Perovskite cell and preparation method thereof, laminated cell and photovoltaic module

Abstract

The invention relates to the technical field of solar cells, in particular to a perovskite cell and a preparation method thereof, a laminated cell and a photovoltaic module, a hole transport material of the perovskite cell has the advantages of low cost, high performance and high stability, and low-cost, high-performance and stable laminated perovskite cell application can be realized. In the scheme, the main chain of the hole transport material is an acrylate structure, oxygen atoms in the acrylate structure can interact with metal ions (such as Pb < 2 + >) of a perovskite absorption layer in the perovskite cell, interface defects are passivated, and non-radiative recombination of an interface is inhibited; meanwhile, a dimethoxytriphenylamine or dimethylthio triphenylamine substituted acridine group is introduced into a side chain, so that the hole transport material has good thermal stability and morphological stability and good charge transport and ionization potential, thereby achieving relatively good mobility and being more beneficial to hole extraction and transport.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to perovskite cells, their preparation methods, tandem cells, and photovoltaic modules. Background Art

[0002] At present, hole transport materials (HTMs) in perovskite solar cells are mainly divided into three categories: inorganic hole transport materials, organic small molecule hole transport materials, and organic polymer hole transport materials. Small molecule HTMs have a definite structure and molecular weight, and can be roughly divided into three categories according to the spatial structure: linear structure, spiro structure, and star structure. They can also be divided into dithienopyrrole type, triphenylamine type, carbazole type, bifluorene type, thiophene type, etc. according to the different groups contained in the molecular structure. Small molecule HTMs have become the most common type of HTM in perovskite solar cells due to their advantages such as synthetic variety, adjustable properties, high purity, and easy solution processing. However, due to their rigid structure, they have low tolerance to perovskite precursor solutions. The films produced by small molecule HTMs always have pinhole morphology defects and are morphologically unstable under external stimuli. Moreover, many small molecule HTMs require the addition of dopants, and these factors also pose obstacles to the large-scale commercialization of PSCs. Summary of the Invention

[0003] In view of the above technical problems, the present application provides a perovskite cell, its preparation method, a tandem cell, and a photovoltaic module. The hole transport material of the perovskite cell has the advantages of low cost, high performance, and high stability, and can realize the application of a large-area inverted perovskite cell with low cost, high performance, and stability.

[0004] In a first aspect, an embodiment of the present application provides a perovskite cell, including a hole transport layer, a perovskite absorption layer, and an electron transport layer sequentially arranged on one surface of a conductive substrate from near to far. The structural formula of the hole transport material is shown in the following formula (1):

[0005] Wherein, 10 < n < 10000, and R1 and R2 are independently selected from any one of the following structures:

[0006]

[0007] In a second aspect, an embodiment of the present application provides a preparation method of a perovskite cell, including preparing a hole transport material. The preparation steps of the hole transport material include:

[0008] Provide 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde, perform a bromination reaction on 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde to obtain Intermediate 1, and the structural formula of the Intermediate 1 is:

[0009] Provide Intermediate 2, mix and react the Intermediate 1 with the Intermediate 2 to obtain Intermediate 3, and the structural formula of the Intermediate 2 is: The structural formula of the Intermediate 3 is: R1 and R2 are independently selected from any one of the following structures:

[0010]

[0011] Reduce the aldehyde group on the Intermediate 3 to obtain Intermediate 4, and the structural formula of the Intermediate 4 is:

[0012] Mix and react the Intermediate 4 with acryloyl chloride to obtain Intermediate 5, and the structural formula of the Intermediate 5 is:

[0013] Mix the Intermediate 5 with a catalyst to carry out a polymerization reaction to obtain the hole transport material, and the structural formula of the hole transport material is shown in the following formula (1):

[0014] 10 < n < 10000.

[0015] In a third aspect, an embodiment of the present application further provides a tandem cell, including:

[0016] A bottom cell, the bottom cell includes at least one crystalline silicon cell and / or amorphous silicon cell;

[0017] A top cell, stacked on the bottom cell, the top cell includes one or more perovskite cells, wherein at least one perovskite cell is the perovskite cell as described in the first aspect, or at least one perovskite cell is prepared by the preparation method as described in the second aspect.

[0018] In a fourth aspect, an embodiment of the present application further provides a photovoltaic module, including the tandem cell as described in the third aspect.

[0019] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:

[0020] The hole transport material of the perovskite battery of the present application has the advantages of low cost, high performance and high stability, and can realize the application of low-cost, high-performance and stable tandem perovskite batteries. In this solution, the main chain of the hole transport material is an acrylate structure, and the oxygen atom in the acrylate structure can interact with metal ions (such as Pb 2+ ) in the perovskite absorption layer of the perovskite battery, passivate interface defects, and inhibit non-radiative recombination at the interface; at the same time, an acridine group substituted with dimethoxytriphenylamine or dimethylthiotriphenylamine is introduced into the side chain, so that the hole transport material has good thermal stability and morphological stability, as well as good charge transport and ionization potential, thereby achieving better mobility, which is more conducive to the extraction and transport of holes. The hole transport material of the perovskite battery of the present application has good solubility in solvents such as dimethyl sulfoxide, N,N'-dimethylformamide, toluene, chlorobenzene, and dichloromethane, has good film-forming properties, and has good wettability with the perovskite precursor solvent, which helps the crystallization and film formation of perovskite; in addition, it also has the advantages of low raw material cost, simple preparation process, high reproducibility, and can be used in inverted perovskite batteries without doping any additives, is suitable for industrial production, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described below in conjunction with the drawings and embodiments.

