Solar cell module and method for manufacturing the same, solar cell

Abstract

This disclosure provides a solar cell module and its fabrication method, as well as a solar cell. The fabrication method of the solar cell module includes: mixing a metal halide, an organic halide, and an additive on one side of a substrate to obtain a mixture; the molecular structure of the additive includes at least one framework ring, at least one carboxyl group, and at least one halogen, wherein the at least one framework ring includes a conjugated ring with a delocalized large π bond; the framework ring includes multiple atoms connected end-to-end, the carboxyl group is connected to atoms on the framework ring, the halogen is connected to atoms on the framework ring, and the atoms connecting the carboxyl group and the halogen are different; the mixture is annealed to obtain a perovskite light-absorbing layer. The coordination of the carboxyl functional group with the cations in the metal halide can passivate cation vacancy defects, and the halogen can fill halogen vacancy defects in the crystal lattice. Through the synergistic effect of the two functional groups within the molecule of a single additive, multiple defects are simultaneously suppressed during the crystallization process.

Description

Technical Field

[0001] This disclosure relates to the field of battery technology, specifically to solar cell modules and their preparation methods, and solar cells. Background Technology

[0002] Perovskite solar cells, as a next-generation photovoltaic technology, boast a wide light absorption range, rapid improvement in photoelectric conversion efficiency, and laboratory efficiencies exceeding those of monocrystalline silicon. Their fabrication process is simple, allowing for low-temperature solution deposition, adaptability to flexible substrates, and low material consumption and cost. The tandem stacking of perovskite and crystalline silicon can break through the efficiency limit of single-junction cells, with current laboratory efficiencies exceeding 34%, far surpassing the upper limit of crystalline silicon single cells. Wide-bandgap perovskite top cells absorb short wavelengths, while narrow-bandgap crystalline silicon bottom cells absorb long wavelengths, significantly improving spectral utilization and reducing power generation losses under weak light and high temperatures. However, due to limitations in related technologies, current perovskite solar cells still require further improvement. Summary of the Invention

[0003] In view of this, the present disclosure provides a solar cell module and its preparation method, as well as a solar cell.

[0004] The first aspect of this disclosure provides a method for preparing a solar cell module, comprising: mixing a metal halide, an organic halide, and an additive on one side of a substrate to obtain a mixture; the molecular structure of the additive includes at least one skeletal ring, at least one carboxyl group, and at least one halogen, wherein the at least one skeletal ring includes a conjugated ring having a delocalized large π bond; the skeletal ring includes a plurality of atoms connected end-to-end, the carboxyl group is connected to an atom on the skeletal ring, the halogen is connected to an atom on the skeletal ring, and the atom connecting the carboxyl group and the atom connecting the halogen are different; and annealing the mixture to obtain a perovskite light-absorbing layer.

[0005] In one embodiment, the number of atoms on the same skeletal ring is greater than or equal to 4 and less than or equal to 8. Preferably, the number of skeletal rings is less than or equal to 3. Preferably, adjacent skeletal rings are connected by chemical bonds, and / or, at least two skeletal rings share two carbon atoms. Preferably, 1-2 atoms on the same skeletal ring are chemically bonded to a halogen. Preferably, 1-2 atoms on the same skeletal ring are chemically bonded to a carboxyl group. Preferably, the halogen and the carboxyl group are chemically bonded to the same skeletal ring. Preferably, the carboxyl group is connected to an atom on a conjugated ring, and / or, the halogen is connected to an atom on a conjugated ring.

[0006] In one embodiment, at least one atom on the skeletal ring is a nitrogen atom. Preferably, the atom connecting the carboxyl group and the nitrogen atom are arranged in a meta-position on the same skeletal ring. Preferably, the halogen includes at least one of chlorine, bromine, and iodine.

[0007] In one embodiment, the skeletal ring comprises a pyridine ring. Preferably, the additive comprises at least one of 2,6-dichloropyridine-3-carboxylic acid, 2,5-dichloropyridine-3-carboxylic acid, 2,4-dichloropyridine-3-carboxylic acid, 2,6-dichloropyridine-4-carboxylic acid, 2,5-dichloropyridine-4-carboxylic acid, 2,3-dichloropyridine-4-carboxylic acid, and 3,5-dichloropyridine-4-carboxylic acid.

[0008] In one embodiment, mixing a metal halide, an organic halide, and an additive on one side of a substrate includes: preparing a framework layer on one side of the substrate, the framework layer comprising the metal halide; dispersing the organic halide and the additive in a solvent to obtain a mixed solution; and coating the mixed solution onto at least a portion of the surface of the framework layer to obtain a mixture.

[0009] In one embodiment, preparing a framework layer on one side of a substrate includes: preparing the framework layer on one side of the substrate by vapor deposition. Preferably, the vapor deposition method includes at least one of single-source vapor deposition, dual-source vapor deposition, and triple-source vapor deposition. Preferably, preparing the framework layer on one side of the substrate by vapor deposition includes: using a first evaporation source and a second evaporation source to vapor deposit the framework layer on one side of the substrate, wherein the first evaporation source vapor deposits PbX2, the second evaporation source vapor deposits CsY, and the ratio of the evaporation rate of the first evaporation source to the evaporation rate of the second evaporation source is greater than or equal to 5:1 and less than or equal to 10:1; X includes I, and Y includes at least one of Br, Cl, and I. Preferably, a framework layer is prepared on one side of the substrate by vapor deposition, comprising: depositing a framework layer on one side of the substrate using a first evaporation source, a second evaporation source, and a third evaporation source; wherein the first evaporation source deposits PbX2, the second evaporation source deposits CsY, and the third evaporation source deposits at least one of PbZ2 and CsM; Z includes at least one of Br and Cl, and M includes at least one of I and Cl, wherein X is different from Z, and Y is different from M. Preferably, the evaporation rate of the first evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s, and / or the evaporation rate of the second evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s, and / or the evaporation rate of the third evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s. Preferably, the thickness of the framework layer is greater than or equal to 300 nm and less than or equal to 550 nm. Preferably, the thickness of the perovskite light-absorbing layer is greater than or equal to 500 nm and less than or equal to 1200 nm.

[0010] In one embodiment, the organic halide includes at least one of formamidine iodide, dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidine chloride. Preferably, the molar ratio of formamidine iodide, dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidine chloride is (40~60):(5~15):(10~30):(5~15):(1~10). Preferably, the concentration of the additive in the mixed solution is greater than or equal to 1 mg / mL and less than or equal to 5 mg / mL. Preferably, the solvent includes isopropanol. Preferably, the method of coating the mixed solution onto at least a portion of the surface of the skeleton layer includes at least one of slot coating and spin coating. Preferably, the annealing treatment satisfies at least one of the following conditions: humidity greater than or equal to 5% and less than or equal to 40%; temperature greater than or equal to 100 °C and less than or equal to 170 °C; time greater than or equal to 15 min and less than or equal to 30 min.

