 of the first passivation material interacts with the uncoordinated Pb on the perovskite surface. 2+ A bidentate coordination bond is formed between the sulfur atom (electronegativity 2.58) in the thiazole ring and the oxygen vacancy (Vo) in SnO2. 2+ The first and second passivation materials suppress deep-level defect states through Lewis acid-base interactions. The sulfoxide groups (dipole moment 4.1D) of the second passivation material (tetramethylene sulfoxide) form hydrogen bonds (O···HI bonds) with the I- on the perovskite surface, reducing surface energy and inducing uniform film formation. Its small molecular size allows it to diffuse into the SnO2 grain boundary gaps, reducing interface defects through physical filling, suppressing electron scattering, and thus improving electron mobility. The first and second passivation materials of this invention can function independently or synergistically. The first and second passivation materials may form a relatively stable chemical interaction, which is beneficial for the effective combination and repair of defects on the perovskite surface by the passivation materials. The combination of chemical coordination and physical filling can effectively improve the quality and performance of the perovskite film, and enhance device efficiency and long-term stability.

[0040] In some embodiments, the first passivating material includes at least one selected from thiazole-2,4-diamine, thiazole-2,5-diamine, 5-fluoro-2-aminothiazole (C3H3FN2S), and 5-amino-1,3,4-thiadiazole-2-thiol (C2H3N3S2). Specifically, 5-amino-1,3,4-thiadiazole-2-thiol replaces the -NH2 group of thiazole-2,4-diamine with -SH, enhancing its binding to oxygen vacancies in SnO2 (the thiol group and Sn...). 3+ (Forms S-Sn bonds). Thiazole-2,5-diamine: Modifies the position of the amino group to adapt to the perovskite lattice. 5-Fluoro-2-aminothiazole enhances the hydrophobicity of the passivation film and improves its hygrothermal stability through the fluorine atom-induced electronic effect.

[0041] In some embodiments, the passivation material includes at least one of tetramethylene sulfoxide, cyclobutyl sulfoxide, diphenyl sulfoxide, and bis(ethylene sulfone)ethane. Retaining the sulfoxide group (-SO-), adjusting the alkyl chain length, or introducing heteroatoms optimizes filling and polar adsorption capabilities. For example, cyclobutyl sulfoxide can shorten the alkyl chain to a cyclic structure, enhancing molecular rigidity and reducing grain boundary penetration resistance. Diphenyl sulfoxide can introduce aromatic rings, enhancing the compactness of the passivation film through π-π stacking. Bis(ethylene sulfone)ethane, through its sulfoxide group, can simultaneously passivate the perovskite surface and the SnO2 interface.

[0042] In some embodiments, the molar ratio of the first passivating material to the second passivating material is (1.1–3.3):1, such as 1.1:1, 1.5:1, 2:1, 2.5:1, 3:1, or 3.3:1. A suitable molar ratio between the first and second passivating materials is more conducive to their coordinated function, improving film performance and enhancing the performance of the perovskite solar cell.

[0043] In some embodiments, other functional materials can be integrated to achieve multiple synergistic effects. In some embodiments, quantum dots are also doped to form a composite layer. In some embodiments, CsPbBr3 quantum dots (4-6 nm in size) are incorporated to improve carrier separation efficiency through quantum confinement effects.

[0044] In some embodiments, a polymer layer is disposed on the outer surface of the passivation film to form a composite passivation film, such as polystyrene. Polystyrene (PS, with a thickness of 1-4 nm) is spin-coated on the outside of the passivation film to form a physical barrier to inhibit water and oxygen permeation.

[0045] In some embodiments, the thickness of the perovskite passivation film is 2 to 5 nm, such as 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm or 5 nm.

[0046] According to another aspect of the present invention, the present invention also relates to a method for preparing the perovskite passivation film, comprising the following steps:

[0047] A first passivation liquid containing a first passivation material and / or a second passivation liquid containing a second passivation material are coated onto the surface of the perovskite film to obtain a coating layer; the coating layer is then annealed.

