Perovskite light absorption layer, perovskite battery, preparation method of perovskite battery and power utilization device

Abstract

The invention relates to a perovskite light absorption layer, a perovskite battery, a preparation method of the perovskite battery and a power utilization device. The perovskite light absorption layer comprises a perovskite light absorption material and a passivation material, a passivation precursor forming the passivation material comprises at least one of substituted or unsubstituted vinylpyridine and derivatives thereof, and the mass ratio of the passivation precursor to a perovskite precursor forming the perovskite light absorption material is (0.0001-0.008): 1. Substituted or unsubstituted vinylpyridine and derivatives thereof which are simple in molecular structure, low in price and easy to obtain are used as passivation precursors, and the mass ratio of the passivation precursors to perovskite precursors forming the perovskite light absorption material is controlled, so that the formed passivation material can stably exist at a grain boundary and an interface; in addition, lone pair electrons on the nitrogen atoms are coordinated with uncoordinated exposed ions to realize a passivation function on grain boundary and interface defects, so that the photoelectric conversion efficiency of the perovskite solar cell is effectively improved, and the stability of the perovskite solar cell can be effectively improved.

Description

Technical Field

[0001] The present application relates to the field of batteries, and in particular to a perovskite light-absorbing layer, a perovskite battery, a preparation method thereof, and an electrical device. Background Art

[0002] After more than ten years of development, organic-inorganic hybrid perovskite solar cells are in the process of commercialization. The stability problem of perovskite solar cells is still a key technical point that needs to be solved urgently. Because the uncoordinated exposed ions on the surface of perovskite are prone to polarization reactions during the preparation process and the use of the device, interface defects will appear, inducing the degradation of the perovskite layer, and eventually leading to the gradual failure of the device. Studies have shown that interface engineering in perovskite solar cell devices has a huge impact on the device. Reducing non-radiative carrier recombination at the surface / interface and increasing the carrier lifetime are effective ways to optimize perovskite cell devices. However, traditional passivation materials have limited improvement in the stability performance of perovskite solar cells.

[0003] Therefore, it is necessary to improve the traditional technology. Summary of the invention

[0004] Based on this, the present application provides a perovskite light-absorbing layer with good stability, a perovskite battery and its preparation method, and an electrical device.

[0005] The technical solution of this application to solve the above technical problems is as follows.

[0006] In a first aspect, the present application provides a perovskite light-absorbing layer, which includes a perovskite light-absorbing material and a passivation material. A passivation precursor forming the passivation material includes at least one of substituted or unsubstituted vinylpyridine and its derivatives. The mass ratio of the passivation precursor to the perovskite precursor forming the perovskite light-absorbing material is 0.0001~0.008:1.

[0007] In some embodiments, in the perovskite light absorbing layer, the substituents in the substituted vinyl pyridine include halogen, nitro, cyano, carboxyl, C1~C 10 Alkyl and C1~C 10 At least one of the alkoxy groups.

[0008] In some of the embodiments, in the perovskite light absorbing layer, the passivation precursor includes at least one of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-6-vinylpyridine, 4-bromo-2-vinylpyridine, 5-bromo-2-vinylpyridine, 4-chloro-2-vinylpyridine, 3-bromo-2-vinylpyridine, 2-bromo-6-vinylpyridine, 2-bromo-4-vinylpyridine, 3-bromo-5-vinylpyridine and 2-fluoro-4-vinylpyridine.

[0009] In some embodiments, in the perovskite light absorbing layer, the passivation material and the perovskite light absorbing material are mixed with each other.

[0010] In some of the embodiments, in the perovskite light absorbing layer, the perovskite light absorbing layer includes a stacked perovskite material layer and a passivation layer, the perovskite material layer includes the perovskite light absorbing material, and the passivation layer includes the passivation material.

[0011] In some embodiments, in the perovskite light absorbing layer, the perovskite light absorbing layer satisfies at least one of the following characteristics:

[0012] (1) The thickness of the passivation layer is 1 nm to 100 nm;

[0013] (2) The thickness of the perovskite material layer is 400-1000 nm;

[0014] (3) The thickness ratio of the passivation layer to the perovskite material layer is 0.001-0.025:1.

[0015] In some of the embodiments, in the perovskite light-absorbing layer, the perovskite light-absorbing material includes ABX3, A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

[0016] The second aspect of the present application provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0017] A perovskite precursor, a passivation precursor and a first solvent are mixed to prepare a precursor mixed solution; the passivation precursor comprises at least one of substituted or unsubstituted vinyl pyridine and its derivatives; the mass ratio of the passivation precursor to the perovskite precursor is 0.0001-0.008:1;

[0018] The precursor mixed solution is subjected to film-forming and first annealing treatment in sequence to prepare the perovskite light-absorbing layer.

[0019] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the concentration of the passivation precursor in the precursor mixed solution is 1 mg / mL to 8 mg / mL.

[0020] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the first annealing treatment includes sequentially performing a low-temperature annealing treatment and a high-temperature annealing treatment; the temperature of the low-temperature annealing treatment is 50°C~95°C, and the time is 5 min~20 min; the temperature of the high-temperature annealing treatment is 100°C~150°C, and the time is 16 min~60 min.