[0022] Figure 1 1H NMR spectrum of compound 7 in Example 1 of the present application;

[0023] Figure 2 1H NMR spectrum of compound 12 in Example 2 of the present application;

[0024] Figure 3 J-V curve diagram of the devices fabricated with the hole transport materials in the examples and comparative examples of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] The raw materials and equipment used in the present invention are all common raw materials and equipment in the art without special instructions; the methods used in the present invention are all conventional methods in the art without special instructions.

[0026] Unless otherwise specified, the meanings of the terms in this specification are the same as those generally understood by those skilled in the art. However, if there is a conflict, the definitions in this specification shall prevail.

[0027] In this text, the terms "include", "comprise", "contain", "have", or other variants are intended to cover non-closed inclusion, and no distinction is made among these terms. The term "comprise" means that other steps and components can be added without affecting the final result. The term "comprise" also includes the terms "consist of" and "consist essentially of". The compositions and methods / processes of the present invention contain, consist of, and consist essentially of the essential elements and limitations described herein, as well as any additional or optional components, ingredients, steps, or limitations described herein.

[0028] All numerical values or expressions related to component amounts, process conditions, etc. used in the specification and claims should be understood to be modified by "about" in all cases. All ranges related to the same component or property include the endpoints, and these endpoints can be combined independently. Since these ranges are continuous, they include every numerical value between the minimum value and the maximum value. It should also be understood that any numerical range cited in this application is expected to include all sub-ranges within that range.

[0029] It should be understood that the term "and / or" used in the present invention is merely a correlative relationship describing related objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Additionally, the character " / " in this text generally represents an "or" relationship between the related objects before and after.

[0030] In a first aspect, the present application provides a perovskite solar cell, which includes a hole transport layer, a perovskite absorption layer, and an electron transport layer sequentially arranged on one surface of a conductive substrate from near to far, and the hole transport layer includes a hole transport material.

[0031] In the embodiments of the present application, the structure of the hole transport material is shown in the following formula (1):

[0032] Wherein, 10 < n < 10000, and R1 and R2 are independently selected from any one of the following structures:

[0033]

[0034] The hole transport material of the perovskite solar cell of the present application has the advantages of low cost, high performance, and high stability, and can realize the application of a low-cost, high-performance, and stable tandem perovskite solar cell. In this solution, the main chain of the hole transport material is an acrylate structure, and the oxygen atom in the acrylate structure can bond with metal ions (such as Pb) in the perovskite absorption layer of the perovskite solar cell. 2+) Interact to passivate interface defects and suppress non-radiative recombination at the interface; meanwhile, introducing an acridine group substituted with dimethoxytriphenylamine or dimethylthiotriphenylamine into the side chain enables the hole transport material to have good thermal stability and morphological stability, as well as good charge transport and ionization potential, thus achieving better mobility and being more conducive to the extraction and transport of holes. The hole transport material of the perovskite solar cell of this application has good solubility in solvents such as dimethyl sulfoxide, N,N'-dimethylformamide, toluene, chlorobenzene, and dichloromethane, has good film-forming properties, and has good wettability with the perovskite precursor solvent, which helps the crystallization and film formation of perovskite; in addition, it also has the advantages of low raw material cost, simple preparation process, high repeatability, and can be used in inverted perovskite solar cells without doping any additives, is suitable for industrial production, and has good application prospects.

[0035] In the embodiments of this application, the conductive substrate can be an ITO glass substrate, a silicon substrate, or other common conductive substrates in the art. The embodiments of this application do not make special limitations on this, and those skilled in the art can choose according to specific application scenarios.

[0036] In the embodiments of this application, the thicknesses of the hole transport layer, the perovskite absorption layer, and the electron transport layer can all be adjusted according to specific application scenarios.

[0037] In some embodiments, the thickness of the hole transport layer is 10 - 30 nm, specifically it can be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, or any value between them. Those skilled in the art can adjust according to actual application requirements.

[0038] In some embodiments, the thickness of the perovskite absorption layer is 500 - 700 mn, specifically it can be 500 nm, 550 nm, 600 nm, 650 nm, 700 mn, or any value between them. Those skilled in the art can adjust according to actual application requirements.

[0039] In some embodiments, the thickness of the electron transport layer is 80 - 120 nm, specifically it can be 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, or any value between them. Those skilled in the art can adjust according to actual application requirements.

[0040] In the embodiments of this application, the material of the perovskite light-absorbing layer can be a three-dimensional perovskite material or a quasi-two-dimensional perovskite material. The embodiments of this application do not make special limitations on this, and those skilled in the art can choose according to actual needs.

