Hole transport layer precursor solution, battery component and preparation method thereof, perovskite solar cell, electric device

Abstract

The application discloses a hole transport layer precursor solution, a battery component and a preparation method thereof, a perovskite solar cell and an electric device, and belongs to the technical field of solar cells. The hole transport layer precursor solution comprises a self-assembled monolayer material and a composite solvent; the composite solvent comprises a phosphate ester solvent, an alcohol ether solvent, an alcohol solvent and a terpineol; the boiling point of the phosphate ester solvent is 190 DEG C-240 DEG C; the boiling point of the alcohol ether solvent is 210 DEG C-250 DEG C; and the boiling point of the alcohol solvent is 70 DEG C-90 DEG C. The hole transport layer precursor solution has improved stability and storability, improves the flexibility of a production process of a perovskite component prepared by the hole transport layer precursor solution, improves the batch stability and efficiency of the perovskite component, and meets the demand of large-area processing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solar cells, in particular to a hole transport layer precursor solution, a cell assembly and a preparation method thereof, a perovskite solar cell and an electric device. BACKGROUND

[0002] Perovskite solar cells (PSCs) are a new type of photovoltaic device. With the advantages of high photoelectric conversion efficiency, low cost and flexible preparation, they have become a hot spot in photovoltaic research. A perovskite solar cell generally includes a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode. The hole transport layer plays a crucial role in the perovskite solar cell, and the material selection and preparation process of the hole transport layer directly affect the photoelectric conversion efficiency and stability of the device. Self-assembled monolayer (SAM) material as a key component of the hole transport layer has attracted much attention in recent years due to its low cost, low parasitic absorption and excellent interface passivation capability.

[0003] However, SAM material is not stable in air and is difficult to achieve uniform preparation on a large scale. In addition, the precursor solution containing SAM material needs to be dried immediately after being coated into a film and subsequent processes are required. The preparation of the corresponding perovskite assembly needs to be continuously processed, which is harsh and has poor batch repeatability, affecting the efficiency of the perovskite assembly. SUMMARY

[0004] Therefore, the main purpose of the present application is to provide a hole transport layer precursor solution that can improve the stability of SAM material and a cell assembly that can be stably stored for a long time. The hole transport layer precursor solution can improve the flexibility of the production process of the perovskite assembly and improve the batch stability and efficiency of the perovskite assembly, meeting the demand for large-area processing.

[0005] In a first aspect, the present application provides a hole transport layer precursor solution, comprising a self-assembled monolayer material and a composite solvent; the composite solvent comprises a phosphate ester solvent, an alcohol ether solvent, an alcohol solvent and a terpineol; the boiling point of the phosphate ester solvent is 190-240℃; the boiling point of the alcohol ether solvent is 210-250℃; and the boiling point of the alcohol solvent is 70-90℃.

[0006] In some embodiments, the phosphate ester solvent comprises trimethyl phosphate and / or triethyl phosphate;

[0007] and / or, the alcohol ether solvent comprises dipropylene glycol butyl ether and / or diethylene glycol butyl ether;

[0008] and / or, the alcohol solvent comprises isopropyl alcohol and / or ethanol.

[0009] In some embodiments, the volume ratio of the phosphate ester solvent, the alcohol ether solvent, the alcohol solvent and the terpineol in the composite solvent is 10-50%, 40-80%, 5-30% and 5-20%, respectively.

[0010] The concentration of the self-assembled monolayer material in the hole transport layer precursor solution is 0.1-2 mg / mL.

