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

Abstract

The invention relates to the technical field of perovskite cells, provides a perovskite cell and a preparation method thereof, a laminated cell and a photovoltaic module, and at least can improve the efficiency of the perovskite cell. The perovskite cell comprises a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, the hole transport layer comprises a hole transport material, and the chemical formula of the hole transport material is # imgabs0 #

Description

Technical Field

[0001] The present application relates to the technical field of perovskite solar cells, and particularly to a perovskite solar cell, a preparation method thereof, a tandem solar cell, and a photovoltaic module. Background Art

[0002] Perovskite solar cells (PSCs) are devices that use perovskite-type organometallic halide semiconductors as light-absorbing materials to directly convert light energy into electrical energy through the photovoltaic effect. The structure of perovskite solar cells mainly includes components such as a conductive substrate, an electron transport layer (ETL), a perovskite layer, a hole transport layer (HTL), and a metal electrode.

[0003] The hole transport layer plays a crucial role in hole extraction and transport, suppressing carrier recombination, and improving the crystallization and film formation of perovskite materials. Therefore, continuously developing hole transport materials (HTMs) with excellent film-forming properties, solvent resistance, thermal stability, hole mobility, and energy levels matching those of perovskite materials is a key factor in preparing efficient and stable perovskite solar cells.

[0004] Currently, how to develop efficient and low-cost HTMs has become an important research topic. Summary of the Invention

[0005] Embodiments of the present application provide a perovskite solar cell, a preparation method thereof, a tandem solar cell, and a photovoltaic module, which are at least beneficial to improving the efficiency of perovskite solar cells while reducing the cost of HTMs.

[0006] According to some embodiments of the present application, on the one hand, the present application provides a perovskite solar cell, which includes a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode. Among them, the hole transport layer includes a hole transport material, and the chemical formula of the hole transport material is as follows:

[0007]

[0008] According to some embodiments of the present application, on the other hand, the present application provides a preparation method of a perovskite solar cell, including: sequentially forming a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode on a transparent conductive substrate. Among them, the preparation step of the hole transport layer includes: configuring the hole transport material in the above embodiment into a solution and then coating it on the transparent conductive substrate. The preparation step of the hole transport material is as follows: performing a substitution reaction on raw material I and pinacol borate to obtain a first product;

[0009] The chemical formula of Raw Material I is:

[0010]

[0011] The chemical formula of the first product is:

[0012]

[0013] The first product and 2,3-dibromothiophene are subjected to a Suzuki coupling reaction to obtain a second product;

[0014] The chemical formula of the second product is:

[0015]

[0016] The second product and pinacol borate are subjected to a substitution reaction to obtain a third product;

[0017] The chemical formula of the third product is:

[0018]

[0019] Raw Material II and N-bromosuccinimide are subjected to a bromination reaction to obtain a fourth product; The chemical formula of Raw Material II is:

[0020]

[0021] The chemical formula of the fourth product is:

[0022]

[0023] The third product and the fourth product are subjected to a Suzuki coupling reaction to obtain a fifth product;

[0024] The chemical formula of the fifth product is:

[0025]

[0026] The fifth product is subjected to a Witting reaction to obtain a sixth product;

[0027] The chemical formula of the sixth product is:

[0028]

[0029] The sixth product and azobisisobutyronitrile are subjected to a radical polymerization reaction to obtain a hole transport material.

[0030] In some embodiments, the method for obtaining the first product includes: adding raw material I, n-butyllithium, and pinacol borate into tetrahydrofuran, reacting at 0 °C for 1 h to 1.5 h, then reacting at room temperature for 10 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the first product; wherein, the molar ratio of raw material I, n-butyllithium, and pinacol borate is 1:(1 - 1.5):(1.1 - 2).

[0031] In some embodiments, the steps for obtaining the second product include: adding the first product, 2,3-dibromothiophene, tetrakis(triphenylphosphine)palladium, and potassium carbonate into toluene, ethanol, and water with a volume ratio of 2:1:1, reacting at 80 °C to 90 °C for 6 h to 12 h, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the second product; wherein, the molar ratio of the first product, 2,3-dibromothiophene, potassium carbonate, and tetrakis(triphenylphosphine)palladium is 1:(2.2 - 3):(4 - 8):(0.01 - 0.1).

[0032] In some embodiments, the method for obtaining the third product includes: adding the second product, n-butyllithium, and pinacol borate into tetrahydrofuran, reacting at 0 °C for 1 h to 1.5 h, then reacting at room temperature for 10 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the third product; wherein, the molar ratio of the second product, n-butyllithium, and pinacol borate is 1:(1 - 1.5):(1.1 - 2).

[0033] In some embodiments, the method for obtaining the fourth product includes: adding raw material II and N-bromosuccinimide into tetrahydrofuran, reacting at -5 °C to 0 °C for 8 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the fourth product; wherein, the molar ratio of raw material II to N-bromosuccinimide is 1:(2.2 - 3).