[0011] In one embodiment, the substrate includes a first battery cell. Preferably, the first battery cell includes a crystalline silicon battery cell having a textured structure, and the perovskite light-absorbing layer is grown conformally along the textured structure.

[0012] The second aspect of this disclosure provides a solar cell module manufactured using the method for fabricating a solar cell module as provided in the first aspect.

[0013] A third aspect of this disclosure provides a solar cell, including a solar cell module as provided in the second aspect.

[0014] According to the method for preparing a solar cell module provided in this disclosure, metal halides, organic halide salts, and additives are mixed. The coordination of carboxyl functional groups with cations in the metal halide can passivate cation vacancy defects, while halogens can fill halogen vacancy defects in the crystal lattice. Through the synergistic effect of the two functional groups within a single additive molecule, multiple defects are simultaneously suppressed during crystallization, and crystal growth is effectively controlled, effectively improving the quality, crystallization uniformity, and structural integrity of the perovskite light-absorbing layer. In addition, the framework ring structure in the additive molecule is conducive to filling the voids in the crystal, easily forming an ordered and dense molecular layer at grain boundaries or interfaces, which is beneficial to improving the density of the perovskite light-absorbing layer and effectively blocking the intrusion of moisture and oxygen. The conjugated ring with delocalized large π bonds has good conductivity, which can passivate perovskite defects without damaging the conductivity of the perovskite light-absorbing layer, thereby improving the photoelectric conversion efficiency and stability of the solar cell module. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the process for preparing a perovskite light-absorbing layer in one embodiment of the present disclosure.

[0016] Figure 2 This is a schematic diagram of a method for preparing a mixture according to one embodiment of the present disclosure.

[0017] Figure 3 This is a schematic cross-sectional view of a solar cell module according to one embodiment of the present disclosure.

[0018] Figure 4 This is a scanning electron microscope image of the perovskite light-absorbing layer in Embodiment 1 of this disclosure.

[0019] Figure 5 This is a scanning electron microscope image of the perovskite light-absorbing layer in Comparative Example 1.

[0020] Figure 6 The images show the X-ray diffraction patterns of the perovskite light-absorbing layer in Example 1 and the perovskite light-absorbing layer in Comparative Example 1. Detailed Implementation

[0021] The technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments of this disclosure, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this disclosure.

[0022] Furthermore, to better illustrate this disclosure, numerous specific details are set forth in the following detailed description. Those skilled in the art will understand that this disclosure can be practiced without certain specific details. In some instances, methods and means well-known to those skilled in the art have not been described in detail in order to highlight the main points of this disclosure.

[0023] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0024] Furthermore, the terms "first" and "second" are used only to distinguish descriptions and should not be interpreted as indicating or implying relative importance.

[0025] The inventors of this disclosure have discovered that, to improve the crystallinity of perovskite light-absorbing layers and reduce their defect density, a common practice is to introduce halide additives, such as methylammonium chloride, into the perovskite precursor solution. This approach achieves this by adding such easily decomposable or volatile halide salts to the perovskite precursor solution. The basic working principle is that, during subsequent crystallization or annealing processes, the halogen components generated by the decomposition or volatilization of the additives can influence crystal nucleation and growth kinetics and partially fill halogen vacancies in the crystal lattice. However, when this approach is applied to high-performance devices that require high photoelectric conversion efficiency and stability, especially perovskite light-absorbing layers that need to simultaneously passivate multiple types of bulk and interface defects, its performance is limited. This is because the decomposition or volatilization of the additives inevitably leads to premature and rapid escape of the additives during film formation, thereby reducing the sustained passivation capability for key defect sites.

[0026] Through in-depth analysis, the inventors discovered that the single halide additives commonly used in related technologies can only provide halogen sources through their chemical functional groups, lacking stable coordination sites with metal ions in the perovskite lattice. Therefore, they cannot synergistically passivate vacancy defects caused by the absence of metal ions. Furthermore, the high volatility of small-molecule additives in related technologies makes it difficult to maintain an effective concentration during the critical heat treatment stage of film formation, resulting in uneven spatial and temporal distribution of defect passivation.

[0027] In view of the above, the first aspect of this disclosure provides a method for preparing a solar cell module, referring to... Figure 1 The diagram shows a process flow chart for the fabrication of a solar cell module. The fabrication process for a solar cell module includes the following steps.

[0028] S100: Metal halides, organic halide salts and additives are mixed on one side of the substrate to obtain a mixture.

[0029] Optionally, the molecular structure of the additive includes at least one skeletal ring, at least one carboxyl group, and at least one halogen. The at least one skeletal ring includes a conjugated ring with delocalized large π bonds. The skeletal ring includes a plurality of atoms connected end to end in sequence. The carboxyl group is connected to an atom on the skeletal ring, and the halogen is connected to an atom on the skeletal ring. The atom connecting the carboxyl group and the atom connecting the halogen are different.

[0030] S200: Anneal the mixture to obtain a perovskite light-absorbing layer.

[0031] According to the method for preparing a solar cell module provided in this disclosure, metal halides, organic halide salts, and additives are mixed. The coordination of carboxyl functional groups with cations in the metal halide can passivate cation vacancy defects, while halogens can fill halogen vacancy defects in the crystal lattice. Through the synergistic effect of the two functional groups within a single additive molecule, multiple defects are simultaneously suppressed during crystallization, and crystal growth is effectively controlled, effectively improving the quality, crystallization uniformity, and structural integrity of the perovskite light-absorbing layer. In addition, the framework ring structure in the additive molecule is conducive to filling the voids in the crystal, easily forming an ordered and dense molecular layer at grain boundaries or interfaces, which is beneficial to improving the density of the perovskite light-absorbing layer and effectively blocking the intrusion of moisture and oxygen. The conjugated ring with delocalized large π bonds has good conductivity, which can passivate perovskite defects without damaging the conductivity of the perovskite light-absorbing layer, thereby improving the photoelectric conversion efficiency and stability of the solar cell module.

[0032] It is understandable that when the same additive molecule contains both carboxyl and halogen groups, the carboxyl group acts as a coordinating agent for metal ions in metal halides, while the halogen acts as a vacancy filler. This ensures that the carboxyl group and halogen are supplied simultaneously and effectively at the crystal growth interface, resulting in excellent passivation. However, if carboxyl-containing coordinating agents and halogen-containing vacancy fillers are added separately, it is difficult to ensure that they are supplied simultaneously and in equal amounts at the crystal growth interface due to the differences in diffusion rates, thermal stability, and interaction forces with the perovskite precursor. This affects the synergistic passivation effect.

