Perovskite solar cells and their preparation methods, tandem solar cells and photovoltaic modules

Abstract

This application relates to a perovskite solar cell, its fabrication method, a tandem solar cell, and a photovoltaic module. The perovskite solar cell includes a first electrode, a hole transport layer, a perovskite light-absorbing layer, and a second electrode. The hole transport layer is located between the first electrode and the perovskite light-absorbing layer, and between the hole transport layer and the second electrode. The hole transport layer comprises a compound shown in formula (I). This perovskite solar cell uses the compound shown in formula (I) as the hole transport layer material. The compound shown in formula (I) is a polymer, and its monomers are based on indolo[3,2-b]carbazole, with fluorine-substituted benzothiadiazole groups and phosphonic acid groups introduced. This can passivate defects in the perovskite light-absorbing layer, suppress interfacial electron recombination, and enable the perovskite solar cell to achieve better photoelectric conversion efficiency.

Description

Technical Field

[0001] This application relates to the field of photovoltaic technology, and in particular to perovskite solar cells and their preparation methods, tandem solar cells and photovoltaic modules. Background Technology

[0002] Perovskite solar cells have become a research hotspot in next-generation photovoltaic technology due to their high photoelectric conversion efficiency and low fabrication cost. The hole transport layer, as a key component, plays a crucial role in promoting perovskite nucleation and charge extraction and transport, significantly impacting device efficiency. However, traditional hole transport materials suffer from poor energy level matching and low carrier mobility, easily leading to charge recombination and consequently, low photoelectric conversion efficiency in perovskite solar cells. Therefore, it is necessary to improve traditional technologies. Summary of the Invention

[0003] Based on this, this application provides a perovskite solar cell with high photoelectric conversion efficiency, its preparation method, a tandem solar cell, and a photovoltaic module.

[0004] The technical solution to the above-mentioned technical problems in this application is as follows.

[0005] This application provides a perovskite solar cell, comprising a first electrode, a hole transport layer, a perovskite light-absorbing layer, and a second electrode. The hole transport layer is located between the first electrode and the perovskite light-absorbing layer, and the perovskite light-absorbing layer is located between the hole transport layer and the second electrode. The hole transport layer comprises a compound of formula (I):

[0006]

[0007] in:

[0008] R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine;

[0009] L is selected from C2~C6 alkylene groups;

[0010] m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups.

[0011] The beneficial effects of the perovskite solar cell of this application are as follows: The compound shown in Formula (I) is used as the hole transport layer material. The compound shown in Formula (I) is a polymer, whose polymer monomer is based on indolo[3,2-b]carbazole, with fluorine-substituted benzothiadiazole groups introduced, which can improve the charge mobility of the polymer; the introduction of phosphonic acid groups allows the phosphorus-oxygen double bond in the phosphonic acid groups to interact with the perovskite, passivating defects in the perovskite light-absorbing layer; simultaneously, the polymer has high HOMO and LUMO energy levels, which can block electrons from jumping from the perovskite layer to the hole transport layer, thereby effectively suppressing the occurrence of interfacial electron recombination; these multiple interactions enable the perovskite solar cell to achieve better photoelectric conversion efficiency.

[0012] A second aspect of this application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0013] A hole transport layer is fabricated on the first electrode;

[0014] A perovskite light-absorbing layer is prepared on the side of the hole transport layer away from the first electrode;

[0015] A second electrode is fabricated on the side of the perovskite light-absorbing layer away from the hole transport layer;

[0016] The hole transport layer comprises the compound shown in formula (I):

[0017]

[0018] in:

[0019] R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine;

[0020] L is selected from C2~C6 alkylene groups;

[0021] m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups;

[0022] n is 10 to 500.

[0023] The third aspect of this application provides a tandem solar cell, including a perovskite solar cell prepared by the preparation method of the perovskite solar cell provided in the first aspect or the perovskite solar cell provided in the second aspect.

[0024] The fourth aspect of this application provides a photovoltaic module, including the perovskite cell provided in the first aspect, the perovskite cell prepared by the method for preparing the perovskite cell provided in the second aspect, or the tandem cell provided in the third aspect. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 A schematic diagram of the structure of an inverted perovskite solar cell provided in one embodiment;

[0027] Figure 2 A schematic diagram of a stacked battery provided in one embodiment;

[0028] Figure 3 A proton spectrum of the compound of formula (I) provided in one embodiment;

[0029] Figure 4 A surface morphology diagram of a perovskite thin film prepared on the compound of formula (I) provided in one embodiment;

[0030] Figure 5 A cross-sectional morphology diagram of a perovskite thin film prepared on the compound of formula (I) provided in one embodiment.

[0031] Figure label:

[0032] 100: Inverted perovskite solar cell; 110: First electrode; 120: Hole transport layer; 130: Perovskite light-absorbing layer; 140: Electron transport layer; 150: Second electrode;

[0033] 200: Stacked cell; 210: Bottom cell; 220: Top cell; 230: Intermediate connecting layer; 240: Back electrode;

[0034] 221: Hole transport layer; 222: Perovskite light-absorbing layer; 223: Electron transport layer; 224: Hole blocking layer; 225: Transparent conductive layer; 226: Anti-reflection layer; 227: Metal electrode. Detailed Implementation

[0035] The present application will be further described in detail below with reference to the embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive.

[0036] It should also be understood that this application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various alterations or modifications without departing from the spirit of this application, and the resulting equivalent forms also fall within the protection scope of this application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of this application; it should be understood that this application can be implemented without one or more of these details.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.

[0038] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0039] In this application, the terms "multiple", "various", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0040] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0041] In this document, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0042] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0043] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0044] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0045] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0046] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0047] In this application, the terms "room temperature" or "normal temperature" generally refer to 4℃ to 35℃, for example, 20℃ ± 5℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10℃ to 30℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20℃ to 30℃.

[0048] In this application, if the unit of a data range is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0049] The mass or weight of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass or weight mentioned in the embodiments of this application can be units known in the chemical industry, such as μg, mg, g, and kg.