[0011] In some embodiments, the self-assembled monolayer material comprises [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl]phosphonic acid (Me-3PACz), [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Me-6PACz), [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl]phosphonic acid (Me-1PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl]phosphonic acid (Me-8PACz), [1-(9H-carbazol-9-yl)methyl]phosphonic acid (1PACz), (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz), [3-(9H-carbazol-9-yl)propyl]phosphonic acid (3PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [6-(9H-carbazol-9-yl)hexyl]phosphonic acid (6PACz), [8-(9H-carbazol-9-yl)octyl]phosphonic acid (8PACz), [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl]phosphonic acid (MeO-TPA-3PA), 2,3,4,5,6-pentafluorobenzylphosphonic acid (F5BPA), [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl]phosphonic acid (2PABCz), [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl]phosphonic acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphonic acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphonic acid (TPA-3PA), [4-(10H-phenothiazin-10-yl)butyl]phosphonic acid (4PAPT), [2-(7H-dibenzo-carbazol-7-yl)ethyl]phosphonic acid (2PADCB), [4-(7H-dibenzo-carbazol-7-yl)butyl]phosphonic acid (4PADCB), [3-(3,6-dibromo-9H-carbazol-9-yl)propyl]phosphonic acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazol-9-yl)butyl]phosphonic acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl]phosphonic acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl]phosphonic acid (tBu-1PACz), [2-(3,6-di-tert-butyl-9H-carbazol-9-yl)ethyl]phosphonic acid (tBu-2PACz), [3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl]phosphonic acid (tBu-3PACz), [4-(3,6-di-tert-butyl-9H-carbazol-9-yl)butyl]phosphonic acid (tBu-4PACz), [6-(3,6-di-tert-butyl-9H-carbazol-9-yl)hexyl]phosphonic acid (tBu-6PACz), [8-(3,6-di-tert-butyl-9H-carbazol-9-yl)octyl]phosphonic acid (tBu-8PACz), [1-(3,6-diphenyl-9H-carbazol-9-yl)methyl]phosphonic acid (Ph-1PACz), [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Ph-2PACz), [3-(3,6-diphenyl-9H-carbazol-9-yl)propyl]phosphonic acid (Ph-3PACz), [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl]phosphonic acid (Ph-4PACz), [6-(3,6-diphenyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Ph-6PACz), [8-(3,6-diphenyl-9H-carbazol-9-yl)octyl]phosphonic acid (Ph-8PACz), [2-(10H-phenoxazine-10-yl)ethyl]phosphonic acid (2PAPXZ), [4-(3,7-dibromo-10H-phenothiazine-10-yl)butyl]phosphonic acid (2Br-4PAPT), and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphonic acid (2Br-4PAPXZ).

[0012] In a second aspect of the present application, a battery assembly is provided, comprising a substrate and a wet film disposed on one side of the substrate; the wet film comprises a self-assembled monolayer material and a complex solvent; the complex solvent comprises a phosphoric acid ester solvent, an alcohol ether solvent, an alcohol solvent, and terpineol; the phosphoric acid ester solvent has a boiling point of 190-240°C; the alcohol ether solvent has a boiling point of 210-250°C; the alcohol solvent has a boiling point of 70-90°C.

[0013] In some embodiments, the battery assembly further comprises a protective film disposed on the side of the wet film away from the substrate.

[0014] In a third aspect of the present application, a preparation method of a battery assembly is provided, comprising the following steps: coating the hole transport layer precursor solution of the first aspect on a substrate to form a wet film.

[0015] In a fourth aspect of the present application, a perovskite solar cell is provided, comprising a hole transport layer prepared by the hole transport layer precursor solution of the first aspect or a hole transport layer prepared by the wet film in the battery assembly of the second aspect.

[0016] In some embodiments, the perovskite solar cell comprises a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer and a back electrode arranged in a stack.

[0017] In a fifth aspect of the present application, a perovskite solar cell is provided.

[0018] The present application has the following beneficial effects:

[0019] The hole transport layer precursor solution of the present application uses a composite solvent composed of a low-boiling alcohol solvent and a high-boiling phosphate ester solvent, an alcohol-ether solvent and a terpineol, which has excellent solubility for the SAM material and has the characteristics of high boiling point, difficult to volatilize and not reacting with the SAM material, thus being conducive to promoting the uniform dispersion of the SAM material, improving the stability and storability of the hole transport layer precursor solution, thereby improving the flexibility of the production process of the perovskite module prepared therefrom, improving the batch stability and efficiency of the perovskite module, and meeting the demand for large-area processing. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solutions and advantages of the present application more clear, and the disclosure of the present application more thorough and comprehensive, the technical solutions of the present application will be described in detail below in conjunction with specific embodiments of the present application. The described embodiments are only a part of the embodiments of the present application, not all the embodiments.