[0041] In the embodiments of the present application, the material of the electron transport layer can be selected from conventional materials in the art, such as: C60, C70, PCBM, etc. The embodiments of the present application do not make special limitations in this regard, and those skilled in the art can select according to actual needs.

[0042] In some embodiments, an electrode is further provided on the side of the electron transport layer facing away from the perovskite absorption layer. The material of the electrode can be selected from conventional materials in the art, such as: Au, Ag, Al, Cu, etc. The embodiments of the present application do not make special limitations in this regard, and those skilled in the art can select according to actual needs.

[0043] In a second aspect, the present application also provides a method for preparing a perovskite solar cell, and this preparation method can be used to prepare the perovskite solar cell described in the first aspect.

[0044] In the embodiments of the present application, the method for preparing a perovskite solar cell includes the steps of:

[0045] Providing a conductive substrate;

[0046] Successively arranging a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode on one side of the conductive substrate.

[0047] In the embodiments of the present application, the hole transport layer includes the hole transport material shown in the above structure (1).

[0048] In the embodiments of the present application, the preparation method of the hole transport material includes the following steps:

[0049] Providing 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde, and performing a bromination reaction on 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde to obtain Intermediate 1. The structural formula of Intermediate 1 is:

[0050] Providing Intermediate 2, mixing and reacting Intermediate 1 with Intermediate 2 to obtain Intermediate 3. The structural formula of Intermediate 2 is: The structural formula of Intermediate 3 is:

[0051] Reducing the aldehyde group on Intermediate 3 to obtain Intermediate 4. The structural formula of Intermediate 4 is:

[0052] Mixing and reacting Intermediate 4 with acryloyl chloride to obtain Intermediate 5. The structural formula of Intermediate 5 is:

[0053] Mixing Intermediate 5 with a catalyst and performing a polymerization reaction to obtain the hole transport material.

[0054] A more detailed description of the preparation method of the hole transport material is as follows:

[0055] In some embodiments, the specific preparation steps of intermediate 1 include: mixing 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde with N-bromosuccinimide solution for reaction, wherein the molar ratio of 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde to N-bromosuccinimide is 1:(2-3), the reaction temperature is -5°C to 5°C, and the reaction time is 3h to 5h; after the reaction is completed, it is cooled to room temperature, and the reaction mixture is purified to obtain intermediate 1.

[0056] In some embodiments, the specific preparation steps of intermediate 3 include: mixing the intermediate 1 with the intermediate 2, tetrakis(triphenylphosphine)palladium and potassium carbonate in a solvent for reaction, wherein the molar ratio of intermediate 1, intermediate 2, tetrakis(triphenylphosphine)palladium and potassium carbonate is 1:(2.2-3):(0.05-0.15):(5-10), the reaction temperature is 80°C to 90°C, and the reaction time is 6h to 12h; after the reaction is completed, it is cooled to room temperature, and the reaction mixture is purified to obtain intermediate 3.

[0057] In some embodiments, the specific preparation steps of intermediate 5 include: in an inert gas atmosphere, mixing the intermediate 4 with dichloromethane and triethylamine evenly, and then slowly dropping acryloyl chloride into the obtained mixture for reaction, wherein the molar ratio of intermediate 3, acryloyl chloride and triethylamine is 1:(1.1-2):(50-300), the reaction temperature is -5°C to 0°C, and the reaction time is 4h to 8h; the reaction mixture is purified to obtain intermediate 5.

[0058] In some embodiments, in the polymerization reaction, the catalyst is azobisisobutyronitrile, the concentration of intermediate 5 is 0.1mol / L to 1.0mol / L, and the concentration of azobisisobutyronitrile is (1.0-10.0)×10 -3 mol / L.

[0059] In the above embodiments, the specific steps of mixing intermediate 5 with an initiator catalyst for polymerization reaction include: adding intermediate 5 and azobisisobutyronitrile into a solvent (such as toluene, tetrahydrofuran, N-methylpyrrolidone, etc.) according to an appropriate ratio, freeze-drying with liquid nitrogen and evacuating for 1 minute, then filling with nitrogen, repeating three times and sealing, initiating at 60°C to 70°C for 3h to 3.5h, and then reacting at 80°C to 90°C for 3 days; after the reaction is completed, it is cooled to room temperature, and the reaction mixture is purified to obtain the final product.

[0060] In some embodiments, the preparation method of intermediate 2 includes:

[0061] Provide raw material 1, which is selected from at least one of 4-bromo-4',4'-dimethoxytriphenylamine and 4-bromo-4',4'-dimercaptotriphenylamine. Mix the raw material 1 with tert-butylpinacol borate and react to obtain the intermediate 2.

[0062] In the above embodiment, more specifically, the preparation steps of the intermediate 2 include: Weigh raw material 1, tert-butylpinacol borate and n-butyllithium according to appropriate ratios. First, dissolve raw material 1, and then dropwise add n-butyllithium to the solution of raw material 1. React at -70°C to -85°C for 1 to 1.5 h. Then continue to add tert-butylpinacol borate and continue to react at -70°C to -85°C for 1 to 1.5 h. Then transfer it to room temperature and continue to react for 10 to 15 h; Quench the reaction with deionized water, and purify the reaction mixture to obtain the intermediate 2.