[0048] The method for preparing the perovskite passivation film of the present invention is simple and easy to implement. The passivation film obtained by this method can effectively passivate defects, isolate the environment, and optimize the interface, thereby improving the efficiency and stability of perovskite solar cells.

[0049] In some embodiments, the molar ratio of the first passivating material to the second passivating material is (1.1–3.3):1, for example, 1.1:1, 1.5:1, 2:1, 2.5:1, 3:1, or 3.3:1. The concentration of the first passivating solution is 0.1–2.0 mg / mL, for example, 0.1 mg / mL, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, or 2 mg / mL. The concentration of the second passivating solution is 0.05–1.5 μL / mL, for example, 0.05 μL / mL, 0.08 μL / mL, 0.1 μL / mL, 0.5 μL / mL, 0.8 μL / mL, 1 μL / mL, or 1.5 μL / mL. In some embodiments, the volume ratio of the first passivating solution to the second passivating solution is 1:(1–5), for example, 1:1, 1:2, 1:3, 1:4, or 1:5.

[0050] In some embodiments, the solvents for the first and second passivation solutions are each organic solvents, including at least one selected from isopropanol, acetonitrile, ethanol, and 1-ethyl-3-methylimidazolium tetrafluoroborate. In some embodiments, the solvent is a mixture of acetonitrile and ethanol (volume ratio 1:1), which can improve the solubility of thiazole-2,4-diamine while lowering the annealing temperature to 70°C (suitable for heat-sensitive substrates). In some embodiments, the ionic liquid solvent 1-ethyl-3-methylimidazolium tetrafluoroborate induces the vertical orientation of passivation molecules through the self-assembly properties of ionic liquids.

[0051] In some embodiments, the first passivating liquid and the second passivating liquid are coated in the form of a mixture. In some embodiments, the mixing time of the first passivating liquid and the second passivating liquid in the form of a mixture is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours. Alternatively, they can be coated sequentially in their independent forms, including: first applying the first passivating liquid, then applying the second passivating liquid; or first applying the second passivating liquid, then applying the first passivating liquid. If the method of applying the first passivating liquid first and then the second passivating liquid is adopted, the first passivating material serves as the bottom layer to preferentially anchor Pb. 2 + and halogen vacancies, then the second passivation solution covering the top layer passivates the remaining defects (some hydrogen bonds) and enhances interface protection; if the second passivation solution is coated first and then the first passivation solution is coated, the second passivation material preferentially occupies Pb. 2 + sites may hinder the direct bonding of amino and sulfur atoms of the first passivation material with the perovskite, reducing passivation efficiency. Furthermore, the second passivation material has a high LUMO energy level, which may affect the charge extraction of the subsequent first passivation material layer.

[0052] In some implementations, quantum dots are incorporated into the first passivation solution and / or the second passivation solution to improve the film performance.

[0053] In some embodiments, coating includes blade coating or spray coating. Blasting speed is 3–15 mm / s, for example, 3 mm / s, 5 mm / s, 8 mm / s, 10 mm / s, or 15 mm / s. Too low a speed results in a film thickness >5 nm, while too high a speed leads to uneven film layers. Environmental control: humidity <10%, temperature 20±2℃. Passivation solution is atomized into microdroplet spraying, with the spraying controlling the droplet size to be less than 10 μm, suitable for large-area flexible substrates.

[0054] In some implementations, the passivation film formation method is modified to adapt to different production scenarios (such as roll-to-roll flexible devices). Coating is replaced by immersion or inkjet printing. Immersion method: The perovskite film is immersed in the passivation solution and self-assembles into a film through surface tension. Inkjet printing: The viscosity of the passivation solution is customized to 5-15 cP, and patterned passivation is achieved through microdroplet positioning (suitable for repairing local defects in tandem batteries).

