Conductive glass composite layer, perovskite solar cell and preparation method thereof

Abstract

This application relates to the field of perovskite cell technology, particularly to a conductive glass composite layer, a perovskite solar cell, and methods for preparing the same. The conductive glass composite layer comprises a sequentially stacked white glass layer, a conductive metal oxide layer, a self-assembled monolayer, and a protective layer; the protective layer comprises an organic salt and a polymer material. The conductive glass composite layer is stable in storage, eliminates interference from water and oxygen, and maintains the integrity and effectiveness of the SAM layer. It can serve as an upstream product for perovskite cell manufacturers, enabling the preparation of perovskite cells with excellent performance and stability.

Description

Technical Field

[0001] The present application relates to the technical field of perovskite cells, and in particular to a conductive glass composite layer, a perovskite solar cell and a preparation method thereof. Background Art

[0002] Perovskite solar cells (PVSCs) utilize perovskite-type organic metal halide semiconductors as light-absorbing materials. Their primary components include a metal counter electrode, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and transparent conductive glass. Due to their high performance, low cost, and simple manufacturing process, perovskite solar cells (PVSCs) have become one of the most promising next-generation solar technologies.

[0003] Self-assembled monolayers (SAMs) are ordered monolayers formed spontaneously by adsorption on solid substrates. They are currently widely used to improve the performance and stability of perovskite solar cells. However, perovskite solar cells using SAMs as charge transport materials face challenges in industrialization, such as low efficiency and poor fabrication reproducibility. These issues are related to the material properties, fabrication process, and equipment precision.

[0004] To promote the application of SAMs in perovskite cells and improve cell efficiency and fabrication reproducibility, one option is to pre-fabricate the charge transport material for perovskite cells onto conductive glass using a stable process and then provide this product as an upstream product for cell manufacturers. However, no relevant technical solutions have been reported so far. Summary of the Invention

[0005] Based on this, this application studies and develops a conductive glass composite layer, which is a prefabricated composite structure with a self-assembled monomolecule functional (SAM) layer. It can be used as an upstream product for perovskite battery manufacturers and used to prepare perovskite batteries with good performance and stability.

[0006] The present application also found that in perovskite cells using SAM as a charge transport material, the SAM material anchored on the metal oxide surface in a single-molecule layer state at the nanoscale is susceptible to environmental factors such as water, oxygen, light, and heat, and gradually desorbs or decomposes over time, resulting in reduced efficiency or even failure of the subsequently prepared cells. Based on this, the purpose of the present application also includes providing a conductive glass composite layer that can be stably stored and can maintain the integrity and effectiveness of the SAM layer during storage, thereby solving the problem of low efficiency or even failure of perovskite cells using SAM as a charge transport material due to interference from water and oxygen during storage.

[0007] The technical solution of this application includes the following contents:

[0008] A first aspect of the present application provides a conductive glass composite layer, the conductive glass composite layer comprising a white glass layer, a conductive metal oxide layer, a self-assembled monolayer and a protective layer stacked in sequence;

[0009] The protective layer comprises an organic salt and a polymer material;

[0010] The polymer material is a homopolymer material or a copolymer material;

[0011] The homopolymer material is polyvinylidene fluoride, polydimethylsiloxane, polyethyl methacrylate, polyethylene glycol diacrylate, polystyrene or poly(2-ethyl-2-oxazoline);

[0012] The monomers of the copolymer material include one or more of ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, acrylamide, N-(hydroxymethyl)acrylamide, isocyanate ethyl acrylate, phenyl methacrylate, N-phenylmethacrylamide and N-[4-cyano-3-(trifluoromethyl)phenyl]methacrylamide.

[0013] Furthermore, the monomers of the copolymer material include any two of ethyl acrylate, ethyl methacrylate, acrylamide and N-hydroxymethyl acrylamide; and / or,

[0014] The preparation method of the copolymer material comprises the following steps: in the presence of an initiator, polymerizing the monomers to obtain the copolymer material.