[0034] In some embodiments, the method for obtaining the fifth product includes: adding the fourth product, the third product, tetrakis(triphenylphosphine)palladium, and potassium carbonate into toluene, ethanol, and water with a volume ratio of 2:1:1, reacting at 80 °C to 90 °C for 6 h to 12 h, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the fifth product; wherein, the molar ratio of the third product, the fourth product, potassium carbonate, and tetrakis(triphenylphosphine)palladium is 1:(2.2 - 3):(4 - 8):(0.01 - 0.1).

[0035] In some embodiments, the method for obtaining the sixth product includes: adding potassium tert-butoxide and methyltriphenylphosphonium bromide into tetrahydrofuran, stirring for 1 h to 2 h at 0°C, then dropwise adding the tetrahydrofuran solution of the fifth product, continuing the reaction at 0°C for 3 h to 5 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the sixth product.

[0036] According to some embodiments of the present application, on the other hand, an embodiment of the present application provides a tandem cell, including: a top cell, which is the perovskite cell in the above embodiment; a crystalline silicon bottom cell, which is located on the side of the transparent conductive substrate of the perovskite cell away from the electrode.

[0037] According to some embodiments of the present application, on yet another aspect, an embodiment of the present application provides a photovoltaic module, including: a plurality of tandem cells in the above embodiments; a connecting member for connecting adjacent tandem cells; a glue film covering the surface of the tandem cells; and a cover plate located on the surface of the glue film away from the tandem cells.

[0038] The technical solution provided by the embodiment of the present application has at least the following advantages:

[0039] The perovskite cell provided by the embodiment of the present application includes a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode. Among them, the hole transport layer includes a hole transport material PTZ-1. Introducing phenothiazine with a sulfur functional group into the HTMs, phenothiazine is a molecule with a nearly planar ternary heterocyclic structure, and the dihedral angles are about 169° and 153° respectively, which can improve the planarity and conductivity of the molecule. The group containing sulfur atoms in the molecule endows the HTMs with appropriate energy levels to increase intra- and / or intermolecular interactions, as well as enhanced buried interface interactions with quasi-two-dimensional layered perovskites, resulting in good mobility of the hole transport material, which is beneficial to the extraction and transport of holes. Moreover, PTZ-1 has a HOMO energy level that matches the perovskite and is relatively deep. PTZ-1 has good solubility in organic solvents, good film-forming properties, good wettability with the perovskite precursor solvent, and is helpful for the crystallization and film formation of perovskite. It can be used in inverted quasi-two-dimensional perovskite solar cells without doping any additives and has good application prospects. Description of the Drawings

[0040] One or more embodiments are exemplarily illustrated by the pictures in the corresponding drawings. These exemplary illustrations do not constitute a limitation on the embodiments. Unless otherwise stated, the figures in the drawings do not constitute a scale limitation. To more clearly illustrate the technical solutions in the embodiments of the present application or in the prior art, the drawings required to be used in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0041] Figure 1 Schematic diagram of a perovskite battery structure provided by an embodiment of the present application;

[0042] Figure 2 1H NMR spectrum of the monomer of PTZ-1 provided by an embodiment of the present application;

[0043] Figure 3 Current density-voltage (J-V) characteristic curves corresponding to perovskite battery 1 and perovskite battery 2. Detailed implementation manners

[0044] As can be seen from the background art, how to develop high-efficiency and low-cost HTMs has become an important research topic.

[0045] Currently, in the exploration of HTMs materials, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), as a poly(triphenyl)amine-based polymer semiconductor, has been at the forefront in the development of high-efficiency PSCs. However, the realization of high-efficiency perovskite devices is inseparable from the use of dopants, and doping additives not only increase the production burden but also the hygroscopic decomposition characteristics of the dopants (such as Li-TFSI) ultimately affect the stability of perovskite devices during operation. Therefore, it is of great significance to develop a non-doped polymer hole transport material that can be used in low-temperature processes.

[0046] Introducing sulfur-containing functional groups into HTMs can improve the planarity and conductivity of molecules. Sulfur can also coordinate with Pb 2+ atoms and passivate the defects at the surface and grain boundaries. The commonly used sulfur-containing functional groups are two functional groups, thiophene and methylthio group. Phenothiazine (PTZ) is a molecule with a nearly planar ternary heterocyclic structure, and the dihedral angles are approximately 169° and 153° respectively, which is a common functional material in PSCs.

[0047] The embodiments of the present application provide a perovskite solar cell, a preparation method thereof, a tandem solar cell, and a photovoltaic module. The hole transport layer of the perovskite solar cell includes a hole transport material PTZ-1. With phenothiazine (PTZ) as the core respectively, under the guidance of reaction mechanisms such as Buchwald-Hartwig type C-N coupling and Suzuki-Miyaura type C-C coupling, non-conjugated polymers HTMs with high hole mobility are constructed, which is at least beneficial to improving the efficiency of perovskite solar cells and reducing the cost of HTMs.

