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 realize low-cost and high-performance stable trans-PSCs application. The perovskite cell comprises a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, the hole transport layer comprises a hole transport material, the structural formula of the hole transport material is # imgabs0 #, and A is independently an O atom or an S atom.

Description

Technical Field

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

[0002] Perovskite solar cells (PSCs) use perovskite-type organometallic halide semiconductors as light-absorbing materials, converting light energy directly into electricity through the photovoltaic effect. The structure of a perovskite solar cell primarily consists of a conductive substrate, an electron transport layer (ETL), a perovskite layer, a hole transport layer (HTL), and metal electrodes.

[0003] The hole transport layer plays a vital role in the extraction and transport of holes, the suppression of carrier recombination, and the improvement of the crystallization and film formation of perovskite materials. Therefore, the continuous development of hole transport materials (HTMs) with excellent film forming properties, solvent resistance, thermal stability and hole mobility, as well as energy levels matching those of perovskite materials, is a key factor in the preparation of efficient and stable perovskite cells. Summary of the Invention

[0004] The embodiments of the present application provide a perovskite cell and a preparation method thereof, a stacked cell, and a photovoltaic module, which are at least beneficial to improving the efficiency of the perovskite cell while reducing the cost of HTMs.

[0005] According to some embodiments of the present application, on one hand, a perovskite cell is provided. The perovskite cell includes a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode. The hole transport layer includes a hole transport material. The structure of the hole transport material is as follows:

[0006] wherein A is independently an O atom or a S atom.

[0007] According to some embodiments of the present application, another aspect of the present application further provides a method for preparing a perovskite battery, which is used to form the perovskite battery in the above embodiment, comprising: sequentially forming a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode on a substrate, wherein the step of preparing the hole transport layer comprises: configuring a hole transport material into a solution and then coating it on the substrate, and the step of preparing the hole transport material is as follows: causing a first compound to undergo an elimination reaction to generate a second compound; the structural formula of the first compound is: The structural formula of the second compound is: The second compound undergoes a substitution reaction to generate a third compound; the structural formula of the third compound is: The third compound undergoes a substitution reaction to generate a fourth compound; the fourth compound has the structural formula: The fifth compound is reacted with the sixth compound to form a seventh compound; the structural formula of the fifth compound is: wherein A is independently an O atom or a S atom; the structural formula of the sixth compound is: The structural formula of the seventh compound is: The seventh compound is reacted with pinacol diboron to generate an eighth compound; the eighth compound has the structural formula: The fourth compound is reacted with the eighth compound to form a hole transport material.

[0008] In some embodiments, the step of preparing the second compound includes: reacting the first compound with acetic anhydride at 100°C to 120°C for 16 hours to 24 hours, cooling to -5°C to 5°C after the reaction, and filtering and collecting the solid to obtain the second compound; wherein the molar ratio of the first compound to acetic anhydride is 1: (30 to 100).

[0009] In some embodiments, the step of preparing the third compound includes: adding the second compound, n-hexylamine and 4-dimethylaminopyridine to a solvent, reacting at 90°C to 100°C for 12h to 20h, then adding acetic anhydride to the mixture, continuing the reaction for 8h to 16h, cooling to 20°C to 25°C, extracting the organic phase with dichloromethane, and obtaining the third compound through drying, filtering and reduced pressure distillation; wherein the molar ratio of the second compound, n-hexylamine, 4-dimethylaminopyridine and acetic anhydride is 1:(1.1~2):(1.1~2):(20~60).

[0010] In some embodiments, the step of preparing the fourth compound includes: adding the third compound to a solvent, cooling to -5°C to 5°C and stirring for 10 min to 15 min, dissolving N-bromosuccinimide in the solvent, adding dropwise to the mixture, continuing the reaction at -5°C to 5°C for 1h to 3h, heating to 20°C to 25°C and stirring for 10h to 16h, quenching the reaction with deionized water, extracting the organic phase with dichloromethane, and obtaining the fourth compound after drying, filtering and distilling under reduced pressure; wherein, the molar ratio of the third compound to N-bromosuccinimide is 1:(2.1~4).

[0011] In some embodiments, the step of preparing the seventh compound includes: adding the fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to a solvent, reacting at 100°C to 120°C for 6h to 12h, cooling to 20°C to 25°C after the reaction, extracting the organic phase with ethyl acetate, and washing the organic phase with saturated sodium chloride, drying, filtering and distilling under reduced pressure to obtain the seventh compound; wherein the molar ratio of the fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl is 1:(0.7~1):(1.1~1.5):(0.01~0.02):(0.02~0.05).

[0012] In some embodiments, the step of preparing the eighth compound includes: adding the seventh compound to a solvent, cooling to -80°C to -70°C and stirring for 10 min to 15 min, then adding n-butyl lithium dropwise, continuing to stir at -80°C to -70°C for 1 h to 2 h, then adding diboric acid pinacol ester, continuing to stir at -80°C to -70°C for 1 h to 2 h, raising the temperature to 20°C to 25°C and reacting for 10 h to 16 h, quenching with deionized water after the reaction, extracting the organic phase with saturated sodium chloride and dichloromethane, drying, filtering and distilling under reduced pressure to obtain the eighth compound; wherein the molar ratio of the seventh compound, n-butyl lithium and diboric acid pinacol ester is 1: (1.1 to 1.3): (1.2 to 2).