[0015] Furthermore, the initiator is a photoinitiator;

[0016] The polymerization conditions include ultraviolet light irradiation.

[0017] In some embodiments, the cation of the organic salt is selected from imidazolium, pyridinium, piperidinium, morpholinium, pyrrolium, ammonium, phosphonium or sulfonium, and the anion is selected from halogen, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, alkyl carboxylate, alkyl sulfate, alkyl sulfonate, alkyl phosphate, alkyl phosphonate, dicyanamide, bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide or trifluoromethanesulfonate.

[0018] Furthermore, the organic salt is selected from 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate or 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

[0019] In some embodiments, the molar ratio of the homopolymer material to the organic salt is 1-3:1; and / or,

[0020] The ratio of the molar number of the monomer of the copolymer material to the molar number of the organic salt is 1.2-1.3:0.6.

[0021] A second aspect of the present application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0022] Distributing a perovskite precursor solution on the protective layer of the conductive glass composite layer described above, and after the protective layer is dissolved, performing vacuum flash evaporation to form a mesophase film;

[0023] The mesophase film is annealed to form a perovskite layer.

[0024] Furthermore, the perovskite precursor solution comprises a precursor of an ABX3 type perovskite material and a solvent;

[0025] The ions corresponding to the A position in the precursor of the ABX3 type perovskite material include CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + and Cs + At least one of the ions corresponding to the B position includes Pb 2+ and Sn 2+ At least one of the ions corresponding to the X position includes Br - , I - 、Cl - and SCN - At least one of;

[0026] The solvent includes at least one of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and 2-methoxyethanol.

[0027] Furthermore, the solvent is a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone.

[0028] The third aspect of the present application provides a perovskite cell produced using the method for producing a perovskite solar cell as described above.

[0029] The conductive glass composite layer of the present application has a specific layered structure, which includes a white glass layer, a conductive metal oxide layer, a self-assembled monolayer and a protective layer stacked in sequence; the protective layer is composed of a polymer and an organic salt, and can effectively isolate water and oxygen in a high-temperature and high-humidity environment to prevent the self-assembled monolayer from being damaged. It can be stored stably and can maintain the integrity and effectiveness of the SAM layer during storage; moreover, the protective layer can be dissolved in a perovskite precursor solution without affecting the preparation of perovskite cells. The residual components after dissolution have no effect on the efficiency of the perovskite cell or can play a certain protective and modifying role. It can be used as an upstream product of perovskite cell manufacturers and used to prepare perovskite cells with good performance and stability, solving the problem of low efficiency or even failure of perovskite cells using SAM as a charge transport material due to interference from water and oxygen during storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0031] Figure 1 The structural formulas and corresponding names of some of the compounds in this application;

[0032] Figure 2 This is a schematic structural diagram of a conductive glass composite layer according to an embodiment of the present application;

[0033] Figure 3 This is a schematic structural diagram of a perovskite battery according to an embodiment of the present application;

[0034] Figure 4 A comparison chart of the photoelectric conversion efficiency over time of Examples 1, 2, 4, 5, 10, and 11 of the present application and Comparative Example 1;

[0035] Reference numerals:

[0036] 1-protective layer, 2-self-assembled monolayer, 3-conductive metal oxide layer, 4-white glass layer, 5-metal electrode, 6-stack of functional layers, from bottom to top including self-assembled monolayer, perovskite layer, passivation layer, electron transport layer, and hole blocking layer. DETAILED DESCRIPTION

[0037] Below in conjunction with embodiment and example, further elaborate the application.It should be understood that these examples are only used to illustrate the application and are not used to limit the scope of the application.In addition, it should be understood that after reading the content taught in this application, those skilled in the art can make various changes or modifications to the application, and these equivalent forms also fall within the protection scope of the claims appended hereto.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0039] the term

[0040] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0041] The term "and / or" as used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, wherein the any and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical and" and technical solutions connected by "logical or". For example, "A and / or B" includes three parallel solutions: A, B, and A+B.