[0033] Optionally, the substrate includes a first battery cell.

[0034] For example, the first battery cell includes a crystalline silicon battery cell having a textured structure, and a perovskite light-absorbing layer is grown conformally along the textured structure.

[0035] It can be understood that conformal growth generally refers to the deposition of functional thin films on substrates with non-uniform surface morphologies (such as textured or velvety surfaces). The deposited film closely adheres to and replicates the surface contour of the substrate, resulting in a relatively uniform film thickness across the contour without completely flattening or significantly altering the original morphological features. For example, on the surface of a crystalline silicon solar cell with a pyramidal textured structure, conformal growth can be achieved through vacuum evaporation, atomic layer deposition, or a suitable solution spin coating process. This allows the perovskite light-absorbing layer, along with its preceding and following transport layers and electrode layers, to be formed sequentially, all maintaining a roughly pyramidal slope morphology, ultimately resulting in a conformal multilayer film stack.

[0036] For example, a crystalline silicon cell can be a crystalline silicon heterojunction cell (HJT) cell, see reference. Figure 3The schematic diagram of the cross-sectional structure of the solar cell module shown indicates that the solar cell module includes: a stacked back electrode 902, a second transparent electrode layer 1100, a silicon heterojunction bottom cell unit 100, a composite layer 200, a hole transport layer 300, a perovskite light absorption layer 400, a passivation layer 500, an electron transport layer 600, a buffer layer 700, a first transparent electrode layer 800, and a positive electrode 901. The solar cell module may also include an antireflection layer 1000 located on the side of the first transparent electrode layer 800 opposite to the buffer layer 700. The positive electrode 901 penetrates the antireflection layer 1000 and is electrically connected to the first transparent electrode layer 800. In this case, the solar cell module is a tandem cell module. The hole transport layer 300, the perovskite light absorption layer 400, the passivation layer 500, the electron transport layer 600, and the buffer layer 700 constitute a perovskite cell unit, which serves as the top cell unit. Below this is the silicon heterojunction bottom cell unit, and the two are electrically and optically coupled through the composite layer 200. The perovskite light-absorbing layer, as the core region for light absorption and carrier generation, directly determines the final performance of solar cell modules.

[0037] For example, the silicon heterojunction bottom cell 100 has a textured structure, with its surface exhibiting regular or irregular pyramidal textures. The subsequently formed composite layer 200, hole transport layer 300, perovskite light absorption layer 400, and other functional layers all need to be deposited and grown on this textured structure with a three-dimensional morphology. The carrier flow is as follows: light enters from the side of the antireflection layer 1000 away from the first transparent electrode layer 800, is absorbed by the perovskite light absorption layer 400 to generate electron-hole pairs, holes are transported downwards through the hole transport layer 300 to the silicon heterojunction bottom cell 100, and electrons are transported upwards through the electron transport layer 600 to the first transparent electrode layer 800 and the positive electrode 901 where they are collected, thus completing the photoelectric conversion.

[0038] For example, the silicon heterojunction bottom cell 100 includes: a stacked p-type silicon layer 140, a first intrinsic silicon layer 120, a crystalline silicon light-absorbing layer 110, a second intrinsic silicon layer 130, and an n-type silicon layer 150, wherein the p-type silicon layer 140 is located on the side of the first intrinsic silicon layer 120 close to the second transparent electrode layer 1100.

[0039] For example, the solar cell module is a tandem solar cell module, and the substrate includes a back electrode 902, a second transparent electrode layer 1100, a silicon heterojunction bottom cell 100, a composite layer 200, and a hole transport layer 300.

[0040] For example, the solar cell module is a single perovskite solar cell module, and the substrate includes a substrate, a bottom electrode, and a hole transport layer; or, the substrate includes a substrate, a bottom electrode, and an electron transport layer. For example, the substrate may include, but is not limited to, glass, flexible polymer substrates, etc.

[0041] In one embodiment, the number of atoms on the same framework ring is greater than or equal to 4 and less than or equal to 8, for example, 4, 5, 6, 7, or 8. Compared to the aforementioned range of atomic numbers, the effect of the additive in promoting perovskite cell growth is relatively poor.

[0042] For example, when the number of atoms on the same skeletal ring is 4, the skeletal ring can be a ring with a nitrogen-containing heterocyclic butadiene structure. When the number of atoms on the same skeletal ring is 5, the skeletal ring can be a ring with a pyrrole structure. When the number of atoms on the same skeletal ring is 6, the skeletal ring can be a ring with a pyridine structure. When the number of atoms on the same skeletal ring is 7, the skeletal ring can be a ring with a nitrogen-containing heterocyclic octatetraene structure.

[0043] In a preferred embodiment, the number of atoms on the framework ring is less than or equal to 6. Therefore, the additive molecules are highly rigid, conformationally stable during the dynamic crystallization of the perovskite light-absorbing layer, and readily provide synergistic and uniform regulation in three-dimensional space. This results in a strong overall control over crystallization kinetics and more comprehensive defect passivation by the additive.

[0044] For example, the number of framework rings is less than or equal to 3, such as 1, 2, or 3. In a preferred embodiment, the number of framework rings is 1. It can be understood that the fewer the number of framework rings, the smaller the molecular weight of the additive. The framework ring structure in the additive molecule is beneficial for filling the gaps in the crystal, and it is easy to form an ordered and dense molecular layer at the grain boundary or interface. This is beneficial for improving the density of the perovskite light absorption layer, effectively blocking the intrusion of moisture and oxygen, and thus improving the photoelectric conversion efficiency and stability of the solar cell module.

[0045] Optionally, adjacent skeletal rings are linked by chemical bonds, and / or at least two skeletal rings share two carbon atoms.

[0046] Optionally, one or two atoms on the same skeletal ring are chemically bonded to halogen atoms. That is, one or two halogen atoms are connected to the same skeletal ring.

[0047] Optionally, one or two atoms on the same skeletal ring are chemically bonded to carboxyl groups. That is, one or two carboxyl groups are connected to the same skeletal ring.

[0048] Optionally, the halogen and carboxyl group are chemically bonded to the same skeletal ring. The carboxyl group and halogen, which perform passivation functions, are directly connected to the same skeletal ring via chemical bonds, which helps maintain a relatively fixed orientation and distance of the functional groups in space, thereby optimizing the synergy between the carboxyl group and halogen and perovskite lattice defects and the stability of the molecule itself. For example, this may include, but is not limited to: the carboxyl group and halogen being connected to a benzene ring, or to a pyridine ring, or to other nitrogen- or oxygen-containing heteroaromatic rings. The relative positions and numbers of the carboxyl group and halogen atoms on the aromatic ring can be optimized based on their influence on defect passivation and molecular steric hindrance. For example, the substitution position of the halogen on the skeletal ring is preferably ortho- or para-position of the carboxyl group. In a preferred example, the additive molecule contains one skeletal ring, one carboxyl group, and two halogen atoms, with the two halogen atoms located ortho-position to the carboxyl group, or one halogen atom located ortho-position to the carboxyl group and the other halogen atom located para-position to the carboxyl group.