[0013] In some embodiments, the step of preparing a hole transport material includes: adding a fourth compound, an eighth compound, tetrakis(triphenylphosphine)palladium and potassium carbonate to a toluene, ethanol and water solvent in a volume ratio of 2:1:1, reacting at 80°C to 90°C for 6h to 12h, cooling to 20°C to 25°C after the reaction, extracting the organic phase with dichloromethane, and obtaining a hole transport material through drying, filtering and reduced pressure distillation; wherein the molar ratio of the fourth compound, the eighth compound, tetrakis(triphenylphosphine)palladium and potassium carbonate is 1:(2~2.5):(0.03~0.07):(5~10).

[0014] According to some embodiments of the present application, another aspect of the embodiments of the present application further provides a stacked cell, comprising: a top cell, which is the perovskite cell in the above embodiment; a composite layer, which is located on the side of the hole transport layer of the perovskite cell away from the electrode; and a crystalline silicon bottom cell, which is located on the side of the composite layer away from the perovskite cell.

[0015] According to some embodiments of the present application, on the other hand, the embodiments of the present application further provide a photovoltaic module, including: a plurality of stacked cells as in the above embodiments; a connecting component, the connecting component is used to connect adjacent stacked cells; an adhesive film, the adhesive film covers the surface of the stacked cells; and a cover plate, the cover plate is located on the surface of the adhesive film away from the stacked cells.

[0016] The technical solution provided by the embodiments of the present application has at least the following advantages:

[0017] The perovskite cell provided in the embodiment of the present application includes a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, wherein the hole transport layer is prepared using the hole transport material OMe-BTTI or SMe-BTTI. The bithiophene imide (BTI) in OMe-BTTI and SMe-BTTI is an electron-deficient acceptor unit based on a strong electron-pulling imide group, and has high molecular planarity and solubility. OMe-BTTI and SMe-BTTI use BTI as the core and introduce thiopheneanilinefluorene as the end group, which effectively combines the following aspects: 1) The DA structure has intramolecular charge transfer characteristics and a large dipole moment, which is conducive to the formation of self-doping characteristics and improved hole extraction efficiency; 2) The aromatic amine unit has excellent hole transport performance, which is conducive to the molecule having a high hole mobility; 3) The planar structure of thiopheneimide is conducive to enhancing intermolecular interactions and achieving effective charge transport performance; 4) The carbonyl group in thiopheneimide can form a weak coordination effect with lead ions, which is conducive to passivating defects on the surface of the perovskite transport layer and stabilizing the performance of perovskite battery devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] One or more embodiments are exemplarily illustrated by the pictures in the corresponding drawings. These exemplified descriptions do not constitute a limitation on the embodiments. Unless otherwise stated, the pictures in the drawings do not constitute a scale limitation. In order to more clearly illustrate the embodiments of the present application or the technical solutions in the traditional technology, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 A schematic structural diagram of a perovskite battery provided in an embodiment of the present application;

[0020] Figure 2 This is the H NMR spectrum corresponding to the hole transport material OMe-BTTI provided in the examples of this application;

[0021] Figure 3 This is the H NMR spectrum corresponding to the hole transport material SMe-BTTI provided in the examples of this application;

[0022] Figure 4 A synthetic route for the hole transport material provided in the examples of this application;

[0023] Figure 5 A schematic structural diagram of a stacked battery provided in an embodiment of the present application;

[0024] Figure 6 Surface morphology SEM images and cross-sectional morphology SEM images corresponding to the ITO glass / OMe-BTTI / perovskite absorber layer provided in the embodiments of the present application;

[0025] Figure 7 The surface morphology SEM images and cross-sectional morphology SEM images corresponding to the ITO glass / SMe-BTTI / perovskite absorption layer provided in the embodiments of the present application. DETAILED DESCRIPTION

[0026] Perovskite solar cells (PSCs) have experienced rapid development in recent years. The power conversion efficiency (PCE) of devices based on the inverted structure has exceeded 25%, rivaling that of traditional silicon-based cells. While the highest PCE of inverted PSCs is lower than that of the inverted structure, they continue to attract widespread attention due to their advantages, including low-temperature solution processing, minimal hysteresis, and ease of fabrication for stacked cells.

[0027] Hole transport materials (HTMs) play a crucial role in PSCs. Compared to inorganic and polymer HTMs, organic small-molecule HTMs offer advantages such as defined molecular structure, good batch reproducibility, excellent film-forming properties, and tunable optoelectronic properties. Furthermore, in inverse PSCs, controlling film thickness allows for the fabrication of undoped devices. However, the development of small-molecule HTMs for inverse PSCs remains relatively slow.

[0028] The embodiments of the present application provide a perovskite cell and a preparation method thereof, a stacked cell and a photovoltaic module. The perovskite cell includes a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, wherein the hole transport layer is prepared using the hole transport material OMe-BTTI or SMe-BTTI. The bithiophene imide (BTI) in OMe-BTTI and SMe-BTTI is an electron-deficient acceptor unit based on a strong electron-pulling imide group, and has high molecular planarity and solubility. OMe-BTTI and SMe-BTTI use BTI as the core and introduce thiopheneanilinefluorene as the end group, which effectively combines the following aspects: 1) The DA structure has intramolecular charge transfer characteristics and a large dipole moment, which is conducive to the formation of self-doping characteristics and improved hole extraction efficiency; 2) The aromatic amine unit has excellent hole transport performance, which is conducive to the molecule having a high hole mobility; 3) The planar structure of thiopheneimide is conducive to enhancing intermolecular interactions and achieving effective charge transport performance; 4) The carbonyl group in thiopheneimide can form a weak coordination effect with lead ions, which is conducive to passivating defects on the surface of the perovskite transport layer and stabilizing the performance of perovskite battery devices.

[0029] 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 indicating the number, specific order or primary and secondary relationship of the indicated technical features.

[0030] In the description of the embodiments of the present application, “multiple” means more than two, unless otherwise clearly and specifically defined.