[0048] In the description of the embodiments of the present application, technical terms such as "first" and "second" are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity, specific order or primary-secondary relationship of the indicated technical features.

[0049] In the description of the embodiments of the present application, the meaning of "a plurality" is more than two, unless otherwise specifically limited.

[0050] Referring to "embodiments" herein means that specific features, structures or characteristics described in connection with the embodiments may be included in at least one embodiment of the present application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein may be combined with other embodiments.

[0051] In the description of the embodiments of the present application, when a component "comprises" another component, unless otherwise stated, it does not exclude other components, and other components may further be included.

[0052] The terms used in the description of the various embodiments herein are only for describing specific embodiments and are not intended to be limiting. As used in the descriptions of the various embodiments and the appended claims, "component" is also intended to include the plural form, unless the context clearly indicates otherwise.

[0053] The embodiments of the present application will be described in detail below with reference to the accompanying drawings. However, those of ordinary skill in the art can understand that in the embodiments of the present application, many technical details are provided for readers to better understand the present application. However, even without these technical details and various changes and modifications based on the following embodiments, the technical solutions claimed in the present application can still be implemented.

[0054] Figure 1 It is a schematic structural diagram of a perovskite solar cell provided by the embodiments of the present application.

[0055] According to some embodiments of the present application, on the one hand, the embodiments of the present application provide a perovskite solar cell, referring toFigure 1 , the perovskite solar cell includes a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode. Among them, the hole transport layer includes a hole transport material PTZ-1, and the chemical formula of the hole transport material PTZ-1 is as follows:

[0056]

[0057] Figure 2 It is the 1H NMR spectrum of the monomer corresponding to PTZ-1 provided by the embodiment of the present application.

[0058] The perovskite solar cell provided by the embodiment of the present application includes a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode. Among them, the hole transport layer includes a hole transport material PTZ-1. Introducing phenothiazine with a sulfur functional group into HTMs, phenothiazine is a molecule with a nearly planar ternary heterocyclic structure, and the dihedral angles are about 169° and 153° respectively, which can improve the planarity and conductivity of the molecule. The group containing sulfur atoms in the molecule endows HTMs with appropriate energy levels to increase intra- and / or intermolecular interactions, as well as enhanced buried interface interactions with quasi-two-dimensional layered perovskites, making the mobility of the hole transport material better, which is beneficial to the extraction and transport of holes, and PTZ-1 has a HOMO energy level that matches the perovskite and is relatively deep. PTZ-1 has good solubility in organic solvents, good film-forming properties, good wettability with the perovskite precursor solvent, which helps the crystallization and film formation of perovskite, and can be used in inverted quasi-two-dimensional perovskite solar cells without doping any additives, showing good application prospects.

[0059] The material of the transparent conductive substrate includes ITO glass, which is fabricated by depositing a layer of indium tin oxide (commonly known as ITO) film on the basis of soda-lime or borosilicate substrate glass by means of magnetron sputtering.

[0060] The material of the perovskite absorption layer can be a compound composed of A, B, and X3. Among them, A can be one or more of FA (HC(NH2)2), MA (CH3NH3), Cs, and Rb, B can be one or more of Pb, Sn, and Sr, and X can be one or more of Br, I, and Cl.

[0061] The materials of the electron transport layer include tin oxide, titanium dioxide, C60, fullerenes, and their derivatives, etc.

[0062] The materials of the electrode include at least one of chromium (Cr) and gold (Au).

[0063] Correspondingly, another embodiment of the present application further provides a method for preparing a perovskite solar cell, which can be used to manufacture the perovskite solar cell provided in the above embodiment. The following will detail the method for preparing the perovskite solar cell provided in another embodiment of the present application. For the same or corresponding parts as those in the previous embodiment, reference can be made to the corresponding description in the previous embodiment, and no detailed description will be given below.

[0064] The method for preparing a perovskite solar cell includes: sequentially forming a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode on a transparent conductive substrate. The specific steps are as follows:

[0065] S11. Cleaning step: Ultrasonically clean the transparent conductive substrate with deionized water, acetone, and ethanol in sequence for 15 - 20 minutes. After drying the transparent conductive substrate, perform oxygen plasma treatment for 10 - 15 minutes, and then transfer the transparent conductive substrate into a nitrogen glove box;

[0066] S12. Preparing the hole transport layer: Weigh 3 - 15 mg of hole transport material PTZ - 1, dissolve it in 1 mL of chlorobenzene solution, take an appropriate amount of the mixed solution and drop it onto the transparent conductive substrate, spin - coat it at a speed of 4000 - 5000 rpm for 20 - 30 s, and then anneal it at 90 - 100 °C for 10 min;

