Perovskite solar cell with controllable oxidation hole transport layer and preparation method thereof

Abstract

The invention discloses a perovskite solar cell with a controllable oxidation hole transport layer and a preparation method of the perovskite solar cell. The method comprises the following steps: preparing an oxide electron transport layer on a conductive substrate, and preparing a perovskite light absorption layer on the surface of the oxide electron transport layer; preparing a solution containing graphdiyne and lithium salt, and drying to obtain a target compound; the method comprises the following steps: dissolving an aromatic amine organic material and a target compound in a poor solvent of perovskite to obtain a target mixed solution which contains an aromatic amine active free radical compound, a lithium embedded graphdiyne compound and a photon-generated carrier transport channel; and spin-coating the surface of the perovskite light absorption layer with the target mixed solution to obtain a hole transport layer, and depositing a metal electrode on the surface of the hole transport layer to obtain the perovskite solar cell. According to the method, controllable oxidation can be realized, the oxidation time is greatly shortened, no by-product is generated, meanwhile, water-oxygen adsorption sites can be effectively reduced, the hole mobility is remarkably enhanced, and the long-term stability and the photoelectric conversion efficiency of the prepared cell are improved.

Description

Technical Field

[0001] The present disclosure relates to the technical field of solar cell preparation, and in particular to a perovskite solar cell with a controllable oxidation hole transport layer and a preparation method thereof. Background Art

[0002] Perovskite solar cells are solar cells that use perovskite-type organic metal halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells, also known as new concept solar cells. Compared with traditional crystalline silicon solar cells, they have the advantages of higher efficiency, lower cost, softer and better transparency.

[0003] However, the preparation of perovskite solar cells in the prior art usually requires the introduction of a hygroscopic dopant, lithium bis(trifluoromethanesulfonyl)imide, to assist the oxidation of aromatic amine hole transport materials in the air to produce active free radicals to improve their hole mobility and conductivity. However, in this process, the oxidation process takes a long time, and the oxidation rate depends on conditions such as oxygen concentration, ambient light, and humidity. It is difficult to control the concentration of active free radicals produced by oxidation, and is accompanied by high hygroscopicity and volatility of Li x O y The generation of by-products such as ions, etc., under the service conditions, the influence of humidity and temperature triggers a chain reaction that accelerates the degradation of the device, resulting in poor stability of the prepared battery and poor photoelectric conversion efficiency. Summary of the invention

[0004] In view of this, the embodiments of the present disclosure provide a perovskite solar cell with a controllable oxidized hole transport layer and a preparation method, which can solve the problems existing in the prior art that the oxidation process in the battery preparation process is time-consuming, uncontrollable, has by-products, and the prepared battery has poor stability and poor photoelectric conversion efficiency.

[0005] In a first aspect, the embodiments of the present disclosure provide a method for preparing a perovskite solar cell having a controllable oxidized hole transport layer, including the following technical solutions:

[0006] preparing an oxide electron transport layer on a conductive substrate;

[0007] preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer;

[0008] preparing a solution containing graphyne and lithium salt, and obtaining a target complex after drying;

[0009] Dissolving the aromatic amine organic material and the target complex in a poor solvent of perovskite to cause a chemical reaction to obtain a target mixed solution containing a lithium embedded graphene compound and an aromatic amine active free radical compound;

[0010] Spin coating the target mixed solution on the surface of the perovskite light absorbing layer to obtain a hole transport layer, wherein the lithium embedded graphene compound and the aromatic amine active free radical compound in the hole transport layer form a photogenerated carrier transport channel;

[0011] A metal electrode is deposited on the surface of the hole transport layer to obtain a perovskite solar cell.

[0012] Optionally, the solution containing graphyne and lithium salt is prepared and dried to obtain the target complex, comprising: adding graphyne derivative and lithium salt to an organic solvent, stirring until the solution is clear, and vacuum drying to obtain the target complex.

[0013] Optionally, the mass ratio of the graphyne derivative to the lithium salt is 1:1.5 to 1:4.

[0014] Optionally, the aromatic amine organic material and the target complex are dissolved in a poor solvent of perovskite to cause a chemical reaction to obtain a target mixed solution containing a lithium embedded graphene compound and an aromatic amine active free radical compound, comprising:

[0015]

[0016] Optionally, the mass ratio of the aromatic amine organic material to the target complex is 1:0.02 to 1:0.05.

[0017] Optionally, the aromatic amine organic material includes any one of 4,4',4"-tri-(3-methylphenylaniline)triphenylamine, N,N'-diphenyl-N,N'-bis-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 2,2',7,7'-tetrakis-(diphenylamine)-9,9'-spirobifluorene, N,N'-diphenyl-N,N'-bis-(1-naphthyl-1,1'-biphenyl)-1,1'-biphenyl-4,4'-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene.

[0018] Optionally, the spin coating speed is 2000 rpm to 5000 rpm;

[0019] The spin coating time is 20s to 40s.

[0020] Optionally, the step of preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer comprises:

[0021] preparing a precursor solution;

[0022] Spin coating the precursor solution onto the surface of the oxide electron transport layer;

[0023] After the spin coating is completed, annealing treatment is performed to form the perovskite light absorbing layer.

[0024] Optionally, the preparation of the precursor solution includes: dissolving formamidine hydroiodide, lead iodide, and methylammonium chloride in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirring until completely dissolved.

[0025] In a second aspect, the present application discloses a perovskite solar cell with a controllable oxidized hole transport layer, which is prepared by the method for preparing a perovskite solar cell with a controllable oxidized hole transport layer.

[0026] In a third aspect, the embodiments of the present disclosure further provide a system for preparing a perovskite solar cell having a controllable oxidation hole transport layer, including the following solutions:

[0027] An oxide electron transport layer preparation module, used for preparing an oxide electron transport layer on a conductive substrate;

[0028] A perovskite light absorbing layer preparation module, used for preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer;

[0029] A target complex preparation module is used to prepare a solution containing graphyne and lithium salt, and obtain the target complex after drying;

[0030] A target mixed solution preparation module is used to dissolve aromatic amine organic materials and target complexes in a poor solvent of perovskite to cause a chemical reaction to obtain a target mixed solution containing lithium embedded graphene compounds and aromatic amine active free radical compounds;

[0031] A hole transport layer preparation module is used to spin-coat the target mixed solution on the surface of the perovskite light-absorbing layer to obtain a hole transport layer, in which the lithium-embedded graphene compound and the aromatic amine active free radical compound form a photogenerated carrier transport channel;

[0032] The deposition module is used to deposit a metal electrode on the surface of the hole transport layer to obtain a perovskite solar cell.