[0063] The preparation method provided by the embodiment of the present application has the advantages of simple synthesis route, low raw material cost and high repeatability. By controlling the raw materials, their feeding amounts, reaction temperature, reaction time and other conditions in each reaction step, the yield of the product can be increased to a relatively high level.

[0064] In some embodiments, the preparation method of the perovskite battery includes the following steps:

[0065] (1) Cleaning: Ultrasonically clean the ITO glass substrate (transparent conductive substrate) with deionized water, acetone and ethanol in sequence for 15 to 20 minutes, then use an N2 gas gun to blow dry the solvent remaining on the surface of the ITO glass substrate, and then perform oxygen plasma treatment for 10 to 15 minutes. Subsequently, transfer the ITO glass substrate to a nitrogen glove box.

[0066] (2) Preparation of the hole transport layer: Weigh 3 to 15 mg of the hole transport material and completely dissolve it in 1 mL of chlorobenzene solution. Take an appropriate amount of the solution and uniformly drop it onto the ITO glass substrate, spin-coat at 4000 to 5000 rpm for 20 to 30 seconds, and then anneal at 90 to 110°C for 10 to 15 minutes to obtain the ITO / hole transport layer composite structure.

[0067] (3) Preparation of perovskite absorption layer: Cool the composite structure obtained in the above step (2) to room temperature, preheat it at 130 - 140 °C for 3 - 5 minutes, take an appropriate amount (such as 50 μL) of perovskite solution to cover the surface of the hole transport layer, spin-coat it at 3000 - 5000 rpm for 20 - 30 seconds, and then anneal it at 90 - 100 °C for 10 - 15 minutes to obtain a composite structure of ITO / hole transport layer / perovskite absorption layer. Among them, the perovskite solution is prepared by mixing one or more of 3-bromo-benzylammonium iodide, 3-chlorobenzylammonium iodide, methylammonium chloride, and lead iodide in a certain molar ratio in DMF or DMSO. For example, it is prepared by dissolving 3-fluoro-benzylammonium iodide (3FBAI), methylammonium chloride (MACl), and lead iodide (PbI2) in DMF in a ratio of 2.2:3.5:4.

[0068] (4) Preparation of electron transport layer: Cool the composite structure obtained in the above step (3) to room temperature, configure PC61BM into a solution of 15 mg / mL, then take an appropriate amount (such as 40 μL) of PC61BM solution to cover the perovskite surface, spin-coat it at 1000 rpm for 30 - 50 seconds, and anneal it at 70 °C for 10 - 15 minutes to obtain a composite structure of ITO / hole transport layer / perovskite absorption layer / electron transport layer.

[0069] (5) Preparation of electrodes: Place the composite structure obtained in the above step (4) in a vacuum evaporation chamber, and evaporate Cr (6 nm) and Au (80 nm) on the PC61BM layer (electron transport layer) respectively to prepare a stacked perovskite battery. Define the area overlapping with the electrode on the ITO glass substrate as the effective area, and the effective area is 0.03 cm 2 .

[0070] In the third aspect, the present application proposes a stacked battery.

[0071] In the embodiments of the present application, the stacked battery includes a bottom battery and a top battery; wherein, the bottom battery includes at least one silicon battery, and the silicon battery is selected from any one of crystalline silicon batteries and amorphous silicon batteries. If the bottom battery includes multiple silicon batteries, the multiple silicon batteries are stacked. The top battery is stacked on the bottom battery, and the top battery includes one or more perovskite batteries. Among them, at least one perovskite battery is the perovskite battery described in the first aspect above, or is prepared by using the preparation method described in the second aspect above. The top battery includes multiple perovskite batteries, and the multiple perovskite batteries are stacked.

[0072] In the embodiments of the present application, the crystalline silicon cell can be selected from any one of TOPCon (Tunnel Oxide Passivated Contact cell), HJT (Heterojunction cell), IBC (Interdigitated Back Contact cell), PERC (Passivated Emitter and Rear Contact cell), or other common crystalline silicon cells in the art. The embodiments of the present application do not make special limitations in this regard, and those skilled in the art can adjust according to the actual application scenario.

[0073] It should be noted that when the top cell includes multiple crystalline silicon cells, the types of the multiple crystalline silicon cells can be the same or different from each other.

[0074] In the embodiments of the present application, the amorphous silicon cell can be selected from any one of a single-junction amorphous silicon cell, an amorphous silicon tandem cell (such as: a double-junction / triple-junction tandem cell), or other common amorphous silicon cells in the art. The embodiments of the present application do not make special limitations in this regard, and those skilled in the art can adjust according to the actual application scenario.