[0050] In the accompanying drawings, the thicknesses of layers, films, regions, substrates, etc., are exaggerated for clarity. Throughout the specification, the same reference numerals refer to the same elements. It should be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element or there may be intervening elements. Conversely, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0051] In this application, "substituted or unsubstituted" means that the hydrogen atom in the group is substituted by a substituent, and "unsubstituted" means that the hydrogen atom in the group is not substituted by other atoms or groups. For example, "substituted or unsubstituted C1~C 10 "alkyl" in "C1~C 10 The number of carbon atoms in "alkyl" does not include the number of carbon atoms in the substituents. "C4~C8 alkyl" means that the hydrogen atoms in the group have not been replaced by other atoms or groups of atoms, and so on.

[0052] The primary function of hole transport materials is to extract holes and transport them to the electrode. The hole transport layer, acting as an interlayer between the electrode and the perovskite light-absorbing layer, prevents both the reverse transport of electrons and charge recombination. Self-assembled monolayers (SAMs) can achieve non-destructive contact and minimize interfacial recombination. However, traditional SAMs struggle to form a uniform and flat monolayer on the electrode, leading to poor ohmic contact between the electrode and the active layer, thus creating defects at the interface.

[0053] Compared to inorganic and small-molecule hole transport materials, polymeric hole transport materials have advantages such as good film formation, tunable energy levels, and high stability. PEDOT:PSS's inherent acidity and hygroscopicity corrode and accelerate the degradation of perovskite materials, affecting the stability of trans-PSCs. PTAA suffers from high cost, excessive hydrophobicity, and shallow HOMO levels, increasing device instability and cost.

[0054] One embodiment of this application provides a perovskite solar cell, including a first electrode, a hole transport layer, a perovskite light-absorbing layer, and a second electrode. The hole transport layer is located between the first electrode and the perovskite light-absorbing layer, and the perovskite light-absorbing layer is located between the hole transport layer and the second electrode. The hole transport layer includes a compound of formula (I):

[0055]

[0056] in:

[0057] R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine;

[0058] L is selected from C2~C6 alkylene groups;

[0059] m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups;

[0060] n is 10 to 500.

[0061] The compound shown in Formula (I) is a polymer, whose monomer is based on indo[3,2-b]carbazole, with fluorine-substituted benzothiadiazole and phosphonic acid groups introduced. Using the compound shown in Formula (I) as the hole transport layer material, the indo[3,2-b]carbazole has a conjugated planar structure and π-π stacking effect, which can lay the foundation for the ordered assembly of molecules. The fluorine-substituted benzothiadiazole group can improve the charge mobility of the polymer. The phosphorus-oxygen double bond in the phosphonic acid group can interact with the perovskite and passivate the defects in the perovskite light-absorbing layer. At the same time, the polymer has high HOMO and LUMO energy levels, which can block electrons from jumping from the perovskite layer to the hole transport layer, thereby effectively suppressing the occurrence of interfacial electron recombination. The multi-faceted interaction can enable the perovskite solar cell to obtain better photoelectric conversion efficiency and stability.

[0062] It is understood that halogens include, but are not limited to, F, Cl, Br, and I; C1~C6 alkylene refers to alkylene containing 1~6 carbon atoms, including but not limited to at least one of methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), butylene (-CH2CH2CH2CH2-), pentylene (-CH2CH2CH2CH2CH2-), and hexylene (-CH2CH2CH2CH2CH2CH2-); m includes 0, 1, 2, or 3, q ​​includes 0, 1, or 2, and w includes 0, 1, 2, or 3; when m, q, or w is 0, the hydrogen on the corresponding benzene ring is not substituted by R3, R4, or R5; when m, q, or w is not 0, the hydrogen on the corresponding benzene ring is substituted by R3, R4, or R5. It can also be understood that when at least two of m, q, and w are not 0, R3, R4, and R5 can be the same or different; when m, q, or w ≥ 2, each R3, each R4, or each R5 can be the same or different; C1~C 10 Alkyl groups refer to those with 1 to 10 carbon atoms, which can be straight-chain or branched; further, C1 to C2... 10 The number of carbon atoms includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10; in some examples, it can be any two of these point values ​​as end values ​​within a range, the same applies below; C1~C 10 Alkoxy groups refer to alkoxy groups containing 1 to 10 carbon atoms; C1 to C2. 10 Alkylthio groups refer to alkoxy groups containing 1 to 10 carbon atoms; C6~C 18 Aryl refers to an aromatic ring with 6 to 18 carbon atoms; n includes, but is not limited to, 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, and 500.

[0063] F has a strong electronegativity, which will affect the energy level of the compound shown in formula (I); and the atomic size of F is small, so it will not affect its molecular packing. Introducing F into the benzothiadiazole group of the compound shown in formula (I) can improve the planarity through non-covalent interactions (such as F…S, F…H and F…π), improve the charge mobility of the material, and at the same time improve the thermal stability and hydrophobicity of the material, thereby improving the stability of the device.

[0064] Compared to the benzothiadiazole in the compound shown in formula (I) which is not fluorinated, the compound shown in formula (I) formed by fluorinated benzothiadiazole has a better effect on improving the open-circuit voltage and photoelectric conversion efficiency of the battery, and the battery has better long-term stability.

[0065] In some of these examples, R1 and R2 are both fluorine in the compound shown in formula (I).

[0066] In some of these examples, in the compound shown in formula (I), L is selected from one of ethylidene, propyleneide, and butylidene.

[0067] In some of these examples, the hole transport layer in the perovskite solar cell comprises at least one of the compounds shown in formulas (I-1), (I-2), and (I-3):

[0068] .

[0069] In some of these examples, the hole transport layer in perovskite solar cells has a thickness of 20 nm to 100 nm.

[0070] In some of these examples, the perovskite light-absorbing layer in the perovskite solar cell comprises ABX3, where A is a monovalent cation, B is a divalent metal cation, and X is a halide anion.

[0071] Optionally, the monovalent cation includes at least one of cesium ion, methylamine ion, ethylamine ion, formamidinium ion, benzylamine ion, and phenylethylamine ion.