[0055] In some implementations, targeted passivation of defects is achieved through layered deposition. For example: a first passivation solution is deposited at the bottom layer, and a second passivation solution is deposited at the top layer; the first passivation solution is first spin-coated to passivate Pb. 2+ Then, a second passivation solution is applied to fill the SnO2 grain boundaries. In some embodiments, the concentration of the first passivation solution is 0.3-1.5 mg / mL. Below 0.3 mg / mL, the passivation film is discontinuous; above 1.5 mg / mL, crystallization is easy to occur. Stirring for 2 hours forms a homogeneous solution. The application rates of the first and second passivation solutions are 6-12 mm / s, respectively. Too low a rate (<6 mm / s) results in a film thickness >5 nm, while too high a rate (>12 mm / s) results in an uneven film. Environmental control: humidity <10%, temperature 20±2℃.

[0056] In some embodiments, the first passivating solution and the second passivating solution mixture are mixed in a concentration gradient: the mixing ratio of the first passivating solution / second passivating solution is dynamically adjusted during the scraping process (the volume ratio gradually changes from 1:1 to 1:3, and the molar ratio gradually changes from 3.3:1 to 1.1:1) to adapt to the defect distribution gradient from the perovskite surface to the SnO2 interface.

[0057] In some embodiments, the annealing temperature is 70–130°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, or 130°C. The low temperature range (70°C) is suitable for flexible PET substrates, while the high temperature range (130°C) accelerates solvent evaporation. The annealing time is 5–15 minutes, such as 5 minutes, 10 minutes, or 15 minutes. Annealing atmosphere: nitrogen glove box (H2O < 0.1 ppm, O2 < 0.1 ppm) to prevent oxidation. This invention utilizes suitable annealing conditions to improve the quality and performance of the passivation film, thereby enhancing the performance of perovskite solar cells.

[0058] According to another aspect of the present invention, the present invention also relates to a perovskite solar cell, comprising a perovskite film layer and a passivation film layer located on the surface of the perovskite film layer; the passivation film layer is a perovskite passivation film layer obtained by the above method.

[0059] The perovskite solar cell of this invention exhibits excellent high efficiency and long-term stability. Efficiency improvement: PCE increased from 18.5% to 24.5% (AM1.5G illumination). Energy consumption reduced by 30%. Raw material price is only one-third of PEAI.

[0060] In some embodiments, the perovskite solar cell further includes a substrate layer, a first charge transport layer, a second charge transport layer, and an electrode layer; the first charge transport layer is located on the surface of the substrate layer, the perovskite film layer is located on the surface of the first charge transport layer, the second charge transport layer is located on the surface of the passivation film layer, and the electrode layer is located on the surface of the second charge transport layer.

[0061] In some embodiments, the substrate layer includes at least one of fluorine-doped tin oxide (FTO), indium tin oxide (ITO) glass, and a flexible conductive substrate of indium tin oxide.

[0062] In some embodiments, the first charge transport layer and hole transport layer are made of nickel oxide (NiO). X The second transport layer is an electron transport layer, and the materials include fullerenes (C). 60 (e.g., fullerene derivatives such as PCBM) and tin oxide (SnO2). In some embodiments, C 60 Prepared using physical vapor deposition (PVD) process, with a thickness of 10–15 nm and a deposition rate of [missing information]. SnO2 is prepared by atomic layer deposition (ALD) with a thickness of 15–18 nm and a reaction temperature of 90–110 °C.

[0063] In some embodiments, the perovskite film is composed of ABX3 type perovskite, where A is Cs. + K + Ru + CH3NH3 + C(NH2)3 + CH(NH2)2 + B is any combination of one or at least two of the following, where B is Pb. 2+ and / or Sn 2+ X is Br - I - or Cl - Any combination of one or at least two of them; where A is Cs + K + Ru + CH3NH3+ C(NH2)3 + CH(NH2)2 + Any one or at least two of them, for example, could be Cs + With K + The combination of CH3NH3 + C(NH2)3 + With CH(NH2)2 + Combination, Cs + K + Ru + With CH3NH3 + The combination, or Cs + K + Ru + CH3NH3 + C(NH2)3 + With CH(NH2)2 + The combination of X and Br; - I - or Cl - Any one or at least two of the above, typical but non-limiting combinations include Br - with I - The combination, I - With Cl - The combination, Br - With Cl - The combination, or Br - I - With Cl - The combination of .