[0075] Fourthly, the present application also proposes a photovoltaic module, which includes a laminate and a frame, and the frame is installed at the edge of the laminate. Specifically, the laminate includes a photovoltaic glass, a first encapsulation film, a cell layer, a second encapsulation film, and a backsheet stacked in sequence, or the laminate includes a first photovoltaic glass, a first encapsulation film, a cell layer, a second encapsulation film, and a second photovoltaic glass; wherein, the cell layer includes multiple strings of cells connected in parallel, and each string of cells includes multiple cells connected in series. The cells are whole cells or cut pieces that are one-Nth of a whole cell, and at least some of the cells are the tandem cells described in the third aspect.

[0076] In some embodiments, adjacent cells in the present application are connected in series through a conductive connector (such as a welding wire or a solder strip) or a conductive adhesive, that is, one end of the conductive connector is welded to the back electrode of one cell, and the other end of the conductive connector is welded to the front electrode of another cell.

[0077] In some embodiments, adjacent cells can also form a photovoltaic module string by using high-density module technology, that is, the shingling technology, the stacked welding technology, or the wafer splicing technology, which greatly reduces or eliminates the gap between cells.

[0078] Shingling technology: The whole cell is cut into several small cell strips by using laser slicing technology, and the small cell strips are stacked and flexibly connected with conductive adhesive. This connection method optimizes the structure of the photovoltaic module string, realizes zero gap between cells, fully utilizes the limited area of the photovoltaic module, and more cells can be placed in the same form compared with other types of modules, effectively increasing the light-receiving area of the module.

[0079] Overlap soldering technology: Adjacent half-cells are micro-spacing 'overlapped' and soldered together through special round wire solder tapes. This connection method greatly reduces the spacing between cells during traditional soldering, achieving high energy density. Compared with ordinary flat solder tapes, the round wire solder tapes have a narrower cross-section, reducing the light shielding of the solder tapes on the cells. In addition, the round side of the solder tape enhances the reflection of incident light and the secondary refractive index of light on the front plate glass. The introduction of round solder tapes effectively solves the inherent contradiction between main grid shielding and increasing current collection ability, improves the light absorption and utilization of the cells, and increases the power of the module.

[0080] Cell splicing technology: Triangular solder tapes are used on the front of the cells, and ultra-flexible flat solder tapes are used on the back. Adjacent half-cells are soldered together with micro-spacing through double solder tape technology, achieving high energy density. The triangular solder tapes used in the cell splicing technology are soldered three-dimensionally on the front of the cell. The reflection ability of the nearly 45° side angle to incident light is further improved compared with round solder tapes, and the reflection can be more fully utilized to increase the light absorption ability of the cell and increase the power of the module.

[0081] In the embodiments of the present application, preferably, the frame is made of high-strength lightweight materials, such as: steel, aluminum, or composite materials made of resin and reinforcing materials. Among them, the resin includes polyurethane, polyester, polycarbonate, etc., and the reinforcing materials include glass fiber, aluminum, steel, etc.

[0082] In the embodiments of the present application, the first adhesive film and the second adhesive film can independently be ethylene-vinyl acetate copolymer (EVA) adhesive film, polyethylene octene co-elastic body (POE) adhesive film, polyethylene terephthalate (PET) adhesive film, PVB adhesive film, EPE adhesive film (EVA and POE three-layer co-extruded adhesive film), EP adhesive film (EVA and POE two-layer co-extruded adhesive film), or other types of adhesive films. Those skilled in the art can select according to the actual situation and are not limited herein.

[0083] The present invention will be further described below through more specific embodiments.

[0084] Example 1

[0085] The synthesis route of PMA-Ac-1 is as follows:

[0086]

[0087] The specific preparation steps of PMA-Ac-1 are as follows:

[0088] Synthesis of Compound 2: Weigh 3.84 g (10 mmol) of Compound 1 and add it to a 500 mL three-necked flask. Then add 30 mL of dry THF. Cool it to -78 °C under N2 and stir for 10 min. Then slowly dropwise add n-butyllithium (3.75 mL, 1.00 equiv, 1.6 M in n-hexane). React at -78 °C for 1 hour. After that, add tert-butylpinacol borate (2.75 mL, 15 mmol). Continue to react at -78 °C for 1 hour. Finally, transfer it to room temperature and react for 12 hours. Add 50 mL of deionized water to quench the reaction. Extract the resulting mixture with saturated NaCl solution and DCM. Dry the organic phase with anhydrous Mg2SO4, filter it, and finally purify it by column chromatography (PE:DCM = 15:1) to obtain 3.4 g of white solid Compound 2, with a yield of 79%.

[0089] Synthesis of Compound 4: Weigh 0.63 g (2 mmol) of Compound 3 and add it to a 100 mL two-necked reaction flask. Then add 30 mL of THF as the solvent. React at room temperature for 10 min under N2. Dissolve NBS (0.72 g, 4 mmol) in 10 mL of THF solution and slowly dropwise add it to the reaction flask while stirring. Continue to react for 12 hours. Add 50 mL of deionized water to quench the reaction. Extract the resulting mixture with DCM. Dry the organic phase with anhydrous Mg2SO4, filter it, and perform vacuum distillation. Finally, purify it by column chromatography (PE:DCM = 6:1) to obtain 6.6 g of Compound 4, with a yield of 69%.