[0049] For example, the carboxyl group is bonded to an atom on the conjugated ring, and the halogen is bonded to an atom on the conjugated ring. Thus, the additive molecule can simultaneously perform defect passivation, lattice stabilization, and carrier transport functions; for example, the carboxyl group coordinates and passivates Pb. 2+ Defects suppress nonradiative recombination; halogens stabilize the lattice and suppress ion migration; conjugated rings ensure good conductivity without hindering carrier transport.

[0050] In one embodiment, at least one atom on the framework ring is a nitrogen atom. Thus, the nitrogen atom, through lone pair electron coordination, hydrogen bonding, electronic effect regulation, steric hindrance, and template effect, enables the regulation of perovskite nucleation-growth kinetics, optimization of crystal structure, defect passivation, and improved stability, thereby significantly enhancing the performance and lifespan of solar cell modules.

[0051] Optionally, the halogen includes at least one of chlorine, bromine, and iodine. It is understood that during the annealing process, the halogen in the organic halide salts volatilizes, potentially leading to halogen deficiency defects in the perovskite calcium lattice. The halogen atoms in the additive can directly fill the halogen vacancies in the lattice, thereby passivating the main types of halogen deficiency defects during the perovskite thin film crystallization process. This effectively reduces the bulk and interface defect density of the perovskite light-absorbing layer, significantly improving the crystal quality and photoelectric performance of the perovskite light-absorbing layer, and ultimately enhancing the efficiency and stability of the solar cell module.

[0052] For example, the atoms connecting the carboxyl groups and nitrogen atoms are arranged meta-positionally on the same skeletal ring. This allows for a more suitable coordination orientation, more stable molecular adsorption, and a stronger passivation effect, while not affecting carrier transport in the conjugated ring, thus better suppressing nonradiative recombination in perovskites.

[0053] For example, the framework ring can be a cyclic group constituting the core structure of the additive molecule, formed by multiple atoms sequentially chemically bonded end-to-end to form a closed ring structure. The atoms constituting the framework ring include carbon atoms, nitrogen atoms, or other atoms. For example, the atoms constituting the framework ring include carbon atoms and at least one nitrogen atom. The framework ring can exist alone, or two to three framework rings can be directly connected by chemical bonds, or exist in the form of sharing two carbon atoms (fused ring structure). At least one ring in the framework ring is a conjugated ring with delocalized large π bonds, and different atoms on the framework ring are used to chemically bond carboxyl groups (-COOH) and halogen atoms (at least one of Cl, Br, I), providing structural support for the crystallization regulation and defect passivation of the perovskite light absorption layer.

[0054] In one embodiment, the framework ring comprises a pyridine ring. Thus, the aromaticity of the framework ring enhances the molecular planarity and conjugation stability, thereby improving the fit between the additive and the perovskite lattice.

[0055] Optionally, the additive includes at least one selected from 2,6-dichloropyridine-3-carboxylic acid, 2,5-dichloropyridine-3-carboxylic acid, 2,4-dichloropyridine-3-carboxylic acid, 2,6-dichloropyridine-4-carboxylic acid, 2,5-dichloropyridine-4-carboxylic acid, 2,3-dichloropyridine-4-carboxylic acid, and 3,5-dichloropyridine-4-carboxylic acid. Thus, the additive can improve crystallization uniformity and defect distribution.

[0056] For example, the structural formula of 2,6-dichloropyridine-3-carboxylic acid is: The structural formula of 2,5-dichloropyridine-3-carboxylic acid is: The structural formula of 2,4-dichloropyridine-3-carboxylic acid is: The structural formula of 2,6-dichloropyridine-4-carboxylic acid is: The structural formula of 2,5-dichloropyridine-4-carboxylic acid is: The structural formula of 2,3-dichloropyridine-4-carboxylic acid is: The structural formula of 3,5-dichloropyridine-4-carboxylic acid is: In a preferred embodiment, the additive includes at least one of 2,6-dichloropyridine-3-carboxylic acid, 2,5-dichloropyridine-3-carboxylic acid, 2,6-dichloropyridine-4-carboxylic acid, and 2,5-dichloropyridine-4-carboxylic acid. This results in a more dispersed carboxyl and chlorine atom distribution with less mutual interference, allowing the carboxyl and chlorine atoms to fully exert their respective passivation effects.

[0057] For example, the carboxyl group (-COOH) in 2,6-dichloropyridine-3-carboxylic acid can react with uncoordinated lead ions (Pb) in the perovskite lattice. 2+The carboxyl group coordinates with the halogen atom, passivating defects caused by lead ions. Simultaneously, the chlorine (Cl) atoms in the molecule effectively fill halogen vacancies in the perovskite lattice (especially Cl deficiencies caused by volatile organic halides), passivating defects caused by halogen deficiency. The synergistic effect of the carboxyl group and halogen atom in the same molecular structure can more comprehensively passivate various defects in the perovskite film, both within and on its surface. This effectively controls the crystal growth process, suppresses non-radiative recombination, and ultimately yields a high-quality perovskite film with larger grain size, higher crystal quality, and fewer surface pores. This significantly improves the photoelectric conversion efficiency (PCE) and fill factor (FF) of the final solar cell device.

[0058] In one embodiment, refer to Figure 2 The schematic diagram of the preparation method of the mixture shown shows that metal halides, organic halide salts and additives are mixed on one side of the substrate to obtain the mixture, including the following steps.

[0059] S110: Prepare a framework layer on one side of the substrate, the framework layer comprising a metal halide.

[0060] For example, the framework layer generally refers to the initial inorganic or organic-inorganic hybrid thin film layer that provides a template and support for subsequent cation insertion and reaction. Its function is to define the basic thickness and morphology of the perovskite light-absorbing layer and affect the crystallinity quality of the final film. For example, methods for preparing the framework layer may include, but are not limited to: forming a lead iodide layer, a blend of lead iodide and cesium bromide, or other metal halide layers required for perovskite structures by vapor deposition or solution methods.

[0061] In one embodiment, the thickness of the skeleton layer is greater than or equal to 300 nm and less than or equal to 550 nm, for example, it can be 300 nm, 350 nm or 400 nm, etc.