[0072] Optionally, the divalent metal cation includes at least one of lead ions, tin ions, and copper ions.

[0073] Optionally, the halide anion includes at least one of bromide ions, chloride ions, and iodide ions.

[0074] In some of these examples, the perovskite solar cell also includes an electron transport layer located between the perovskite light-absorbing layer and the second electrode.

[0075] Optionally, the electron transport layer includes at least one of a metal oxide, a fullerene, and its derivatives. Optionally, the metal oxide includes, but is not limited to, at least one of tin oxide, zinc oxide, etc.; fullerenes and their derivatives include C... 60 PC 61 BM, PC 71 At least one of BM, etc.

[0076] In some examples, in perovskite solar cells, at least one of the first and second electrodes is a transparent conductive electrode, and the other is either a transparent conductive electrode or a metal electrode. Optionally, the transparent conductive electrode includes, but is not limited to, at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), and antimony-doped tin oxide (ATO). The metal electrode includes, but is not limited to, at least one of gold (Au), silver (Ag), copper (Cu), and aluminum (Al). Optionally, the metal electrode includes one of chromium / gold (Cr / Au), chromium / silver (Cr / Ag), silver (Ag), copper (Cu), and aluminum (Al).

[0077] Perovskite solar cells (PSCs) include conventional perovskite solar cells (upright) and inverted perovskite solar cells (inverted). A conventional perovskite solar cell consists of a transparent conductive oxide, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, and a metal electrode, from bottom to top. An inverted perovskite solar cell reverses the positions of the electron transport layer and the hole transport layer, and its structure typically consists of a transparent conductive oxide, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a metal electrode, from bottom to top.

[0078] In some of these examples, the perovskite solar cell is an inverted perovskite solar cell, meaning the first electrode is a transparent conductive electrode. Further, the second electrode is a metallic electrode; optionally, the second electrode includes chromium and copper.

[0079] In inverted perovskite solar cells, the compound shown in formula (I) serves as an important hole transport material (HTM) between the perovskite layer and the transparent electrode. It is responsible not only for the extraction and transport of holes and the blocking of electron flow, but also directly affects the crystallization properties of the perovskite. It plays a decisive role in improving the performance of the battery and realizing its large-scale commercial application.

[0080] See Figure 1 In some examples, the inverted perovskite solar cell 100 includes a first electrode 110, a hole transport layer 120, a perovskite light-absorbing layer 130, an electron transport layer 140, and a second electrode 150 stacked in sequence. The first electrode 110 is a transparent conductive electrode, and the second electrode 150 is a metal electrode.

[0081] One embodiment of this application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0082] Step S10: Prepare a hole transport layer on the first electrode; the hole transport layer comprises the compound shown in formula (I):

[0083]

[0084] in:

[0085] R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine;

[0086] L is selected from C2~C6 alkylene groups;

[0087] m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups;

[0088] n is 10 to 500.

[0089] The perovskite solar cell preparation method provided in this application includes a hole transport layer comprising a compound shown in formula (I). The compound shown in formula (I) is a polymer whose polymer monomer is based on indolo[3,2-b]carbazole, and introduces fluorine-substituted benzothiadiazole groups and phosphonic acid groups, which can passivate defects in the perovskite light-absorbing layer, suppress the occurrence of interfacial electron recombination, and enable the perovskite solar cell to obtain better photoelectric conversion efficiency.

[0090] The interface and crystallinity of the perovskite light-absorbing layer play a decisive role in determining device performance, while the hole transport material has a significant impact on device performance when the perovskite light-absorbing layer is fabricated on the hole transport layer.

[0091] In some of these examples, step S10, the preparation of the compound represented by formula (I) includes the following steps:

[0092] Step S11: The compound shown in formula (II) and the compound shown in formula (III) are subjected to a substitution reaction to prepare the compound shown in formula (IV).

[0093] Step S12: The compound shown in formula (IV) and the phosphite compound are subjected to an Arbuzov reaction to prepare the compound shown in formula (V).

[0094] Step S13: The compound shown in formula (V) and the compound shown in formula (VI) are subjected to a Suzuki coupling reaction to prepare the compound shown in formula (VII).

[0095] Step S14: Hydrolyze the compound shown in formula (VII) to prepare the compound shown in formula (I);

[0096]

[0097] R7 is selected from C1~C4 alkyl groups, and X and Y are halogens, each independently.

[0098] The compound shown in formula (I) has a simple synthesis procedure, low cost, good solubility, thermal stability and film-forming properties, high hole mobility, and good energy level matching with the perovskite phase. Applying it as a hole transport material in perovskite solar cells can effectively improve the photoelectric conversion efficiency of perovskite solar cells, especially the photoelectric conversion efficiency of perovskite / TOPCon tandem solar cells, and it has high reproducibility.

[0099] It can be understood that R1, R2, L, m, q, w or n in the compounds shown in formulas (II) to (VII) correspond to R1, R2, L, m, q, w and n in the compound shown in formula (I), that is, they are the same.

[0100] In some examples, in step S11, the molar ratio of the compound shown in formula (III) to the compound shown in formula (II) is 50 to 250:1. It is understood that the molar ratio of the compound shown in formula (III) to the compound shown in formula (II) includes, but is not limited to, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, 200:1, 210:1, 220:1, 230:1, 240:1, and 250:1. Optionally, the molar ratio of the compound shown in formula (III) to the compound shown in formula (II) is 80 to 150:1.

[0101] In some examples, in step S11, the substitution reaction is carried out under the condition of a first catalyst; optionally, the first catalyst comprises tetrabutylammonium bromide; optionally, the molar ratio of the first catalyst to the compound shown in formula (II) is 0.1 to 0.2:1. It is understood that the molar ratio of the first catalyst to the compound shown in formula (II) includes, but is not limited to, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.17:1, 0.18:1, 0.19:1, and 0.2:1.

[0102] In some examples, in step S11, the substitution reaction is carried out under the conditions of a first base; optionally, the first base includes potassium hydroxide; optionally, the molar ratio of the first base to the compound shown in formula (II) is 5 to 10:1. It is understood that the molar ratio of the first base to the compound shown in formula (II) includes, but is not limited to, 5:1, 6:1, 7:1, 8:1, 9:1, and 10:1.