[0033] The invention discloses a method for preparing a perovskite solar cell with a controllable oxidized hole transport layer, which comprises preparing an oxide electron transport layer on a conductive substrate, preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer, and then spin-coating a target mixed solution on the surface of the perovskite light absorbing layer to obtain a hole transport layer, and then depositing a metal electrode on the surface of the hole transport layer to obtain a perovskite solar cell; specifically, the hole transport layer is formed by spin-coating a target mixed solution obtained by dissolving an aromatic amine organic material and a target complex in a poor solvent for perovskite, wherein the target complex, as a dopant, can provide graphyne and anions in a film, and these components can effectively control the oxidation state of the aromatic amine material; graphyne can react with the aromatic amine organic material, and no external interference is required in the poor solvent for perovskite. The electronic properties can be changed and the redox behavior can be controlled under certain conditions. There is no need for the time-consuming post-treatment process of traditional air oxidation methods, which avoids the degradation and damage of materials by the intervention of environmental water and oxygen, that is, the controllable oxidation of aromatic amine organic materials is achieved, and the oxidation time is greatly shortened. At the same time, the anions and the oxidized cationic free radicals of the aromatic amine materials form stable complexes, which can avoid the formation of by-products in traditional air oxidation technology. In addition, lithium ions combine with the changed graphyne derivatives to form stable complexes, that is, lithium-embedded graphyne compounds, which can effectively reduce water and oxygen adsorption sites, prevent the penetration of water vapor in the service environment, improve the long-term stability of perovskite solar cells, and improve the photoelectric conversion efficiency of perovskite solar cells. The preparation process of this application is simple and has good repeatability, is suitable for large-scale industrial production, and has certain application prospects.

[0034] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present invention more obvious and easy to understand, the following preferred embodiments are specifically cited and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present disclosure. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0036] Figure 1 A schematic flow chart of a method for preparing a perovskite solar cell with a controllable oxidized hole transport layer according to an embodiment of the present disclosure.

[0037] Figure 2 A schematic flow chart of a method for preparing a perovskite light absorbing layer according to an embodiment of the present disclosure.

[0038] Figure 3 Schematic diagram of the strong charge transfer effect between graphyne and triphenylamine group molecules provided in an embodiment of the present disclosure.

[0039] Figure 4 A comparison diagram of current density-voltage characteristic curves provided for FAPbI3 perovskite solar cells corresponding to comparative examples 1 and 2 and embodiments 1, 3, and 5 of the present disclosure.

[0040] Figure 5 A comparison diagram of the current-voltage characteristic curves provided for the single hole devices of Comparative Example 2 and Example 3 of the present disclosure.

[0041] Figure 6 A schematic diagram of the water contact angle provided for the hole transport layer of Comparative Example 2 of the present disclosure.

[0042] Figure 7 Schematic diagram of the water contact angle provided for the hole transport layer of Example 3 of the present disclosure.

[0043] Figure 8 A statistical comparison chart of long-term stability of FAPbI3 perovskite solar cells provided for Comparative Example 2 and Example 3 of the present disclosure. DETAILED DESCRIPTION

[0044] The embodiments of the present disclosure are described in detail below with reference to the accompanying drawings.

[0045] It should be clear that the following embodiments of the present disclosure are described by specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present disclosure from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, rather than all of the embodiments. The present disclosure can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present disclosure. It should be noted that the following embodiments and features in the embodiments can be combined with each other in the absence of conflict. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present disclosure.

[0046] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein may be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present disclosure, it should be understood by those skilled in the art that an aspect described herein may be implemented independently of any other aspect, and two or more of these aspects may be combined in various ways. For example, any number of aspects described herein may be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein may be used to implement this device and / or practice this method.

[0047] It should also be noted that the illustrations provided in the following embodiments are only schematic illustrations of the basic concept of the present disclosure. The drawings only show components related to the present disclosure rather than being drawn according to the number, shape and size of components in actual implementation. In actual implementation, the type, quantity and proportion of each component may be changed arbitrarily, and the component layout may also be more complicated.

[0048] Additionally, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects described may be practiced without these specific details.

[0049] Reference Figure 1 The present application discloses a method for preparing a perovskite solar cell with a controllable oxidized hole transport layer, which is used to prepare a perovskite solar cell. The structure of the perovskite solar cell specifically includes: an electron transport layer, a perovskite light absorption layer, and a hole transport layer sequentially prepared on a conductive substrate. The specific preparation method includes the following contents:

[0050] S100, preparing an oxide electron transport layer on a conductive substrate.

[0051] Specifically, the initial transparent conductive substrate is ultrasonically cleaned in deionized water, acetone, ethanol, and isopropanol for 15 to 30 minutes in sequence. After cleaning, it is blown dry with compressed air or inert gas to obtain a treated conductive substrate (i.e., a clean transparent conductive substrate), which is then treated with oxygen plasma or ultraviolet ozone to enhance wettability.

[0052] On the treated conductive substrate, an oxide electron transport layer is prepared by spin coating, chemical bath deposition, blade coating or atomic layer deposition.

[0053] The conductive substrate is preferably indium tin oxide (ITO) conductive glass or fluorine-doped tin oxide (FTO) conductive glass. The oxide electron transport layer includes any one of titanium oxide, tin oxide, zinc oxide, tungsten oxide, niobium oxide, indium oxide, chromium oxide, and cerium oxide.

[0054] S200, preparing a perovskite light absorbing layer (i.e., a FAPbI3 perovskite film) on the surface of the oxide electron transport layer.

[0055] Further reference Figure 2 The preparation method of the perovskite light absorbing layer specifically comprises the following steps:

[0056] S210, preparing a precursor solution.

[0057] The specific preparation method includes: in a nitrogen environment, dissolving formamidine hydroiodide, lead iodide, and methylammonium chloride in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) at a molar ratio of 1:1.05:0.35 to 1:1.15:0.35, stirring for 12 to 24 hours until completely dissolved, and a precursor solution with a concentration of 1.4 to 1.8 mol / L can be prepared.

[0058] This step ensures the uniformity and proper concentration of the precursor solution, which helps to form a uniform perovskite layer without defects or inhomogeneities.