[0090] Synthesis of Compound 5: Weigh 0.94 g (2 mmol) of Compound 4, 1.89 g (4.4 mmol) of Compound 2, 114 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 1.4 g (10 mmol) of potassium carbonate and add them to a 100 mL two-necked flask. The solvent is toluene, ethanol, and water (in a ratio of 2:1:1). React at 85 °C for 6 hours. After the reaction is completed, cool it to room temperature. Extract the resulting mixture with saturated sodium chloride solution and dichloromethane. Dry the organic phase with anhydrous magnesium sulfate, filter it, and perform vacuum distillation. Finally, purify it by column chromatography (PE:DCM = 4:1) to obtain 1.25 g of Compound 5, with a yield of 68%.

[0091] Synthesis of Compound 6: Weigh compound 5 (0.92 g, 1 mmol), add it to 40 mL of dry THF, stir for 10 min at 0 °C, add sodium borohydride (0.38 g, 10 mmol) in three portions to the reaction system, continuously stir at 0 °C for 3 h, then transfer to room temperature and react for 12 h; add 50 mL of water to quench the reaction, extract the resulting mixture with saturated sodium chloride solution and dichloromethane three times repeatedly. The organic phase is successively dried over anhydrous magnesium sulfate, filtered, and subjected to reduced pressure distillation. Finally, it is precipitated with n - hexane / dichloromethane and filtered by suction to obtain 0.82 g of compound 6, with a yield of 89%.

[0092] Synthesis of Compound 7: Weigh compound 6 (0.92 g, 1 mmol), add it to 15 mL of dry DCM and 15 mL of dry triethylamine, flush with N2 to remove oxygen, stir for 10 min at 0 °C, slowly drop in acryloyl chloride (0.2 mL), and then react for 6 h; add 50 mL of deionized water to quench the reaction, extract with saturated sodium chloride solution and dichloromethane. The organic phase is successively dried over anhydrous magnesium sulfate, filtered, and subjected to reduced pressure distillation. Finally, it is precipitated with n - hexane / dichloromethane and filtered by suction to obtain 0.85 g of compound 7, with a yield of 88%. Figure 1 It is the 1H - NMR spectrum of compound 7.

[0093] Synthesis of PMA - Ac - 1: Weigh 300 mg of compound 7 and azobisisobutyronitrile with a mass ratio of 1% (pre - recrystallized from ethanol; 3 mg), add them to a solution of toluene (or tetrahydrofuran, N - methylpyrrolidone), freeze - dry with liquid nitrogen and evacuate for 1 minute, then fill with nitrogen, repeat three times and seal. After initiating the reaction at 65 °C for 3 h, react at 85 °C for 3 days; after the reaction is completed, cool to room temperature, crystallize with n - hexane (ethanol) / dichloromethane, filter and dry by suction, then use acetone as the solvent and extract with a Soxhlet extractor for three days to obtain 175 mg of PMA - Ac - 1.

[0094] Example 2

[0095] The synthesis route of PMA - Ac - 2 is as follows:

[0096]

[0097] The specific preparation steps of PMA - Ac - 2 are as follows:

[0098] Synthesis of Compound 9: Weigh Compound 8 (4.2 g, 10 mmol) and add it to a 500 mL three-necked flask. Then add 30 mL of dry THF. Cool it to -78 °C under N2 and stir for 10 min. Then slowly add n-butyllithium (3.75 mL, 1.00 equiv, 1.6 M in n-hexane) dropwise. React at -78 °C for 1 hour. After that, add tert-butylpinacol borate (2.75 mL, 15 mmol) and continue to react at -78 °C for 1 hour. Finally, transfer it to room temperature and react for 12 hours. Add 50 mL of deionized water to quench the reaction. Then extract the reaction mixture with saturated NaCl solution and DCM. Dry the organic phase with anhydrous Mg2SO4, filter it, and finally purify it by column chromatography (PE:DCM = 15:1) to obtain 3.5 g of solid Compound 9 with a yield of 75%.

[0099] Synthesis of Compound 4: Weigh Compound 3 (0.63 g, 2 mmol) and add it to a 100 mL two-necked reaction flask. Then add 30 mL of THF as the solvent. React at room temperature for 10 min under N2. Dissolve NBS (0.72 g, 4 mmol) in 10 mL of THF solution and slowly add it dropwise to the reaction flask while stirring. Continue to react for 12 hours. Add 50 mL of deionized water to quench the reaction. Extract the reaction mixture with DCM. Dry the organic phase with anhydrous Mg2SO4, filter it, and perform vacuum distillation. Finally, purify it by column chromatography (PE:DCM = 6:1) to obtain 6.6 g of Compound 4 with a yield of 69%.