[0031] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0032] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists, A and B exist at the same time, and B exists. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0033] In the description of the embodiments of the present application, when a component “includes” another component, unless otherwise stated, other components are not excluded, and other components may be further included.

[0034] The terms used in the description of the various embodiments described herein are for describing specific embodiments only and are not intended to be limiting. As used in the description of the various embodiments described and the appended claims, "components" are also intended to include plural forms unless the context clearly indicates otherwise.

[0035] The following detailed description of the various embodiments of the present application is provided in conjunction with the accompanying drawings. However, those skilled in the art will appreciate that many technical details are provided in the various embodiments of the present application to facilitate a better understanding of the present application. However, even without these technical details and the various variations and modifications based on the following embodiments, the technical solutions claimed in the present application can still be implemented.

[0036] Figure 1 A schematic structural diagram of a perovskite battery provided in an embodiment of the present application.

[0037] refer to Figure 1 On the one hand, an embodiment of the present application provides a perovskite battery, which includes a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode.

[0038] The hole transport layer includes a hole transport material, and the hole transport material has the following structural formula:

[0039] wherein A is independently an O atom or a S atom.

[0040] For example, the hole transport material is OMe-BTTI, and the structural formula of OMe-BTTI is as follows:

[0041]

[0042] Alternatively, the hole transport material is SMe-BTTI, and the structural formula of SMe-BTTI is as follows:

[0043]

[0044] The material of the perovskite absorption layer can be a compound composed of A, B and X3, wherein A can be one or more of FA (HC (NH2) 2), MA (CH3NH3), Cs, Rb, B can be one or more of Pb, Sn, Sr, and X can be one or more of Br, I, Cl.

[0045] Materials for the electron transport layer include tin oxide, titanium dioxide, C60, fullerene and its derivatives.

[0046] The material of the electrode includes at least one of chromium (Cr) and gold (Au).

[0047] Figure 2This is the H NMR spectrum corresponding to the hole transport material OMe-BTTI provided in the examples of this application; Figure 3 This is the nuclear magnetic hydrogen spectrum corresponding to the hole transport material SMe-BTTI provided in the examples of this application.

[0048] The perovskite cell provided in the embodiment of the present application includes a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, wherein the hole transport layer is prepared using the hole transport material OMe-BTTI or SMe-BTTI. The bithiophene imide (BTI) in OMe-BTTI and SMe-BTTI is an electron-deficient acceptor unit based on a strong electron-pulling imide group, and has high molecular planarity and solubility. OMe-BTTI and SMe-BTTI use BTI as the core and introduce thiopheneanilinefluorene as the end group, which effectively combines the following aspects: 1) The DA structure has intramolecular charge transfer characteristics and a large dipole moment, which is conducive to the formation of self-doping characteristics and improved hole extraction efficiency; 2) The aromatic amine unit has excellent hole transport performance, which is conducive to the molecule having a high hole mobility; 3) The planar structure of thiopheneimide is conducive to enhancing intermolecular interactions and achieving effective charge transport performance; 4) The carbonyl group in thiopheneimide can form a weak coordination effect with lead ions, which is conducive to passivating defects on the surface of the perovskite transport layer and stabilizing the performance of perovskite battery devices.

[0049] Accordingly, another embodiment of the present application further provides a method for preparing a perovskite battery, which is used to form the perovskite battery in the above embodiment, comprising: sequentially forming a hole transport layer, a perovskite absorption layer, an electron transport layer, and an electrode on a substrate. The specific steps are as follows:

[0050] S11, cleaning step: ultrasonically clean the substrate with deionized water, acetone and ethanol in sequence, blow dry the substrate and treat it in a UV-ozone cleaner, and then transfer the substrate to a nitrogen glove box.

[0051] If a separate perovskite cell is prepared, the substrate material includes ITO glass. ITO glass is made by coating a layer of indium tin oxide (commonly known as ITO) film on a soda-lime-based or silicon boron-based substrate glass using a magnetron sputtering method.

[0052] If a stacked cell is prepared, the substrate may include a crystalline silicon bottom cell and a composite layer, and the subsequently formed hole transport layer is located on a side of the composite layer away from the crystalline silicon bottom cell.

[0053] Crystalline silicon bottom cells include any one of PERC cells (Passivated Emitter and Rear Cell, emitter and rear passivated cells), PERT cells (Passivated Emitter and Rear Totally-diffused cell, passivated emitter rear surface fully diffused cells), TOPCon cells (Tunnel Oxide Passivated Contact, tunnel oxide passivated contact cells), HIT / HJT cells (Heterojunction Technology, heterojunction cells) or BC cells (Back Contact, back contact cells). Crystalline silicon bottom cells also include single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells or multi-compound solar cells, and multi-compound solar cells can specifically be cadmium sulfide solar cells, gallium arsenide solar cells, copper indium selenide solar cells or perovskite solar cells.

[0054] The composite layer is made of a transparent conductive oxide (TCO) to provide lateral conductivity and transmit light, such as indium tin oxide (ITO), hydrogenated indium oxide (IO:H), or zinc oxide (ZnO).

[0055] S12. Prepare a hole transport layer: dissolve the hole transport material OMe-BTTI or SMe-BTTI in chlorobenzene solution, add an appropriate amount of the mixed solution dropwise onto the substrate, spin coat with a coater for 20s to 30s, and anneal at 90°C to 100°C for 10min.