[0059] S220, spin coating the precursor solution onto the surface of the oxide electron transport layer.

[0060] Specifically, the spin coating process is divided into two stages: the first stage has a rotation speed of 500 rpm to 1500 rpm.

[0061] rpm, the spin coating time is 5s to 20s; the second stage speed is 3000rpm to 6000rpm, and the spin coating time is 20s to 50s.

[0062] S230, after the spin coating is completed, annealing treatment is performed to form a perovskite light absorbing layer.

[0063] Specifically, the post-spin coating annealing treatment includes: placing the spin-coated sample into a heat treatment furnace, with the annealing temperatures being 150° C. and 100° C., and the annealing times being 5 minutes and 15 minutes, respectively, to obtain a perovskite absorption layer.

[0064] Specifically, an appropriate annealing time can be selected according to the specific precursor and solvent to ensure the complete formation of the perovskite light-absorbing layer. The annealing treatment helps the crystallization of the precursor compound to form a high-quality perovskite crystal structure, thereby improving the photoelectric conversion efficiency. Annealing can also remove solvent residues and improve the surface flatness and performance of the perovskite film.

[0065] The spin coating method can form a uniform perovskite precursor layer, ensuring the consistency of the photoelectric performance of the film. By optimizing the spin coating process, a perovskite light-absorbing layer with good coverage and surface flatness can be obtained.

[0066] Next, a hole transport layer is prepared on the surface of the perovskite light absorbing layer, and a metal electrode is deposited on the surface of the hole transport layer to obtain a perovskite solar cell. The specific steps are detailed in S300 to S600:

[0067] S300, preparing a solution containing graphyne and lithium salt, and obtaining a target composite (i.e., target composite powder) after drying;

[0068] S400, dissolving aromatic amine organic materials and target complexes in a poor solvent for perovskite to cause a chemical reaction, thereby obtaining a target mixed solution containing lithium embedded graphene compounds and aromatic amine active free radical compounds.

[0069] S500, spin coating the target mixed solution on the surface of the perovskite light absorbing layer to obtain a hole transport layer, wherein the lithium embedded graphene compound and the aromatic amine active free radical compound in the hole transport layer form a photogenerated carrier transport channel;

[0070] S600, depositing a metal electrode on the surface of the hole transport layer to obtain a perovskite solar cell.

[0071] For S300, the method for obtaining the target complex specifically includes: adding a graphyne derivative and a lithium salt into an organic solvent, stirring until the solution is clarified, and performing vacuum drying to obtain the target complex.

[0072] Wherein, the mass ratio of graphyne derivative to lithium salt is 1:1.5 to 1:4.

[0073] Furthermore, the graphyne derivatives include any one of graphene monoacetylene, graphene diacetylene, graphene triacetylene, oxidized graphyne, hydrogenated graphyne, triazine graphyne, halogenated graphyne, amino graphyne, and carbonyl graphyne.

[0074] The basic structural unit of graphyne derivatives is alternating acetylene bonds and benzene rings. The acetylene bonds have strong electron-withdrawing properties and provide abundant chemically active sites in chemical reactions, while the benzene rings, as highly conjugated carbon skeletons, form π-electron clouds in a two-dimensional network and have efficient charge transport properties.

[0075] In this embodiment, the graphene derivative is preferably graphene diyne (GDY). The specific preparation method includes: dissolving 30 mg of hexa(trimethylsilylethynyl)benzene powder into 100 mL of tetrahydrofuran, adding 1 mL of tetrabutylammonium fluoride / tetrahydrofuran solution with a mass concentration of 261 mg / mL, reacting at 0°C for 15 min, then adding 100 mL of ethyl acetate to the mixed solution, mixing thoroughly, extracting with a saturated sodium chloride solution through a separatory funnel, taking the clarified extract and removing the solvent by rotary evaporation to obtain graphene diyne monomer powder. Take 20 mg of graphene diyne monomer powder and add it to 20 mL of copper acetate / pyridine solution with a mass concentration of 1 mg / mL, and undergo Glaser coupling reaction at room temperature for 24 hours. After filtration, black graphene diyne powder is obtained.

[0076] The lithium salt includes one or more of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoromethanesulfonyl)imide (LiPFSI).

[0077] In this embodiment, the lithium salt is preferably lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The lithium salt provides anion and cation coordination balance with the hole transport material to form a stable compound, specifically comprising: adding graphyne derivative (GDY) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to an organic solvent, stirring and mixing until the solution is clear, and vacuum drying to obtain the target complex, i.e. [Li + @GDY]TFSI - Powder.

[0078] In S300, the drying process includes: filtering the mixed solution to remove impurities, then recrystallizing with ether, removing the solvent by suction filtration, placing the obtained powder in a vacuum drying oven, and keeping it warm at 60° C. for 3 hours to obtain a dry and clean target composite powder.

[0079] This step can ensure that the graphyne derivative and the lithium salt are combined in a specific ratio, which is conducive to the full progress of the subsequent chemical reaction and avoids the incomplete reaction and by-product generation caused by uneven dispersion when the graphyne derivative and the lithium salt are directly added to the organic hole transport material. For S400, it specifically includes: dissolving the aromatic amine organic material and the target complex in a poor solvent for perovskite, stirring at room temperature, and the aromatic amine group in the aromatic amine organic material is oxidized and loses electrons to form a positively charged aromatic amine active free radical. The specific reaction chemical formula is as follows:

[0080]

[0081] The positively charged aromatic amine active radical reacts with the negatively charged bis(trifluoromethanesulfonyl)imide (TFSI) in the target complex. -) to form aromatic amine reactive free radical compounds (i.e., spiro-OMeTAD + TFSI - ), the aromatic amine active radical compound formed can effectively stabilize the aromatic amine active radical, improve the charge transport performance of the hole transport material, and enhance the stability of the hole transport layer. The specific reaction chemical formula is as follows:

[0082]

[0083] The graphyne derivative of the target complex absorbs electrons and undergoes an alkyne-olefin transformation. The changed graphyne derivative reacts with the positively charged lithium ion (Li + ) forms a stable lithium-intercalated graphene compound (Li@GDY), and the specific reaction chemical formula is as follows:

[0084]

[0085] In this step, the strong intermolecular electron transfer effect is used to realize the instantaneous oxidation of aromatic amine organic materials without byproducts in an inert environment. The concentration of active free radicals is controllable, the quality of the hole transport layer film is improved, and the lithium embedded Graphene compound formed has excellent conductivity and stability, and is not easy to react with water or oxygen, which helps to improve the transport efficiency of photogenerated carriers. In addition, the lithium embedded Graphene compound can be used as a water and oxygen barrier on the top of the device, reducing the water and oxygen adsorption sites and preventing water vapor from penetrating into the perovskite active layer. This barrier effect can significantly reduce the erosion of water and oxygen on the perovskite layer and prevent the degradation of the perovskite material; by effectively isolating water and oxygen, the lithium embedded Graphene compound can improve the long-term stability of the perovskite solar cell. The perovskite material is highly sensitive to water and oxygen. The use of this barrier material can extend the service life of the battery and maintain its stable performance.