[0100] Synthesis of Compound 10: Weigh Compound 4 (0.94 g, 2 mmol), Compound 9 (2.01 g, 4.4 mmol), tetrakis(triphenylphosphine)palladium (114 mg, 0.1 mmol), and potassium carbonate (1.4 g, 10 mmol) and add them to a 100 mL two-necked flask. The solvent is toluene, ethanol, and water (in a ratio of 2:1:1). React at 85 °C for 6 hours. After the reaction, cool it to room temperature. Extract the reaction mixture with saturated sodium chloride solution and dichloromethane. Dry the organic phase with anhydrous magnesium sulfate, filter it, and perform vacuum distillation. Finally, purify it by column chromatography (PE:DCM = 4:1) to obtain 1.4 g of Compound 10 with a yield of 72%.

[0101] Synthesis of Compound 11: Weigh 0.98 g (1 mmol) of Compound 5 and add it to 40 mL of dry THF. Stir for 10 min at 0 °C, and add sodium borohydride (0.38 g, 10 mmol) to the reaction system in three portions. Continuously stir at 0 °C for 3 h, then transfer it to room temperature and react for 12 h. Add 50 mL of water to quench the reaction. Repeatedly extract the obtained mixture with saturated sodium chloride solution and dichloromethane three times. Dry the organic phase with anhydrous magnesium sulfate, filter, and distill under reduced pressure. Finally, precipitate with n-hexane / dichloromethane and filter by suction to obtain 0.88 g of Compound 11 with a yield of 91%.

[0102] Synthesis of Compound 12: Weigh 0.98 g (1 mmol) of Compound 11 and add it to 15 mL of dry DCM and 15 mL of dry triethylamine. Flush with N2 to remove oxygen and stir for 10 min at 0 °C. Slowly drop in acryloyl chloride (0.2 mL) and react for 6 h. Add 50 mL of deionized water to quench the reaction. Extract with saturated sodium chloride solution and dichloromethane. Successively dry the organic phase with anhydrous magnesium sulfate, filter, and distill under reduced pressure. Finally, precipitate with n-hexane / dichloromethane and filter by suction to obtain 0.86 g of Compound 12 with a yield of 87%. Figure 2 1H NMR spectrum of Compound 12

[0103] Synthesis of PMA-Ac-2: Weigh 300 mg of Compound 12 and azobisisobutyronitrile (previously recrystallized from ethanol; 3 mg) with a mass ratio of 1% of the monomer and add them to toluene (or tetrahydrofuran, N-methylpyrrolidone) solution. Freeze-dry with liquid nitrogen and evacuate for 1 minute, then refill with nitrogen, and repeat three times and seal. Initiate the reaction at 65 °C for 3 h, and then react at 85 °C for 3 days. After the reaction is completed, cool to room temperature, crystallize with n-hexane (ethanol) / dichloromethane, filter by suction and dry. Use acetone as the solvent and extract with a Soxhlet extractor for three days to obtain 163 mg of PMA-Ac-2.

[0104] Performance Testing

[0105] 1. Hole Mobility Testing:

[0106] Test by the space charge limited current method. Prepare a single-hole device of ITO / PEDOT:PSS / HTMs to be tested / MoO3 / Ag. Determine the film thickness of each layer by a step profiler. Obtain the J-V characteristic curve of the device with a Keithley 2450 Source-Measure instrument under dark conditions, and perform nonlinear fitting analysis on the curve to obtain the hole mobility of the sample. The test results of each example are shown in Table 1 below:

[0107] Table 1. Hole Mobility Test Results of Hole Transport Materials Prepared in Each Example

[0108] sample <![CDATA[Hole mobility / cm 2 ·V -1 ·S -1 <!-- 10 -->]]> PMA-Ac-1 <![CDATA[4.55×10 -4 > PMA-Ac-2 <![CDATA[6.26×10 -4 >

[0109] 2. Film-forming performance test:

[0110] Use atomic force microscopy (AFM) to study the crystal growth of quasi-two-dimensional perovskite thin films (perovskite absorption layer) on different polymer HTMs, and measure the RMS roughness on different polymer HTMs. The test results of each example are shown in Table 2 below:

[0111] Table 2. RMS roughness test results of the hole transport material film layers prepared in each example

[0112] sample RMS roughness / nm PMA-Ac-1 1.691 PMA-Ac-2 1.541

[0113] As can be seen from the results shown in Table 2, both of the two HTMs, PMA-Ac-1 and PMA-Ac-1, show good film-forming properties, with RMS values of 1.691 nm and 1.541 nm respectively, indicating that the films formed by PMA-Ac-1 and PMA-Ac-1 are uniform and smooth, can completely cover the IT0 glass well, inhibit the interfacial non-radiative recombination caused by the direct contact between the perovskite layer and the IT0 glass, and are beneficial to the growth of the perovskite layer thin film.

[0114] 3. Photoelectric performance test:

[0115] Use the same preparation method to fabricate inverted quasi-two-dimensional perovskite solar cell devices with PMA-Ac-1, PMA-Ac-2, and PTAA as hole transport materials respectively. For the specific preparation method, refer to the preparation method of the perovskite solar cell above;

[0116] Adjust the power of the solar simulator to 100 mw / cm 2 to simulate the AM 1.5G radiation standard, and read the current and voltage values of the device through a computer connected to a Keithley 2450 source meter. Before measuring the current density-voltage curve, calibrate the light intensity using a Newport standard silicon cell 91150. The device adopts a forward and reverse scan mode, and the scan rate is 0.05 V / s. The current density-voltage curve after the test is as Figure 3 shown, and the photoelectric performance test results are shown in Table 3.