[0103] In some examples, in step S11, the temperature of the substitution reaction is 70℃~90℃, and the reaction time is 12 h~30 h. It is understood that the temperature of the substitution reaction includes, but is not limited to, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 86℃, 88℃, and 90℃; and the reaction time includes, but is not limited to, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, and 30 h.

[0104] In some of these examples, in step S11, the substitution reaction is carried out under an inert gas.

[0105] It is understandable that in step S12, the Arbuzov reaction (also known as the Michaelis-Arbuzov reaction) is a classic transformation in which trivalent phosphite (such as trialkyl phosphite) undergoes nucleophilic substitution and rearrangement of phosphine salt intermediates to generate pentavalent phosphorus phosphonates and by-product haloalkanes. The core of this transformation is used to construct CP bonds and synthesize organophosphorus compounds.

[0106] In some of these examples, in step S12, the phosphite compound includes triethyl phosphite.

[0107] In some examples, in step S12, the molar ratio of the phosphite compound to the compound shown in formula (IV) is 25 to 70:1. It is understood that the molar ratio of the phosphite compound to the compound shown in formula (IV) includes, but is not limited to, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, and 70:1.

[0108] In some examples, in step S12, the Arbuzov reaction temperature is 140℃~150℃, and the reaction time is 12 h~16 h. It can be understood that the Arbuzov reaction temperature includes, but is not limited to, 140℃, 141℃, 142℃, 143℃, 144℃, 145℃, 146℃, 147℃, 148℃, 149℃, and 150℃; and the reaction time includes, but is not limited to, 12 h, 13 h, 14 h, 15 h, and 16 h.

[0109] In some of these examples, the Arbuzov reaction in step S12 is carried out under an inert gas.

[0110] In some examples, in step S13, the molar ratio of the compound shown in formula (VI) to the compound shown in formula (V) is 1 to 1.05:1. It is understood that the molar ratio of the compound shown in formula (VI) to the compound shown in formula (V) includes, but is not limited to, 1.00:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, and 1.05:1.

[0111] In some examples, in step S13, the Suzuki coupling reaction is carried out under the condition of a second catalyst; optionally, the second catalyst comprises tetrakis(triphenylphosphine)palladium; optionally, the molar ratio of the second catalyst to the compound shown in formula (V) is 0.03 to 0.1:1. It is understood that the molar ratio of the second catalyst to the compound shown in formula (V) includes, but is not limited to, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, and 0.1:1.

[0112] In some examples, in step S13, the Suzuki coupling reaction is carried out under the condition of a second base; optionally, the second base includes potassium carbonate; optionally, the molar ratio of the second base to the compound shown in formula (V) is 5 to 10:1. It is understood that the molar ratio of the second base to the compound shown in formula (V) includes, but is not limited to, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, and 10:1.

[0113] In some examples, in step S13, the Suzuki coupling reaction is carried out in a first solvent, which includes at least one of toluene, ethanol, and water. Optionally, the first solvent includes toluene, ethanol, and water; optionally, the volume ratio of toluene, ethanol, and water is 2~3:1~2:1.

[0114] In some examples, in step S13, the temperature of the Suzuki coupling reaction is 80℃~90℃, and the reaction time is 24 h~36 h. It can be understood that the temperature of the Suzuki coupling reaction includes, but is not limited to, 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃, and 90℃; and the reaction time includes, but is not limited to, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h, 31 h, 32 h, 33 h, 34 h, 35 h, and 36 h.

[0115] In some of these examples, the Suzuki coupling reaction in step S13 is carried out under an inert gas.

[0116] In some of these examples, step S14, the hydrolysis reaction includes the following steps:

[0117] The compound shown in formula (VII) is dissolved in a second solvent, and a dealkylation agent is added to generate an intermediate;

[0118] The intermediate was dissolved in a third solvent, and water was added to prepare the compound shown in formula (I).

[0119] In some examples, in step S14, the dealkylating agent comprises trimethylbromosilane. Optionally, the dealkylating agent is added dropwise.

[0120] In some examples, in step S14, the molar ratio of the dealkylating agent to the compound shown in formula (VII) is 8 to 20:1. It is understood that the molar ratio of the dealkylating agent to the compound shown in formula (VII) includes, but is not limited to, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, and 20:1.

[0121] In some of these examples, in step S14, the second solvent comprises 1,4-dioxane.

[0122] In some of these examples, in step S14, the third solvent includes methanol.

[0123] In some of these examples, the hydrolysis reaction in step S14 is carried out under an inert gas.

[0124] In some of these examples, step S10, fabricating a hole transport layer on the first electrode, includes:

[0125] Step S15: Mix the compound shown in formula (I) with the fourth solvent to prepare a hole transport solution;

[0126] Step S16: Spin-coat the hole transport solution onto the surface of the first electrode and anneal it.

[0127] In some of these examples, in step S15, the fourth solvent includes at least one of ethanol and DMSO.

[0128] In some examples, in step S15, the concentration of the compound represented by formula (I) in the hole transport solution is 0.5 mg / mL to 3 mg / mL. It is understood that the concentration of the compound represented by formula (I) in the hole transport solution includes, but is not limited to, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, and 3 mg / mL.

[0129] In some examples, in step S16, the annealing temperature is 90℃~110℃, and the time is 10 min~20 min. It is understood that the annealing temperature includes, but is not limited to, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃, 102℃, 104℃, 106℃, 108℃, and 110℃; and the time includes, but is not limited to, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, and 20 min.

[0130] Step S20: Prepare a perovskite light-absorbing layer on the side of the hole transport layer away from the first electrode.

[0131] Step S30: Prepare a second electrode on the side of the perovskite light-absorbing layer away from the hole transport layer.

[0132] It is understood that this application does not limit the method of preparing the perovskite light-absorbing layer and the second electrode, as long as it can be implemented in the field.