[0086] In S400 , specifically, the mass ratio of the aromatic amine organic material to the target composite is 1:0.02 to 1:0.05.

[0087] The mass concentration of the aromatic amine organic material in the poor solvent for perovskite is preferably 72.0 mg / mL to 90.0 mg / mL; the mass concentration of the target complex in the poor solvent for perovskite is 1.0 mg / mL to 3.5 mg / mL.

[0088] Among them, the aromatic amine organic material includes any one of 4,4',4"-tris-(3-methylphenylanilino)triphenylamine (m-MTDATA), N,N'-diphenyl-N,N'-bis-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 2,2',7,7'-tetrakis-(diphenylamine)-9,9'-spirobifluorene (spiro-TAD), N,N'-diphenyl-N,N'-bis-(1-naphthyl-1,1'-biphenyl)-1,1'-biphenyl-4,4'-diamine (NPD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), and 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD).

[0089] In this embodiment, the aromatic amine organic material is preferably 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD). Aromatic amine organic materials exhibit strong electropositivity and tend to donate electrons in chemical reactions to generate cationic free radicals with excellent charge transport properties; in addition, the aromatic hydrocarbon groups in the aromatic amine organic materials enhance the morphological uniformity, thermal stability and three-dimensional carrier transport properties of the hole transport layer, and reduce carrier recombination losses.

[0090] Among them, poor solvents for perovskite include chlorobenzene, dichlorobenzene, chloroform, dichloromethane, anisole, tetrahydrofuran, and ethyl acetate.

[0091] In this embodiment, the poor solvent for perovskite is preferably chlorobenzene.

[0092] Among them, aromatic amine organic materials and target composites are both powders.

[0093] In this embodiment, the selected poor solvent for perovskite has high solubility for aromatic amine organic materials and target complexes, ensuring uniform dispersion of the material in the solvent, enhancing the density and flatness of the film morphology, and ensuring that the organic hole transport layer film completely covers the perovskite layer to hinder the interaction between the perovskite and the electrode; at the same time, as a poor solvent for perovskite, the solvent can effectively avoid dissolution and damage to the upper interface of the perovskite during the spin coating process of the target mixed solution, thereby ensuring the performance stability of the hole transport layer.

[0094] Among them, spiro-OMeTAD and GDY in the target mixed solution undergo electron transfer reaction and conjugation reaction, and form a stable compound under the coordination equilibrium of LiTFSI.

[0095] Reference Figure 3In this embodiment, the aromatic amine organic material is preferably a triphenylamine organic hole transport material, that is, the basic structural unit of the aromatic amine organic hole transport material is triphenylamine (TPA) or 4,4'-biphenylenediamine (BPDA); the nitrogen atom in the structural unit has a strong electron donating ability and exhibits a strong electropositivity; the aromatic hydrocarbon maintains the morphology and thermal stability of the hole transport layer and the three-dimensional carrier transport performance, reducing carrier recombination.

[0096] The traditional hole oxidation reaction equation of triphenylamine hole transport layer is:

[0097] TPA+LiTFSI+O2→TPA + TFSI - +Li x O y , the reaction produces unstable lithium oxide by-product impurities.

[0098] In this embodiment [Li + @GDY]TFSI - :TPA-based hole transport layer directly generates active free radicals without air oxidation. The reaction equation includes:

[0099] TPA+[Li + @GDY]TFSI - →TPA + TFSI - +Li@GDY, in this reaction process, no by-products are generated, the reaction process occurs instantly, and there is no time cost. Aromatic amines Aromatic amines

[0100] In S500, by spin coating the target mixed solution on the surface of the perovskite light absorbing layer, the active free radical TPA can be directly generated in the obtained hole transport layer without air oxidation. + Enhance the transport of photogenerated holes.

[0101] The lithium-intercalated graphyne compound and the aromatic amine active radical compound in the hole transport layer form a photogenerated carrier transport channel. Specifically, a strong π-π interaction is formed between the benzene ring in the lithium-intercalated graphyne compound and the benzene ring in the aromatic amine active radical compound (that is, they exist in a π-π parallel stacking manner, and such a stacking manner produces a conjugated effect). This interaction can stabilize the intermolecular binding and enhance their electron transport capabilities; the extended π-conjugated structure serves as a photogenerated carrier transport channel, enhances the electrical conductivity and hole mobility, and improves the photoelectric conversion efficiency of the prepared perovskite solar cell.

[0102] Among them, the basic structural unit of graphyne derivatives is the alternating arrangement of acetylene bonds (-C≡C-) and benzene rings. The carbon atom in the acetylene bond unit is connected to two carbon atoms through sp hybridization, which has strong electron-withdrawing properties and provides abundant chemically active sites in chemical reactions. The benzene ring, as a highly conjugated carbon skeleton, forms a π electron cloud in the two-dimensional network to achieve efficient charge transport.

[0103] In this embodiment, the spin coating speed is preferably 2000 rpm to 5000 rpm; the spin coating time is preferably 20 s to 40 s.

[0104] The spin coating method can form a uniform hole transport layer, which helps to improve the efficiency of the battery; suitable drying conditions can optimize the performance of the hole transport layer and ensure its stability and functionality.

[0105] For S600, a metal electrode is deposited on the surface of the hole transport layer to obtain a perovskite solar cell, which specifically includes: depositing a metal electrode on the hole transport layer by vacuum thermal evaporation; wherein the metal electrode includes any one of gold, silver, and copper.

[0106] Metal electrodes can effectively collect and transmit electric current, improving the power output of the battery; good electrode deposition technology can reduce resistance losses and improve overall battery efficiency.