[0056] S13. Preparation of perovskite absorption layer: Cool the substrate with hole transport layer to 20℃~25℃, dissolve 0.075mmol of CsI, 1.098mmol of FAI, 0.327mmol of MABr, 0.354mmol of PbBr2 and 1.146mmol of PbI2 in 1mL of DMF:DMSO (volume ratio 4:1) mixed solvent to prepare 1.5M perovskite precursor solution, the corresponding chemical formula is Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 )3 (wide band gap of 1.68 eV), spin coating at 3000 rpm ~ 4000 rpm for 30 seconds ~ 40 seconds, 5 seconds ~ 7 seconds before the end of spin coating, add 150 microliters ~ 200 microliters of ethyl acetate (EA) as anti-solvent to the center of the film, and then immediately transfer the transparent conductive substrate to a heating stage and anneal at 90 ° C ~ 100 ° C for 10 minutes.

[0057] S14, preparing the electron transport layer: cooling the substrate with the perovskite absorption layer to 20°C to 25°C, and -4 Pa) and thermally evaporate 13nm~30nm of C60 at a deposition rate of

[0058] S15, preparation of hole blocking layer: in high vacuum (5×10 -4 Pa) thermal evaporation of 5nm to 10nm of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) at a deposition rate of

[0059] S16. Prepare the electrode: Place the substrate with the hole blocking layer in a vacuum deposition chamber, put in a mask, and sequentially deposit Cr (5nm to 8nm) and Cu (70nm to 90nm) using a thermal evaporation system.

[0060] The preparation method of the perovskite battery provided in the embodiment of the present application uses the hole transport material OMe-BTTI or SMe-BTTI to prepare the hole transport layer. The hole transport material OMe-BTTI or SMe-BTTI has good solubility in organic solvents and good film-forming properties. It has good wettability with the perovskite precursor solvent, which is helpful for the crystallization and film formation of the perovskite.

[0061] Figure 4 This is a synthetic route for the hole transport material provided in the examples of this application.

[0062] refer to Figure 4 The preparation steps of hole transport material OMe-BTTI or SMe-BTTI are as follows:

[0063] S21, make (First compound) undergoes elimination reaction to generate (Second compound).

[0064] The step of preparing the second compound includes: reacting the first compound with acetic anhydride at 100° C. to 120° C. for 16 hours to 24 hours, cooling to -5° C. to 5° C. after the reaction is completed, and filtering and collecting the solid to obtain the second compound.

[0065] The molar ratio of the first compound to acetic anhydride is 1:(30-100).

[0066] S22, causing the second compound to undergo a substitution reaction to generate (Third compound).

[0067] The steps of preparing the third compound include: adding the second compound, n-hexylamine and 4-dimethylaminopyridine to a solvent, reacting at 90°C to 100°C for 12 hours to 20 hours, then adding acetic anhydride to the mixture, continuing the reaction for 8 hours to 16 hours, cooling to 20°C to 25°C, extracting the organic phase with dichloromethane, and obtaining the third compound through drying, filtering and reduced pressure distillation.

[0068] The molar ratio of the second compound, n-hexylamine, 4-dimethylaminopyridine and acetic anhydride is 1:(1.1-2):(1.1-2):(20-60).

[0069] In some embodiments, the preparation of the third compound further comprises purifying the third compound by column chromatography, wherein the eluent of the column chromatography is petroleum ether and dichloromethane in a volume ratio of 3:1.

[0070] S23, causing the third compound to undergo a substitution reaction to generate (Fourth compound).

[0071] The steps of preparing the fourth compound include: adding the third compound to a solvent, cooling to -5°C to 5°C and stirring for 10 minutes to 15 minutes, dissolving N-bromosuccinimide in the solvent, adding dropwise to the mixture, continuing to react at -5°C to 5°C for 1 hour to 3 hours, heating to 20°C to 25°C and stirring for 10 hours to 16 hours, quenching the reaction with deionized water, extracting the organic phase with dichloromethane, and obtaining the fourth compound through drying, filtering and reduced pressure distillation.

[0072] The molar ratio of the third compound to N-bromosuccinimide is 1:(2.1-4).

[0073] In some embodiments, after preparing the fourth compound, the method further comprises purifying the fourth compound by flash chromatography, wherein the eluent of the flash chromatography is petroleum ether and dichloromethane in a ratio of 10:1.

[0074] S24, make (Fifth compound) and (Sixth compound) reacts to produce (Seventh compound) wherein each A is independently an O atom or a S atom.

[0075] The steps of preparing the seventh compound include: adding the fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to a solvent, reacting at 100°C to 120°C for 6h to 12h, cooling to 20°C to 25°C after the reaction, extracting the organic phase with ethyl acetate, washing the organic phase with saturated sodium chloride, and obtaining the seventh compound through drying, filtering and reduced pressure distillation.

[0076] The molar ratio of the fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl is 1:(0.7-1):(1.1-1.5):(0.01-0.02):(0.02-0.05).

[0077] In some embodiments, after preparing the seventh compound, the method further comprises purifying the seventh compound by column chromatography, wherein the eluent of the column chromatography is petroleum ether and dichloromethane in a volume ratio of 4:1.

[0078] S25, reacting the seventh compound with diboric acid pinacol ester to generate (Eighth compound).

[0079] The steps of preparing the eighth compound include: adding the seventh compound to a solvent, cooling to -80°C to -70°C and stirring for 10 minutes to 15 minutes, then adding n-butyl lithium dropwise, continuing to stir at -80°C to -70°C for 1 hour to 2 hours, then adding biboric acid pinacol ester, continuing to stir at -80°C to -70°C for 1 hour to 2 hours, raising the temperature to 20°C to 25°C and reacting for 10 hours to 16 hours, quenching with deionized water after the reaction is completed, extracting the organic phase with saturated sodium chloride and dichloromethane, and obtaining the eighth compound through drying, filtering and reduced pressure distillation.

[0080] The molar ratio of the seventh compound, n-butyl lithium and biboronic acid pinacol ester is 1: (1.1-1.3): (1.2-2).