[0133] It is understandable that tandem solar cells are composed of multiple sub-cells with different band gaps stacked together. The wide band gap top cell and the narrow band gap bottom cell absorb short-wavelength and long-wavelength sunlight respectively, which can effectively broaden the range of solar energy spectrum utilization and improve the photoelectric conversion efficiency of solar cells.

[0134] One embodiment of this application provides a stacked battery, including the perovskite battery described above or a perovskite battery prepared by the above method for preparing perovskite batteries.

[0135] It is understood that tandem solar cells include, but are not limited to, two-terminal tandem solar cells, three-terminal tandem solar cells, and four-terminal tandem solar cells. Further, tandem solar cells include, but are not limited to, perovskite solar cells stacked with crystalline silicon solar cells, perovskite solar cells stacked with perovskite solar cells, and perovskite solar cells stacked with thin-film solar cells. Thin-film solar cells include, but are not limited to, perovskite solar thin-film solar cells, copper indium selenide solar thin-film solar cells, gallium arsenide solar thin-film solar cells, and cadmium sulfide solar thin-film solar cells; crystalline silicon solar cells include, but are not limited to, SHJ cells (silicon heterojunction cells), PERC cells (passivated emitter and back contact cells), IBC cells (interdigitated back contact cells), TOPCon cells (tunneling oxide passivated contact cells), HJT cells (heterojunction cells), and HBC cells (back contact heterojunction cells).

[0136] like Figure 2 As shown, in some examples, the stacked battery 200 includes a bottom battery 210, a top battery 220, an intermediate connecting layer 230, and a back electrode 240. The intermediate connecting layer 230 connects the bottom battery 210 and the top battery 220, and the back electrode 240 is located on the side of the bottom battery 210 away from the top battery 220. Optionally, the bottom battery 210 is a TOPCon battery. Further, the bottom battery 210 is an N-type TOPCon battery. Optionally, the top battery 220 includes a hole transport layer 221, a perovskite light-absorbing layer 222, an electron transport layer 223, a hole blocking layer 224, a transparent conductive layer 225, an anti-reflection layer 226, and a metal electrode 227 stacked sequentially. The perovskite light-absorbing layer 222 is located on the side of the hole transport layer 221 away from the intermediate connecting layer 230.

[0137] It is understood that the hole transport layer 221 includes the compound shown in formula (I) above. Optionally, the hole transport layer 221 includes a first sublayer and a second sublayer, the second sublayer being disposed between the first sublayer and the perovskite light-absorbing layer; the first sublayer includes nickel oxide, and the second sublayer includes the compound shown in formula (I) above.

[0138] Furthermore, the hole transport layer 221, perovskite light-absorbing layer 222, electron transport layer 223, and metal electrode 227 in the top cell 220 adopt the hole transport layer, perovskite light-absorbing layer, electron transport layer, and second electrode of the above-mentioned perovskite cell.

[0139] In some of these examples, the TOPCon battery includes:

[0140] Silicon wafers;

[0141] Along a first direction, a tunneling oxide layer and a doped polycrystalline silicon layer are sequentially stacked on the first surface of a silicon wafer, the first direction being the thickness direction of the silicon wafer; the first surface is the back side of the battery.

[0142] In some examples of TOPCon cells, along a first direction, the silicon wafer also includes P-type electrodes disposed on a second surface of the silicon wafer. + The emitter and the second surface are the front of the battery.

[0143] In some of these examples, the intermediate interconnect layer comprises an inductively coupled transparent (IZO) film; optionally, the hole blocking layer comprises copper bath (BCP); optionally, the antireflection layer comprises MgF2; optionally, the back electrode comprises a silver grid line electrode.

[0144] One embodiment of this application provides a method for preparing a stacked battery, comprising the following steps:

[0145] Step S300: The intermediate connecting layer 230 and the top cell 220 are sequentially fabricated on the front side of the bottom cell 210;

[0146] Step S400: Prepare a back electrode 240 on the back side of the bottom cell 210.

[0147] It is understood that other functional layers can be prepared by referring to the above-mentioned stacked battery. There are no restrictions on the preparation method of each film layer, as long as it can be achieved in this field.

[0148] In some of these examples, the fabrication method of the tandem solar cell includes the following steps:

[0149] (1) Sputter an ITO composite layer on the front side of the TOPCon crystalline silicon substrate and perform oxygen plasma treatment; optionally, the oxygen plasma treatment time is 10 min to 15 min.

[0150] (2) NiO was deposited at room temperature using radio frequency sputtering. x Layer; optionally, NiO x The layer thickness is 2 nm to 10 nm; optionally, the sputtering pressure is 0.4 Pa to 0.5 Pa, the RF power is 90 W to 100 W, the argon flow rate is 20 sccm to 30 sccm, and the deposition time is 5 min to 15 min; optionally, the layer is annealed in air for 30 min to 40 min after deposition at a temperature of 350℃ to 400℃.

[0151] Subsequently, NiO xThe substrate is directly transferred to a nitrogen glove box for subsequent spin coating.

[0152] (3) Preparation of hole transport layer: The hole transport solution is prepared by mixing the compound shown in formula (I) above with the fourth solvent, and the hole transport solution is spin-coated onto NiO. x On the upper level.

[0153] (4) Preparation of perovskite light-absorbing layer: The crystalline silicon / ITO / NiO obtained above is used as a light-absorbing layer. x / Cool the hole transport layer substrate to room temperature, spin-coat the perovskite precursor solution onto the hole transport layer, add an antisolvent, and anneal; optionally, the antisolvent includes ethyl acetate; optionally, the annealing temperature is 100℃~110℃, and the time is 10 min~20 min.

[0154] (5) Preparation of electron transport layer: The electron transport layer is deposited by thermal evaporation.

[0155] (6) Preparation of hole blocking layer: Hole blocking layer is prepared by thermal evaporation deposition.

[0156] (7) Preparation of transparent conductive layer: The transparent conductive layer is deposited by radio frequency (RF) magnetron sputtering; optionally, the thickness of the transparent conductive layer is 40 nm to 50 nm; optionally, the RF power is 80 W to 90 W.

[0157] (8) Fabrication of gate line metal electrodes: The gate line metal electrodes are deposited by thermal evaporation; optionally, the thickness of the gate line metal electrodes is 500 nm to 800 nm.