[0021] The third aspect of the present application provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0022] preparing a perovskite material layer;

[0023] A passivation precursor is disposed on the surface of the perovskite material layer, and after a second annealing treatment, a passivation layer is formed on the surface of the perovskite material layer to obtain the perovskite light-absorbing layer; the perovskite light-absorbing layer includes the perovskite material layer and the passivation layer; the passivation precursor includes at least one of substituted or unsubstituted vinylpyridine and its derivatives, and the mass ratio of the passivation precursor to the perovskite precursor for preparing the perovskite material layer is 0.0001~0.008:1.

[0024] In some embodiments, in the method for preparing the perovskite light absorbing layer, placing a passivation precursor on the surface of the perovskite material layer comprises the following steps:

[0025] mixing a passivation precursor and a second solvent to prepare a passivation solution;

[0026] The passivation solution is disposed on the surface of the perovskite material layer.

[0027] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the temperature of the second annealing treatment is 50° C. to 120° C., and the time is 15 min to 60 min.

[0028] A fourth aspect of the present application provides a perovskite cell, comprising a first electrode, the above-mentioned perovskite light-absorbing layer or the perovskite light-absorbing layer prepared by the above-mentioned preparation method, and a second electrode.

[0029] In some of the embodiments, in the perovskite cell, the perovskite cell further includes a hole transport layer, the perovskite light absorption layer includes a perovskite material layer and a passivation layer, and the perovskite material layer is disposed between the hole transport layer and the passivation layer.

[0030] A fifth aspect of the present application provides a method for preparing a perovskite battery, comprising the following steps:

[0031] providing a first electrode;

[0032] Forming the above-mentioned perovskite light-absorbing layer or the perovskite light-absorbing layer prepared by the above-mentioned preparation method on the surface of the first electrode;

[0033] A second electrode is formed on a surface of the perovskite light absorbing layer away from the first electrode.

[0034] A sixth aspect of the present application provides an electrical device, comprising the above-mentioned perovskite battery or the perovskite battery prepared by the above-mentioned preparation method.

[0035] Compared with the prior art, the perovskite light absorbing layer of the present application has the following beneficial effects:

[0036] The perovskite light-absorbing layer of the present application includes a perovskite light-absorbing material and a passivation material. A substituted or unsubstituted vinyl pyridine and its derivatives with a simple molecular structure, low cost and easy availability are used as a passivation precursor, and the mass ratio of the passivation precursor to the perovskite precursor that forms the perovskite light-absorbing material is controlled. The formed passivation material will be stably present at the grain boundaries and interfaces, and the lone pair of electrons on the nitrogen atom will coordinate with the uncoordinated exposed ions to achieve the passivation function of the grain boundaries and interface defects, thereby effectively improving the photoelectric conversion efficiency of the perovskite solar cell and the stability performance of the perovskite solar cell. DETAILED DESCRIPTION

[0037] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0038] Therefore, it is intended that the present invention covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0040] The term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of more restrictions, the elements defined by the sentence "comprising one..." do not exclude the presence of other identical elements in the process, method, article or equipment including the elements. The indefinite articles "a kind of" and "an" before the elements or components of the present invention are not restrictive to the quantity requirements (i.e., the number of occurrences) of the elements or components. Therefore, "a" or "a kind of" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number clearly refers only to the singular form. The meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0041] The weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also indicate the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0042] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0043] An embodiment of the present application provides a perovskite light-absorbing layer, which includes a perovskite light-absorbing material and a passivation material. A passivation precursor for forming the passivation material includes at least one of substituted or unsubstituted vinylpyridine and its derivatives. The mass ratio of the passivation precursor to the perovskite precursor for forming the perovskite light-absorbing material is 0.0001~0.008:1.

[0044] The perovskite light-absorbing layer of the present application includes a perovskite light-absorbing material and a passivation material. A substituted or unsubstituted vinyl pyridine and its derivatives with a simple molecular structure, low cost and easy availability are used as a passivation precursor, and the mass ratio of the passivation precursor to the perovskite precursor that forms the perovskite light-absorbing material is controlled. The formed passivation material will be stably present at the grain boundaries and interfaces, and the lone pair of electrons on the nitrogen atom will coordinate with the uncoordinated exposed ions to achieve the passivation function of the grain boundaries and interface defects, thereby effectively improving the photoelectric conversion efficiency of the perovskite solar cell and the stability performance of the perovskite solar cell.

[0045] It can be understood that the mass ratio of the passivation precursor to the perovskite precursor that forms the perovskite light-absorbing material includes but is not limited to 0.0001:1, 0.0005:1, 0.001:1, 0.0015:1, 0.002:1, 0.0025:1, 0.003:1, 0.0035:1, 0.004:1, 0.0045:1, 0.005:1, 0.0055:1, 0.006:1, 0.0065:1, 0.007:1, 0.0075:1, 0.008:1; in some examples, it can be within the range formed by any two of these point values ​​as end values, the same below.

[0046] Optionally, the mass ratio of the passivation precursor to the perovskite precursor for forming the perovskite light absorbing material is 0.001-0.006:1.

[0047] Furthermore, the mass ratio of the passivation precursor to the perovskite precursor for forming the perovskite light absorbing material is 0.001-0.004:1.

[0048] By controlling the mass ratio of the passivation precursor to the perovskite precursor that forms the perovskite light-absorbing material, the photoelectric conversion efficiency and stability of the perovskite cell can be further improved.

[0049] The study found that when butylpyridine and other pyridine derivative small molecules are directly added to the perovskite precursor solution as passivation materials, the efficiency decreases rapidly during device operation and the stability is poor. Analysis shows that the interactions between these independent pyridine derivative small molecules are mainly hydrogen bonds, dispersion forces, and van der Waals forces, and they cannot form a stable passivation molecular network to resist the gradual decomposition of perovskite during device operation.