[0042] In this application, "further" is used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

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

[0044] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0045] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the numerical interval is considered continuous and includes the two numerical endpoints of the numerical range (i.e., the minimum and maximum values), as well as every numerical value between these two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two numerical endpoints of the numerical range, as well as every integer between the two endpoints. In addition, when multiple ranges are provided to describe a feature or characteristic, these ranges can be combined. In other words, unless otherwise specified, ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0046] Unless otherwise specified, the temperature parameters in this application may be either constant temperature or fluctuating within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the precision range of the instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0047] In this application, weight can be μg, mg, g, kg and other mass units known in the chemical and material fields.

[0048] The structural formulas and corresponding names of some of the compounds involved in this application are shown in the attached Figure 1 . Figure 1Substituents such as R, R1, R2, R3, and R4 refer to alkyl groups, preferably C1-C9 alkyl groups. As used herein, the term "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, secondary carbon atoms, tertiary carbon atoms, quaternary carbon atoms, or combinations thereof. Phrases containing this term, such as "C1-C9 alkyl," refer to alkyl groups containing 1 to 9 carbon atoms, and each occurrence may independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( 2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0049] In this application, the mole number of a homopolymer refers to the mole number of its repeating units.

[0050] In a first aspect, one or more embodiments of the present application provide a conductive glass composite layer, the conductive glass composite layer comprising a white glass layer, a conductive metal oxide layer, a self-assembled monolayer, and a protective layer stacked in sequence;

[0051] The protective layer comprises a polymer material;

[0052] The polymer material is a homopolymer material or a copolymer material;

[0053] The homopolymer material is polyvinylidene fluoride, polydimethylsiloxane, polyethyl methacrylate, polyethylene glycol diacrylate, polystyrene or poly(2-ethyl-2-oxazoline);

[0054] The monomers of the copolymer material include one or more of ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, acrylamide, N-(hydroxymethyl)acrylamide, isocyanate ethyl acrylate, phenyl methacrylate, N-phenylmethacrylamide and N-[4-cyano-3-(trifluoromethyl)phenyl]methacrylamide.

[0055] The conductive glass composite layer of the present application has a specific layered structure, and the conductive glass composite layer includes a white glass layer, a conductive metal oxide layer, a self-assembled monolayer and a protective layer stacked in sequence; the protective layer is composed of a polymer material prepared by polymerization of polymer monomers and organic salts. The polymer material can effectively isolate water and oxygen in a high temperature and high humidity environment, prevent the self-assembled monolayer from being damaged, can be stably stored, and can maintain the functional integrity and effectiveness of the SAM layer during storage; and the polymer material can be dissolved in the precursor solution of the perovskite without affecting the preparation of the perovskite battery. At the same time, the residual components after dissolution have no effect on the efficiency of the perovskite battery, or can play a certain protective and modifying role, thereby having a positive impact. It can be used as an upstream product of perovskite battery manufacturers and used to prepare perovskite batteries with good performance and stability, solving the problem of low efficiency or even failure of perovskite batteries using SAM as a charge transport material due to interference from water and oxygen during storage.

[0056] In some embodiments, the polymer material is a homopolymer material, such as polyvinylidene fluoride (PVDF), polydimethylsiloxane (PDMS), polyethyl methacrylate (PMMA), polyethylene glycol diacrylate (PEGDA), polystyrene (PS), poly(2-ethyl-2-oxazoline) (PEOz), etc.

[0057] In some embodiments, the polymer material is a copolymer material, and the monomers of the copolymer material include any one or more of ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, acrylamide, N-(hydroxymethyl)acrylamide, isocyanate ethyl acrylate, phenyl methacrylate, N-phenylmethylacrylamide, N-[4-cyano-3-(trifluoromethyl)phenyl]methylacrylamide, etc.

[0058] In some embodiments, the monomers of the copolymer material include any two of ethyl acrylate, ethyl methacrylate, acrylamide, and N-methylol acrylamide.