[0067] S13. Preparing the perovskite absorption layer: Cool the transparent conductive substrate with the hole transport layer to room temperature, preheat it at 130 - 140 °C for 3 - 5 min, take 50 μL of perovskite solution and spread it over the surface of the hole transport layer, spin - coat it at a speed of 3000 - 5000 rpm for 20 - 30 s, and then anneal it at 90 - 100 °C for 10 min. Among them, the solute of the perovskite solution is 3 - bromo - benzylammonium iodide or 3 - chloro - benzylammonium iodide, methylammonium chloride, and lead iodide, and the solvent is N,N - dimethylformamide and dimethyl sulfoxide;

[0068] S14. Preparing the electron transport layer: Cool the transparent conductive substrate with the perovskite absorption layer to room temperature, take 40 μL of (6,6) - phenyl - C61 - butyric acid methyl ester solution with a concentration of 15 mg / mL, spread the (6,6) - phenyl - C61 - butyric acid methyl ester solution over the perovskite absorption layer, spin - coat it at a speed of 1000 - 2000 rpm for 30 - 50 s, and then anneal it at 70 - 80 °C for 10 min;

[0069] S15. Preparing the electrode: Place the transparent conductive substrate with the electron transport layer in a vacuum evaporation chamber, and evaporate at least one of metal chromium or gold onto the electron transport layer.

[0070] The preparation method of the perovskite battery provided by the embodiment of the present application uses the hole transport material PTZ-1 to make the hole transport layer. The hole transport material PTZ-1 has good solubility in organic solvents, good film-forming property, good wettability with the perovskite precursor solvent, and is helpful for the crystallization and film formation of perovskite.

[0071] The preparation steps of the hole transport material PTZ-1 are as follows:

[0072] S21. Carry out a substitution reaction between raw material I and pinacol borate to obtain a first product.

[0073] The chemical formula of raw material I is:

[0074]

[0075] The chemical formula of the first product is:

[0076]

[0077] The reaction formula for preparing the first product is:

[0078]

[0079] In some embodiments, the method for obtaining the first product includes: adding raw material I, n-butyllithium, and pinacol borate to tetrahydrofuran, reacting at 0 °C for 1 h to 1.5 h, then reacting at room temperature for 10 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the first product; wherein, the molar ratio of raw material I, n-butyllithium, and pinacol borate is 1:(1 to 1.5):(1.1 to 2).

[0080] In some embodiments, after preparing the first product, it further includes purifying the first product by column chromatography, and the eluent for column chromatography is petroleum ether and dichloromethane with a volume ratio of 15:1.

[0081] S22. Carry out a Suzuki coupling reaction between the first product and 2,3-dibromothiophene to obtain a second product.

[0082] The chemical formula of the second product is:

[0083]

[0084] The chemical formula for preparing the second product is:

[0085]

[0086] In some embodiments, the step of obtaining the second product includes: adding the first product, 2,3-dibromothiophene, tetrakis(triphenylphosphine)palladium, and potassium carbonate into toluene, ethanol, and water with a volume ratio of 2:1:1, reacting at 80°C to 90°C for 6 h to 12 h, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and performing vacuum distillation to obtain the second product; wherein, the molar ratio of the first product, 2,3-dibromothiophene, potassium carbonate, and tetrakis(triphenylphosphine)palladium is 1:(2.2 - 3):(4 - 8):(0.01 - 0.1).

[0087] In some embodiments, after preparing the second product, it further includes purifying the second product by column chromatography, and the eluent for column chromatography is petroleum ether and dichloromethane with a volume ratio of 6:1.

[0088] S23. Perform a substitution reaction on the second product and pinacol borate to obtain the third product.

[0089] The chemical formula of the third product is:

[0090]

[0091] The reaction formula for preparing the third product is:

[0092]

[0093] In some embodiments, the method for obtaining the third product includes: adding the second product, n-butyllithium, and pinacol borate into tetrahydrofuran, reacting at 0°C for 1 h to 1.5 h, then reacting at room temperature for 10 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and performing vacuum distillation to obtain the third product; wherein, the molar ratio of the second product, n-butyllithium, and pinacol borate is 1:(1 - 1.5):(1.1 - 2).

[0094] In some embodiments, after preparing the third product, it further includes purifying the third product by column chromatography, and the eluent for column chromatography is petroleum ether and dichloromethane with a volume ratio of 15:1.

[0095] S24. Perform a bromination reaction on raw material II and N-bromosuccinimide to obtain the fourth product.

[0096] The chemical formula of raw material II is:

[0097]

[0098] The chemical formula of the fourth product is:

[0099]

[0100] The reaction formula for preparing the fourth product is:

[0101]

[0102] In some embodiments, the method for obtaining the fourth product includes: adding raw material II and N-bromosuccinimide to tetrahydrofuran, reacting at -5°C to 0°C for 8 h to 16 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and performing vacuum distillation to obtain the fourth product; wherein, the molar ratio of raw material II to N-bromosuccinimide is 1:(2.2 to 3).