[0158] (9) Preparation of antireflection layer: The antireflection layer is deposited by thermal evaporation; optionally, the thickness of the antireflection layer is 95 nm to 105 nm.

[0159] (10) Preparation of back electrode: The back electrode is deposited by thermal evaporation; optionally, the thickness of the back electrode is 300 nm to 500 nm.

[0160] One embodiment of this application provides a photovoltaic module, including the perovskite cell provided above, the perovskite cell prepared by the method for preparing the perovskite cell provided above, or the tandem cell provided above.

[0161] In some of these examples, the photovoltaic modules include:

[0162] The battery string is formed by electrically connecting multiple perovskite cells prepared by the above-described solar cells or the above-described solar cell preparation method, or by electrically connecting multiple above-described stacked cells.

[0163] Encapsulating film, used to cover the surface of the battery string; and

[0164] A cover plate is used to cover the surface of the encapsulating film that faces away from the battery string.

[0165] It can be understood that solar cells or tandem cells are electrically connected in the form of a single sheet or multiple segments to form multiple cell strings, and multiple cell strings are electrically connected in series and / or parallel. Furthermore, solar cells or tandem cells can be single-sheet cells or sliced ​​cells; sliced ​​cells refer to cells formed from a single, complete cell through a cutting process.

[0166] In some of these examples, multiple battery strings can be electrically connected via conductive strips.

[0167] In some examples, the encapsulating film includes a first encapsulating layer and a second encapsulating layer, the first encapsulating layer covering one of the front and back sides of the battery, and the second encapsulating layer covering the other of the front and back sides of the battery; further, the first encapsulating layer and the second encapsulating layer may each independently include at least one of organic encapsulating films such as polyvinyl butyral (PVB) film, ethylene-vinyl acetate copolymer (EVA) film, polyvinyl octene coelastomer (POE) film, and polyethylene terephthalate (PET) film.

[0168] In some of these examples, the cover can be a glass cover, a plastic cover, or other light-transmitting cover.

[0169] It's understandable that photovoltaic (PV) modules have wide applications, such as in power plants and building-integrated photovoltaics (BIPV). In power plants, they can be deployed on a large scale in centralized or distributed power plants. BIPV is a technology that integrates photovoltaic power generation products into buildings. By designing solar panels as various architectural decorative materials, they replace traditional decorative materials such as glass curtain walls or roof tiles. For example, photovoltaic roof tiles can provide shelter from wind and rain while also serving as a solar power generation system, providing environmentally friendly electricity. Photovoltaic tiles are an important component of rooftop power plants, used to convert received solar energy into electricity to meet the electricity needs of daily production and life.

[0170] One embodiment of this application provides an electrical device including the aforementioned photovoltaic module.

[0171] It is understood that electrical devices can be vehicles, mobile phones, portable devices, laptops, ships, electric toys, and power tools, etc. Vehicles can be gasoline-powered cars, natural gas-powered cars, or new energy vehicles, etc.; electric toys include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc.; power tools include metal cutting power tools, grinding power tools, assembly power tools, and railway power tools, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators, and electric planers, etc. This application does not impose any special limitations on the above-mentioned electrical devices.

[0172] The present application will be described in further detail below with reference to specific embodiments, but the embodiments of the present application are not limited thereto.

[0173] Example 1

[0174] (1) Compound 1 (1.25 g, 3 mmol) was added to a 100 mL double-necked flask. Tetrabutylammonium bromide (0.36 g, 0.3 mmol) was dissolved in dibromobutane (35 mL), and 50% potassium hydroxide aqueous solution (5 mL) was added dropwise. The mixture was heated to 65 °C and stirred overnight. The reaction solution was quenched with water and extracted with dichloromethane. The organic layer was dried in combination with anhydrous magnesium sulfate, and the organic solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 12 / 1 (v / v) as the eluent to obtain compound 2 (1.8 g, yield 89%).

[0175]

[0176] (2) Compound 2 (2.1 g, 3.0 mmol) and triethyl phosphite (10 mL) were added to a 100 mL double-necked flask. The mixture was heated to 160 °C and stirred overnight under a nitrogen atmosphere. The organic solvent was removed by a rotary evaporator to give 1.9 g of crude product compound 3, with a yield of 86%.

[0177]

[0178] (3) Compound 3 (0.8 g, 1 mmol), compound 4 (0.43 g, 1 mmol), tetrakis(triphenylphosphine)palladium (57 mg, 0.05 mmol), and potassium carbonate (0.83 g, 6 mmol) were added to a 100 mL double-necked flask in a solvent of toluene, ethanol, and water (volume ratio 2:1:1). The mixture was reacted at 85 °C for 6 h. After cooling to room temperature, the mixture was extracted with DCM, the organic phase was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and finally purified by recrystallization to obtain 0.5 g of compound 5.

[0179]

[0180] (4) 2 g of compound 5 was added to anhydrous 1,4-1,4-dioxane (15 mL) at room temperature in a 100 mL double-necked flask, and trimethylbromosilane (4.6 g, 30 mmol) was added dropwise, and the mixture was stirred overnight. 1,4-dioxane was removed using a rotary evaporator to obtain a solid powder. The solid powder was dissolved in methanol (10 mL) at room temperature, and deionized water was added dropwise until the mixture became opaque, and then stirred for 14 h. The crude product was collected by filtration and washed with deionized water. The crude product was dissolved in THF (7 mL), precipitated again in acetone (20 mL), and filtered to obtain the final product poly-4PA-ICz with a yield of 50%. The proton NMR spectrum is shown below. Figure 3 As shown.

[0181]

[0182] Example 2

[0183] Poly-3PA-ICz and poly-2PA-ICz were prepared according to Example 1. In the preparation of poly-3PA-ICz, the "dibromobutane" in step (1) of Example 1 was replaced with an equal volume of "dibromopropane"; in the preparation of poly-2PA-ICz, the "dibromobutane" in step (1) of Example 1 was replaced with an equal volume of "dibromoethane".