[0059] In some embodiments, the monomers of the copolymer material include a first monomer and a second monomer, wherein the first monomer and the second monomer are respectively selected from ethyl acrylate, ethyl methacrylate, acrylamide, and N-methylol acrylamide, and are different from each other.

[0060] Furthermore, the molar ratio of the first monomer to the second monomer is 1:0.2-0.3, for example 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29, 1:0.3, etc.

[0061] In some embodiments, the method for preparing the copolymer material comprises the following steps: subjecting the monomers to a polymerization reaction in the presence of an initiator to obtain the copolymer material.

[0062] In some embodiments, the step of polymerizing a polymer monomer and an organic salt in the presence of an initiator to prepare the polymer material comprises:

[0063] The polymer monomer and the organic salt are stirred at a suitable temperature until all the solids are dissolved, the organic salt is added and stirred evenly to obtain a mixed solution; and the mixed solution is subjected to a polymerization reaction.

[0064] In this embodiment, the suitable temperature can be 50-70°C, for example 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C, etc., and the time for stirring until all solids are dissolved can be 1-2h, for example 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, etc., or adjusted according to actual conditions in order to obtain a uniform polymerization reaction system; the organic salt is added and continued to be stirred evenly, and the required time can be 20-40min, for example 20min, 22min, 25min, 28min, 30min, 32min, 35min, 38min, 40min, etc., or adjusted according to actual conditions in order to obtain a uniform polymerization reaction system.

[0065] In some embodiments, the initiator is a photoinitiator;

[0066] The polymerization conditions include ultraviolet light irradiation.

[0067] Furthermore, the wavelength of the ultraviolet light is 365 nm, and the ultraviolet light irradiation time is 1-2 h, for example, 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h, etc.

[0068] In some embodiments, the amount of initiator added is 0.2-0.3% of the first monomer, for example 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, etc., to ensure that the polymerization reaction can proceed in a controlled manner.

[0069] In some embodiments, the cation of the organic salt is selected from imidazolium, pyridinium, piperidinium, morpholinium, pyrrolium, ammonium, phosphonium or sulfonium, and the anion is selected from halogen, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, alkyl carboxylate, alkyl sulfate, alkyl sulfonate, alkyl phosphate, alkyl phosphonate, dicyanamide, bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide or trifluoromethanesulfonate.

[0070] Furthermore, the organic salt is selected from 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate or 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

[0071] In some embodiments, the molar ratio of the homopolymer material to the organic salt is 1-3:1, for example 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.1:1, 2.2:1, 2.5:1, 2.8:1, 3:1, etc.

[0072] In some embodiments, the ratio of the total molar number of monomers of the copolymer material to the molar number of the organic salt is 1.2-1.3:0.6, for example 2:1 (1.2:0.6), 121:6 (1.21:0.6), 61:3 (1.22:0.6), 125:6 (1.25:0.6), 63:3 (1.26:0.6), 64:3 (1.28:0.6), 13:6 (1.3:0.6), etc.

[0073] In a second aspect, one or more embodiments of the present application provide a method for preparing a perovskite solar cell, comprising the following steps:

[0074] distributing a perovskite precursor solution on the protective layer of the conductive glass composite layer, and after the protective layer is dissolved, performing vacuum flash evaporation to form an intermediate phase film;

[0075] The mesophase film is annealed to form a perovskite layer.

[0076] Furthermore, the perovskite precursor solution comprises a precursor of an ABX3 type perovskite material and a solvent;

[0077] The ions corresponding to the A position in the precursor of the ABX3 type perovskite material include CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + and Cs + At least one of the ions corresponding to the B position includes Pb 2+ and Sn 2+ At least one of the ions corresponding to the X position includes Br - , I - 、Cl - and SCN - At least one of;

[0078] The solvent includes at least one of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and 2-methoxyethanol.

[0079] Furthermore, the solvent is a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone.