[0103] In some embodiments, after preparing the fourth product, it further includes purifying the fourth product by flash column chromatography, and the eluent of the flash column chromatography is petroleum ether and dichloromethane with a volume ratio of 10:1.

[0104] S25. Perform a Suzuki coupling reaction on the third product and the fourth product to obtain the fifth product.

[0105] The chemical formula of the fifth product is:

[0106]

[0107] The reaction formula for preparing the fifth product is:

[0108]

[0109] In some embodiments, the method for obtaining the fifth product includes: adding the fourth product, the third product, tetrakis(triphenylphosphine)palladium, and potassium carbonate to toluene, ethanol, and water with a volume ratio of 2:1:1, reacting at 80°C to 90°C for 6 h to 12 h, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and performing vacuum distillation to obtain the fifth product; wherein, the molar ratio of the third product, the fourth product, potassium carbonate, and tetrakis(triphenylphosphine)palladium is 1:(2.2 to 3):(4 to 8):(0.01 to 0.1).

[0110] In some embodiments, after preparing the fifth product, it further includes purifying the fifth product by column chromatography, and the eluent of the column chromatography is petroleum ether and dichloromethane with a volume ratio of 6:1.

[0111] S26. Perform a Witting reaction on the fifth product to obtain the sixth product.

[0112] The chemical formula of the sixth product is:

[0113]

[0114] The reaction formula for preparing the sixth product is:

[0115]

[0116] In some embodiments, the method for obtaining the sixth product includes: adding potassium tert-butoxide and methyltriphenylphosphonium bromide to tetrahydrofuran, stirring at 0 °C for 1 h to 2 h, then dropwise adding a tetrahydrofuran solution of the fifth product, continuing the reaction at 0 °C for 3 h to 5 h, quenching with water, extracting the organic phase with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain the sixth product.

[0117] In some embodiments, after preparing the sixth product, it further includes purifying the sixth product by column chromatography, and the eluent for column chromatography is petroleum ether and dichloromethane with a volume ratio of 4:1.

[0118] S27. Carry out a radical polymerization reaction on the sixth product and azobisisobutyronitrile to obtain the hole transport material PZT-1.

[0119] The reaction formula for preparing the hole transport material PZT-1 is:

[0120]

[0121] In some embodiments, the method for obtaining the hole transport material PZT-1 includes: providing a reaction flask, soaking and cleaning the reaction flask in potassium dichromate cleaning solution, then removing the salt layer on the inner wall with saturated water vapor, and then baking in a flame and cooling the reaction flask under nitrogen protection to remove the oxygen on the bottle wall; under the protection of nitrogen, prepare a toluene or tetrahydrofuran solution with a sixth product concentration of 0.1 to 1.0 mol / L and an azobisisobutyronitrile concentration of 1.0 to 10.0×10 -3 mol / L, stir well by bubbling nitrogen; add the above-prepared solution to the reaction flask, and remove the oxygen in the system by cycling through liquid nitrogen cooling - vacuum pumping - heating - nitrogen passing three times; then seal the bottle and place it in an oil bath at 65 °C to initiate the reaction for 2 to 3 h, and then raise the temperature to 85 °C and react for 72 h; after the reaction is completed, quench the reaction with methanol, and then precipitate and filter with n-hexane or dichloromethane to obtain the PZT-1 crude product; extract the PZT-1 crude product with absolute ethanol or acetone to obtain the hole transport material PZT-1 with a narrow molecular weight distribution.

[0122] The preparation method of the hole transport material PZT-1 provided by the embodiments of the present application has low raw material cost, simple preparation process, and is suitable for industrial production.

[0123] According to some embodiments of the present application, on the other hand, the present application provides a stacked battery, including: a top battery, the top battery being the perovskite battery in the above embodiments; a crystalline silicon bottom battery, the crystalline silicon bottom battery being located on the side of the transparent conductive substrate of the perovskite battery away from the electrode.

[0124] The crystalline silicon bottom cell includes any one of PERC cells (Passivated Emitter and Rear Cell), PERT cells (Passivated Emitter and Rear Totally-diffused cell), TOPCon cells (Tunnel Oxide Passivated Contact), HIT / HJT cells (Heterojunction Technology), or BC cells (BackContact).

[0125] The crystalline silicon bottom cell also includes monocrystalline silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, or multi-component compound solar cells. The multi-component compound solar cell can specifically be a cadmium sulfide solar cell, a gallium arsenide solar cell, a copper indium selenide solar cell, or a perovskite solar cell.