[0117] Table 3. Photoelectric performance test results of the devices fabricated using the hole transport materials of each example

[0118]

[0119] The above test results can prove that: the hole transport material designed and synthesized in this application has excellent film-forming properties, which is beneficial to the diffusion and growth of perovskite as the HTL substrate, thereby obtaining a dense, uniform and smooth perovskite film, and it also has excellent hole mobility. These characteristics enable the inverted perovskite solar cell device prepared based on the hole transport material provided in this application to have excellent photoelectric conversion efficiency.

[0120] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A perovskite cell, comprising a hole transport layer, a perovskite absorption layer and an electron transport layer arranged on a surface of one side of a conductive substrate in sequence from near to far, wherein the hole transport layer comprises a hole transport material, characterized in that: The structural formula of the hole transport material is as shown in the following formula (1): Wherein, 10 < n < 10000, and R1 and R2 are independently selected from any one of the following structures:

2. The perovskite battery according to claim 1, characterized in that The thickness of the hole transport layer is 10 - 30 nm; and / or, The thickness of the perovskite absorption layer is 500 - 700 mn; and / or, The thickness of the electron transport layer is 80 - 120 nm.

3. A method for preparing a perovskite battery, characterized in that: It includes preparing a hole transport material, and the preparation steps of the hole transport material: Providing 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde, and subjecting 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde to bromination reaction to obtain intermediate 1, wherein the structural formula of intermediate 1 is: Provide intermediate 2, mix intermediate 1 and intermediate 2 to react, and obtain intermediate 3. The structural formula of intermediate 2 is: The structural formula of the intermediate 3 is: R1 and R2 are independently selected from any one of the following structures: Reducing the aldehyde group on the intermediate 3 to obtain intermediate 4, and the structural formula of the intermediate 4 is: Mixing and reacting the intermediate 4 with acryloyl chloride to obtain intermediate 5, and the structural formula of the intermediate 5 is: Mixing the intermediate 5 with a catalyst for polymerization reaction to obtain the hole transport material, and the structural formula of the hole transport material is as shown in the following formula (1): 10<n<10000。 4. The method for preparing a perovskite battery according to claim 3, characterized in that: The specific preparation steps of the intermediate 1 include: mixing and reacting 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde with N-bromosuccinimide solution, wherein the molar ratio of 4-(9,9-dimethylacridin-10(9H)-yl)benzaldehyde to N-bromosuccinimide is 1:(2 - 3), the reaction temperature is -5°C to 5°C, and the reaction time is 3h to 5h.

5. The method for preparing a perovskite battery according to claim 3, characterized in that: The specific preparation steps of the intermediate 3 include: mixing and reacting the intermediate 1 with the intermediate 2, tetrakis(triphenylphosphine)palladium, and potassium carbonate in a solvent, wherein the molar ratio of the intermediate 1, the intermediate 2, tetrakis(triphenylphosphine)palladium, and potassium carbonate is 1:(2.2 - 3):(0.05 - 0.15):(5 - 10), the reaction temperature is 80°C to 90°C, and the reaction time is 6h to 12h.

6. The method for preparing a perovskite battery according to claim 3, characterized in that: The specific preparation steps of the intermediate 5 include: in an inert gas atmosphere, mixing the intermediate 4 evenly with dichloromethane and triethylamine, and then slowly dropping acryloyl chloride into the obtained mixed solution for reaction, wherein the molar ratio of the intermediate 3, acryloyl chloride, and triethylamine is 1:(1.1 - 2):(50 - 300), the reaction temperature is -5°C to 0°C, and the reaction time is 4h to 8h.

7. The method for preparing a perovskite battery according to claim 3, characterized in that: In the polymerization reaction, the catalyst is azobisisobutyronitrile, the concentration of the intermediate 5 is 0.1 mol / L to 1.0 mol / L, and the concentration of the azobisisobutyronitrile is (1.0 to 10.0)×10 -3 mol / L.

8. The method for preparing a perovskite battery according to any one of claims 3 to 7, characterized in that: The preparation method of the intermediate 2 includes: Providing raw material 1, wherein the raw material 1 is selected from at least one of 4-bromo-4',4'-dimethoxytriphenylamine and 4-bromo-4',4'-dimercaptotriphenylamine, and mixing and reacting the raw material 1 with tert-butylpinacol borate to obtain the intermediate 2.

9. A laminated battery, characterized in that: It includes: A bottom cell, which includes at least one crystalline silicon cell and / or amorphous silicon cell; A top cell, stacked on the bottom cell, and the top cell includes one or more perovskite cells, wherein at least one perovskite cell is the perovskite cell as described in claim 1 or 2, or at least one perovskite cell is prepared by the preparation method of the perovskite cell as described in any one of claims 3 - 8.

10. A photovoltaic module, characterized in that: It includes the tandem cell as described in claim 9.

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