[0080] Preferably, the volume ratio of N, N-dimethylformamide and N-methylpyrrolidone is 8-12:1, for example 8:1, 9:1, 10:1, 11:1, 12:1, etc., which is beneficial to improve the wettability of the perovskite precursor solution on the protective layer of the conductive glass composite layer and better dissolve the material of the protective layer.

[0081] The following are some specific examples.

[0082] For experimental parameters not specified in the following specific examples, reference is made to the guidance given in this application document, and reference may also be made to experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.

[0083] The raw materials and reagents involved in the following specific examples can be obtained commercially, or can be prepared by those skilled in the art according to known methods.

[0084] Some raw material abbreviations and source information:

[0085] Photoinitiator 2959: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (UV2959) was purchased from Aladdin.

[0086] EA: ethyl acrylate, purchased from Aladdin.

[0087] EMA: ethyl methacrylate, purchased from Aladdin.

[0088] AM: Acrylamide, purchased from Aladdin.

[0089] HMAM: N-hydroxymethyl acrylamide, purchased from Aladdin.

[0090] B: 1-Ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4), purchased from Aladdin.

[0091] P: 1-ethyl-3-methylimidazolium hexafluorophosphate (EmimPF6), purchased from Aladdin.

[0092] T: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (EmimTFSI), purchased from Aladdin.

[0093] SAM (MeO-2PACz): [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, purchased from Aladdin.

[0094] The instruments used in this article can all be purchased.

[0095] 1. Preparation of Conductive Glass Composite Layers of Various Examples and Comparative Examples

[0096] 1. Prepare the raw materials according to Table 1.

[0097] Table 1 Formulations of polymer materials of Examples 1 to 12

[0098]

[0099] 2. The polymer materials of each embodiment were prepared in the following general manner:

[0100] Under nitrogen protection, the first monomer, the second monomer and the organic salt were added to a reaction flask and mixed. After stirring at 60°C until all the solids were dissolved, an initiator was added and stirring was continued for 30 minutes to obtain a mixed solution. The mixed solution was placed under ultraviolet light with a wavelength of 365 nm and polymerized for 1.5 hours to obtain a polymer material.

[0101] 3. The conductive glass composite layer of each embodiment is prepared in the following general manner:

[0102] (1) Ultrasonic cleaning of FTO glass with surfactant, deionized water, acetone, and isopropanol for 20 minutes respectively, and drying for later use;

[0103] (2) SAM (MeO-2PACz) ethanol solution (concentration of 1 mg / mL) was slit-coated on FTO glass and annealed at 100°C for 10 minutes to obtain FTO glass with SAM deposited (thickness 1 nm);

[0104] (3) Use laser scribing equipment to etch P1 lines on the FTO glass with SAM deposited;

[0105] (4) An ethanol solution of the polymer material (concentration of 2 mg / mL) was slit-coated onto the FTO glass with SAM deposited on it, and then annealed at 100°C for 5 minutes to obtain a conductive glass with a functional layer (thickness of 10 nm).

[0106] Comparative Example 1

[0107] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that step (4) was omitted compared to Example 1. The specific steps were as follows:

[0108] (1) Ultrasonic cleaning of FTO glass with surfactant, deionized water, acetone, and isopropanol for 20 minutes respectively, and drying for later use;

[0109] (2) SAM (MeO-2PACz) ethanol solution (concentration of 1 mg / mL) was slit-coated on FTO glass and annealed at 100°C for 10 minutes to obtain FTO glass with SAM deposited (thickness 1 nm);

[0110] (3) Using a laser scribing device, a P1 line is etched on the FTO glass on which the SAM is deposited, thereby obtaining the conductive glass composite layer of Comparative Example 1.

[0111] Comparative Example 2

[0112] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 2.

[0113] Table 2 Formula of polymer material of Comparative Example 2

[0114]

[0115] Comparative Example 3

[0116] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 3.

[0117] Table 3 Formula of polymer materials of comparative example

[0118]

[0119] Example 13

[0120] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 4.