[0021] The implementation of the present application will be described in detail below. The present embodiment is implemented on the premise of the technical solutions of the present application, and gives detailed implementation modes and specific operation processes, but the protection scope of the present application is not limited to the following embodiments.

[0022] Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing the specific embodiments of the present application, and are not intended to limit the present application.

[0023] Terminology

[0024] Unless otherwise stated or contradictory, the terms or phrases used in the present application have the following meanings:

[0025] In the present application, "a plurality of", "a plurality of", etc. are used without special limitation, which means more than two or equal to two in quantity. For example, "one or more", "at least one" means one or more than two.

[0026] In the present application, "further", "particularly" and the like are used for the purpose of description, which means the difference in content, but should not be understood as limiting the scope of protection of the present application.

[0027] In the present application, the technical features described in an open way include both the closed technical solutions consisting of the listed features and the open technical solutions containing the listed features.

[0028] In the present application, when referring to a numerical interval (i.e. a numerical range), unless otherwise specified, the distribution of the selectable values within the numerical interval is considered to be continuous and includes both numerical end points (i.e. the minimum and maximum values) of the numerical interval and every value between the two numerical end points. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, the two end point integers of the numerical range and every integer between the two end points are equivalent to directly listing each integer. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges can be combined. In other words, unless otherwise indicated, numerical ranges disclosed in the present application are to be understood to include any and all sub-ranges subsumed therein. The "numerical" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" is intended to broadly include percentage intervals, ratio intervals, value intervals, etc.

[0029] In the present application, unless otherwise specified, the temperature parameter allows both constant temperature treatment and treatment within a certain temperature interval. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuation within a range such as ±5°C, ±4°C, ±3°C, ±2°C and ±1°C is allowed.

[0030] The term "and / or" as used in the present application includes any and all combinations of one or more of the associated listed items.

[0031] In the present application, unless otherwise specified, the percentage content referred to refers to mass percentage for solid-liquid mixing and solid-solid mixing, and refers to volume percentage for liquid-liquid mixing.

[0032] In the present application, unless otherwise specified, the percentage concentration referred to refers to the final concentration. The final concentration refers to the proportion of the added ingredient in the system after the ingredient is added.

[0033] In the present application, unless otherwise specified, the temperature parameter allows both constant temperature treatment and treatment within a certain temperature interval. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0034] In a first aspect of the present application, a hole transport layer precursor solution is provided, comprising a self-assembled monolayer material and a composite solvent; the composite solvent comprises a phosphate ester solvent, an alcohol ether solvent, an alcohol solvent and terpineol; the boiling point of the phosphate ester solvent is 190-240°C; the boiling point of the alcohol ether solvent is 210-250°C; the boiling point of the alcohol solvent is 70-90°C.

[0035] The hole transport layer precursor solution of the present application uses a composite solvent composed of an alcohol solvent with low boiling point and a phosphate ester solvent, an alcohol ether solvent and terpineol with high boiling point, which has excellent solubility for the SAM material, and has the characteristics of high boiling point, difficult evaporation and no reaction with the SAM material, thus being conducive to promoting the uniform dispersion of the SAM material, improving the stability and storability of the hole transport layer precursor solution, thereby improving the flexibility of the production process of the perovskite module prepared therefrom, and improving the batch stability and efficiency of the perovskite module, meeting the demand for large-area processing.

[0036] Specifically, the components of the composite solvent of the present application all have strong polarity, have good solubility for the SAM which also has strong polarity, and do not react with the SAM, which is conducive to the stability of the SAM. Further, the phosphate ester solvent, the alcohol ether solvent and terpineol have high boiling points and are not easy to evaporate, which can improve the stability and storability of the hole transport layer precursor solution. In particular, the phosphate ester solvent has high polarity and amphiphilicity, and its polarity is similar to that of the SAM molecule. The phosphate ester group contained therein can simultaneously act as a hydrogen bond donor and acceptor, forming a multiple hydrogen bond network with the amino group, carboxyl group or adenine nitrogen atom of the SAM, promoting the dispersion and stability of the SAM; the alcohol ether solvent is conducive to improving the leveling property, and terpineol can adjust the viscosity of the hole transport layer precursor solution; the alcohol solvent with low boiling point can adjust the volatility of the hole transport layer precursor solution. The use of the above composite solvent is conducive to providing a hole transport layer precursor solution with appropriate viscosity and volatility, promoting the uniform dispersion of the SAM material, and improving the stability and storability of the hole transport layer precursor solution.