[0081] In some embodiments, after preparing the eighth compound, the eighth compound is further purified by column chromatography, and the eluent of the column chromatography is petroleum ether and dichloromethane in a ratio of 15:1.

[0082] S26 , reacting the fourth compound with the eighth compound to generate a hole transport material OMe-BTTI or SMe-BTTI.

[0083] The steps of preparing the hole transport material include: adding the fourth compound, the eighth compound, tetrakis(triphenylphosphine)palladium and potassium carbonate to a toluene, ethanol and water solvent with a volume ratio of 2:1:1, reacting at 80°C to 90°C for 6h to 12h, cooling to 20°C to 25°C after the reaction, extracting the organic phase with dichloromethane, and obtaining the hole transport material through drying, filtering and reduced pressure distillation.

[0084] The molar ratio of the fourth compound, the eighth compound, tetrakistriphenylphosphine palladium and potassium carbonate is 1:(2-2.5):(0.03-0.07):(5-10).

[0085] In some embodiments, after preparing the hole transport material, the hole transport material is further purified by column chromatography. When the hole transport material is OMe-BTTI, the eluent of the column chromatography is 6:1 petroleum ether and dichloromethane; when the hole transport material is SMe-BTTI, the eluent of the column chromatography is 3:1 petroleum ether and dichloromethane.

[0086] The preparation method of the hole transport material OMe-BTTI or SMe-BTTI provided in the embodiments of the present application has low raw material cost, simple preparation process, and is suitable for industrial production.

[0087] Figure 5 A schematic structural diagram of a stacked battery provided in an embodiment of the present application.

[0088] Correspondingly, another aspect of the embodiment of the present application further provides a stacked cell, including: a top cell 100, the top cell 100 is the perovskite cell in the above embodiment, the perovskite cell includes a hole transport layer 103, a perovskite absorption layer 101, an electron transport layer 102 and an electrode 104; a composite layer 300, the composite layer 300 is located on the side of the hole transport layer 103 of the perovskite cell away from the electrode 104; a crystalline silicon bottom cell 200, the crystalline silicon bottom cell 200 is located on the side of the composite layer 300 away from the perovskite cell, and a bottom electrode 201 can be provided on the surface of the crystalline silicon bottom cell 200 away from the composite layer 300.

[0089] The crystalline silicon bottom cell 200 also includes a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell or a multi-compound solar cell. The multi-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.

[0090] The composite layer 300 is made of a transparent conductive oxide (TCO) to provide lateral conductivity and transmit light, such as indium tin oxide (ITO), hydrogenated indium oxide (IO:H), or zinc oxide (ZnO).

[0091] According to some embodiments of the present application, on the other hand, the embodiments of the present application further provide a photovoltaic module, including: a plurality of stacked cells as in the above embodiments; a connecting component, the connecting component is used to connect adjacent stacked cells; an adhesive film, the adhesive film covers the surface of the stacked cells; and a cover plate, the cover plate is located on the surface of the adhesive film away from the stacked cells.

[0092] The connecting components include interconnecting ribbons and busbar ribbons. The interconnecting ribbons are tin-coated ribbons used to connect the laminated batteries, collect and transmit the current of the laminated batteries; the busbar ribbons are tin-coated ribbons used to connect the laminated battery strings and junction boxes, and transmit the current of the laminated battery strings.

[0093] The adhesive film may be an organic encapsulation film such as an ethylene-vinyl acetate copolymer (EVA) film, a polyethylene octene co-elastomer (POE) film or a polyvinyl butyral (PVB) film.

[0094] The cover plate can be a glass cover plate, a plastic cover plate, or other light-transmitting cover plate. In some embodiments, the surface of the cover plate facing the encapsulation layer can be a concave-convex surface, thereby increasing the utilization rate of the incident light.

[0095] The following are specific embodiments of this application:

[0096] Example 1

[0097] Preparation of hole transport material OMe-BTTI:

[0098] S31, 1.1g (Compound 1) was reacted with 4 mL of acetic anhydride at 120°C for 16 h. After the reaction, the mixture was cooled to 0°C, the solid was collected by filtration and dried by distillation under reduced pressure to obtain (Second compound), yield 83%.

[0099] S32, 0.7 g of the second compound, 6 mL of n-hexylamine and 0.55 g of 4-dimethylaminopyridine were added to 40 mL of 1,4-dioxane, and the mixture was reacted at 90 ° C for 12 h, and then 40 mL of acetic anhydride was added to the mixture, and the reaction was continued for 12 h. After cooling to 25 ° C, the organic phase was extracted with dichloromethane, and dried, filtered and distilled under reduced pressure to obtain (Third compound) The third compound was purified by column chromatography using petroleum ether and dichloromethane in a volume ratio of 3:1 to obtain the purified third compound with a yield of 87%.

[0100] S33, add 1.3g of the third compound to 30mL of dichloromethane, cool to 0℃ and stir for 10min, dissolve 2.13g of N-bromosuccinimide in dichloromethane, add dropwise to the mixture, continue to react at 0℃ for 1h, heat to 25℃ and stir for 16h, quench the reaction with deionized water, extract the organic phase with dichloromethane, dry, filter and distill under reduced pressure to obtain (Fourth compound) The fourth compound was purified by flash chromatography using petroleum ether and dichloromethane in a volume ratio of 10:1 to obtain the purified fourth compound in a yield of 91%.