[0064] In some embodiments, the electrode layer includes at least one of gold, silver, and copper.

[0065] A method for preparing a perovskite solar cell includes the following steps:

[0066] (1) Base layer cleaning: ultrasonically clean with acetone, isopropanol and deionized water for 10-15 minutes each, and dry with nitrogen; ozone treatment: treat in a UV ozone cleaner for 10-25 minutes to improve surface hydrophilicity.

[0067] (2) A hole transport layer is prepared on the surface of a clean substrate and deposited on the substrate by magnetron sputtering. Radio frequency sputtering can be selected as the sputtering method.

[0068] (3) A perovskite film is prepared on the surface of the hole transport layer. A blade coating device is used to uniformly disperse the perovskite precursor solution, which includes ABX3 type perovskite and an organic solvent, wherein A is Cs. + K + Ru+ CH3NH3 + C(NH2)3 + CH(NH2)2 + B is any combination of one or at least two of the following, where B is Pb. 2+ and / or Sn 2+ X is Br - I - or Cl - The organic solvent comprises any one or at least two of the following: a mixture of dimethylformamide and dimethyl sulfoxide, or a mixture of γ-butyrolactone and N-methylpyrrolidone, wherein the volume ratio of dimethylformamide to dimethyl sulfoxide and γ-butyrolactone to N-methylpyrrolidone is in the range of 3-5:1. Annealing yields a perovskite film (thickness 300–500 μm).

[0069] (4) Prepare a passivation film on the surface of the perovskite film: Coat the perovskite film surface with a perovskite film passivation liquid after mixing the first passivation liquid and the second passivation liquid, or coat the first passivation liquid and the second passivation liquid separately to obtain a coating layer; perform annealing treatment on the coating layer at a temperature of 70 to 130°C for 5 to 15 minutes to obtain a passivation film layer.

[0070] (5) Preparation of an electron transport layer on the surface of the passivation film: Placed in the PVD and ALD cavities, C is deposited by vapor deposition respectively. 60 SnO2 is used to obtain an electron transport layer.

[0071] (6) Place it into the vacuum coating machine cavity and evacuate it to 10°C. -6 Below Pa, electrode material is vapor-deposited to obtain an electrode layer (50-70 nm), thus obtaining a perovskite solar cell.

[0072] The following explanation, combined with specific embodiments and comparative examples, further illustrates the point.

[0073] Example 1

[0074] A method for preparing a perovskite film passivation solution, comprising:

[0075] A 0.8 mg / mL thiazole-2,4-diamine solution and a 0.2 μL / mL tetramethylene sulfoxide solution were mixed at a volume ratio of 1:1 (molar ratio of 3.3:1), with isopropanol as the solvent. The mixture was stirred for 2 h to obtain a passivation solution.

[0076] A perovskite solar cell, the structural schematic diagram of which is shown below. Figure 1As shown, it includes a substrate layer 1, a first charge transport layer, a second charge transport layer, and an electrode layer 6; the first charge transport layer is located on the surface of the substrate layer 1, the perovskite film layer 3 is located on the surface of the first charge transport layer, the second charge transport layer is located on the surface of the passivation film layer 4, and the electrode layer 6 is located on the surface of the second charge transport layer.

[0077] The preparation method of perovskite solar cells includes the following steps:

[0078] (1) Clean the FTO glass slide (5cm×5cm) sequentially with acetone, isopropanol and deionized water for 15min each, and dry with nitrogen; ozone treatment: treat in a UV ozone cleaner for 20min to improve surface hydrophilicity.

[0079] (2) A hole transport layer 2 is prepared on the surface of a clean substrate, wherein the hole transport layer 2 is nickel oxide (NiO). x The material is deposited on the substrate by magnetron sputtering, and the sputtering method can be radio frequency sputtering.

[0080] (3) In NiO x The perovskite precursor solution was uniformly dispersed using a blade coating device on the modified FTO glass, and after annealing, a perovskite film (400 μm thick) was obtained.