[0126] According to some embodiments of the present application, on the other hand, an embodiment of the present application provides a photovoltaic module, including: a plurality of the stacked cells in the above embodiments; a connecting member for connecting adjacent stacked cells; a glue film covering the surface of the stacked cells; and a cover plate located on the surface of the glue film away from the stacked cells.

[0127] The connecting member includes an interconnecting solder tape and a bus bar solder tape. The interconnecting solder tape is a tinned solder tape for connecting the stacked cells, collecting, and transmitting the current of the stacked cells. The bus bar solder tape is a tinned solder tape for connecting the stacked cell string and the junction box and transmitting the current of the stacked cell string.

[0128] The glue film can be an organic encapsulation glue film such as an ethylene-vinyl acetate copolymer (EVA) glue film, a polyethylene octene copolymer elastomer (POE) glue film, or a polyvinyl butyral (PVB) glue film.

[0129] The cover plate can be a cover plate with a light-transmitting function such as a glass cover plate or a plastic cover plate. In some embodiments, the surface of the cover plate facing the encapsulation layer can be an uneven surface to increase the utilization rate of incident light.

[0130] The following are specific embodiments of the present application:

[0131] Embodiment 1

[0132] To prepare the first product, 4.17 g of raw material I was added to a 500 mL three-necked flask, 30 mL of tetrahydrofuran was added, and the mixture was cooled to -78 °C and stirred for 10 min. 3.75 mL of n-butyllithium (the molar concentration of n-butyllithium in hexane was 1.6 M) was added dropwise. After reacting at -78 °C for 1 h, 2.75 mL of pinacol borate was added, and the reaction was continued at -78 °C for 1 h. Subsequently, the reaction was transferred to room temperature and reacted for 12 h. After quenching with 50 mL of deionized water, the organic phase was extracted with saturated sodium chloride and dichloromethane. After drying the organic phase with anhydrous magnesium sulfate, it was filtered and distilled under reduced pressure to obtain the first product. The first product was purified by column chromatography. The eluent for column chromatography was petroleum ether and dichloromethane with a volume ratio of 15:1, and the purified first product was obtained (yield 78%).

[0133] To prepare the second product, 1.12 g of the first product, 0.48 g of 2,3-dibromothiophene, 57 g of tetrakis(triphenylphosphine)palladium, 1.38 g of potassium carbonate, and a solvent were added to a 100 mL two-necked flask. The solvent was toluene, ethanol, and water with a volume ratio of 2:1:1. The reaction was carried out at 80 °C for 6 h. After cooling to room temperature, the organic phase was extracted with dichloromethane. After drying the organic phase with anhydrous magnesium sulfate, it was filtered and distilled under reduced pressure to obtain the second product. The second product was purified by column chromatography. The eluent for column chromatography was petroleum ether and dichloromethane with a volume ratio of 6:1, and the purified second product was obtained (yield 68%).

[0134] To prepare the third product, 7.6 g of the second product was added to a 500 mL three-necked flask, and then 30 mL of tetrahydrofuran was added. The mixture was cooled to -78 °C and stirred for 10 min. 3.75 mL of n-butyllithium (the molar concentration of n-butyllithium in hexane was 1.6 M) was added dropwise. After reacting at -78 °C for 1 h, 2.75 mL of pinacol borate was added, and the reaction was carried out at -78 °C for 1 h. Subsequently, the reaction was transferred to room temperature and reacted for 12 h. After quenching with 50 mL of deionized water, the organic phase was extracted with saturated sodium chloride and dichloromethane. After drying the organic phase with anhydrous magnesium sulfate, it was filtered and distilled under reduced pressure to obtain the third product. The third product was purified by column chromatography. The eluent for column chromatography was petroleum ether and dichloromethane with a volume ratio of 15:1, and the purified third product was obtained (yield 75%).

[0135] To prepare the fourth product, 1.2 g of raw material II and 10 mL of dichloromethane were added to a 100 mL round-bottom flask, and then 1.51 g of N-bromosuccinimide was added. After heating to room temperature, the mixture was stirred for 12 h. After quenching with water, the organic phase was extracted with dichloromethane. After drying the organic phase with anhydrous magnesium sulfate, it was filtered and distilled under reduced pressure to obtain the fourth product. The fourth product was purified by flash column chromatography. The eluent for flash column chromatography was petroleum ether and dichloromethane with a volume ratio of 10:1, and the purified fourth product was obtained (yield 91%).

[0136] To prepare the fifth product, add 2.1 g of the third product, 0.96 g of the fourth product, 57 mg of tetrakis(triphenylphosphine)palladium, 1.38 g of potassium carbonate and a solvent into a 100 mL two-necked flask. The solvent is a mixture of toluene, ethanol and water with a volume ratio of 2:1:1. React at 85 °C for 6 h. After cooling to room temperature, extract the organic phase with dichloromethane, dry the organic phase with anhydrous magnesium sulfate, filter, and distill under reduced pressure to obtain the fifth product. Purify the fifth product by column chromatography. The eluent for column chromatography is a mixture of petroleum ether and dichloromethane with a volume ratio of 6:1 to obtain the purified fifth product (yield 50%).