[0050] In some of these examples, the substituents in the substituted vinyl pyridine in the perovskite light absorbing layer include halogen, nitro, cyano, carboxyl, C1~C 10 Alkyl and C1~C 10 At least one of the alkoxy groups.

[0051] Understandably, C1~C 10Alkyl refers to an alkyl group with 1 to 10 carbon atoms. 10 Alkyl refers to an alkoxy group with 1 to 10 carbon atoms; further, C1~C 10 The alkyl group includes but is not limited to at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., wherein the propyl group includes at least one of n-propyl and isopropyl, and the butyl group includes at least one of n-butyl, isobutyl, tert-butyl and sec-butyl, etc.; the halogen group includes but is not limited to at least one of F, Cl, Br, I, etc.

[0052] In some of the examples, in the perovskite light absorbing layer, the substituent in the substituted vinyl pyridine includes at least one of a halogen, a C1~C4 alkyl, and a C1~C4 alkoxy.

[0053] In some of these examples, in the perovskite light absorbing layer, the substituent in the substituted vinyl pyridine includes at least one of a halogen, a methyl group, and an ethyl group.

[0054] In some of the examples, in the perovskite light absorbing layer, the passivation precursor includes at least one of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-6-vinylpyridine, 4-bromo-2-vinylpyridine, 5-bromo-2-vinylpyridine, 4-chloro-2-vinylpyridine, 3-bromo-2-vinylpyridine, 2-bromo-6-vinylpyridine, 2-bromo-4-vinylpyridine, 3-bromo-5-vinylpyridine and 2-fluoro-4-vinylpyridine.

[0055] It can be understood that the perovskite light-absorbing layer includes a perovskite light-absorbing material and a passivation material, including two methods: bulk passivation and surface passivation:

[0056] Bulk passivation (the perovskite light-absorbing layer can be only one layer): the passivation material and the perovskite light-absorbing material are mixed with each other.

[0057] Surface passivation (the perovskite light-absorbing layer is composed of at least two layers): the perovskite light-absorbing layer includes a stacked perovskite material layer and a passivation layer, the perovskite material layer includes a perovskite light-absorbing material, and the passivation layer includes a passivation material.

[0058] Among them, bulk passivation is to reduce the bulk defect density by introducing passivation materials into the bulk phase (internal main part) of the perovskite material, thereby improving the overall stability and photoelectric performance of the perovskite light-absorbing layer; surface passivation is to reduce the surface defect density by introducing a passivation layer on the surface of the perovskite material layer, thereby improving the surface properties of the perovskite light-absorbing layer.

[0059] In some of these examples, the thickness of the passivation layer in the perovskite absorber is 1 nm to 100 nm.

[0060] It will be appreciated that the thickness of the passivation layer includes but is not limited to 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, and 100 nm.

[0061] In some of these examples, the thickness of the perovskite material layer in the perovskite light-absorbing layer is 400 nm to 1000 nm.

[0062] It can be understood that the thickness of the perovskite material layer includes but is not limited to 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, and 1000 nm.

[0063] In some of these examples, in the perovskite light-absorbing layer, the thickness ratio of the passivation layer to the perovskite material layer is 0.001~0.025:1.

[0064] It can be understood that the thickness ratio of the passivation layer to the perovskite material layer includes but is not limited to 0.001:1, 0.005:1, 0.01:1, 0.02:1, and 0.025:1.

[0065] In some of the examples, in the perovskite light-absorbing layer, the perovskite light-absorbing material includes ABX3, A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

[0066] It is understood that the present application does not limit the types of A monovalent cation, B divalent cation, and X monovalent anion in ABX3, and any type that can be used as a light absorbing material in the art can be used.

[0067] Optionally, A includes Cs + , Rb + 、CH3NH3 + and CH2(NH2)2 + At least one of .

[0068] Optionally, B includes Pb 2+ , Cu 2+ 、Zn 2+ , Ga 2+ Sn 2+ and Ca 2+ At least one of .

[0069] Optionally, X includes I - Br - , Cl - 、F - and SCN - At least one of .

[0070] It can be understood that A, B, and X can each independently be one type, or can each independently be multiple types.

[0071] An embodiment of the present application provides a method for preparing a perovskite light absorbing layer, comprising:

[0072] Step S10: mixing a perovskite precursor, a passivation precursor and a first solvent to prepare a precursor mixed solution; the passivation precursor includes at least one of substituted or unsubstituted vinyl pyridine and its derivatives;

[0073] Step S20: subjecting the precursor mixed solution to film-forming and first annealing treatment in sequence to prepare a perovskite light-absorbing layer.

[0074] After the first annealing treatment, the thin film made of the precursor mixed solution containing the passivation precursor undergoes thermal cross-linking and exists stably at the grain boundaries and interfaces, thereby achieving the passivation function of the grain boundaries and interface defects and effectively improving the photovoltaic performance and stability of the device.

[0075] It can be understood that in the perovskite light absorbing layer prepared in steps S10 to S20, the passivation material and the titanium ore light absorbing material are doped and mixed with each other. It can be further understood that the perovskite light absorbing layer prepared in steps S10 to S20 belongs to bulk passivation. Furthermore, the perovskite precursor includes but is not limited to monovalent organic cation halides and divalent organic cation halides.