[0081] (4) The passivation solution of this embodiment is scraped onto the surface of the perovskite film 3 at a speed of 9 mm / s, and then annealed at 100°C for 10 min. Annealing atmosphere: nitrogen glove box (H2O<0.1ppm, O2<0.1ppm) to form a passivation film 4 with a thickness of 3 nm.

[0082] (5) Place it into the PVD and ALD cavities and vapor deposit C respectively. 60 And SnO2 electron transport layer 5.

[0083] (6) Place it into the vacuum coating machine cavity and evacuate it to 10°C. -6 Below Pa, Ag electrodes are deposited by vapor deposition to obtain electrode layer 6 (60 nm), thus obtaining a perovskite solar cell.

[0084] Example 2

[0085] A method for preparing a perovskite film passivation solution, comprising:

[0086] A 0.8 mg / mL thiazole-2,4-diamine solution and a 0.2 μL / mL tetramethylene sulfoxide solution were mixed at a volume ratio of 1:2 (molar ratio of 2.2:1), with isopropanol as the solvent. The mixture was stirred for 2 h to obtain a passivation solution.

[0087] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is used, is the same as in Example 1.

[0088] Example 3

[0089] A method for preparing a perovskite film passivation solution, comprising:

[0090] A 0.8 mg / mL thiazole-2,4-diamine solution and a 0.2 μL / mL tetramethylene sulfoxide solution were mixed at a volume ratio of 1:3 (molar ratio of 1.1:1), with isopropanol as the solvent. The mixture was stirred for 2 h to obtain a passivation solution.

[0091] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is used, is the same as in Example 1.

[0092] Example 4

[0093] A method for preparing a perovskite film passivation solution, comprising:

[0094] A 0.8 mg / mL solution of 2-amino-5-mercapto-1,3,4-thiazole was mixed with a 0.2 μL / mL solution of cyclobutyl sulfoxide at a volume ratio of 1:2 (molar ratio of 1.48:1), with isopropanol as the solvent. The mixture was stirred for 2 h to obtain a passivation solution.

[0095] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is used, is the same as in Example 1.

[0096] Example 5

[0097] A method for preparing a perovskite film passivation solution, comprising:

[0098] A mixture of 5-fluoro-2-aminothiazole and thiazole-2,5-diamine (mass ratio 1:2, molar ratio 1:2.1) with a total concentration of 0.8 mg / mL was mixed with a solution of tetramethylene sulfoxide and diphenyl sulfoxide (mass ratio 1:2, molar ratio 1:0.97) at a volume ratio of 1:2 (the total molar ratio of the first and second mixed passivation solutions was approximately 2.27:1). The solvent was isopropanol. The mixture was stirred for 2 hours to obtain the passivation solution.

[0099] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is used, is the same as in Example 1.

[0100] Example 6

[0101] A method for preparing a perovskite solar cell differs from Example 2 in that:

[0102] Step (4): First, 0.8 mg / mL thiazole-2,4-diamine is scraped onto the surface of the perovskite film 3, and then 0.2 μL / mL tetramethylene sulfoxide solution is scraped at 9 mm / s with a volume ratio of 1:2 (molar ratio 2.2:1); then annealing is performed at 100 °C for 10 min to form a passivation film 4 with a thickness of 3 nm.

[0103] Example 7

[0104] A method for preparing a perovskite solar cell differs from that in Example 6 in that:

[0105] Step (4): First, apply 0.2 μL / mL tetramethylene sulfoxide solution to the surface of the perovskite film 3 at 9 mm / s, then apply 0.8 mg / mL thiazole-2,4-diamine solution at a volume ratio of 2:1 (molar ratio 1:2.2); then anneal at 100 °C for 10 min to form a passivation film 4 with a thickness of 3 nm.

[0106] Example 8

[0107] A method for preparing a perovskite film passivation solution differs from that in Example 1 in that:

[0108] The passivation solution is also doped with quantum dots CsPbBr3 (5nm).

[0109] A method for preparing a perovskite solar cell differs from Example 2 in that:

[0110] Using the passivation solution of this embodiment, after annealing, polystyrene is coated to obtain a 2nm polymer layer, thus obtaining a passivation film layer.