[0137] To prepare the sixth product, add 0.47 g of methyltriphenylphosphonium bromide and 0.11 g of potassium tert-butoxide into a 250 mL two-necked flask, then add 10 mL of tetrahydrofuran. Stir at 0 °C for 1 h. Weigh 1.8 g of the fifth product and dissolve it in 10 mL of tetrahydrofuran, and add it dropwise to the reaction flask. React at 0 °C for 4 h. After the reaction is completed, quench with 50 mL of deionized water, extract the organic phase with dichloromethane, dry the organic phase with anhydrous magnesium sulfate, filter, and distill under reduced pressure to obtain the sixth product. Purify the sixth product by column chromatography. The eluent for column chromatography is a mixture of petroleum ether and dichloromethane with a volume ratio of 4:1 to obtain the purified sixth product (yield 96%).

[0138] To prepare PZT-1, weigh 300 mg of the sixth product and azobisisobutyronitrile. The mass ratio of azobisisobutyronitrile to the monomer is 1%. Add them into toluene. After cooling with liquid nitrogen - evacuating - heating - introducing nitrogen, cycle three times and then seal. Initiate the reaction at 65 °C for 3 h, and then react at 85 °C for 72 h. After the reaction is completed, cool to room temperature, precipitate and filter with dichloromethane to obtain the crude product of PZT-1. After suction filtration and drying, use acetone as the solvent and extract with a Soxhlet extractor for 72 h to obtain the hole transport material PZT-1.

[0139] Use PZT-1 as the hole transport material to prepare the corresponding perovskite solar cell 1.

[0140] Comparative Example 1

[0141] Use poly(triarylamine) (PTAA) as the hole transport material to prepare the corresponding perovskite solar cell 2.

[0142] Perform photoelectric conversion efficiency tests on perovskite solar cell 1 and perovskite solar cell 2. Under the illumination condition of AM 1.5G, measure the current density - voltage (J-V) characteristic curves by forward and reverse scans at a speed of 0.02 V s -1 The detailed photovoltaic parameters open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF) and photoelectric conversion efficiency (PCE) are shown in Table 1. Figure 3They are the current density-voltage (J-V) characteristic curves corresponding to perovskite solar cell 1 and perovskite solar cell 2.

[0143] Table 1 Photovoltaic indices corresponding to perovskite solar cell 1 and perovskite solar cell 2

[0144] Experimental Example PCE / % Voc / V <![CDATA[Jsc / mA·cm -2 > FF / % Example 1 19.87 1.22 20.69 78.93 Comparative Example 1 19.67 1.21 20.79 77.94

[0145] Combined with Table 1 and Figure 3 It is found that perovskite solar cell 1 provided by the embodiments of the present application has a higher fill factor and open-circuit voltage. Although the short-circuit current density is lower than that of a perovskite solar cell with conventional poly(triarylamine) (PTAA) as the hole transport material, generally speaking, perovskite solar cell 1 provided by the embodiments of the present application has a higher photoelectric conversion efficiency.

[0146] Example 2

[0147] A single-hole device is prepared. The single-hole device is composed of an ITO layer, a polymer layer (poly(2,3-dihydrothieno-[3,4-b][1,4]dioxin)-poly(styrenesulfonate), PEDOT:PSS), a PZT-1 layer (PZT-1 prepared in Example 1), a molybdenum trioxide layer (MoO3), and a silver electrode (Ag) stacked in sequence.

[0148] The space charge limited current method is used to test the hole mobility of the single-hole device. The thickness of each layer is determined by a profilometer. The J-V characteristic curve of the device is obtained by a Keithley 2450 Source-Measure instrument under dark conditions, and a non-linear fitting analysis is performed on the J-V curve. The test results are shown in Table 2.

[0149] Table 2 Hole mobility and HOMO energy level of the single-hole device

[0150] Example HOMO Energy Level / eV <![CDATA[Hole mobility / cm 2 ·V -1 ·S -1 > Example 2 -5.29 <![CDATA[4.12×10 -4 >

[0151] According to the test results in Table 2, the hole transport material PTZ-1 provided by the embodiments of the present application has a high hole mobility, which is beneficial to the extraction and transport of holes. The hole transport material PTZ-1 is matched with the perovskite and has a relatively deep HOMO energy level.

[0152] Those of ordinary skill in the art can understand that the above embodiments are specific examples for implementing the present application. In actual applications, various changes can be made in form and details without departing from the spirit and scope of the present application. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present application. Therefore, the protection scope of the present application should be subject to the scope defined by the claims.