[0076] In some of the examples, in step S10, the concentration of the passivation precursor in the precursor mixture solution is 1 mg / mL to 8 mg / mL.

[0077] It is understood that the concentration of the passivation precursor in the precursor mixture solution includes but is not limited to 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, and 8 mg / mL.

[0078] Optionally, in step S10, the concentration of the passivation precursor in the precursor mixed solution is 1 mg / mL to 5 mg / mL.

[0079] Furthermore, in step S10, the concentration of the passivation precursor in the precursor mixed solution is 1 mg / mL to 3 mg / mL.

[0080] In some of the examples, in step S20, the first annealing treatment includes sequentially performing a low-temperature annealing treatment and a high-temperature annealing treatment; the temperature of the low-temperature annealing treatment is 50°C~95°C, and the time is 5 min~20 min; the temperature of the high-temperature annealing treatment is 100°C~150°C, and the time is 16 min~60 min.

[0081] It can be understood that the temperature of the low-temperature annealing treatment includes but is not limited to 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, and 95°C, and the time includes but is not limited to 5 min, 8 min, 10 min, 12 min, 15 min, 18 min, and 20 min; the temperature of the high-temperature annealing treatment includes but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, and 150°C, and the time includes but is not limited to 16 min, 20 min, 25 min, 30 min, 35min, 40 min, 45 min, 50 min, 55 min, and 60 min.

[0082] Optionally, in step S20, the temperature of the low-temperature annealing treatment is 70° C. to 90° C., and the time is 5 min to 15 min.

[0083] Optionally, in step S20, the high temperature annealing treatment is performed at a temperature of 100°C to 120°C and for a time of 16 min to 40 min.

[0084] By sequentially performing low temperature annealing treatment and high temperature annealing treatment, it is ensured that the vinyl monomer can be fully cross-linked.

[0085] Another embodiment of the present application provides a method for preparing a perovskite light absorbing layer, comprising:

[0086] Step S30: preparing a perovskite material layer;

[0087] Step S40: placing a passivation precursor on the surface of the perovskite material layer, and performing a second annealing treatment to form a passivation layer on the surface of the perovskite material layer to obtain a perovskite light-absorbing layer; the perovskite light-absorbing layer includes a perovskite material layer and a passivation layer; the passivation precursor includes at least one of substituted or unsubstituted vinylpyridine and its derivatives.

[0088] It can be understood that in the perovskite light absorbing layer prepared in steps S30 to S40, the perovskite light absorbing layer includes a perovskite material layer and a passivation layer, wherein the perovskite material layer includes a perovskite light absorbing material, and the passivation layer includes a passivation material. It can be further understood that the perovskite light absorbing layer prepared in steps S30 to S40 is surface passivation.

[0089] Vinylpyridine has a simple molecular structure and low cost. The lone pair of electrons on the nitrogen atom will coordinate with the uncoordinated exposed ions to achieve the passivation function of grain boundaries and interface defects. The presence of vinyl groups enables vinylpyridine to achieve in-situ thermal crosslinking during annealing, enhancing the stability of the coordinated passivation functional layer. At the same time, the formed passivation layer also has good hydrophobicity and water vapor barrier properties, which can effectively improve the tolerance of the perovskite light-absorbing layer to water vapor.

[0090] In some examples, in step S40, the temperature of the second annealing treatment is 50° C. to 120° C., and the time is 15 min to 60 min.

[0091] It can be understood that the temperature of the second annealing treatment includes but is not limited to 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C, and the time includes but is not limited to 15 min, 20 min, 25 min, 30 min, 45 min, and 60 min.

[0092] In some examples, in step S40, placing a passivation precursor on the surface of the perovskite material layer includes:

[0093] Step S41: mixing a passivation precursor and a second solvent to prepare a passivation solution;

[0094] Step S42: applying a passivation solution on the surface of the perovskite material layer.

[0095] In some examples, in step S41, the second solvent includes diethyl ether.

[0096] It can be understood that the preparation method of the perovskite light absorbing layer provided in the present application can prepare the above-mentioned perovskite light absorbing layer, and the above-mentioned perovskite light absorbing layer can be prepared by the preparation method of the perovskite light absorbing layer provided in the present application, and the parameters between the perovskite light absorbing layer provided in the present application and the preparation method of the perovskite light absorbing layer can be mutually applicable.

[0097] One embodiment of the present application provides a perovskite cell, comprising a first electrode, the above-mentioned perovskite light-absorbing layer or the perovskite light-absorbing layer prepared by the above-mentioned preparation method, and a second electrode.

[0098] It is understood that perovskite cells include but are not limited to pin-type perovskite cells.

[0099] In some of the examples, in the perovskite cell, at least one of the first electrode and the second electrode is a transparent conductive electrode.

[0100] In some of the examples, in the perovskite cell, one of the first electrode and the second electrode is a transparent conductive electrode, and the other is one of a transparent conductive electrode, a carbon electrode, and a metal electrode.

[0101] It can be understood that in the perovskite battery, the first electrode and the second electrode may be both transparent conductive electrodes; the first electrode may be a transparent conductive electrode and the second electrode may be a metal electrode; or the first electrode may be a metal electrode and the second electrode may be a transparent conductive electrode. Furthermore, when one of the first electrode and the second electrode is a transparent conductive electrode and the other is a metal electrode, the transparent conductive electrode is a transparent conductive substrate.

[0102] In some of these examples, in the perovskite cell, the metal electrode includes at least one of silver (Ag) and copper (Cu).