[0037] In some embodiments, the phosphate ester solvent comprises trimethyl phosphate and / or triethyl phosphate;

[0038] And / or, the alcohol ether solvent comprises dipropylene glycol butyl ether and / or diethylene glycol butyl ether;

[0039] And / or, the alcohol solvent comprises isopropyl alcohol and / or ethanol.

[0040] In some embodiments, the volume ratio of the phosphate ester solvent, the alcohol ether solvent, the alcohol solvent and the terpineol in the composite solvent is 10-50%, 40-80%, 5-30% and 5-20%, respectively. Specifically, the volume ratio of the phosphate ester solvent can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.; the volume ratio of the alcohol ether solvent can be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.; the volume ratio of the alcohol solvent can be 5%, 10%, 15%, 20%, 25%, 30%, etc.; and the volume ratio of the terpineol can be 5%, 10%, 15%, 20%, etc.

[0041] In some embodiments, the concentration of the self-assembled monolayer material in the hole transport layer precursor solution is 0.1 mg / mL-2 mg / mL, such as 0.1 mg / mL, 0.2 mg / mL, 0.3 mg / mL, 0.4 mg / mL, 0.2 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL, 1 mg / mL, 1.2 mg / mL, 2 mg / mL, etc.

[0042] In some embodiments, the self-assembled monolayer material comprises [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl]phosphonic acid (MeO-3PACz), [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl]phosphonic acid (MeO-6PACz), [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl]phosphonic acid (Me-3PACz), [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Me-6PACz), [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl]phosphonic acid (Me-1PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl]phosphonic acid (Me-8PACz), [1-(9H-carbazol-9-yl)methyl]phosphonic acid (1PACz), (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz), [3-(9H-carbazol-9-yl)propyl]phosphonic acid (3PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [6-(9H-carbazol-9-yl)hexyl]phosphonic acid (6PACz), [8-(9H-carbazol-9-yl)octyl]phosphonic acid (8PACz), [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl]phosphonic acid (MeO-TPA-3PA), 2,3,4,5,6-pentafluorobenzylphosphonic acid (F5BPA), [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl]phosphonic acid (2PABCz), [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl]phosphonic acid (4PABCz), [4-(diphenylamino)phenyl)ethyl]phosphonic acid (TPA-2PA), [4-(diphenylamino)phenyl)propyl]phosphonic acid (TPA-3PA), [4-(10H-phenothiazin-10-yl)butyl]phosphonic acid (4PAPT), [2-(7H-dibenzo-carbazol-7-yl)ethyl]phosphonic acid (2PADCB), [4-(7H-dibenzo-carbazol-7-yl)butyl]phosphonic acid (4PADCB), [3-(3,6-dibromo-9H-carbazol-9-yl)propyl]phosphonic acid (2Br-3PACz), [4-(3,6-dibromo-9H-carbazol-9-yl)butyl]phosphonic acid (2Br-4PACz), [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl]phosphonic acid (2Br-6PACz), [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl]phosphonic acid (tBu-1PACz), [2-(3,6-di-tert-butyl-9H-carbazol-9-yl)ethyl]phosphonic acid (tBu-2PACz), [3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl]phosphonic acid (tBu-3PACz), [4-(3,6-di-tert-butyl-9H-carbazol-9-yl)butyl]phosphonic acid (tBu-4PACz), [6-(3,6-di-tert-butyl-9H-carbazol-9-yl)hexyl]phosphonic acid (tBu-6PACz), [8-(3,6-di-tert-butyl-9H-carbazol-9-yl)octyl]phosphonic acid (tBu-8PACz), [1-(3,6-diphenyl-9H-carbazol-9-yl)methyl]phosphonic acid (Ph-1PACz), [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Ph-2PACz), [3-(3,6-diphenyl-9H-carbazol-9-yl)propyl]phosphonic acid (Ph-3PACz), [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl]phosphonic acid (Ph-4PACz), [6-(3,6-diphenyl-9H-carbazol-9-yl)hexyl]phosphonic acid (Ph-6PACz), [8-(3,6-diphenyl-9H-carbazol-9-yl)octyl]phosphonic acid (Ph-8PACz), [2-(10H-phenoxazine-10-yl)ethyl]phosphonic acid (2PAPXZ), [4-(3,7-dibromo-10H-phenothiazine-10-yl)butyl]phosphonic acid (2Br-4PAPT), and [4-(3,7-dibromo-10H-phenoxazine-10-yl)butyl]phosphonic acid (2Br-4PAPXZ).