[0107] In the prior art, the reaction equation of the conventional oxidation method of the aromatic amine hole transport layer is:

[0108] spiro-OMeTAD+LiTFSI+O2→spiro-OMeTAD + TFSI - +Li x O y , the reaction produces unstable lithium oxide by-product impurities, and the reaction process is uncontrollable.

[0109] In the embodiments disclosed in the present application, the hole transport layer directly generates active free radicals without air oxidation, and the reaction equation includes:

[0110] spiro-OMeTAD+[Li + @GDY]TFSI - →spiro-OMeTAD + TFSI - +Li@GDY, in this

[0111] During the process, no by-products are generated, the reaction process occurs instantly, and there is no time cost.

[0112] Specifically, the traditional oxidation method is to directly expose the aromatic amine organic hole transport layer film to dry air for 12-24 hours. Oxygen, as an electron acceptor, slowly diffuses into the organic hole transport layer to induce the aromatic amine compound to produce cationic free radicals. The degree of oxidation depends on the permeating oxygen concentration. Low oxygen concentration is prone to incomplete oxidation, and high oxygen concentration forms superoxide ions that destroy the perovskite photoactive layer. The presence of trace moisture in the air helps promote the uniform dispersion of LiTFSI and improve the oxidation effect and uniformity. However, the penetration of excessive water vapor acts as a perovskite degradation initiator and destroys the device structure. Therefore, the traditional oxidation method greatly increases the time cost and uncertainty.

[0113] The method uses a poor solvent for perovskite to dissolve aromatic amine organic materials and target complex powders, pre-generates a target mixed solution containing aromatic amine active free radical compounds, and performs spin coating to form a hole transport layer. In this process, a solution containing a graphene derivative and a lithium salt is prepared, and the target complex is obtained after drying. Generally, the solution is preferably stirred for 1 hour during preparation, and the drying is preferably 2 to 4 hours. Then, the aromatic amine organic material and the target complex are dissolved in a poor solvent for perovskite to obtain a target mixed solution, preferably for 0.5 to 1 hour.

[0114] During the stirring process at room temperature, the cationic free radicals generated by the activation of aromatic amine organic materials have visible spectrum absorption at 520nm. The characteristic absorption of the spectrum causes the color of the target mixed solution to darken. The higher the degree of activation, the higher the concentration of cationic free radicals, and the darker the color of the corresponding solution. Therefore, the concentration of active free radicals can be accurately controlled by directly observing the color of the target mixed solution.

[0115] In this embodiment, the strong electron transfer effect activates the active free radicals of the aromatic amine organic material.

[0116] Specifically, graphyne has a higher oxidation potential than aromatic amine organic materials. The large potential difference between the two can easily trigger an oxidation reaction. The π* antibonding orbital of the acetylene bond with strong electron-withdrawing properties in graphyne can accept the lone pair of electrons on the p orbital of the central nitrogen atom of the aromatic amine organic material, and promote the transfer of electrons from the central nitrogen atom of the aromatic amine organic material to the acetylene bond in graphyne through electron feedback. Finally, the aromatic amine compound is activated to generate a cationic free radical. The cationic free radical introduces a hole on the highest occupied molecular orbital of the aromatic amine compound, which lowers the Fermi level and achieves a balance in the energy level difference between the hole transport layer and the perovskite photoactive layer and the metal electrode, weakens the Schottky barrier between the interfaces, and effectively optimizes the extraction and transport performance of photogenerated carriers.

[0117] The traditional air oxidation method is to prepare the hole transport material into a film by spin coating, and then place the film in the air to activate the hole transport material with the oxygen in the air. The oxidation reaction is uncontrolled. In the absence of oxygen, the concentration of active free radicals is insufficient, the hole mobility is low, and even the active free radicals are induced to return to neutral aromatic amine groups. Excessive oxygen leads to rapid degradation of the oxidative transition-induced material. Graphdiyne initiator allows the activation of aromatic amine compounds without oxygen assistance. By optimizing the Graphdiyne concentration, rapid and accurate p-type doping of organic hole transport materials can be achieved, greatly improving the hole transport performance.

[0118] In this embodiment, the benzene rings in the graphyne molecule tend to form a "face-to-face" stacking conformation with the benzene rings in the aromatic amine organic material, and the π electron clouds of multiple benzene rings interact with each other to form a parallel stacking structure, thereby establishing a large π electron conjugated structure. The π electron conjugated structure can form an extended electron cloud sharing system, expand the nonlocal range of electrons, and enable the π electron cloud to transfer and share electron density in a continuous manner. The mobility of electrons in the molecule is enhanced, thereby improving the photogenerated carrier transmission capacity.

[0119] In this embodiment, the d-orbital electrons of lithium ions can interact with the π electrons in graphyne to form chemical bonds, turning the hydrophilic lithium ions into hydrophobic ones. At the same time, the abundant double bonds and triple bonds of graphyne act as oxidation sites to dominate the reaction with oxygen, thus preventing the erosion of the organic hole transport material by oxygen in the air. The synergistic effect of hydrophobicity and antioxidant activity enables the stable operation of the organic hole transport material under working conditions.

[0120] The method disclosed in this embodiment is equivalent to achieving oxidation of the aromatic amine organic material through chemical reaction during the stage of mixing the aromatic amine organic material and the target composite powder. The spin-coated film already contains oxidized components and can be used directly without post-processing steps. Therefore, the inert atmosphere in this embodiment means that there is no need to place it in the air for post-processing.

[0121] The hole transport layer in Comparative Example 1 is prepared under an inert atmosphere, and the graphyne composite (i.e., the target composite) is not introduced. The corresponding perovskite solar cell preparation method includes the following steps:

[0122] Step 1: Ultrasonic clean the 1.5cm*1.5cm FTO conductive glass in deionized water, acetone, ethanol, and isopropanol for 20 minutes, blow dry with compressed nitrogen, and etch with oxygen plasma for 25 minutes to obtain a clean FTO conductive substrate; take 274mg SnCl2·2H2O and 1250mg urea and add them to 1000mL ice-water mixture, slowly add 25μL thioglycolic acid and 1250μL concentrated hydrochloric acid, stir evenly, pour the mixed solution into a culture dish containing the FTO conductive substrate, place it in a 90℃ forced air drying oven to react for 4 to 6 hours, and after the reaction is completed, wash it with deionized water and isopropanol for 10 minutes in turn, blow dry it with compressed nitrogen, and anneal it on a 180℃ heating table for 40 minutes to prepare a SnO2 electron transport layer with a thickness of about 20nm.