[0062] In one embodiment, preparing a framework layer on one side of the substrate includes: preparing the framework layer on one side of the substrate using a vapor deposition method. This results in a higher density framework layer, which is beneficial for reducing subsequent interlayer defects.

[0063] Optionally, the vapor deposition method includes at least one of single-source vapor deposition, dual-source vapor deposition, and triple-source vapor deposition.

[0064] Optionally, the raw material for single-source vapor deposition is lead iodide.

[0065] Optionally, a framework layer is prepared on one side of the substrate by vapor deposition, comprising: depositing a framework layer on one side of the substrate using a first evaporation source and a second evaporation source, wherein the first evaporation source deposits PbX2 and the second evaporation source deposits CsY, and the ratio of the evaporation rate of the first evaporation source to the evaporation rate of the second evaporation source is greater than or equal to 5:1 and less than or equal to 10:1, for example, it can be 5:1, 6:1, 8:1 or 10:1, etc. Wherein, X includes I, and Y includes at least one of Br, Cl and I.

[0066] In a specific example, a dual-source co-evaporation process can be used to evaporate PbI2 and CsBr separately. By precisely controlling their respective evaporation rates (e.g., the evaporation rate ratio of PbI2 to CsBr is between 5:1 and 10:1), a vacuum level below 1×10⁻⁶ can be achieved. -3 Under the condition of Pa, a hybrid framework layer with a thickness of approximately 300 to 550 nanometers was deposited on the substrate.

[0067] Optionally, a framework layer is prepared on one side of the substrate by vapor deposition, including: vapor deposition of the framework layer on one side of the substrate using a first evaporation source, a second evaporation source and a third evaporation source, wherein the first evaporation source vapor deposits PbX2, the second evaporation source vapor deposits CsY, and the third evaporation source vapor deposits at least one of PbZ2 and CsM; Z includes at least one of Br and Cl, and M includes at least one of I and Cl, wherein X is different from Z, and Y is different from M.

[0068] Optionally, the evaporation rate of the first evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s (e.g., 0.2 Å / s, 0.3 Å / s, or 0.4 Å / s, etc.), and / or the evaporation rate of the second evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s (e.g., 0.2 Å / s, 0.3 Å / s, or 0.4 Å / s, etc.), and the evaporation rate of the third evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s (e.g., 0.2 Å / s, 0.3 Å / s, or 0.4 Å / s, etc.). This facilitates the acquisition of a uniform and dense framework layer film.

[0069] S120: Disperse organic halide salts and additives in a solvent to obtain a mixed solution.

[0070] In one embodiment, the organic halide includes at least one of formamidinium iodide, dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidinium chloride.

[0071] Optionally, the molar ratio of formamidinium iodide (FAI), dimethylammonium iodide (DMAI), methylammonium iodide (MAI), methylammonium chloride (MACl), and formamidinium chloride (FACl) is (40~60):(5~15):(10~30):(5~15):(1~10), for example, it can be (40, 42, 44, 46, 48, 50, 52, 54, 56, 58 or 60, etc.):(5, 7, 9, 11, 13 or 15, etc.):(10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30, etc.):(5, 7, 9, 11, 13 or 15, etc.):(1, 2, 4, 6, 8 or 10, etc.). This formulation system, based on formamidinium iodide and compounded with dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidinium chloride, allows for precise control of the perovskite crystallization process, resulting in high-quality thin films with uniform grains, high density, and no pinholes. The mixed cations synergistically stabilize the perovskite α-phase, suppressing the formation of inactive impurity phases and halogen volatilization; chloride ions effectively passivate defects such as iodine vacancies and lead dangling bonds, reducing nonradiative recombination of charge carriers. Simultaneously, it optimizes the band structure and lattice stability, significantly improving the device's photoelectric conversion efficiency and enhancing the stability of the perovskite.

[0072] Optionally, in the mixed solution, the concentration of the additive is greater than or equal to 1 mg / mL and less than or equal to 5 mg / mL, for example, it can be 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, etc. Relative to the above concentration range, when the concentration of the additive is less than 1 mg / mL, the additive cannot adequately cover the defect sites, resulting in insufficient passivation and crystallization control effects. This leads to numerous defects and poor density in the perovskite light absorption layer, severe carrier recombination, and limited improvement in the efficiency and stability of the solar cell module. When the concentration of the additive is greater than 5 mg / mL, it easily accumulates at grain boundaries or on the surface of the framework layer, forming non-radiative recombination centers that hinder carrier transport. This can further disrupt perovskite crystal growth, leading to a deterioration in the morphology and impurity of the perovskite light absorption film layer, thereby reducing the photoelectric efficiency and lifetime of the solar cell module.

[0073] Optionally, the solvent may include isopropanol.

[0074] S130: The mixed solution is coated onto at least a portion of the surface of the skeleton layer to obtain the mixture.

[0075] For example, the perovskite light-absorbing layer generally refers to a photoactive thin film layer with a perovskite crystal structure that can effectively absorb sunlight, prepared by the method described in this disclosure, and whose function is to convert photons into electron-hole pairs. This layer comprises a three-dimensional, two-dimensional, or low-dimensional perovskite crystal structure composed of organic cations, metal cations, and halide anions.

[0076] Optionally, the thickness of the perovskite light-absorbing layer is greater than or equal to 500 nm and less than or equal to 1200 nm, for example, it can be 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, etc.

[0077] Optionally, the method of coating the mixed solution onto at least a portion of the surface of the skeleton layer includes at least one of slot coating and spin coating. Annealing can provide thermal energy to drive the components in the permeated mixed solution to react with the skeleton layer, crystallize, and remove residual solvent.

[0078] For example, during the annealing process, organic halide salts in the solution react with PbI2 in the framework layer to generate perovskite crystals, while additive molecules participate in and regulate this process, ultimately forming a perovskite light-absorbing layer.

[0079] For example, the crystallization status of perovskite can be determined by characterization methods such as X-ray diffraction and scanning transmission electron microscopy.

[0080] For example, the introduction of additives alters the properties of organic halides in the mixed solution, enabling them to initiate a more gentle and orderly reaction upon contact with the framework layer. Through their multiple interactions, these additives guide preferential grain growth and passivate newly formed defects. The synergy between the additives and the organic halides results in a perovskite light-absorbing layer with larger grains, fewer grain boundary defects, and superior interfacial properties, thereby regulating the degree of perovskite crystallinity and improving defect passivation.

[0081] Optionally, the annealing treatment meets at least one of the following conditions: humidity greater than or equal to 5% and less than or equal to 40% (e.g., 5%, 10%, 20%, 30%, or 40%); temperature greater than or equal to 100 °C and less than or equal to 170 °C (e.g., 100 °C, 120 °C, 140 °C, 160 °C, or 170 °C); and time greater than or equal to 15 min and less than or equal to 30 min (e.g., 15 min, 20 min, 25 min, or 30 min). It is understood that within the above annealing temperature range, the additive will not decompose, and during the annealing process, the halogens in the additive can continuously fill the halogen vacancies in the perovskite, and the carboxyl groups can continuously lock the metal ions in the framework layer, resulting in a more uniform and dense perovskite film.