[0111] Example 9

[0112] A method for preparing a perovskite film passivation solution, comprising:

[0113] Thiazole-2,4-diamine at a concentration of 0.8 mg / mL (6.95 mM) was dissolved in isopropanol and stirred for 2 h to obtain a passivation solution.

[0114] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is employed and the coating speed is 10 mm / s, with other conditions being the same as in Example 1.

[0115] Example 10

[0116] A method for preparing a perovskite film passivation solution, comprising:

[0117] 0.2 μL / mL (2.22 mM molar concentration) of tetramethylene sulfoxide was dissolved in isopropanol and stirred for 2 h to obtain a passivation solution.

[0118] A method for preparing a perovskite solar cell, except that the passivation solution used in this embodiment is employed and the coating speed is 10 mm / s, with other conditions being the same as in Example 1.

[0119] Comparative Example 1

[0120] A method for preparing a perovskite solar cell, except that the passivation film layer is not prepared, is the same as in Example 1.

[0121] Experimental Example

[0122] The perovskite solar cells of each embodiment and comparative example were subjected to performance tests, including: current density (J / L). sc ), open circuit voltage (V) oc The test parameters included fill factor (FF) and power conversion efficiency (PCE). Test conditions were: AM1.5, 1000 W / m². 2 , 25±2℃.

[0123] The test results are shown in Table 1.

[0124] Table 1 Performance test results of perovskite solar cells

[0125] Group <![CDATA[J sc (mA / cm 2 )]]> <![CDATA[V oc (V)]]> FF (%) PCE (%) Example 1 24.6 1.18 78.5 22.9 Example 2 25.1 1.2 80.1 23.7 Example 3 24.8 1.17 77.8 22.6 Example 4 25.2 1.21 79 23.7 Example 5 25.4 1.22 80 24.2 Example 6 25.0 1.19 79.5 23.3 Example 7 24.6 1.15 76.2 21.5 Example 8 25.5 1.23 81 24.5 Example 9 24.3 1.12 76.8 21.5 Example 10 23.9 1.06 75.2 20.8 Comparative Example 1 23.2 1.04 72.1 18.5

[0126] As shown in Table 1, when the first and second passivation solutions of the present invention are used alone (as in Examples 9-10), the performance of the resulting perovskite solar cells is slightly improved compared to Comparative Example 1. When the first and second passivation solutions are used in combination (as in Examples 1-8), the first and second passivation materials can form a synergistic effect. The combination of chemical coordination and physical filling can effectively improve the quality and performance of the perovskite film, thereby improving device efficiency and long-term stability.

[0127] Comparing Examples 1-3, it is evident that the molar ratio of the first passivating material to the second passivating material in Example 2 is superior. Increasing or decreasing the molar ratio of the first and second passivating materials leads to problems such as decreased passivation coverage and slight reductions in Voc and FF. If the first passivating material (thiazole-2,4-diamine) is in excess (increased molar ratio), the excess molecules aggregate in the solution, resulting in decreased film uniformity. Furthermore, after the binding sites with perovskite surface defects become saturated, excess molecules cannot be effectively adsorbed, forming a loose film layer. When the second passivating material (tetramethylene sulfoxide) is in excess (decreased molar ratio), the excess of highly polar solvents (sulfoxides) may alter the surface tension of the passivation solution, causing film rupture during coating. Solvent residues or decomposition products during annealing form defects, affecting the electron transport layer (such as C). 60 Interface contact of / SnO2).

[0128] In Example 4, although the thiol group enhances passivation, the solubilization ability of cyclobutyl sulfoxide is weaker than that of tetramethylene sulfoxide, which limits the depth of defect repair.

[0129] In Example 5, the multi-component synergy can further optimize interface defects, resulting in improved performance of the perovskite solar cell.

[0130] Examples 6 and 7 employ a step-by-step coating method. The method in Example 6 is superior to that in Example 7, as it facilitates the synergistic effect of the first and second passivation materials, improves film performance, and enhances the performance of the perovskite solar cell.