[0101] S34, 1.61g (Fifth compound), 1.02 g (Sixth compound), 0.61 g of sodium tert-butoxide, 0.077 g of tris(dibenzylideneacetone)dipalladium and 0.081 g of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl were added to 30 mL of toluene, and the mixture was reacted at 110° C. for 8 h. After the reaction was completed, the mixture was cooled to 25° C., the organic phase was extracted with ethyl acetate, and the organic phase was washed three times with saturated sodium chloride. The mixture was dried, filtered and distilled under reduced pressure to obtain (Seventh compound) The seventh compound was purified using petroleum ether and dichloromethane in a volume ratio of 4:1 to obtain the purified seventh compound with a yield of 73%.

[0102] S35, 4.74g of the seventh compound was added to 30mL of tetrahydrofuran, cooled to -78 °C and stirred for 10min, then 3.75mL of n-butyl lithium was added dropwise, and the mixture was continued to be stirred at -78 °C for 1h, then 2.75mL of biboric acid pinacol ester was added, and the mixture was continued to be stirred at -78 °C for 1h, the temperature was raised to 25 °C and the reaction was continued for 12h, and after the reaction was completed, the mixture was quenched with deionized water, and the organic phase was extracted with saturated sodium chloride and dichloromethane, and the mixture was dried, filtered and distilled under reduced pressure to obtain (Eighth Compound) The eighth compound was purified using petroleum ether and dichloromethane in a volume ratio of 15:1 to obtain the purified eighth compound with a yield of 80%.

[0103] S36. Add 0.48 g of the fourth compound, 1.29 g of the eighth compound, 58 mg of tetrakis(triphenylphosphine)palladium, and 0.98 g of potassium carbonate to a solvent of toluene, ethanol, and water in a volume ratio of 2:1:1. The mixture was reacted at 85°C for 6 h. After the reaction, the mixture was cooled to 25°C. The organic phase was extracted with dichloromethane, dried, filtered, and distilled under reduced pressure to obtain the hole transport material OMe-BTTI. The OMe-BTTI was purified using petroleum ether and dichloromethane in a volume ratio of 6:1 to obtain purified OMe-BTTI in a yield of 54%.

[0104] Example 2

[0105] Preparation of hole transport material SMe-BTTI:

[0106] S41, 1.1g (Compound 1) was reacted with 4 mL of acetic anhydride at 120°C for 16 h. After the reaction, the mixture was cooled to 0°C, the solid was collected by filtration and dried by distillation under reduced pressure to obtain (Second compound), yield 83%.

[0107] S42, 0.7 g of the second compound, 6 mL of n-hexylamine and 0.55 g of 4-dimethylaminopyridine were added to 40 mL of 1,4-dioxane, and the mixture was reacted at 90 ° C for 12 h, and then 40 mL of acetic anhydride was added to the mixture, and the reaction was continued for 12 h. After cooling to 25 ° C, the organic phase was extracted with dichloromethane, and dried, filtered and distilled under reduced pressure to obtain (Third compound) The third compound was purified by column chromatography using petroleum ether and dichloromethane in a volume ratio of 3:1 to obtain the purified third compound with a yield of 87%.

[0108] S43, add 1.3g of the third compound to 30mL of dichloromethane, cool to 0℃ and stir for 10min, dissolve 2.13g of N-bromosuccinimide in dichloromethane, add dropwise to the mixture, continue to react at 0℃ for 1h, heat to 25℃ and stir for 16h, quench the reaction with deionized water, extract the organic phase with dichloromethane, dry, filter and distill under reduced pressure to obtain (Fourth compound) The fourth compound was purified by flash chromatography using petroleum ether and dichloromethane in a volume ratio of 10:1 to obtain the purified fourth compound in a yield of 91%.

[0109] S44, 1.7g (Fifth compound), 1.02 g (Sixth compound), 0.61 g of sodium tert-butoxide, 0.077 g of tris(dibenzylideneacetone)dipalladium and 0.081 g of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl were added to 30 mL of toluene, and the mixture was reacted at 110° C. for 8 h. After the reaction was completed, the mixture was cooled to 25° C., the organic phase was extracted with ethyl acetate, and the organic phase was washed three times with saturated sodium chloride. The mixture was dried, filtered and distilled under reduced pressure to obtain (Seventh compound) The seventh compound was purified using petroleum ether and dichloromethane in a volume ratio of 4:1 to obtain the purified seventh compound with a yield of 70%.

[0110] S45, 4.9g of the seventh compound was added to 30mL of tetrahydrofuran, cooled to -78°C and stirred for 10min, then 3.75mL of n-butyl lithium was added dropwise, and the mixture was continued to be stirred at -78°C for 1h, then 2.75mL of biboric acid pinacol ester was added, and the mixture was continued to be stirred at -78°C for 1h, the temperature was raised to 25°C and the reaction was continued for 12h, and after the reaction was completed, the mixture was quenched with deionized water, and the organic phase was extracted with saturated sodium chloride and dichloromethane, and the mixture was dried, filtered and distilled under reduced pressure to obtain (Eighth Compound) The eighth compound was purified using petroleum ether and dichloromethane in a volume ratio of 15:1 to obtain the purified eighth compound with a yield of 83%.

[0111] S46. Add 0.48 g of the fourth compound, 1.33 g of the eighth compound, 58 mg of tetrakis(triphenylphosphine)palladium, and 0.98 g of potassium carbonate to a solvent of toluene, ethanol, and water in a volume ratio of 2:1:1. The mixture was reacted at 85°C for 6 h. After the reaction, the mixture was cooled to 25°C. The organic phase was extracted with dichloromethane, dried, filtered, and distilled under reduced pressure to obtain the hole transport material SMe-BTTI. The SMe-BTTI was purified using petroleum ether and dichloromethane in a volume ratio of 3:1 to obtain purified SMe-BTTI in a yield of 51%.