Claims

1. A perovskite battery, characterized in that: The perovskite cell comprises a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, wherein the hole transport layer comprises a hole transport material, and the chemical formula of the hole transport material is as follows:

2. A method for preparing a perovskite battery, characterized in that: include: A hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode are sequentially formed on a transparent conductive substrate, wherein the step of preparing the hole transport layer comprises: preparing the hole transport material according to claim 1 into a solution and then coating it on the transparent conductive substrate, and the step of preparing the hole transport material is as follows: Substitution reaction of raw material I with pinacol borate to obtain a first product; The chemical formula of the raw material I is: The chemical formula of the first product is: The first product and 2,3-dibromothiophene are subjected to a Suzuki coupling reaction to obtain a second product; The chemical formula of the second product is: The second product is subjected to a substitution reaction with pinacol borate to obtain a third product; The chemical formula of the third product is: Brominating the raw material II with N-bromosuccinimide to obtain a fourth product; The chemical formula of the raw material II is: The chemical formula of the fourth product is: Performing a Suzuki coupling reaction on the third product and the fourth product to obtain a fifth product; The chemical formula of the fifth product is: The fifth product is subjected to a Witting reaction to obtain a sixth product; The chemical formula of the sixth product is: The sixth product is subjected to a free radical polymerization reaction with azobisisobutyronitrile to obtain the hole transport material.

3. The method for preparing a perovskite battery according to claim 2, characterized in that: The method for obtaining the first product comprises: The raw material I, n-butyl lithium and pinacol borate are added to tetrahydrofuran, reacted at 0°C for 1h to 1.5h, then reacted at room temperature for 10h to 16h, quenched with water, extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain the first product; wherein the molar ratio of the raw material I, n-butyl lithium and pinacol borate is 1:(1 to 1.5):(1.1 to 2).

4. The method for preparing a perovskite battery according to claim 2, characterized in that: The step of obtaining the second product comprises: The first product, 2,3-dibromothiophene, tetrakis(triphenylphosphine)palladium and potassium carbonate are added to toluene, ethanol and water in a volume ratio of 2:1:1, and reacted at 80°C to 90°C for 6h to 12h. The organic phase is extracted with dichloromethane, and the organic phase is dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the second product; wherein the molar ratio of the first product, 2,3-dibromothiophene, potassium carbonate and tetrakis(triphenylphosphine)palladium is 1:(2.2-3):(4-8):(0.01-0.1).

5. The method for preparing a perovskite battery according to claim 2, characterized in that: The method for obtaining the third product includes: The second product, n-butyl lithium and pinacol borate are added to tetrahydrofuran, reacted at 0°C for 1h to 1.5h, then reacted at room temperature for 10h to 16h, quenched with water, extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain the third product; wherein the molar ratio of the second product, n-butyl lithium and pinacol borate is 1:(1 to 1.5):(1.1 to 2).

6. The method for preparing a perovskite battery according to claim 2, characterized in that: The method for obtaining the fourth product comprises: The raw material II and N-bromosuccinimide are added to tetrahydrofuran, reacted at -5°C to 0°C for 8h to 16h, quenched with water, and the organic phase is extracted with dichloromethane. The organic phase is dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain the fourth product; wherein the molar ratio of the raw material II to N-bromosuccinimide is 1:(2.2~3).

7. The method for preparing a perovskite battery according to claim 2, characterized in that: The method for obtaining the fifth product includes: The fourth product, the third product, tetrakis(triphenylphosphine)palladium and potassium carbonate are added to toluene, ethanol and water in a volume ratio of 2:1:1, and reacted at 80°C to 90°C for 6h to 12h, and the organic phase is extracted with dichloromethane. The organic phase is dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the fifth product; wherein the molar ratio of the third product, the fourth product, potassium carbonate and tetrakis(triphenylphosphine)palladium is 1:(2.2-3):(4-8):(0.01-0.1).

8. The method for preparing a perovskite battery according to claim 2, characterized in that: The method for obtaining the sixth product includes: Potassium tert-butoxide and methyltriphenylphosphonium bromide are added to tetrahydrofuran, and after stirring at 0°C for 1h to 2h, a tetrahydrofuran solution of the fifth product is added dropwise, and the reaction is continued at 0°C for 3h to 5h. After quenching with water, the organic phase is extracted with dichloromethane, and the organic phase is dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain the sixth product.

9. A laminated battery, characterized in that: include: A top cell, wherein the top cell is the perovskite cell according to claim 1; A crystalline silicon bottom cell, wherein the crystalline silicon bottom cell is located on a side of the transparent conductive substrate of the perovskite cell away from the electrode.

10. A photovoltaic module, characterized in that: include: A plurality of stacked batteries as claimed in claim 9; A connecting component, the connecting component is used to connect adjacent stacked batteries; An adhesive film, the adhesive film covers the surface of the laminated battery; A cover plate is located on a surface of the adhesive film away from the laminated battery.

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