[0043] In a second aspect of the present application, a battery assembly is provided, comprising a substrate and a wet film arranged on one side of the substrate; the wet film comprises a self-assembled monolayer material and a composite solvent; the composite solvent comprises a phosphoric acid ester solvent, an alcohol ether solvent, an alcohol solvent, and terpineol; the boiling point of the phosphoric acid ester solvent is 190-240°C; the boiling point of the alcohol ether solvent is 210-250°C; and the boiling point of the alcohol solvent is 70-90°C.

[0044] The composite solvent of the wet film of the battery assembly of the present application is composed of an alcohol solvent with a low boiling point and a phosphoric acid ester solvent, an alcohol ether solvent, and terpineol with a high boiling point. On the one hand, the composite solvent has excellent solubility to the SAM material, which is conducive to promoting the uniform dispersion of the SAM material. On the other hand, the composite solvent has the characteristics of high boiling point, difficult evaporation, and no reaction with the SAM material. It is not easy to evaporate in the preparation process of the wet film, which can to some extent reduce the contact of the SAM material with the air, improve the stability and storability of the SAM material, thereby improving the flexibility of the production process of the perovskite assembly prepared therefrom, and improving the batch stability and efficiency of the perovskite assembly, meeting the demand for large-area processing.

[0045] In some embodiments, the battery assembly further comprises a protective film disposed on the side of the wet film distal to the substrate.

[0046] By disposing a protective film on the side of the wet film distal to the substrate, the volatilization of the composite solvent can be further reduced, and air can be isolated, thereby allowing the wet film to be stored for a long time while maintaining the stability of the performance of the wet film. At the same time, since the composite solvent has good solubility for the SAM material, the dispersion uniformity of the wet film can still be ensured during storage. In this way, the wet film can be "pre-fabricated", and when production of the perovskite assembly is needed, the protective film can be removed and the production can continue, thereby improving the flexibility of the perovskite assembly production process and improving the batch stability and efficiency of the perovskite assembly.

[0047] In some embodiments, the material of the protective film comprises at least one of high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), chlorinated polyethylene (CPE), polyethylene terephthalate (PET), polydimethylsiloxane film (PDMS), polyethylene naphthalate (PEN), and polyimide (PI).

[0048] A third aspect of the present application provides a method for preparing a battery assembly, comprising the following steps: coating the hole transport layer precursor solution of the first aspect on a substrate to form a wet film.

[0049] In a specific example, the coating comprises at least one of spin coating, blade coating, slot coating, and inkjet printing.

[0050] A fourth aspect of the present application provides a perovskite solar cell comprising a hole transport layer prepared by the hole transport layer precursor solution of the first aspect or a hole transport layer prepared by the wet film in the battery assembly of the second aspect.

[0051] In some embodiments, the perovskite solar cell comprises a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, and a back electrode arranged in layers.

[0052] In a specific example, the substrate is an FTO substrate.

[0053] In a specific example, the material of the perovskite layer comprises perovskite.

[0054] In a specific example, the perovskite has a general formula of AB(X n Y 1-n )3, wherein A is a monovalent cation, B is a divalent metal ion, X and Y are each independently a halide anion, and 0≤n≤1.

[0055] In one specific example, the electron transport layer is an n-type semiconductor.

[0056] In one specific example, the material of the electron transport layer comprises C60 and / or PCBM.

[0057] In one specific example, the material of the buffer layer comprises ALD SnO2 and / or BCP.

[0058] In one specific example, the material of the electrode comprises at least one of ITO, IZO and Cu.

[0059] In a fifth aspect of the present application, a perovskite solar cell is provided.