[0103] In some of these examples, in the perovskite cell, the transparent conductive electrode includes at least one of indium tin oxide (ITO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), and aluminum-doped zinc oxide (AZO).

[0104] In some of the examples, in the perovskite cell, the thickness of the first electrode and the second electrode are independently 20 nm to 200 nm.

[0105] It can be understood that the thickness of the first electrode and the second electrode independently include but are not limited to 20 nm, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, and 200 nm.

[0106] In some of the examples, in the perovskite cell, the perovskite light-absorbing layer includes a perovskite material layer and a passivation layer, and the perovskite material layer is disposed between the first electrode and the passivation layer.

[0107] In some of the examples, the perovskite cell further includes a first transmission layer and a second transmission layer, and the first transmission layer and the second transmission layer are respectively arranged between the first electrode and the perovskite light absorbing layer and between the perovskite light absorbing layer and the second electrode.

[0108] It can be understood that the perovskite cell includes a first electrode, a first transmission layer, the above-mentioned perovskite light-absorbing layer or the perovskite light-absorbing layer prepared by the above-mentioned preparation method, a second transmission layer and a second electrode.

[0109] In some of these examples, in the perovskite cell, one of the first transport layer and the second transport layer is a hole transport layer, and the other is an electron transport layer.

[0110] Furthermore, the perovskite cell includes a first electrode, a hole transport layer, the perovskite light absorbing layer or the perovskite light absorbing layer prepared by the above preparation method, an electron transport layer and a second electrode which are stacked.

[0111] In some of the examples, in the perovskite cell, the perovskite light absorbing layer or the perovskite light absorbing layer prepared by the preparation method comprises a perovskite material layer and a passivation layer, and the perovskite material layer is disposed between the hole transport layer and the passivation layer. That is, the perovskite material layer is disposed on the surface of the hole transport layer away from the first electrode, and the passivation layer is disposed on the side of the perovskite material layer away from the hole transport layer.

[0112] In some of these examples, in the perovskite cell, the hole transport material in the hole transport layer includes but is not limited to at least one of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) and [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB).

[0113] In some of these examples, the thickness of the hole transport layer in perovskite cells is 1 nm to 50 nm.

[0114] In some of the examples, in the perovskite cell, the electron transport material in the electron transport layer includes at least one of tin oxide, fullerene and their derivatives.

[0115] It is understood that fullerene and its derivatives include but are not limited to at least one of C60, C70 and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester).

[0116] In some of these examples, the thickness of the electron transport layer in perovskite cells is 10 nm~50 nm.

[0117] In some of the examples, the perovskite cell further includes a hole blocking layer, which is located between the electron transport layer and the second electrode.

[0118] In some of these examples, in the perovskite cell, the hole blocking layer includes at least one of bathocuproine (BCP, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and zirconium acetylacetonate.

[0119] In some of these examples, the hole-blocking layer in perovskite cells is 3 nm to 10 nm thick.

[0120] It can be understood that the thickness of the hole blocking layer includes but is not limited to 3 nm, 5 nm, 8 nm, and 10 nm.

[0121] An embodiment of the present application provides a method for preparing a perovskite battery, comprising:

[0122] Step S50: providing a first electrode;

[0123] Step S60: forming the above-mentioned perovskite light-absorbing layer or the perovskite light-absorbing layer prepared by the above-mentioned preparation method on the surface of the first electrode;

[0124] Step S70: forming a second electrode on a surface of the perovskite light absorbing layer away from the first electrode.

[0125] In some of the examples, the method for preparing the perovskite cell further includes the steps of setting a first transmission layer and a second transmission layer between the first electrode and the perovskite light absorbing layer and between the perovskite light absorbing layer and the second electrode.

[0126] Furthermore, a first transmission layer is arranged between the first electrode and the perovskite light absorbing layer, and a second transmission layer is arranged between the perovskite light absorbing layer and the second electrode.

[0127] In some of the examples, the method for preparing a perovskite cell further includes the step of providing a hole blocking layer between the electron transport layer and the second electrode.

[0128] It can be understood that the present application includes but is not limited to the types and thicknesses of the first electrode, the first transport layer, the second transport layer and the second electrode as described above; and does not limit the formation method of each layer, for example, including but not limited to one of magnetron sputtering, spin coating, slit coating and evaporation.

[0129] One embodiment of the present application provides a perovskite stack cell, including the above-mentioned perovskite cell or the perovskite cell prepared by the above-mentioned preparation method.

[0130] It can be understood that perovskite tandem cells include but are not limited to crystalline silicon / perovskite tandem cells, full perovskite tandem cells, copper indium gallium selenide and other thin film cells / perovskite tandem cells.

[0131] One embodiment of the present application provides the use of the above-mentioned perovskite solar cell or the above-mentioned perovskite tandem cell in preparing a photovoltaic module. Another embodiment of the present application provides a photovoltaic module, including the above-mentioned perovskite solar cell or the above-mentioned perovskite tandem cell.

[0132] It can be understood that photovoltaic modules can be used in photovoltaic power stations, such as ground power stations, rooftop power stations, water power stations, etc., and can also be used in equipment or devices that use solar energy to generate electricity, such as user solar power supplies, solar street lights, solar cars, solar buildings, etc. It can also be understood that the application scenarios of photovoltaic systems include but are not limited to this, that is, photovoltaic systems can be used in all fields that require solar energy to generate electricity. Taking the photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a junction box and an inverter. The photovoltaic array can be an array combination of multiple photovoltaic modules. For example, multiple photovoltaic modules can form multiple photovoltaic arrays. The photovoltaic array is connected to the junction box. The junction box can converge the current generated by the photovoltaic array. The converged current flows through the inverter and is converted into the alternating current required by the mains power grid, and then connected to the mains network to achieve solar power supply.