[0121] Table 4 Formulation of polymer materials of Example

[0122]

[0123] Example 14

[0124] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 5.

[0125] Table 5 Formulation of polymer materials of Example

[0126]

[0127] Example 15

[0128] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 6.

[0129] Table 6 Formulation of polymer materials of Example

[0130]

[0131] The molar number of polyaniline in Table 6 refers to the molar number of repeating units of polyaniline.

[0132] Example 16

[0133] The conductive glass composite layer was prepared in a manner substantially the same as in Example 1, except that the formula of the polymer material in step (4) was as shown in Table 7.

[0134] Table 7 Formulation of polymer materials of Example

[0135]

[0136] The number of moles of polyvinylidene fluoride in Table 7 refers to the number of moles of repeating units of polyvinylidene fluoride.

[0137] 2. Preparation of Perovskite Cells Using Conductive Glass Composite Layers from Various Examples and Comparative Examples

[0138] The following general method is used to prepare perovskite cells:

[0139] (1) Dissolve 11 mol of lead iodide (PbI2), 9.5 mmol of formamidine hydroiodide (FAI), 0.5 mmol of cesium iodide (CsI), and 3 mmol of methylamine hydrochloride (MACl) in 10 mL of a mixed solvent of DMF: NMP = 10:1 and stir to obtain a perovskite precursor solution for later use;

[0140] (2) The perovskite precursor solution was coated on the slits of the conductive glass composite layer that had been stored for different days, and then the intermediate phase film was obtained by vacuum flash evaporation, and the perovskite layer was obtained by annealing at 120 °C for 15 minutes;

[0141] (3) A 1 mg / mL phenylethylamine hydroiodide (PEAI) isopropanol solution was slit-coated on the perovskite film, followed by annealing at 100 °C for 10 minutes to passivate the perovskite layer.

[0142] (4) Using laser scribing equipment to etch P2 lines on the perovskite layer;

[0143] (5) The component is transferred to the evaporation equipment, and fullerene (C 60 , 25 nm), bathocuproin (BCP, 8 nm), copper (Cu, 200 nm);

[0144] (6) Use laser scribing equipment to etch the P3 line on the copper electrode layer and clean the edge to complete the battery component preparation. The component structure is glass / FTO / SAM / FA 0.95 Cs 0.05 PbI3 / PEAI / C 60 / BCP / Cu, the active area of ​​the component is 63.18 cm 2 .

[0145] 3. Photovoltaic performance test of perovskite cells

[0146] Based on the unstored comparative example and the embodiment, a perovskite battery assembly was prepared, and a series of photoelectric performance parameters of the battery were obtained through testing. The specific data are shown in Table 8.

[0147] Table 8 Photoelectric performance parameters of perovskite battery modules prepared based on the comparative example and the embodiment based on storage for 0 days

[0148]

[0149] According to Table 8, the examples generally have good photoelectric performance, the photoelectric performance of Comparative Example 1 is not much different from that of the examples, and the PCE (%) values ​​of Comparative Example 2 and Comparative Example 3 are significantly reduced. OC(V) value, J SC (mA / cm 2 ) value, FF (%) value, and PCE (%) value are higher, indicating better photoelectric performance, and are used for storage stability testing.

[0150] 4. Storage stability test

[0151] Comparative Example 1 and Examples 1, 2, 4, 5, 10, and 11 were stored in a constant temperature and humidity chamber at 30°C and 75 RH% for 0, 2, 4, 7, and 14 days, respectively, to conduct storage stability tests. The results are shown in FIG. Figure 4 Considering the battery efficiency and the protective effect of the composite material on the SAM layer, the best combination is Example 11.

[0152] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited in their entirety and for all purposes. When cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be adaptively amended according to the description in this application.

[0153] The various technical features of the above-mentioned implementation modes and examples can be combined in any appropriate manner. In order to make the description concise, not all possible combinations of the various technical features in the above-mentioned implementation modes and examples 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 the description in this specification.