[0184]

[0185] Five mg of the compound was dissolved in a 0.1 M solution of tetrabutylammonium hexafluorophosphate (Bu4NPF6) in dichloromethane and calibrated using ferrocene as an external standard. Cyclic voltammetry curves were obtained on an electrochemical workstation at a purge rate of 0.01 V / s. The redox potentials of the curves were analyzed, and the HOMO level of the material was calculated according to the formula.

[0186] Hole mobility, used to define the ability of HTLs to extract holes, is one of the important parameters for evaluating the performance of HTMs and even the overall device performance. Hole mobility was tested using the space charge-limited current method. A single-hole device of ITO / PEDOT:PSS / HTMs under test / MoO3 / Ag was fabricated, and the thickness of each layer was determined using a profilometer. The JV characteristic curves of the device were obtained under dark conditions using a Keithley 2450 Source-Measure instrument. Nonlinear fitting analysis was performed on the curves to obtain the carrier mobility of the sample. The test results are shown in Table 1.

[0187] Table 1

[0188]

[0189] As shown in Table 1, the energy levels of poly-4PA-ICz, poly-3PA-ICz, and poly-2PA-ICz match those of wide-bandgap perovskite materials, enabling the formation of good ohmic contacts and facilitating hole transport. Furthermore, the higher hole mobility of poly-4PA-ICz, poly-3PA-ICz, and poly-2PA-ICz can improve the fill factor (FF) of the cell, thereby enhancing the photovoltaic performance of the perovskite solar cell.

[0190] Perovskite thin films were prepared on crystalline silicon substrates coated with the HTMs (poly-4PA-ICz) to be tested. The surface morphology and cross-section of the perovskite thin films were scanned using a scanning electron microscope, as shown in the figures below. Figure 4 and Figure 5 As shown.

[0191] Depend on Figure 4 and Figure 5 It can be seen that the perovskite thin film grown based on poly-4PA-ICz has relatively uniform crystal size and no obvious boundary defects. This indicates that poly-4PA-ICz can promote the crystallization and growth of the perovskite thin film during the fabrication of PSCs devices, and has a high coverage on the hole transport layer, which is beneficial to improving the photovoltaic efficiency of the device.

[0192] Perovskite / TOPCon crystalline silicon tandem solar cells were fabricated using poly-4PA-Icz, poly-3PA-ICz, poly-2PA-ICz, and 2PACZ as hole transport materials, respectively.

[0193] (1) Sputter an ITO composite layer on the front side of the TOPCon crystalline silicon substrate and perform oxygen plasma treatment for 10 min;

[0194] (2) NiO was deposited at room temperature by radio frequency sputtering. x The NiO layer was sputtered at a pressure of 0.4 Pa, an RF power of 90 W, an argon flow rate of 20 sccm, and a deposition time of 15 min. After deposition, it was annealed in air for 40 min at a temperature of 350 °C. Subsequently, NiO was... x The substrate is directly transferred to a nitrogen glove box for subsequent spin coating.

[0195] (3) Preparation of hole transport layer: Weigh 1 mg of hole transport material (poly-4PA-Icz, poly-3PA-ICz, poly-2PA-ICz or 2PACZ) and dissolve it completely in 1 mL of anhydrous ethanol and DMSO mixed solution. Take 120 μL of the solution and add it dropwise evenly to NiO. xPlace on the surface and let stand for 10 seconds, spin coat at 3000 rpm for 30 seconds, and then anneal at 110℃ for 10 minutes.

[0196] (4) Preparation of perovskite light-absorbing layer: The crystalline silicon / ITO / NiO obtained above is used as a light-absorbing layer. x After cooling the hole transport layer substrate to room temperature, CsI, FAI, MABr, PbBr2, and PbI2 were dissolved in a mixed solvent of DMF:DMSO (volume ratio 4:1) to prepare a 1.5 M perovskite precursor solution with the corresponding chemical formula CsI. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 3) A wide-bandgap perovskite with a wavelength of 1.68 eV was formed. The film was spin-coated at 4000 rpm for 40 s. 7 s before the end of spin-coating, 200 μL of ethyl acetate was dropped into the center of the film as an antisolvent. The substrate was then immediately transferred to a heating stage and annealed at 100 °C for 10 min.

[0197] (5) Fabrication of the electron transport layer: in a high vacuum (5×10⁻⁶) -4 Pa) thermal evaporation deposition C 60 The layer has a deposition rate of 0.1 Å / s.

[0198] (6) Preparation of hole blocking layer: in high vacuum (5×10 -4 The BCP layer was thermally evaporated at a rate of 1 Å / s under Pa.

[0199] (7) Fabrication of transparent electrode: Indium zinc oxide (IZO) transparent electrode was deposited at room temperature by radio frequency (RF) magnetron sputtering with a sheet resistance of 60Ω and an RF power of 80 W.

[0200] (8) Fabrication of Ag grid lines: In high vacuum (5×10⁻⁶), -4 Ag gate lines were thermally evaporated and deposited at a rate of 1 Å / s under Pa conditions.

[0201] (9) Preparation of the antireflection layer: under high vacuum (5×10⁻⁶) -4 MgF2 was thermally evaporated at Pa, with a deposition rate of 0.5 Å / s.

[0202] (10) Preparation of back electrode Ag: Under high vacuum (5×10-4Pa), Ag electrode was thermally evaporated on the back of a crystalline silicon substrate at a deposition rate of 1 Å / s.

[0203] Under AM 1.5G illumination, the speed is 0.02V / s. -1The optimal device JV curves were obtained by forward and reverse scanning, and the effective area of ​​the perovskite / TOPCon crystalline silicon tandem solar cell was 1 cm². 2 Detailed open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and power conversion efficiency (PCE) are shown in Table 2.

[0204] Table 2

[0205]

[0206] As can be seen from Table 2, compared with perovskite solar cells prepared using 2PACZ as the hole transport material, the perovskite / TOPCon crystalline silicon tandem cells prepared using poly-4PA-ICz, poly-3PA-ICz, and poly-2PA-ICz as the hole transport materials obtained in the examples have better photovoltaic performance.