[0060] The raw materials used in the following tests are commercially available unless otherwise specified.

[0061] The following are specific examples.

[0062] Example 1

[0063] Preparation of perovskite battery assembly:

[0064] The specific steps are as follows:

[0065] 1) Configuration of hole transport layer precursor solution: dissolve SAM material (4PADCB) in composite solvent (45v / v% triethyl phosphate, 45v / v% diethylene glycol butyl ether, 5v / v% ethanol, 5v / v% terpineol), configure the hole transport layer precursor solution with a concentration of 0.5mg / mL, and if the SAM material cannot be dissolved to form a clear solution, filter it with a 0.22μm PTFE filter and try to use it;

[0066] 2) Preparation of battery assembly: P1 laser scribing on FTO substrate (50mm×50mm), inkjet printing hole transport layer precursor solution on the treated FTO substrate to form a wet film; attach a layer of PEN barrier film on the wet film to slow down the evaporation speed of the solvent, block air and prevent dust, form a FTO substrate-wet film-PEN film sandwich structure, and place it in the air environment (room temperature, 25℃) for 2 days;

[0067] 3) Preparation of hole transport layer: after 2 days, tear off the PEN film and place the FTO substrate-wet film into a vacuum flash evaporation device for drying (flash evaporation to 5Pa, pressure maintaining for more than 60s until the wet film is obviously dried by the flash evaporation device), forming a hole transport layer (2nm);

[0068] 4) Preparation of perovskite layer on the hole transport layer: use Cs 0.2 FA 0.8 Pb(I0.85 Br 0.15 )3 as the main raw material, 4% of MaCl was added to promote crystallization, 5% of PbCl2 was added to optimize the crystallization kinetics and prolong the carrier lifetime, after blade coating, it was placed in a flash evaporation device, and then placed on a 120℃ hot stage for annealing for 30min to form a perovskite layer (500nm);

[0069] 5) An electron transport layer (25nm C 60 ), a buffer layer (7nm SnO2) was prepared on the perovskite layer in turn, and P2 laser scribing was performed; a back electrode (120nm Cu) was continuously prepared and P3 laser scribing was performed, and finally P4 laser edge cleaning was performed to complete the preparation of the perovskite battery component.

[0070] Example 2

[0071] Except that the standing time in step 2) was 1 day, the rest was the same as example 1.

[0072] Example 3

[0073] Except that the standing time in step 2) was 5 days, the rest was the same as example 1.

[0074] Example 4

[0075] Except that the standing time in step 2) was 10 days, the rest was the same as example 1.

[0076] Example 5

[0077] Except that after preparing the wet film, the FTO substrate-wet film was directly placed into a vacuum flash evaporation device for drying, the rest was the same as example 1.

[0078] Example 6

[0079] Except that the composition of the composite solvent was: triethyl phosphate 30v / v%, diethylene glycol butyl ether 30v / v%, ethanol 30v / v%, and terpineol 10v / v%, the rest was the same as example 1.

[0080] Example 7

[0081] Except that the composition of the composite solvent was: trimethyl phosphate 20v / v%, dipropylene glycol butyl ether 40v / v%, isopropyl alcohol 20v / v%, and terpineol 20v / v%, the rest was the same as example 1.

[0082] Example 8

[0083] Except that the composition of the composite solvent was: trimethyl phosphate 30v / v%, dipropylene glycol butyl ether 50v / v%, isopropyl alcohol 10v / v%, and terpineol 10v / v%, the rest was the same as example 1.

[0084] Example 9

[0085] Example 1 except that the composite solvent was composed of trimethyl phosphate 10 v / v%, dipropylene glycol butyl ether 80 v / v%, isopropyl alcohol 5 v / v%, and terpineol 5 v / v%.

[0086] Comparative Example 1

[0087] Example 1 except that the composite solvent was replaced by methanol, and after the wet film was prepared, the FTO substrate-wet film was directly placed into a vacuum flash equipment for drying.

[0088] Comparative Example 2

[0089] Example 1 except that the composite solvent was replaced by methanol.

[0090] Comparative Example 3

[0091] Example 1 except that the composite solvent was composed of triethyl phosphate 45 v / v%, diethylene glycol butyl ether 45 v / v%, and ethanol 10 v / v%.