[0082] For example, before fabricating the framework layer on one side of the substrate, the method further includes: sequentially fabricating a composite layer and a hole transport layer on one side of the first battery cell.

[0083] For example, the composite layer can be made of at least one of indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), and the composite layer has high mobility and transmittance, with a thickness of 2 nm to 30 nm (e.g., 2 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, or 30 nm, etc.).

[0084] For example, the method for fabricating a solar cell module further includes: sequentially fabricating a passivation layer, an electron transport layer, a buffer layer, a transparent electrode layer, and a positive electrode on the side of the perovskite light-absorbing layer facing away from the substrate.

[0085] In one embodiment, the substrate includes a first cell. Exemplarily, the method for fabricating a solar cell module further includes: fabricating a back electrode on the side of the first cell facing away from the perovskite light-absorbing layer, and fabricating an anti-reflection layer on the side of the positive electrode facing away from the substrate.

[0086] For example, a method for manufacturing a solar cell module includes the following steps: 1. Provide HJT battery cells. HJT battery cells can be commercially available batteries.

[0087] 2. A composite layer is prepared on the HJT battery cell. The composite layer material is at least one of IZO and ITO. The thickness of the composite layer is 2 nm to 30 nm.

[0088] 3. A hole transport layer and a modification layer are sequentially prepared on the composite layer. The hole transport layer is made of nickel oxide, and the modification layer is made of a single-molecule self-assembled material (such as at least one of (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2PACz) and (2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl)phosphonic acid (MeO-2PACz); the hole transport layer has a thickness of 5 nm to 30 nm.

[0089] 4. Preparation of the perovskite light-absorbing layer. The specific method is as follows: PbI2 and CsBr were co-deposited using a vacuum thermal evaporation coating apparatus to obtain a framework layer. The evaporation ratio of PbI2 to CsBr was 6:1, and the thickness of the framework layer was 300 nm to 550 nm.

[0090] FAI, DMAI, MAI, MACl, FACl, and 2,6-dichloropyridine-3-carboxylic acid were dissolved in isopropanol to obtain a mixed solution. The molar ratio of FAI, DMAI, MAI, MACl, and FACl was 50:10:20:10:5, and the concentration of 2,6-dichloropyridine-3-carboxylic acid was 1 mg / mL to 5 mg / mL.

[0091] The mixed solution was applied to the framework layer via slit coating, and finally annealed to obtain the perovskite light-absorbing layer. The thickness of the perovskite light-absorbing layer ranged from 500 nm to 1200 nm.

[0092] 5. A passivation layer is prepared on the perovskite light-absorbing layer using a slit coating process; the passivation layer material is LiF or MgF2, and the thickness is 0.5 nm to 5 nm.

[0093] 6. An electron transport layer is deposited on the passivation layer by vapor deposition; the electron transport layer material is C60, the thickness is 5 nm to 30 nm, and the evaporation rate is 0.2 Å / s to 0.3 Å / s.

[0094] 7. A buffer layer is prepared on the electron transport layer by atomic layer deposition (ALD); the buffer layer material is tin dioxide (SnO2), and the thickness of the buffer layer is 5 nm to 30 nm.

[0095] 8. On the buffer layer, a patterned transparent electrode is prepared by physical vapor deposition (PVD); the transparent electrode material can be ITO or IZO, and the thickness is 30 nm-150 nm.

[0096] 9. Deposit a positive electrode onto a transparent electrode; the positive electrode is a patterned metal electrode, which can be made of silver (Ag) or copper (Cu), with a thickness of 150 nm-300 nm and an evaporation rate of 2 Å / s-4 Å / s.

[0097] 10. After completing the above steps, deposit a back electrode on the side of the HJT cell away from the perovskite light absorption layer. The material of the back electrode can be silver (Ag) or copper (Cu), with a thickness of 150 nm-300 nm and an evaporation rate of 2 Å / s-4 Å / s.

[0098] 11. Prepare an antireflection layer on the positive electrode. The antireflection layer is prepared by vapor deposition. The material of the antireflection layer can be MgF2 or LiF, the thickness is 100 nm-120 nm, and the evaporation rate is 0.5 Å / s-2 Å / s.

[0099] The second aspect of this disclosure provides a solar cell module, which is prepared using the method for preparing a solar cell module as provided in the first aspect.

[0100] A third aspect of this disclosure provides a solar cell, including a solar cell module as provided in the second aspect.

[0101] It should be noted that, in addition to the aforementioned solar cell modules, solar cells may also include the structures that conventional solar cells should have, such as the casing and encapsulation structure, which will not be elaborated on further here.

[0102] The present disclosure will be further illustrated below with reference to the embodiments. It should be noted that the following embodiments are only used to explain the present disclosure and should not be construed as limiting the present disclosure.

[0103] Example 1 The method for manufacturing solar cell modules includes the following steps: 1. Provide HJT battery cells. HJT battery cells can be commercially available batteries.

[0104] 2. A composite layer is prepared on the HJT battery cell. The composite layer material is ITO and the thickness of the composite layer is 20 nm.

[0105] 3. A hole transport layer and a modification layer were sequentially prepared on the composite layer. The hole transport layer was made of nickel oxide, and the modification layer was made of the single-molecule self-assembled material 2PACz; the hole transport layer had a thickness of 20 nm.

[0106] 4. Prepare a perovskite light-absorbing layer.

[0107] PbI2 and CsBr were co-deposited using a vacuum thermal evaporation coating apparatus to obtain a framework layer. The evaporation ratio of PbI2 to CsBr was 6:1, and the thickness of the framework layer was 450 nm.

[0108] FAI, DMAI, MAI, MACl, FACl, and 2,6-dichloropyridine-3-carboxylic acid were dissolved in isopropanol to obtain a mixed solution. The molar ratio of FAI, DMAI, MAI, MACl, and FACl was 50:10:20:10:5, and the concentration of 2,6-dichloropyridine-3-carboxylic acid was 3 mg / mL.

[0109] The mixed solution was coated onto the framework layer using slit coating, and then annealed at 150°C for 20 min under conditions of 20% humidity to obtain the perovskite light-absorbing layer. The thickness of the perovskite light-absorbing layer was 600 nm. A scanning electron microscope image of the perovskite light-absorbing layer is shown below. Figure 4 As shown, the X-ray diffraction pattern (XRD) of the perovskite light-absorbing layer is as follows: Figure 6 As shown.