[0112] Perovskite cell 1 was prepared using OMe-BTTI, and perovskite cell 2 was prepared using SMe-BTTI. The structures of perovskite cell 1 and perovskite cell 2 are basically the same, except that the hole transport layers of perovskite cell 1 and perovskite cell 2 are prepared using OMe-BTTI and SMe-BTTI, respectively.

[0113] At 20℃ to 30℃, 1 atmosphere, under standard simulated sunlight (AM 1.5G, 100mW / cm 2 ) irradiation, the performance of perovskite cell 1 and perovskite cell 2 was tested to obtain IV curves (volt-ampere characteristic curves). Based on the IV curves and the data feedback from the test equipment (four-channel digital source meter, Keithley 2440), the short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF), and photoelectric conversion efficiency (PCE1) were calculated. After storing perovskite cell 1 and perovskite cell 2 in an inert environment for 1200 hours, the photoelectric conversion efficiency (PCE2) of perovskite cell 1 and perovskite cell 2 was tested to characterize the stability of perovskite cell 1 and perovskite cell 2 (PCE2 / PCE1) × 100%. The test results are shown in Table 1.

[0114] Table 1

[0115]

[0116] According to the test results in Table 1, the perovskite cell produced by using the hole transport materials OMe-BTTI and SMe-BTTI provided in the embodiments of the present application as the hole transport layer has good performance.

[0117] Single-hole device 1 and single-hole device 2 were prepared. Single-hole device 1 was composed of an ITO layer, a polymer layer (poly(2,3-dihydrothieno-1,4-dioxin-poly(styrenesulfonate), PEDOT:PSS), an OMe-BTTI layer, a molybdenum trioxide layer (MoO3) and a silver electrode (Ag) stacked in sequence; single-hole device 2 was composed of an ITO layer, a polymer layer (poly(2,3-dihydrothieno-1,4-dioxin-poly(styrenesulfonate), PEDOT:PSS), an SMe-BTTI layer, a molybdenum trioxide layer (MoO3) and a silver electrode (Ag) stacked in sequence.

[0118] The hole mobility of single-hole device 1 and single-hole device 2 was tested using the space charge limited current method. The JV characteristic curves of the devices were obtained using a Keithley 2450 Source-Measure instrument under dark conditions. The hole mobility of single-hole device 1 and single-hole device 2 was obtained by performing nonlinear fitting analysis on the JV characteristic curves.

[0119] The HOMO energy levels of the hole-transport materials OMe-BTTI and SMe-BTTI were measured by dissolving 5 mg of OMe-BTTI or SMe-BTTI in a 0.1 M solution of tetrabutylammonium hexafluorophosphate (Bu4NPF6) in dichloromethane. Calibration was performed using ferrocene as an external standard. Cyclic voltammetry (CV) curves were obtained on an electrochemical workstation at a purge rate of 0.01 V / s. The redox potentials of the curves were analyzed to calculate the HOMO energy levels of OMe-BTTI or SMe-BTTI.

[0120] The hole mobility and HOMO energy levels of OMe-BTTI and SMe-BTTI are shown in Table 2.

[0121] Table 2

[0122] hole transport materials HOMO energy level / eV <![CDATA[Hole mobility / cm 2 ·V -1 ·S -1 > OMe-BTTI -5.25 <![CDATA[6.59×10 -5 ]]> SMe-BTTI -5.29 <![CDATA[8.96×10 -5 ]]>

[0123] According to the test results in Table 2, the HOMO energy levels of OMe-BTTI and SMe-BTTI match the energy levels of wide-bandgap perovskite materials, and can form good ohmic contacts, which is conducive to hole transport.

[0124] To further investigate the effects of OMe-BTTI and SMe-BTTI on wide-bandgap perovskite crystal growth, the present invention also uses scanning electron microscopy (SEM) to characterize the growth of wide-bandgap perovskite films grown on the surface of hole transport layers prepared with OMe-BTTI and SMe-BTTI. Hole transport layers prepared with OMe-BTTI and SMe-BTTI were formed on ITO glass, respectively, and perovskite absorber layers were formed on the hole transport layers. The surface formation of the perovskite absorber layers on OMe-BTTI and SMe-BTTI, as well as the cross-sectional morphology of the ITO glass / hole transport layer / perovskite absorber layer, were captured using SEM.

[0125] Figure 6 Surface morphology SEM images and cross-sectional morphology SEM images corresponding to the ITO glass / OMe-BTTI / perovskite absorber layer provided in the embodiments of the present application; Figure 7 The surface morphology SEM image and cross-sectional morphology SEM image of the ITO glass / SMe-BTTI / perovskite absorption layer provided in the embodiment of the present application. Figure 6 (A) is the surface morphology SEM image of the perovskite absorber layer in ITO glass / OMe-BTTI / perovskite absorber layer; Figure 6 (B) is the cross-sectional SEM image of the ITO glass / OMe-BTTI / perovskite absorber layer; Figure 7 (A) is the surface morphology SEM image of the perovskite absorber layer in ITO glass / SMe-BTTI / perovskite absorber layer; Figure 7 (B) is the cross-sectional morphology SEM image of the ITO glass / SMe-BTTI / perovskite absorption layer.

[0126] according to Figure 6 and Figure 7 It can be observed that when a perovskite absorption layer is formed on the hole transport layer prepared with OMe-BTTI and SMe-BTTI as hole transport materials, the crystal size of the perovskite absorption layer is relatively uniform and tightly arranged, without obvious boundary defects, indicating that the hole transport layer prepared with OMe-BTTI and SMe-BTTI as hole transport materials can promote the crystallization growth of the perovskite absorption layer, and is beneficial for the perovskite absorption layer to completely cover the hole transport layer, which is beneficial to suppressing the charge recombination defects caused by direct contact between the electron transport layer and the hole transport layer.