[0092] Comparative Example 4

[0093] Example 1 except that the composite solvent was composed of triethyl phosphate 90 v / v%, ethanol 5 v / v%, and terpineol 5 v / v%.

[0094] Comparative Example 5

[0095] Example 1 except that the composite solvent was composed of diethylene glycol butyl ether 90 v / v%, ethanol 5 v / v%, and terpineol 5 v / v%.

[0096] Test Example

[0097] 1. Test the solubility of SAM material (4PADCB) in Example 1 and methanol (i.e. Comparative Example 1), and the test method is as follows: gradually add SAM powder to the corresponding 1 mL solvent at a rate of 0.05 mg / time, put into a shaker, and shake at a speed of 600 for 5 min, then take out and stand for 5 min, observe the solution dissolution state, until it cannot be dissolved and appears non-clear state, record the weight of the added SAM powder at that time, and the results are shown in Table 1.

[0098] 2. Test the open-circuit voltage (Voc), current density (J), fill factor (FF), and initial photoelectric conversion efficiency (PCE) of the perovskite battery assembly under the intensity of one sun light by a solar light simulator and a Keithley 2400 source meter. Test the performance of the perovskite battery assemblies prepared in the examples and comparative examples, and the results are shown in Table 1.

[0099] Table 1 Performance summary of examples and comparative examples

[0100]

[0101] As can be seen from Table 1, Examples 1-9 use phosphonate solvents, alcohol ether solvents, alcohol solvents and composite solvents composed of terpineol, and the prepared batteries have good photoelectric efficiency. And as can be seen from Examples 1-5, the wet film prepared from the hole transport layer precursor solution containing the above composite solvent has good stability and storability, even if stored for 10 days, it still has photoelectric efficiency comparable to that without storage. It can be seen that the present application can realize the "preparation" of SAM wet film, and when the production of perovskite assembly is needed, the protective film is removed and the production is continued, thus the flexibility of perovskite assembly production process can be realized, and the batch stability and efficiency of perovskite assembly can be improved.

[0102] And as can be seen from Comparative Examples 1 and Comparative Examples 1-5, the composition of the composite solvent has a significant effect on the performance, and the composite solvent of the present application has significantly better performance than methanol. At the same time, as can be seen from Examples 1 and Comparative Examples 3-5, the use of terpineol and ethanol in combination has a significantly improved effect compared to the use of ethanol, and the use of triethyl phosphate and diethylene glycol butyl ether in combination has a significantly improved effect compared to the use of triethyl phosphate or diethylene glycol butyl ether alone, indicating that there is a synergistic effect between terpineol and ethanol, and triethyl phosphate and diethylene glycol butyl ether.

[0103] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, however, as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0104] The above-described embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the patent of the present application should be subject to the appended claims.

Claims

1. A hole transport layer precursor solution, characterized in that, The self-assembled monolayer material and the composite solvent; the composite solvent includes phosphate ester solvents, alcohol ether solvents, alcohol solvents and terpineol; the boiling point of the phosphate ester solvent is 190-240 DEG C; the boiling point of the alcohol ether solvent is 210-250 DEG C; the boiling point of the alcohol solvent is 70-90 DEG C; The phosphate ester solvent includes trimethyl phosphate and / or triethyl phosphate; The alcohol ether solvent includes dipropylene glycol butyl ether and / or diethylene glycol butyl ether; The alcohol solvent includes isopropyl alcohol and / or ethanol; In the composite solvent, the volume ratio of the phosphate ester solvent, the alcohol ether solvent, the alcohol solvent and the terpineol is 10-50%, 40-80%, 5-30% and 5-20% respectively; The concentration of the self-assembled monolayer material in the hole transport layer precursor solution is 0.1-2 mg / mL.