[0133] The photovoltaic module provided in the present application can be used in, but is not limited to, electrical devices such as vehicles, ships or aircraft.

[0134] The embodiment of the present application provides an electric device, including the above-mentioned perovskite battery, the perovskite battery prepared by the above-mentioned preparation method, or the above-mentioned photovoltaic module. The electric device can be, but is not limited to, a mobile phone, a tablet, a laptop computer, an electric toy, an electric tool, a battery car, an electric car, a ship, a spacecraft, and the like. Among them, the electric toy can include a fixed or mobile electric toy, for example, a game console, an electric car toy, an electric ship toy, and an electric airplane toy, and the like, and the spacecraft can include an airplane, a rocket, a space shuttle, and a spacecraft, and the like.

[0135] The present application is further described in detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0136] Example 1

[0137] (1) The TCO conductive glass was ultrasonically cleaned with deionized water, acetone and isopropanol for 15 min respectively, and finally dried in a drying oven at 75°C for later use; the dried TCO glass substrate was treated in a UV ozone machine for 25 min to remove organic impurities on its surface and optimize its surface wettability;

[0138] (2) Dissolve 1 mg of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid in 1 mL of isopropanol to prepare a hole transport material solution, coat it on a TCO glass substrate, and then anneal at 100 °C for 10 min to form a hole transport layer;

[0139] (3) Dissolve the perovskite precursor (722.08 mg lead iodide, 238.50 mg iodomethylamine) and 2 mg passivation precursor (2-vinylpyridine) in 1 mL of N, N-dimethylformamide (DMF) and stir at room temperature until completely dissolved to obtain a perovskite precursor solution. The concentration of the passivation precursor in the precursor mixed solution is 2 mg / mL. In a nitrogen glove box, take 30 μL of the perovskite precursor solution and drop it onto the ITO conductive glass that forms the hole transport layer. First, spin coat it at 1000 rpm for 10 s, then spin coat it at 5000 rpm for 30 s. After 25 s, quickly add 125 μL of chlorobenzene. Then, place the TCO glass on a heating table and anneal it at 80 °C for 10 min. Then, heat it to 100 °C and anneal it at 30 °C. min, a perovskite light-absorbing layer is formed, and the mass ratio of the passivation precursor to the perovskite precursor is 0.002:1;

[0140] (4) Dissolve 20 mg of methanefullerene phenyl-C61-butyric acid methyl ester (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain [6,6]-phenyl-C61-butyric acid methyl ester solution; take 30 μL of [6,6]-phenyl-C61-butyric acid methyl ester solution on the ITO conductive glass with a perovskite light absorption layer, and spin coat at 3000 rpm for 60 seconds to form a 30 nm electron transport layer;

[0141] (5) Dissolve 0.5 mg of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in 1 mL of isopropanol and stir at room temperature to obtain a hole blocking layer solution; take 40 μL of the hole blocking layer solution and drop it onto the electron transport layer, and spin coat at 5000 rpm for 35 s to form a hole blocking layer of 6 nm;

[0142] (6) Transfer the TCO conductive glass forming the hole blocking layer, electron transport layer, perovskite light absorbing layer, and hole transport layer to the vacuum coating instrument and wait until the vacuum degree is drawn to 3*10 -4 A silver electrode was evaporated at 500 Pa to form a silver electrode with a thickness of 100 nm on the hole blocking layer to obtain an electrode layer.

[0143] Example 2

[0144] The process is basically the same as Example 1, except that the 2-vinylpyridine in step (3) of Example 1 is replaced by an equal amount of 4-vinylpyridine.

[0145] Example 3

[0146] The process is basically the same as Example 1, except that the 2-vinylpyridine in step (3) of Example 1 is replaced by an equal amount of 3-vinylpyridine.

[0147] Example 4

[0148] The process is basically the same as Example 1, except that the 2-vinylpyridine in step (3) of Example 1 is replaced by an equal amount of 2-fluoro-4-vinylpyridine.

[0149] Example 5

[0150] The method is basically the same as Example 1, except that in step (3), the amount of the passivation precursor added is 5 mg, and the concentration of the passivation precursor in the precursor mixed solution is 5 mg / mL; in the perovskite light absorbing layer, the mass ratio of the passivation precursor to the perovskite precursor is 0.0052:1.

[0151] Example 6

[0152] The method is basically the same as Example 1, except that in step (3), the low-temperature annealing at 80°C is omitted and the high-temperature annealing at 100°C for 40 min is performed directly.

[0153] Example 7

[0154] (1) The TCO conductive glass was ultrasonically cleaned with deionized water, acetone and isopropanol for 15 min respectively, and finally dried in a drying oven at 75°C for later use; the dried TCO glass substrate was treated in a UV ozone machine for 25 min to remove organic impurities on its surface and optimize its surface wettability;

[0155] (2) Dissolve 1 mg of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid in 1 mL of isopropanol to prepare a hole transport material solution, coat the TCO glass substrate with the hole transport material solution, and then anneal at 100°C for 10 min to form a hole transport layer;

[0156] (3) Dissolve 722.08 mg of lead iodide and 238.50 mg of iodomethylamine solid in 1 mL of N, N-dimethylformamide (DMF) and stir at room temperature until completely dissolved to obtain a perovskite precursor solution. In a nitrogen glove box, take 30 μL of the perovskite precursor solution and drop it onto the ITO conductive glass that forms the hole transport layer. First, spin coat it at 1000 rpm for 10 s, then spin coat it at 5000 rpm for 30 s. After 25 s, quickly drop 125 μL of chlorobenzene. Then, place the TCO glass on a hot plate and heat it at 100 °C for 40 min to form a 500 nm perovskite material layer.