[0207] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0208] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A perovskite solar cell, characterized in that, The system includes a first electrode, a hole transport layer, a perovskite light-absorbing layer, and a second electrode. The hole transport layer is located between the first electrode and the perovskite light-absorbing layer, and the perovskite light-absorbing layer is located between the hole transport layer and the second electrode. The hole transport layer comprises a compound of formula (I). in: R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine; L is selected from C2~C6 alkylene groups; m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups; n is 10 to 500.

2. The perovskite solar cell as described in claim 1, characterized in that, In the compound shown in formula (I), both R1 and R2 are fluorine.

3. The perovskite solar cell as described in claim 2, characterized in that, In the compound shown in formula (I), L is selected from one of ethylidene, propyleneide and butylide.

4. The perovskite solar cell as described in claim 1, characterized in that, The hole transport layer comprises at least one of the compounds shown in formulas (I-1), (I-2), and (I-3): 。 5. The perovskite solar cell according to any one of claims 1 to 4, characterized in that, The perovskite light-absorbing layer comprises ABX3, where A is a monovalent cation, B is a divalent metal cation, and X is a halide anion; And / or, the perovskite solar cell further includes an electron transport layer located between the perovskite light-absorbing layer and the second electrode.

6. A method for preparing a perovskite solar cell, characterized in that, Includes the following steps: A hole transport layer is fabricated on the first electrode; A perovskite light-absorbing layer is prepared on the side of the hole transport layer away from the first electrode; A second electrode is fabricated on the side of the perovskite light-absorbing layer away from the hole transport layer; The hole transport layer comprises the compound shown in formula (I): in: R1 and R2 are each independently selected from hydrogen, halogen and trifluoromethyl, and at least one of R1 and R2 is fluorine; L is selected from C2~C6 alkylene groups; m is selected from integers 0 to 3, q ​​is selected from integers 0 to 2, and w is selected from integers 0 to 3; R3 to R5 are independently selected from substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylthio, halogen, trifluoromethyl, hydroxyl, mercapto, cyano, amino, and substituted or unsubstituted C6~C 18 One of the aryl groups, wherein the substituents are independently selected from one of C1-C4 alkyl, amino, halogen, nitro, hydroxyl, mercapto, carboxyl and cyano groups; n is 10 to 500.

7. The method for preparing a perovskite solar cell as described in claim 6, characterized in that, The preparation of the compound shown in formula (I) includes the following steps: The compound shown in formula (II) and the compound shown in formula (III) were subjected to a substitution reaction to prepare the compound shown in formula (IV); The compound shown in formula (IV) and the phosphite compound were subjected to an Arbuzov reaction to prepare the compound shown in formula (V); Compound of formula (VII) was prepared by subjecting the compound shown in formula (V) and the compound shown in formula (VI) to a Suzuki coupling reaction. The compound shown in formula (VII) is subjected to a hydrolysis reaction to prepare the compound shown in formula (I); R7 is selected from C1~C4 alkyl groups, and X and Y are halogens, each independently.

8. The method for preparing a perovskite solar cell as described in claim 7, characterized in that, The substitution reaction satisfies at least one of the following characteristics: (1) The molar ratio of the compound shown in formula (III) to the compound shown in formula (II) is 50~250:1; (2) The substitution reaction is carried out under the condition of a first catalyst; the first catalyst comprises tetrabutylammonium bromide; and / or the molar ratio of the first catalyst to the compound shown in formula (II) is 0.1 to 0.2:1; (3) The substitution reaction is carried out under the condition of a first base; the first base includes potassium hydroxide; and / or the molar ratio of the first base to the compound shown in formula (II) is 5 to 10:1; (4) The temperature of the substitution reaction is 70℃~90℃ and the reaction time is 12 h~30 h; (5) The substitution reaction is carried out under an inert gas; And / or, the Arbuzov reaction satisfies at least one of the following characteristics: (1) The phosphite compound includes triethyl phosphite; (2) The molar ratio of the phosphite compound to the compound shown in formula (IV) is 25~70:1; (3) The temperature of the Arbuzov reaction is 140℃~150℃ and the reaction time is 12 h~16 h; (4) The Arbuzov reaction is carried out under an inert gas atmosphere; And / or, the Suzuki coupling reaction satisfies at least one of the following characteristics: (1) The molar ratio of the compound shown in formula (VI) to the compound shown in formula (V) is 1~1.05:1; (2) The Suzuki coupling reaction is carried out under the condition of a second catalyst; the second catalyst comprises tetra(triphenylphosphine)palladium; and / or the molar ratio of the second catalyst to the compound shown in formula (V) is 0.03 to 0.1:1; (3) The Suzuki coupling reaction is carried out under the condition of a second base; the second base includes potassium carbonate; and / or the molar ratio of the second base to the compound shown in formula (V) is 5 to 10:1; (4) The Suzuki coupling reaction is carried out in a first solvent, which includes at least one of toluene, ethanol and water; (5) The temperature of the Suzuki coupling reaction is 80℃~90℃ and the reaction time is 24 h~36 h; (6) The Suzuki coupling reaction is carried out under an inert gas atmosphere; And / or, the hydrolysis reaction includes the following steps: The compound of formula (VII) is dissolved in a second solvent, and a dealkylation agent is added to generate an intermediate; The intermediate was dissolved in a third solvent, and water was added to prepare the compound shown in formula (I); The hydrolysis reaction satisfies at least one of the following characteristics: (1) The dealkylating agent includes trimethylbromosilane; (2) The molar ratio of the dealkylating agent to the compound shown in formula (VII) is 8~20:1; (3) The second solvent includes 1,4-dioxane; (4) The third solvent includes methanol; (5) The hydrolysis reaction is carried out under an inert gas.

9. A stacked battery, characterized in that, The perovskite battery includes the perovskite battery as described in any one of claims 1 to 5 or the perovskite battery prepared by the preparation method as described in any one of claims 6 to 8.

10. A photovoltaic module, characterized in that, This includes the perovskite battery as described in any one of claims 1 to 5, the perovskite battery prepared by the method described in any one of claims 6 to 8, or the stacked battery as described in claim 9.

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