[0123] Step 2: Prepare a 1.8 mol / L FAPbI3 perovskite precursor solution. The specific process is: dissolve formamidine hydroiodide, lead iodide and methylammonium chloride in a molar ratio of 1:1.09:0.35 in a mixed solvent of N,N-dimethylformamide: dimethyl sulfoxide with a volume ratio of 4:1, stir at room temperature for 12 to 24 hours until completely dissolved, and filter with a 0.22 μm PTFE filter head for later use.

[0124] The perovskite precursor solution was spin-coated on the electron transport layer of step 1 using a segmented spin coating method. The specific process parameters included: in the first stage, the rotation speed was 1000 rpm for 5 s, and the acceleration was set to 200 rpm / s. In the second stage, the rotation speed was 5000 rpm for 30 s, and the acceleration was set to 1500 rpm / s. 150 μL of chlorobenzene was added 10 s before the end of the second stage of spin coating. After spin coating, the solution was transferred to a 150°C heating table for annealing for 10 min and then cooled to 100°C for annealing for 20 min to obtain a FAPbI3 perovskite absorption layer.

[0125] Step 3: Prepare 72.5 mg / mL spiro-OMeTAD / chlorobenzene solution, add 35.0 μL of 260 mg / mL Li-TFSI / acetonitrile solution to 1 mL of the solution, and spin-coat the hole transport layer precursor solution on the perovskite absorption layer prepared in step 2 at a spin coating speed of 4000 rpm for 30 s to obtain a hole transport layer.

[0126] Step 4: Evaporate a 80nm thick gold electrode on the hole transport layer of step 3, with an electrode area of ​​0.1cm 2 , and FAPbI3 perovskite solar cells were obtained.

[0127] Comparative Example 2

[0128] In step 3 of this comparative example, the prepared hole transport layer is placed in air for oxidation for 12 hours, and the other steps are the same as those in comparative example 1 to obtain a FAPbI3 perovskite solar cell.

[0129] Example 1

[0130] Based on the method for preparing a perovskite solar cell disclosed in this embodiment, a hole transport layer (i.e. [Li + @GDY]TFSI - :spiro-OMeTAD hole transport layer), the corresponding perovskite solar cell preparation method comprises the following steps:

[0131] Step 1: Ultrasonic clean the 1.5cm*1.5cm FTO conductive glass in deionized water, acetone, ethanol, and isopropanol for 20 minutes, blow dry with compressed nitrogen, and etch with oxygen plasma for 25 minutes to obtain a clean FTO conductive substrate; take 274mg SnCl2·2H2O and 1250mg urea and add them to 1000mL ice-water mixture, slowly add 25μL thioglycolic acid and 1250μL concentrated hydrochloric acid, stir evenly, pour the mixed solution into a culture dish containing the FTO conductive substrate, place it in a 90℃ forced air drying oven to react for 4 to 6 hours, and after the reaction is completed, wash it with deionized water and isopropanol for 10 minutes in turn, blow dry it with compressed nitrogen, and anneal it on a 180℃ heating table for 40 minutes to prepare a SnO2 electron transport layer with a thickness of about 20nm.

[0132] Step 2: Prepare a 1.8 mol / L FAPbI3 perovskite precursor solution. The specific process is: dissolve formamidine hydroiodide, lead iodide and methylammonium chloride in a molar ratio of 1:1.09:0.35 in a mixed solvent of N,N-dimethylformamide: dimethyl sulfoxide with a volume ratio of 4:1, stir at room temperature for 12 to 24 hours until completely dissolved, and filter with a 0.22 μm PTFE filter head for later use.

[0133] The perovskite precursor solution was spin-coated on the electron transport layer of step 1 using a segmented spin coating method. The specific process parameters included: in the first stage, the rotation speed was 1000 rpm for 5 s, and the acceleration was set to 200 rpm / s. In the second stage, the rotation speed was 5000 rpm for 30 s, and the acceleration was set to 1500 rpm / s. 150 μL of chlorobenzene was added 10 s before the end of the second stage of spin coating. After spin coating, the solution was transferred to a 150°C heating table for annealing for 10 min and then cooled to 100°C for annealing for 20 min to obtain a FAPbI3 perovskite absorption layer.

[0134] Step 3: Prepare a 72.5 mg / mL spiro-OMeTAD / chlorobenzene solution and add 10.0 μL of 100 mg / mL [Li+ @GDY]TFSI - / chlorobenzene solution, and spin-coat the hole transport layer precursor solution on the perovskite absorption layer prepared in step 2 at a spin-coating speed of 4000 rpm for 30 s to obtain a hole transport layer.

[0135] Specifically, [Li + @GDY]TFSI - The preparation method of the powder comprises: adding a graphene derivative and lithium bis(trifluoromethanesulfonyl)imide to acetonitrile, pyridine or tetrahydrofuran in a molar ratio of 1:3 to 1:6, stirring and mixing until the solution is clear, and vacuum drying to obtain [Li + @GDY]TFSI - Powder.

[0136] Step 4: Evaporate a 80nm thick gold electrode on the hole transport layer of step 3, with an electrode area of ​​0.1cm 2 , and FAPbI3 perovskite solar cells were obtained.

[0137] Example 2

[0138] In step 3 of this example, 15.0 μL of 100 mg / mL [Li + @GDY]TFSI - / chlorobenzene solution, and the other steps are the same as in Example 1 to obtain a FAPbI3 perovskite solar cell.

[0139] Example 3

[0140] In step 3 of this embodiment, 20.0 μL of a [Li+@GDY]TFSI- / chlorobenzene solution with a concentration of 100 mg / mL was added, and the other steps were the same as in Example 1 to obtain a FAPbI3 perovskite solar cell.

[0141] Example 4

[0142] In step 3 of this embodiment, 25.0 μL of a [Li+@GDY]TFSI- / chlorobenzene solution with a concentration of 100 mg / mL was added, and the other steps were the same as in Example 1 to obtain a FAPbI3 perovskite solar cell.

[0143] Example 5

[0144] In step 3 of this embodiment, 30.0 μL of a [Li+@GDY]TFSI- / chlorobenzene solution with a concentration of 100 mg / mL was added, and the other steps were the same as in Example 1 to obtain a FAPbI3 perovskite solar cell.

[0145] Example 6

[0146] In step 3 of this embodiment, 35.0 μL of a [Li+@GDY]TFSI- / chlorobenzene solution with a concentration of 100 mg / mL was added, and the other steps were the same as in Example 1 to obtain a FAPbI3 perovskite solar cell.