[0110] 5. A passivation layer is prepared on the perovskite light-absorbing layer using a slit coating process; the passivation layer material is LiF or MgF2, and the thickness is 3 nm.

[0111] 6. An electron transport layer is deposited on the passivation layer by vapor deposition; the electron transport layer material is C60, the thickness is 20 nm, and the evaporation rate is 0.3 Å / s.

[0112] 7. A buffer layer is prepared on the electron transport layer by atomic layer deposition; the buffer layer material is tin dioxide (SnO2), and the thickness of the buffer layer is 20 nm.

[0113] 8. A patterned transparent electrode is fabricated on the buffer layer by physical vapor deposition; the transparent electrode material is ITO and the thickness is 100 nm.

[0114] 9. A positive electrode is deposited on the transparent electrode by vapor deposition; the positive electrode is a patterned metal electrode made of silver with a thickness of 200 nm and an evaporation rate of 3 Å / s.

[0115] 10. After completing the above steps, deposit a back electrode on the side of the HJT cell away from the perovskite light absorption layer; the material of the back electrode is silver, the thickness is 200 nm, and the evaporation rate is 3 Å / s.

[0116] 11. An antireflection layer is prepared on the positive electrode. The antireflection layer is prepared by vapor deposition. The material of the antireflection layer is MgF2, the thickness is 120 nm, and the evaporation rate is 1 Å / s.

[0117] Example 2 The preparation method of the solar cell module is basically the same as that in Example 1, except that the concentration of 2,6-dichloropyridine-3-carboxylic acid in step 4 is 1 mg / mL.

[0118] Example 3 The preparation method of the solar cell module is basically the same as that in Example 1, except that the concentration of 2,6-dichloropyridine-3-carboxylic acid in step 4 is 5 mg / mL.

[0119] Example 4 The preparation method of the solar cell module is basically the same as that in Example 1, except that the concentration of 2,6-dichloropyridine-3-carboxylic acid in step 4 is 0.1 mg / mL.

[0120] Example 5 The preparation method of the solar cell module is basically the same as that in Example 1, except that the concentration of 2,6-dichloropyridine-3-carboxylic acid in step 4 is 8 mg / mL.

[0121] Example 6 The preparation method of the solar cell module is basically the same as in Example 1, except that 2,6-dichloropyridine-3-carboxylic acid in step 4 is replaced with 2,5-dichloropyridine-3-carboxylic acid.

[0122] Example 7 The preparation method of the solar cell module is basically the same as in Example 1, except that 2,6-dichloropyridine-3-carboxylic acid in step 4 is replaced with 2,4-dichloropyridine-3-carboxylic acid.

[0123] Example 8 The preparation method of the solar cell module is basically the same as in Example 1, except that 2,6-dichloropyridine-3-carboxylic acid in step 4 is replaced with 2,6-dichloropyridine-4-carboxylic acid.

[0124] Example 9 The preparation method of the solar cell module is basically the same as in Example 1, except that 2,6-dichloropyridine-3-carboxylic acid in step 4 is replaced with 2,5-dichloropyridine-4-carboxylic acid.

[0125] Example 10 The preparation method of the solar cell module is basically the same as in Example 1, except that 2,6-dichloropyridine-3-carboxylic acid in step 4 is replaced with 2,3-dichloropyridine-4-carboxylic acid.

[0126] Example 11 The fabrication method of the solar cell module is basically the same as in Example 1, except that step 4 is replaced with the following steps: PbI2, CsBr, FAI, DMAI, MAI, MACl, FACl, and 2,6-dichloropyridine-3-carboxylic acid were dissolved in isopropanol to obtain a mixed solution. The molar ratio of FAI, DMAI, MAI, MACl, and FACl was 50:10:20:10:5, and the concentration of 2,6-dichloropyridine-3-carboxylic acid was 3 mg / mL.

[0127] The mixed solution was applied to the modified layer via slit coating, and then annealed at 150°C for 20 min under conditions of 20% humidity to obtain the perovskite light-absorbing layer. The thickness of the perovskite light-absorbing layer was 600 nm.

[0128] Comparative Example 1 The fabrication method of the solar cell module is basically the same as in Example 1, except that the mixed solution in step 4 does not contain 2,6-dichloropyridine-3-carboxylic acid. A scanning electron microscope image of the perovskite light-absorbing layer is shown below. Figure 5 As shown, the XRD pattern of the perovskite light-absorbing layer is as follows: Figure 6 As shown.

[0129] Comparative Example 2 The preparation method of the solar cell module is basically the same as in Example 1, except that in step 4, 2,6-dichloropyridine-3-carboxylic acid is replaced with 6-chlorohexanoic acid.

[0130] Comparative Example 3 The preparation method of the solar cell module is basically the same as in Example 1, except that in step 4, 2,6-dichloropyridine-3-carboxylic acid is replaced with an equal amount of a mixture of 1,3-dichlorobenzene and nicotinic acid, and the molar ratio of 1,3-dichlorobenzene and nicotinic acid is 1:1.

[0131] Comparative Example 4 The preparation method of the solar cell module is basically the same as in Example 1, except that in step 4, 2,6-dichloropyridine-3-carboxylic acid is replaced with 2,6-dichloropyridine-3-phosphoric acid.

[0132] Comparative Example 5 The preparation method of the solar cell module is basically the same as that in Example 1, except that in step 4, 2,6-dichloropyridine-3-carboxylic acid is replaced with methylammonium chloride.

[0133] Performance testing of solar cell modules (including open-circuit voltage, V) OC Fill factor (FF), Short-circuit current density (J) SC The photoelectric conversion efficiency (PCE) was measured under global standard solar spectrum (standard AM 1.5G illumination) conditions of atmospheric mass 1.5. The stability test of the solar cell module involved placing it in an air environment (temperature 25±5°C, relative humidity 30%±10%). Before testing, the simulated solar intensity was calibrated using a standard silicon cell.

[0134] The performance test results of the solar cell modules of Examples 1-11 and Comparative Examples 1-4 are shown in Table 1 below: Table 1 As can be seen from the data of Examples 1 to 11 and Comparative Example 1, the fill factor of the solar cell module with the additives of the present disclosure is significantly improved when the perovskite light-absorbing layer is prepared.

[0135] from Figure 6 It can be seen that the perovskite characteristic peak intensity of the perovskite light-absorbing layer obtained in Example 1 is higher than that of the perovskite light-absorbing layer in Comparative Example 1, indicating that the introduction of 2,6-dichloropyridine-3-carboxylic acid is beneficial to the crystallization of perovskite.

[0136] The data from Example 1 and Comparative Example 2 show that additives with large π bonds in their molecular skeleton rings are more effective.