[0157] (4) Dissolve 5 mg of 4-vinylpyridine in 5 mL of ether and stir at room temperature in the dark until dissolved to obtain a passivation solution. Take 100 μL of the above solution and dynamically spin-coat it on the surface of the perovskite layer at a speed of 3000 rpm for 30 seconds, then anneal at 50°C for 30 min to cross-link the passivation molecules to form a passivation layer. The perovskite material layer and the passivation layer are the perovskite light-absorbing layer.

[0158] (5) Dissolve 20 mg of methanefullerene phenyl-C61-butyric acid methyl ester (PCBM) in 1 mL of chlorobenzene and stir at room temperature to obtain [6,6]-phenyl-C61-butyric acid methyl ester solution; Take 30 μL of [6,6]-phenyl-C61-butyric acid methyl ester solution and spin coat it on the ITO conductive glass with a perovskite light absorption layer at 3000 rpm for 60 seconds to form a 30 nm electron transport layer;

[0159] (6) Dissolve 0.5 mg of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in 1 mL of isopropanol and stir at room temperature to obtain a hole blocking layer solution; take 40 μL of the hole blocking layer solution and drop it onto the electron transport layer, and spin coat at 5000 rpm for 35 s to form a hole blocking layer of 6 nm;

[0160] (7) Transfer the TCO conductive glass forming the hole blocking layer, electron transport layer, perovskite light absorbing layer, and hole transport layer to the vacuum coating instrument and wait until the vacuum degree is drawn to 3*10 -4 A silver electrode was evaporated at 500 Pa to form a silver electrode with a thickness of 100 nm on the hole blocking layer to obtain an electrode layer.

[0161] Example 8

[0162] The process is basically the same as Example 7, except that the 4-vinylpyridine in step (4) of Example 7 is replaced by an equal amount of 2-vinylpyridine.

[0163] Example 9

[0164] The process is substantially the same as Example 7, except that the 4-vinylpyridine in step (4) of Example 7 is replaced by an equal amount of 3-vinylpyridine.

[0165] Example 10

[0166] The process is basically the same as Example 7, except that the 4-vinylpyridine in step (4) of Example 7 is replaced by an equal amount of 2-fluoro-4-vinylpyridine.

[0167] Comparative Example 1

[0168] The method is basically the same as Example 1, except that 2-vinylpyridine is not added to the perovskite precursor solution prepared in step (3).

[0169] Comparative Example 2

[0170] The process is basically the same as Example 1, except that the 2-vinylpyridine in step (3) of Example 1 is replaced by an equal amount of pyridine.

[0171] Comparative Example 3

[0172] The method is basically the same as Example 5, except that the 2-vinylpyridine in step (3) of Example 5 is replaced by an equal mass of poly(4-vinylpyridine).

[0173] Comparative Example 4

[0174] The method is basically the same as Example 1, except that in step (3), the amount of the passivation precursor added is 10 mg, and the concentration of the passivation precursor in the precursor mixed solution is 10 mg / mL; in the perovskite light absorbing layer, the mass ratio of the passivation precursor to the perovskite precursor is 0.010:1.

[0175] Comparative Example 5

[0176] The process is basically the same as Example 7, except that step (4) is omitted.

[0177] Comparative Example 6

[0178] The method is basically the same as Example 7, except that the 2-vinylpyridine in step (4) of Example 7 is replaced by an equal mass of phenethylammonium iodide.

[0179] Some parameters of various embodiments and comparative examples are shown in Table 1.

[0180] The perovskite cells prepared in each embodiment and comparative example were subjected to performance tests of open circuit voltage, short circuit current density, fill factor and energy conversion efficiency. The IV curve was used for the test. The test conditions were: AM 1.5G standard solar spectrum, irradiance of 1000W / m 2 The experimental test results are shown in Table 1. PCE represents the energy conversion efficiency in %, Voc represents the open circuit voltage in V, and Jsc represents the short circuit current density in mA / cm 2 , FF stands for fill factor, the unit is %.

[0181] The battery was placed at 100°C for 200 h for stability testing. The percentage of the photoelectric conversion efficiency decayed to the initial efficiency after 200 h is shown in Table 1.

[0182] Table 1

[0183]

[0184] As can be seen from Table 1, compared with the comparative example, the embodiment uses vinyl pyridine compounds as passivation precursors, and the prepared perovskite battery has higher photoelectric conversion efficiency and better stability; while comparative example 2 uses pyridine for bulk passivation, and comparative example 6 uses phenethylammonium iodide for surface passivation, and its photoelectric conversion efficiency and stability are obviously not as good as those of the embodiment; comparative example 3 directly uses poly (4-vinyl pyridine) for bulk passivation. Due to the entangled network structure and larger molecular size characteristics of the polymer molecules themselves, after part of the pyridine forms coordination passivation with the defects, the other parts of the polymer are restricted in the passivation defect area and cannot move, resulting in self-aggregation to form a polymer molecular defect center, and it may also lead to the inability to achieve passivation effect on defects in other regions. Therefore, the overall passivation effect is worse than that of the small molecule self-crosslinking passivator.