[0147] Table 1

[0148] sample <![CDATA[J SC (mA cm -2 )]]> <![CDATA[V OC (V)]]> FF(%) PCE(%) Comparative Example 1 20.20 0.85 56.35 9.70 Comparative Example 2 24.79 1.09 78.21 21.13 Example 1 24.95 1.14 80.67 22.94 Example 3 25.24 1.19 82.45 24.76 Example 5 25.04 1.16 81.26 23.60

[0149] Refer to Table 1 and Figure 4 Compared with the comparative examples, the efficiency of the embodiments is improved. In particular, the photoelectric conversion efficiency of the battery prepared in Example 3 is as high as 24.76%, which is 60.82% higher than that of the unoxidized comparative example 1 and 14.66% higher than that of the conventional air-oxidized comparative example 2. This is because the target composite powder (i.e. [Li + @GDY]TFSI - ) doped with aromatic aromatic amine organic materials (spiro-OMeTAD), the by-product-free controllable oxidation of aromatic aromatic amine organic materials in an inert environment was achieved. At the same time, lithium embedded graphene compound (Li@GDY) formed a strong π-π interaction with spiro-OMeTAD, and the extended π conjugated structure enhanced the conductivity and hole mobility. The reason for the low efficiency at low doping concentration is incomplete oxidation, and at high doping concentration, agglomeration occurs, which hinders carrier transport and reduces the photoelectric conversion efficiency.

[0150] Reference Figure 5 , which is a comparison diagram of the current-voltage characteristic curves provided by the single hole devices of Comparative Example 2 and Example 3 of the present disclosure. Compared with Comparative Example 2, the hole mobility of the hole transport layer of Example 3 is increased by 6.6 times, showing excellent hole transport performance.

[0151] Reference Figure 6 and Figure 7 , which are comparison diagrams of water contact angles provided by the hole transport layers of comparative example 2 and example 3 of the present disclosure. As shown in the figure, the water contact angle of example 3 is significantly increased, and Li@GDY reduces water adsorption sites, preventing the degradation effect of water vapor penetration on the device.

[0152] Reference Figure 8 , which is a statistical comparison chart of the long-term stability of the perovskite solar cells corresponding to Comparative Example 2 and Example 3 of the present disclosure. Within the test time of 750h, the efficiency of the device prepared in Comparative Example 2 dropped to below 60%, while the efficiency of the device prepared in Example 3 remained above 90% of the initial value after 1500h. This is because the addition of Li@GDY can not only enhance the hydrophobicity of the hole transport layer, but also form a strong π-π interaction with spiro-OMeTAD to stabilize the hole transport layer. This result strongly illustrates that the addition of [Li@GDY to the hole transport layer +@GDY]TFSI - The FAPbI3 perovskite solar cells have excellent service stability.

[0153] As described above, in the perovskite solar cell structure of the embodiment of the present disclosure, the target composite powder (i.e. [Li + @GDY]TFSI - ) doped with aromatic aromatic amine aromatic amine organic materials (spiro-OMeTAD) realizes the controllable oxidation of spiro-OMeTAD in an inert environment, greatly shortens the oxidation time, avoids the generation of by-products in traditional air oxidation technology, and the lithium embedded graphyne compound obtained can effectively reduce the water and oxygen adsorption sites, prevent the penetration of water vapor, and improve the long-term stability of perovskite solar cells. At the same time, Li@GDY and spiro-OMeTAD form a strong π-π interaction, and the extended π conjugated structure enhances the conductivity and hole mobility, and improves the photoelectric conversion efficiency of perovskite solar cells. The preparation process of the present invention is simple, repeatable, and suitable for large-scale industrial production of roll-to-roll.

[0154] The method for preparing a perovskite solar cell disclosed in the present invention comprises the following steps: preparing an oxide electron transport layer on a conductive substrate, and then preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer; then, spin coating a target mixed solution on the surface of the perovskite light absorbing layer to obtain a hole transport layer; and then depositing a metal electrode on the surface of the hole transport layer to obtain a perovskite solar cell; specifically, the hole transport layer is formed by spin coating a target mixed solution obtained by dissolving an aromatic amine organic material and a target complex in a poor solvent for perovskite, wherein the target complex, as a dopant, can provide graphyne and anions in a film, and these components can effectively control the oxidation state of the aromatic amine material; graphyne can react with the aromatic amine organic material, and can change the oxidation state of the aromatic amine material in a poor solvent for perovskite without external interference. The electronic properties are changed and the redox behavior is controlled. There is no need for the time-consuming post-treatment process of traditional air oxidation methods, which avoids the degradation and damage of materials by the intervention of environmental water and oxygen, that is, the controllable oxidation of aromatic amine organic materials is achieved, and the oxidation time is greatly shortened. At the same time, the anions and the oxidized cationic radicals of the aromatic amine materials form stable complexes, which can avoid the formation of by-products in traditional air oxidation technology. In addition, lithium ions combine with the changed graphyne derivatives to form stable complexes, that is, lithium-embedded graphyne compounds, which can effectively reduce water and oxygen adsorption sites, prevent the penetration of water vapor in the service environment, improve the long-term stability of perovskite solar cells, and improve the photoelectric conversion efficiency of perovskite solar cells. The preparation process of this application is simple, repeatable, suitable for large-scale industrial production, and has certain application prospects.

[0155] In a second aspect, the embodiments of the present disclosure further provide a system for preparing a perovskite solar cell having a controllable oxidized hole transport layer, including the following solutions:

[0156] An oxide electron transport layer preparation module, used for preparing an oxide electron transport layer on a conductive substrate;

[0157] A perovskite light-absorbing layer preparation module is used to prepare a perovskite light-absorbing layer on the surface of the oxide electron transport layer;

[0158] A target compound preparation module is used to prepare a solution containing a graphyne derivative and a lithium salt, and obtain the target compound after drying;

[0159] The target mixed solution preparation module is used to dissolve aromatic amine organic hole transport materials and target complexes in a poor solvent of perovskite, and to carry out electron transfer and conjugation reaction under stirring at room temperature to obtain a uniform target mixed solution, wherein the target mixed solution contains stable lithium embedded graphyne compounds, aromatic amine active free radical compounds and photogenerated carrier transport channels;

[0160] A hole transport layer preparation module is used to spin-coat the target mixed solution on the surface of the perovskite light absorption layer to obtain a hole transport layer;

[0161] The deposition module is used to deposit a metal electrode on the surface of the hole transport layer to obtain a perovskite solar cell.