[0127] Those skilled in the art will appreciate that the above-described embodiments are specific examples for implementing the present application, and that in actual applications, various changes in form and detail may be made thereto without departing from the spirit and scope of the present application. Any person skilled in the art may make various changes and modifications without departing from the spirit and scope of the present application. Therefore, the scope of protection of the present application shall be based on the scope defined in the claims.

Claims

1. A perovskite battery, characterized in that: The perovskite cell includes a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode, wherein the hole transport layer includes a hole transport material, and the structural formula of the hole transport material is as follows: wherein A is independently an O atom or a S atom.

2. A method for preparing a perovskite battery, for forming the perovskite battery according to claim 1, characterized in that: include: The hole transport layer, the perovskite absorption layer, the electron transport layer and the electrode are sequentially formed on a substrate, wherein the step of preparing the hole transport layer comprises: preparing the hole transport material into a solution and then coating the solution on the substrate, and the step of preparing the hole transport material is as follows: causing the first compound to undergo an elimination reaction to generate a second compound; The structural formula of the first compound is: The structural formula of the second compound is: causing the second compound to undergo a substitution reaction to generate a third compound; The structural formula of the third compound is: subjecting the third compound to a substitution reaction to produce a fourth compound; The structural formula of the fourth compound is: reacting the fifth compound with the sixth compound to produce a seventh compound; The structural formula of the fifth compound is: Wherein, A is independently an O atom or a S atom; the structural formula of the sixth compound is: The structural formula of the seventh compound is: reacting the seventh compound with pinacol diboronate to form an eighth compound; The structural formula of the eighth compound is: The fourth compound is reacted with the eighth compound to generate the hole transport material.

3. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the second compound include: The first compound and acetic anhydride are reacted at 100°C to 120°C for 16 hours to 24 hours, cooled to -5°C to 5°C after the reaction, and the solid is collected by filtration to obtain the second compound; wherein the molar ratio of the first compound to acetic anhydride is 1: (30～100)。 4. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the third compound include: The second compound, n-hexylamine and 4-dimethylaminopyridine are added to a solvent, reacted at 90°C to 100°C for 12h to 20h, then acetic anhydride is added to the mixture, the reaction is continued for 8h to 16h, and the organic phase is extracted with dichloromethane after cooling to 20°C to 25°C. The third compound is obtained by drying, filtering and distillation under reduced pressure; wherein the molar ratio of the second compound, n-hexylamine, 4-dimethylaminopyridine and acetic anhydride is 1:(1.1~2):(1.1~2):(20~60).

5. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the fourth compound include: The third compound is added to a solvent, cooled to -5°C to 5°C and stirred for 10 min to 15 min, N-bromosuccinimide is dissolved in the solvent and added dropwise to the mixture, and the reaction is continued at -5°C to 5°C for 1 h to 3 h. The temperature is raised to 20°C to 25°C and stirred for 10 h to 16 h. The reaction is quenched with deionized water, and the organic phase is extracted with dichloromethane. The fourth compound is obtained after drying, filtering and distillation under reduced pressure; wherein the molar ratio of the third compound to N-bromosuccinimide is 1:(2.1~4).

6. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the seventh compound include: The fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl are added to a solvent, reacted at 100° C. to 120° C. for 6 h to 12 h, cooled to 20° C. to 25° C. after the reaction, extracted with ethyl acetate, and washed with saturated sodium chloride, dried, filtered and distilled under reduced pressure to obtain the seventh compound; wherein the molar ratio of the fifth compound, the sixth compound, sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl is 1:(0.7-1): (1.1～1.5)：(0.01～0.02)：(0.02～0.05)。 7. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the eighth compound include: The seventh compound is added to a solvent, cooled to -80°C to -70°C and stirred for 10 min to 15 min, then n-butyl lithium is added dropwise, and the mixture is stirred at -80°C to -70°C for 1 h to 2 h, then biboric acid pinacol ester is added, and the mixture is stirred at -80°C to -70°C for 1 h to 2 h, the temperature is raised to 20°C to 25°C, and the reaction is carried out for 10 h to 16 h. After the reaction is completed, the mixture is quenched with deionized water, and the organic phase is extracted with saturated sodium chloride and dichloromethane, and the organic phase is dried, filtered, and distilled under reduced pressure to obtain the eighth compound; wherein the molar ratio of the seventh compound, n-butyl lithium, and biboric acid pinacol ester is 1: (1.1 to 1.3): (1.2～2)。 8. The method for preparing a perovskite battery according to claim 2, wherein: The steps of preparing the hole transport material include: The fourth compound, the eighth compound, tetrakis(triphenylphosphine)palladium and potassium carbonate are added to a toluene, ethanol and water solvent in a volume ratio of 2:1:1, and reacted at 80°C to 90°C for 6h to 12h. After the reaction, the mixture is cooled to 20°C to 25°C, and the organic phase is extracted with dichloromethane. The organic phase is dried, filtered and distilled under reduced pressure to obtain the hole transport material; wherein the molar ratio of the fourth compound, the eighth compound, tetrakis(triphenylphosphine)palladium and potassium carbonate is 1:(2-2.5): (0.03～0.07)：(5～10)。 9. A laminated battery, characterized in that: include: A top cell, wherein the top cell is the perovskite cell according to claim 1; a composite layer, the composite layer being located on a side of the hole transport layer of the perovskite cell away from the electrode; A crystalline silicon bottom cell is located on a side of the composite layer away from the perovskite cell.

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 covering the surface of the laminated battery; A cover plate is located on a surface of the adhesive film away from the laminated battery.

Images