[0131] Example 8 employs a dual enhancement of quantum dots and polymers. Quantum dots can improve carrier extraction efficiency, while the polystyrene layer can suppress ion migration, thereby further improving the performance of the resulting perovskite solar cell.

[0132] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A perovskite passivation film, characterized in that, It includes a first passivating material and / or a second passivating material, wherein the first passivating material is a compound containing a thiazole ring and an amino group, and the second passivating material is a compound containing a sulfoxide group.

2. The perovskite passivation film according to claim 1, characterized in that, It includes at least one of the following features (1) to (2): (1) The first passivation material includes at least one of thiazole-2,4-diamine, thiazole-2,5-diamine, 5-fluoro-2-aminothiazole and 5-amino-1,3,4-thiadiazole-2-thiol; (2) The passivation material includes at least one of tetramethylene sulfoxide, cyclobutyl sulfoxide, diphenyl sulfoxide and bis(ethylene sulfone) ethane.

3. The perovskite passivation film according to claim 1, characterized in that, The molar ratio of the first passivating material to the second passivating material is (1.1 to 3.3):

1.

4. The perovskite passivation film according to claim 1, characterized in that, It includes at least one of the following features (1) to (3): (1) The perovskite passivation film is also doped with quantum dots; (2) A polymer layer is further disposed on the surface of the perovskite passivation film, and the thickness of the polymer layer is 1 to 4 nm; (3) The thickness of the perovskite passivation film is 2 to 5 nm.

5. The method for preparing the perovskite passivation film as described in any one of claims 1 to 4, characterized in that, Includes the following steps: A first passivation liquid containing a first passivation material and / or a second passivation liquid containing a second passivation material are coated onto the surface of the perovskite film to obtain a coating layer. The coating layer is then annealed.

6. The method for preparing the perovskite passivation film according to claim 5, characterized in that, It includes at least one of the following features (1) to (3): (1) The concentration of the first passivation solution is 0.1 to 2.0 mg / mL; the concentration of the second passivation solution is 0.05 to 1.5 μL / mL; the volume ratio of the first passivation solution to the second passivation solution is 1:(1 to 5); (2) The first passivation solution and the second passivation solution each independently include a solvent, wherein the solvent includes at least one of isopropanol, acetonitrile, ethanol and 1-ethyl-3-methylimidazolium tetrafluoroborate; (3) The first passivation liquid and the second passivation liquid are coated in the form of a mixture or in the form of independent substances in sequence.

7. The method for preparing the perovskite passivation film according to claim 6, characterized in that, It includes at least one of the following features (1) to (3): (1) The mixing time of the first passivation solution and the second passivation solution in the form of a mixture is 1 to 3 hours; (2) The method for preparing the perovskite passivation film further includes: incorporating quantum dots into the first passivation solution and / or the second passivation solution; (3) The method for preparing the perovskite passivation film further includes: coating the surface of the perovskite passivation film with a polymer to form a polymer layer.

8. The method for preparing the perovskite passivation film according to claim 5, characterized in that, It includes at least one of the following features (1) to (3): (1) The coating includes scraping or spraying, wherein the scraping speed is 3 to 15 mm / s, and the spraying controls the droplet size to be less than 10 μm; (2) Replace the coating with immersion or inkjet printing; (3) The annealing temperature is 70-130℃ and the annealing time is 5-15min.

9. A perovskite battery, characterized in that, It includes a perovskite film layer and a perovskite passivation film layer located on the surface of the perovskite film layer; the perovskite passivation film layer is the perovskite passivation film layer according to any one of claims 1 to 4, or the perovskite passivation film layer obtained by any one of claims 5 to 8.

10. The perovskite solar cell according to claim 9, characterized in that, The perovskite solar cell further includes a substrate layer, a first charge transport layer, a second charge transport layer, and an electrode layer; the first charge transport layer is located on the surface of the substrate layer, the perovskite film layer is located on the surface of the first charge transport layer, the second charge transport layer is located on the surface of the perovskite passivation film layer, and the electrode layer is located on the surface of the second charge transport layer.

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