[0185] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0186] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should 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 of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A perovskite light absorbing layer, characterized in that: The perovskite light-absorbing layer includes a perovskite light-absorbing material and a passivation material. The passivation precursor forming the passivation material includes at least one of substituted or unsubstituted vinyl pyridine and its derivatives. The mass ratio of the passivation precursor to the perovskite precursor forming the perovskite light-absorbing material is 0.0001~0.008:

1.

2. The perovskite light absorbing layer according to claim 1, characterized in that: The substituents in the substituted vinyl pyridine include halogen, nitro, cyano, carboxyl, C1~C 10 Alkyl and C1~C 10 At least one of the alkoxy groups.

3. The perovskite light absorbing layer according to claim 1, characterized in that: The passivation precursor includes at least one of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-6-vinylpyridine, 4-bromo-2-vinylpyridine, 5-bromo-2-vinylpyridine, 4-chloro-2-vinylpyridine, 3-bromo-2-vinylpyridine, 2-bromo-6-vinylpyridine, 2-bromo-4-vinylpyridine, 3-bromo-5-vinylpyridine and 2-fluoro-4-vinylpyridine.

4. The perovskite light absorbing layer according to any one of claims 1 to 3, characterized in that: The passivation material and the perovskite light absorbing material are mixed with each other.

5. The perovskite light absorbing layer according to any one of claims 1 to 3, characterized in that: The perovskite light-absorbing layer comprises a perovskite material layer and a passivation layer which are stacked, the perovskite material layer comprises the perovskite light-absorbing material, and the passivation layer comprises the passivation material.

6. The perovskite light absorbing layer according to claim 5, characterized in that: The perovskite light absorbing layer satisfies at least one of the following characteristics: (1) The thickness of the passivation layer is 1 nm to 100 nm; (2) The thickness of the perovskite material layer is 400 nm to 1000 nm; (3) The thickness ratio of the passivation layer to the perovskite material layer is 0.001-0.025:

1.

7. The perovskite light absorbing layer according to any one of claims 1 to 3 and 6, characterized in that: The perovskite light-absorbing material includes ABX3, A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

8. A method for preparing a perovskite light-absorbing layer, characterized in that: The following steps are involved: A perovskite precursor, a passivation precursor and a first solvent are mixed to prepare a precursor mixed solution; the passivation precursor comprises at least one of substituted or unsubstituted vinyl pyridine and its derivatives; the mass ratio of the passivation precursor to the perovskite precursor is 0.0001-0.008:1; The precursor mixed solution is subjected to film-forming and first annealing treatment in sequence to prepare the perovskite light-absorbing layer.

9. The preparation method according to claim 8, characterized in that: The concentration of the passivation precursor in the precursor mixed solution is 1 mg / mL to 8 mg / mL.

10. The preparation method according to claim 8 or 9, characterized in that: The first annealing treatment includes performing low-temperature annealing treatment and high-temperature annealing treatment in sequence; the temperature of the low-temperature annealing treatment is 50°C~95°C, and the time is 5 min~20 min; the temperature of the high-temperature annealing treatment is 100°C~150°C, and the time is 16 min~60 min.

11. A method for preparing a perovskite light-absorbing layer, characterized in that: The following steps are involved: preparing a perovskite material layer; A passivation precursor is disposed on the surface of the perovskite material layer, and after a second annealing treatment, a passivation layer is formed on the surface of the perovskite material layer to obtain the perovskite light-absorbing layer; the perovskite light-absorbing layer includes the perovskite material layer and the passivation layer; the passivation precursor includes at least one of substituted or unsubstituted vinylpyridine and its derivatives, and the mass ratio of the passivation precursor to the perovskite precursor for preparing the perovskite material layer is 0.0001~0.008:

1.

12. The preparation method according to claim 11, characterized in that: Placing a passivation precursor on the surface of the perovskite material layer comprises the following steps: mixing a passivation precursor and a second solvent to prepare a passivation solution; The passivation solution is disposed on the surface of the perovskite material layer.

13. The preparation method according to claim 11 or 12, characterized in that: The temperature of the second annealing treatment is 50° C. to 120° C., and the time is 15 min to 60 min.

14. A perovskite battery, characterized in that: It comprises a first electrode, a perovskite light absorbing layer as claimed in any one of claims 1 to 7 or a perovskite light absorbing layer prepared by the preparation method as claimed in any one of claims 8 to 13, and a second electrode.

15. The perovskite cell according to claim 14, characterized in that: The perovskite cell further includes a hole transport layer, the perovskite light absorption layer includes a perovskite material layer and a passivation layer, and the perovskite material layer is arranged between the hole transport layer and the passivation layer.

16. A method for preparing a perovskite battery, characterized in that: The following steps are involved: providing a first electrode; Forming a perovskite light-absorbing layer as claimed in any one of claims 1 to 7 or a perovskite light-absorbing layer prepared by the preparation method as claimed in any one of claims 8 to 14 on the surface of the first electrode; A second electrode is formed on a surface of the perovskite light absorbing layer away from the first electrode.

17. An electrical device, characterized in that: Including the perovskite battery as claimed in claim 14 or 15 or the perovskite battery prepared by the preparation method as claimed in claim 16.

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