[0137] As can be seen from the data of Example 1 and Comparative Example 3, setting halogens and carboxyl groups in the same additive molecule is more effective than setting halogens and carboxyl groups in different additive molecules.

[0138] The data from Example 1 and Comparative Example 4 show that additives containing both halogens and carboxyl groups are more effective.

[0139] As can be seen from the data of Example 1 and Comparative Example 5, the additive in Example 1 is more effective than conventional methyl ammonium chloride.

[0140] The basic principles of this disclosure have been described above with reference to specific embodiments. However, it should be noted that the advantages, benefits, and effects mentioned in this disclosure are merely examples and not limitations, and should not be considered as essential features of each embodiment of this disclosure. Furthermore, the specific details disclosed above are for illustrative and facilitative purposes only, and are not limitations. These details do not limit the scope of this disclosure to the necessity of employing the aforementioned specific details for implementation.

[0141] The above description has been given for purposes of illustration and description. Furthermore, this description is not intended to limit the embodiments of this disclosure to the forms disclosed herein. Although numerous exemplary aspects and embodiments have been discussed above, those skilled in the art will recognize certain variations, modifications, alterations, additions, and sub-combinations thereof.

Claims

1. A method for producing a solar cell module, characterized by, include: A metal halide, an organic halide, and an additive are mixed on one side of a substrate to obtain a mixture; the molecular structure of the additive includes at least one skeletal ring, at least one carboxyl group, and at least one halogen, wherein the at least one skeletal ring includes a conjugated ring with a delocalized large π bond; the skeletal ring includes a plurality of atoms connected end-to-end, the carboxyl group is connected to the atom on the skeletal ring, the halogen is connected to the atom on the skeletal ring, and the atom connecting the carboxyl group and the atom connecting the halogen are different; The mixture is annealed to obtain a perovskite light-absorbing layer.

2. The production method according to claim 1, characterized by, The number of atoms on the same skeletal ring is greater than or equal to 4 and less than or equal to 8; Preferably, the number of the skeleton rings is less than or equal to 3; Preferably, adjacent skeletal rings are connected by chemical bonds, and / or at least two skeletal rings share two carbon atoms; Preferably, one or two atoms on the same skeletal ring are chemically bonded to the halogen; Preferably, one or two atoms on the same skeletal ring are chemically bonded to the carboxyl group; Preferably, the halogen is chemically bonded to the carboxyl group within the same skeletal ring; Preferably, the carboxyl group is connected to the atom on the conjugated ring, and / or, the halogen is connected to the atom on the conjugated ring.

3. The method of claim 1, wherein, At least one atom on the skeleton ring is a nitrogen atom; Preferably, the atom connecting the carboxyl group and the nitrogen atom are arranged in a meta-position on the same skeletal ring; Preferably, the halogen includes at least one of chlorine, bromine, and iodine.

4. The production method according to any one of claims 1 to 3, characterized by, The skeletal ring includes a pyridine ring; Preferably, the additive comprises at least one selected from 2,6-dichloropyridine-3-carboxylic acid, 2,5-dichloropyridine-3-carboxylic acid, 2,4-dichloropyridine-3-carboxylic acid, 2,6-dichloropyridine-4-carboxylic acid, 2,5-dichloropyridine-4-carboxylic acid, 2,3-dichloropyridine-4-carboxylic acid, and 3,5-dichloropyridine-4-carboxylic acid.

5. The preparation method according to claim 1, characterized in that, The process of mixing metal halides, organic halide salts, and additives on one side of the substrate includes: A framework layer is prepared on one side of the substrate, the framework layer comprising the metal halide; The organic halide and the additive are dispersed in a solvent to obtain a mixed solution; The mixture is obtained by coating the mixed solution onto at least a portion of the surface of the skeleton layer.

6. The production method according to claim 5, wherein The preparation of the skeleton layer on one side of the substrate includes: The framework layer is prepared on one side of the substrate by vapor deposition. Preferably, the vapor deposition method includes at least one of single-source vapor deposition, dual-source vapor deposition, and triple-source vapor deposition; Preferably, the preparation of the framework layer on one side of the substrate by vapor deposition includes: The skeleton layer is obtained by evaporating a first evaporation source and a second evaporation source together on one side of the substrate. The first evaporation source evaporates PbX2 and the second evaporation source evaporates CsY. The ratio of the evaporation rate of the first evaporation source to the evaporation rate of the second evaporation source is greater than or equal to 5:1 and less than or equal to 10:

1. X includes I, and Y includes at least one of Br, Cl and I; Preferably, the preparation of the framework layer on one side of the substrate by vapor deposition includes: The framework layer is obtained by evaporating a first evaporation source, a second evaporation source, and a third evaporation source together on one side of the substrate. The first evaporation source evaporates PbX2, the second evaporation source evaporates CsY, and the third evaporation source evaporates at least one of PbZ2 and CsM. Z includes at least one of Br and Cl, and M includes at least one of I and Cl. X is different from Z, and Y is different from M. Preferably, the evaporation rate of the first evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s, and / or the evaporation rate of the second evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s, and / or the evaporation rate of the third evaporation source is greater than or equal to 0.2 Å / s and less than or equal to 0.4 Å / s; Preferably, the thickness of the skeleton layer is greater than or equal to 300 nm and less than or equal to 550 nm; Preferably, the thickness of the perovskite light-absorbing layer is greater than or equal to 500 nm and less than or equal to 1200 nm.

7. The preparation method according to claim 5, characterized in that, The organic halide includes at least one of formamidinium iodide, dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidinium chloride; Preferably, the molar ratio of formamidinium iodide, dimethylammonium iodide, methylammonium iodide, methylammonium chloride, and formamidinium chloride is (40~60):(5~15):(10~30):(5~15):(1~10). Preferably, in the mixed solution, the concentration of the additive is greater than or equal to 1 mg / mL and less than or equal to 5 mg / mL; Preferably, the solvent includes isopropanol; Preferably, the method of coating the mixed solution onto at least a portion of the surface of the skeleton layer includes at least one of slot coating and spin coating; Preferably, the annealing process satisfies at least one of the following conditions: Humidity is greater than or equal to 5% and less than or equal to 40%; The temperature is greater than or equal to 100 ℃ and less than or equal to 170 ℃; The time is greater than or equal to 15 minutes and less than or equal to 30 minutes.

8. The method of claim 1, wherein, The substrate includes a first battery cell; Preferably, the first battery cell includes a crystalline silicon battery cell having a textured surface, and the perovskite light-absorbing layer is grown conformally along the textured surface.

9. A solar cell module characterized by comprising: The solar cell module is prepared using the method described in any one of claims 1 to 8.

10. A solar cell, characterized by, Includes the solar cell module as described in claim 9.

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