[0162] It should be noted that all preparation methods disclosed in the method for preparing a perovskite solar cell with a controllable oxidation hole transport layer disclosed in the first aspect of the present application are applicable to the specific preparation in the system for preparing a perovskite solar cell with a controllable oxidation hole transport layer disclosed in the second aspect of the present application.

[0163] In a third aspect, the present application discloses a perovskite solar cell with a controllable oxidized hole transport layer, which is prepared by the method for preparing a perovskite solar cell with a controllable oxidized hole transport layer.

[0164] For detailed description of this embodiment, reference may be made to the corresponding descriptions in the aforementioned embodiments, which will not be repeated here.

[0165] The basic principles of the present disclosure are described above in conjunction with specific embodiments. However, it should be noted that the advantages, strengths, effects, etc. mentioned in the present disclosure are only examples and not limitations, and it cannot be considered that these advantages, strengths, effects, etc. are required by each embodiment of the present disclosure. In addition, the specific details disclosed above are only for the purpose of illustration and ease of understanding, and are not limitations. The above details do not limit the present disclosure to the necessity of adopting the above specific details to be implemented.

[0166] In the present disclosure, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. The block diagrams of the devices, devices, equipment, and systems involved in the present disclosure are only illustrative examples and are not intended to require or imply that they must be connected, arranged, and configured in the manner shown in the block diagram. As will be appreciated by those skilled in the art, these devices, devices, equipment, and systems can be connected, arranged, and configured in any manner. Words such as "including", "comprising", "having", etc. are open words, referring to "including but not limited to", and can be used interchangeably with them. The words "or" and "and" used here refer to the words "and / or" and can be used interchangeably with them, unless the context clearly indicates otherwise. The words "such as" used here refer to the phrase "such as but not limited to", and can be used interchangeably with them.

[0167] Additionally, as used herein, "or" used in a list of items beginning with "at least one" indicates a separate list, so that, for example, a list of "at least one of A, B, or C" means A or B or C, or AB or AC or BC, or ABC (i.e., A and B and C). Furthermore, the word "exemplary" does not mean that the example described is preferred or better than other examples.

[0168] It should also be noted that in the system and method of the present disclosure, each component or each step can be decomposed and / or recombined. Such decomposition and / or recombination should be regarded as equivalent solutions of the present disclosure.

[0169] Various changes, substitutions, and modifications of the techniques described herein may be made without departing from the teachings defined by the appended claims. Furthermore, the scope of the claims of the present disclosure is not limited to the specific aspects of the processes, machines, manufactures, compositions of events, means, methods, and actions described above. Currently existing or later to be developed processes, machines, manufactures, compositions of events, means, methods, or actions that perform substantially the same functions or achieve substantially the same results as the corresponding aspects described herein may be utilized. Thus, the appended claims include such processes, machines, manufactures, compositions of events, means, methods, or actions within their scope.

[0170] The above description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present disclosure. Various modifications to these aspects will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other aspects without departing from the scope of the present disclosure. Therefore, the present disclosure is not intended to be limited to the aspects shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

[0171] The above description has been given for the purpose of illustration and description. In addition, this description is not intended to limit the embodiments of the present disclosure to the forms disclosed herein. Although multiple example aspects and embodiments have been discussed above, those skilled in the art will recognize certain variations, modifications, changes, additions and sub-combinations thereof.

Claims

1. A method for preparing a perovskite solar cell with a controllable oxidation hole transport layer, characterized in that: include: preparing an oxide electron transport layer on a conductive substrate; preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer; preparing a solution containing graphyne and lithium salt, and obtaining a target complex after drying; Dissolving the aromatic amine organic material and the target complex in a poor solvent of perovskite to cause a chemical reaction to obtain a target mixed solution containing a lithium embedded graphene compound and an aromatic amine active free radical compound; Spin coating the target mixed solution on the surface of the perovskite light absorbing layer to obtain a hole transport layer, wherein the lithium embedded graphene compound and the aromatic amine active free radical compound in the hole transport layer form a photogenerated carrier transport channel; A metal electrode is deposited on the surface of the hole transport layer to obtain a perovskite solar cell.

2. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 1, characterized in that: The solution containing graphyne and lithium salt is prepared and dried to obtain the target compound, which includes: adding graphyne derivative and lithium salt into an organic solvent, stirring until the solution is clear, and vacuum drying to obtain the target compound.

3. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 2, characterized in that: The mass ratio of the graphyne derivative to the lithium salt is 1:1.5 to 1:

4.

4. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 1, characterized in that: The aromatic amine organic material and the target complex are dissolved in a poor solvent of perovskite to cause a chemical reaction to obtain a target mixed solution containing a lithium embedded graphene compound and an aromatic amine active free radical compound, including:

5. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 1, characterized in that: The mass ratio of the aromatic amine organic material to the target complex is 1:0.02 to 1:0.

05.

6. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 5, characterized in that: The aromatic amine organic material includes any one of 4,4',4"-tris-(3-methylphenylanilino)triphenylamine, N,N'-diphenyl-N,N'-bis-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 2,2',7,7'-tetrakis-(diphenylamine)-9,9'-spirobifluorene, N,N'-diphenyl-N,N'-bis-(1-naphthyl-1,1'-biphenyl)-1,1'-biphenyl-4,4'-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene.

7. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 1, characterized in that: The spin coating speed is 2000 rpm to 5000 rpm; The spin coating time is 20s to 40s.

8. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 1, characterized in that: The step of preparing a perovskite light absorbing layer on the surface of the oxide electron transport layer comprises: preparing a precursor solution; Spin coating the precursor solution onto the surface of the oxide electron transport layer; After the spin coating is completed, annealing treatment is performed to form the perovskite light absorbing layer.

9. The method for preparing a perovskite solar cell with a controllable oxidation hole transport layer according to claim 8, characterized in that: The preparation of the precursor solution comprises: dissolving formamidine hydroiodide, lead iodide and methylammonium chloride in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and stirring until the mixture is completely dissolved.

10. A perovskite solar cell with a controllable oxidation hole transport layer, characterized in that: The perovskite solar cell with a controllable oxidized hole transport layer is prepared by the preparation method of any one of claims 1 to 9.

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