2. The hole transport layer precursor solution of claim 1, wherein, The self-assembled monolayer material comprises [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid, [3-(3,6-dimethoxy-9H-carbazol-9-yl)propyl] phosphonic acid, [6-(3,6-dimethoxy-9H-carbazol-9-yl)hexyl] phosphonic acid, [2-(3,6-dimethyl-9H-carbazol-9-yl)ethyl] phosphonic acid, [3-(3,6-dimethyl-9H-carbazol-9-yl)propyl] phosphonic acid, [6-(3,6-dimethyl-9H-carbazol-9-yl)hexyl] phosphonic acid, [1-(3,6-dimethyl-9H-carbazol-9-yl)methyl] phosphonic acid, [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl] phosphonic acid, [8-(3,6-dimethyl-9H-carbazol-9-yl)octyl] phosphonic acid, [1-(9H-carbazol-9-yl)methyl] phosphonic acid, (2-(9H-carbazol-9-yl)ethyl) phosphonic acid, [3-(9H-carbazol-9-yl)propyl] phosphonic acid, [4-(9H-carbazol-9-yl)butyl] phosphonic acid, [6-(9H-carbazol-9-yl)hexyl] phosphonic acid, [8-(9H-carbazol-9-yl)octyl] phosphonic acid, [4-(N,N-di(4-methoxyphenylamino)phenyl)propyl] phosphonic acid, 2,3,4,5,6-pentafluorobenzyl phosphonic acid, [2-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)ethyl] phosphonic acid, [4-(9H-9'-phenyl-3,3'-bicarbazol-9-yl)butyl] phosphonic acid, [4-(diphenylamino)phenyl)ethyl] phosphonic acid, [4-(diphenylamino)phenyl)propyl] phosphonic acid, [4-(10H-phenothiazin-10-yl)butyl] phosphonic acid, [2-(7H-dibenzo-carbazol-7-yl)ethyl] phosphonic acid, [4-(7H-dibenzo-carbazol-7-yl)butyl] phosphonic acid, [3-(3,6-dibromo-9H-carbazol-9-yl)propyl] phosphonic acid, [4-(3,6-dibromo-9H-carbazol-9-yl)butyl] phosphonic acid, [6-(3,6-dibromo-9H-carbazol-9-yl)hexyl] phosphonic acid, [1-(3,6-di-tert-butyl-9H-carbazol-9-yl)methyl] phosphonic acid, [2-(3,6-di-tert-butyl-9H-carbazol-9-yl)ethyl] phosphonic acid, [3-(3,6-di-tert-butyl-9H-carbazol-9-yl)propyl] phosphonic acid, [4-(3,6-di-tert-butyl-9H-carbazol-9-yl)butyl] phosphonic acid, [6-(3,6-di-tert-butyl-9H-carbazol-9-yl)hexyl] phosphonic acid, [8-(3,6-di-tert-butyl-9H-carbazol-9-yl)octyl] phosphonic acid, [1-(3,6-diphenyl-9H-carbazol-9-yl)methyl] phosphonic acid, [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl] phosphonic acid, [3-(3,6-diphenyl-9H-carbazol-9-yl)propyl] phosphonic acid, [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl] phosphonic acid, [6-(3,6-diphenyl-9H-carbazol-9-yl)hexyl]phosphonic acid, [8-(3,6-diphenyl-9H-carbazol-9-yl)octyl]phosphonic acid, [2-(10H-phenoxazin-10-yl)ethyl]phosphonic acid, [4-(3,7-dibromo-10H-phenothiazin-10-yl)butyl]phosphonic acid, and [4-(3,7-dibromo-10H-phenoxazin-10-yl)butyl]phosphonic acid.

3. A battery assembly characterized by, The battery assembly further comprises a protective film arranged on the side of the wet film away from the substrate.

4. The battery assembly of claim 3, wherein, The battery assembly further comprises a protective film arranged on the side of the wet film away from the substrate.

5. A method of producing a battery assembly, characterized by, The battery assembly further comprises a protective film arranged on the side of the wet film away from the substrate.

6. A perovskite solar cell, characterized by, The battery assembly further comprises a protective film arranged on the side of the wet film away from the substrate.

7. The perovskite solar cell of claim 6, wherein the perovskite layer is formed by a two-step method. The battery assembly further comprises a protective film arranged on the side of the wet film away from the substrate.

8. An electrical device, characterized by The perovskite solar cell comprises a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer and a back electrode which are arranged in layers. The perovskite solar cell comprises a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer and a back electrode which are arranged in layers.

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