[0154] The embodiments described above only express several implementation methods of the present application, but they should not be understood as limiting the scope of the patent application. It should be pointed out that, for those of ordinary skill in the art, without departing from the concept of the present application, several variations and improvements can be made, which all fall within the scope of protection of the present application. In addition, it should be understood that after reading the above-mentioned teaching content of the present application, those skilled in the art can make various changes or modifications to the present application, and the equivalent forms obtained also fall within the scope of protection of the present application. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent application of the present application shall be based on the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A conductive glass composite layer for a perovskite cell, characterized in that: The conductive glass composite layer comprises a white glass layer, a conductive metal oxide layer, a self-assembled monolayer and a protective layer stacked in sequence; The protective layer comprises an organic salt and a polymer material; The polymer material is a homopolymer material or a copolymer material; The homopolymer material is polyvinylidene fluoride, polydimethylsiloxane, polyethyl methacrylate, polyethylene glycol diacrylate, polystyrene or poly(2-ethyl-2-oxazoline); The monomers of the copolymer material include one or more of ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, acrylamide, N-(hydroxymethyl)acrylamide, ethyl isocyanate acrylate, phenyl methacrylate, N-phenylmethacrylamide and N-[4-cyano-3-(trifluoromethyl)phenyl]methacrylamide; The cation of the organic salt is selected from azolium, pyridinium, piperidinium, morpholinium, pyrrolium, ammonium, phosphonium or sulfonium, and the anion is selected from halogen, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, alkyl carboxylate, alkyl sulfate, alkyl sulfonate, alkyl phosphate, alkyl phosphonate, dicyanamide, bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide or trifluoromethanesulfonate; The protective layer can be dissolved in the perovskite precursor solution.

2. The conductive glass composite layer for perovskite cells according to claim 1, characterized in that: The monomers of the copolymer material include any two of ethyl acrylate, ethyl methacrylate, acrylamide and N-hydroxymethyl acrylamide; and / or, The preparation method of the copolymer material comprises the following steps: in the presence of an initiator, polymerizing the monomers to obtain the copolymer material.

3. The conductive glass composite layer for perovskite cells according to claim 2, characterized in that: The initiator is a photoinitiator; The polymerization conditions include ultraviolet light irradiation.

4. The conductive glass composite layer for perovskite cells according to any one of claims 1 to 3, characterized in that: The organic salt is selected from 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate or 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

5. The conductive glass composite layer for perovskite cells according to any one of claims 1 to 3, characterized in that: The molar ratio of the homopolymer material to the organic salt is 1-3:

1.

6. The conductive glass composite layer for perovskite cells according to any one of claims 1 to 3, characterized in that: The ratio of the molar number of the monomer of the copolymer material to the molar number of the organic salt is 1.2-1.3:0.

6.

7. A method for preparing a perovskite solar cell, characterized in that: The steps include: Distributing a perovskite precursor solution on the protective layer of the conductive glass composite layer for a perovskite cell according to any one of claims 1 to 6, and after the protective layer is dissolved, performing vacuum flash evaporation to form an intermediate phase film; The mesophase film is annealed to form a perovskite layer.

8. The method for preparing a perovskite solar cell according to claim 7, wherein: The perovskite precursor solution comprises a precursor of an ABX3 type perovskite material and a solvent; The ions corresponding to the A position in the precursor of the ABX3 type perovskite material include CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + and Cs + At least one of the ions corresponding to the B position includes Pb 2+ and Sn 2+ At least one of the ions corresponding to the X position includes Br - , I - 、Cl - and SCN - At least one of; The solvent includes at least one of N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and 2-methoxyethanol.

9. The method for preparing a perovskite solar cell according to claim 8, wherein: The solvent is a mixed solvent of N,N-dimethylformamide and N-methylpyrrolidone.

10. A perovskite cell produced by the method for producing a perovskite solar cell according to any one of claims 7 to 9.

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