Perovskite cell and preparation method thereof, laminated cell, photovoltaic module, power generation device and electric equipment

Abstract

The invention discloses a perovskite cell and a preparation method thereof, a laminated cell, a photovoltaic module, a power generation device and electric equipment, the perovskite cell comprises a compound layer, the compound layer comprises a compound composed of a repetitive unit, the repetitive unit comprises (R3-R1-R2) d (MaXb) cM comprising at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu, x comprises at least one of F, Cl, Br, I, SCN <->, CNO <->, OCN <->, OSCN <->, SH <->, OH <->, CP <->, CN <->, SeCN <->, N3 <-> or NO2 <->, R1 comprises at least one of alkyl with the carbon atom number being smaller than or equal to 6, aryl with the carbon atom number being 6-12, five-membered aromatic heterocyclic group or six-membered aromatic heterocyclic group, R2 comprises at least one of a group containing O-C-O, a group containing O-P = O-O or a group containing S, and R3 comprises at least one of alkyl with the carbon atom number being smaller than or equal to 6. And R3 comprises at least one of H, F, carboxyl, amino or acylamino. On the premise of high efficiency, the stability of the perovskite cell is improved.

Description

Technical Field

[0001] The present application relates to the field of batteries, and in particular, to a perovskite battery, a preparation method thereof, a tandem battery, a photovoltaic module, a power generation device, and an electrical equipment. Background Art

[0002] Perovskite batteries have received extensive attention due to their excellent optoelectronic properties such as tunable bandgap, high light absorption coefficient, long carrier lifetime and diffusion length, high defect tolerance, and low-cost low-temperature solution preparation methods. In just over a decade, the efficiency of perovskite batteries has increased from 3.8% to over 25%, showing great potential. However, the existing perovskite batteries have low stability and efficiency. Summary of the Invention

[0003] In view of the technical problems existing in the background art, the present application provides a perovskite battery, which can improve the stability of the perovskite battery on the premise of high efficiency.

[0004] The first aspect of the present application provides a perovskite battery, which includes a perovskite layer and a composite layer disposed on at least one side of the perovskite layer. The composite layer includes a compound composed of at least one repeating unit, and the repeating unit includes:

[0005] (R3-R1-R2) d (M a X b ) c

[0006] Formula 1

[0007] Wherein, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo, or Eu; X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3, or -NO2; R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group; R2 includes at least one of a group containing O-C-O, a group containing O-P=O-O, or a group containing S; R3 includes at least one of H, F, a carboxyl group, an amino group, or an amide group; 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

[0008] The perovskite solar cell proposed in this application is provided with a composite layer on the perovskite layer. The composite layer includes a compound composed of at least one repeating unit, and the repeating unit includes an organic-inorganic hybrid composite compound shown in Formula 1, which can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0009] According to some embodiments of the present application, R1 includes at least one of a straight-chain alkyl group with 3 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0010] According to some embodiments of the present application, R3 includes any one of F, a carboxyl group, an amino group, or an amide group. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0011] According to some embodiments of the present application, M includes at least one of Pb or Sn. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0012] According to some embodiments of the present application, 0.5 ≤ a ≤ 6. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0013] According to some embodiments of the present application, 1 ≤ b ≤ 12. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0014] According to some embodiments of the present application, 1 ≤ c ≤ 25. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0015] According to some embodiments of the present application, 1 ≤ d ≤ 25. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0016] According to some embodiments of the present application, R3-R1-R2 includes at least one of the following structures:

[0017]

[0018] Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0019] According to some embodiments of the present application, the repeating unit includes at least one of the following chemical formulas:

[0020]

[0021]

[0022] Among them, 1 ≤ c ≤ 50 and 1 ≤ d ≤ 50.

[0023] Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0024] According to some embodiments of the present application, the ratio of the thickness of the composite layer to the thickness of the perovskite layer is (0.1 - 50):100. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0025] According to some embodiments of the present application, the thickness of the composite layer is 1 nm - 100 nm. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0026] According to some embodiments of the present application, the thickness of the composite layer is 2 nm - 10 nm. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0027] According to some embodiments of the present application, the thickness of the perovskite layer is 200 nm - 800 nm. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0028] According to some embodiments of the present application, the perovskite layer comprises at least one of the following chemical formulas:

[0029]

[0030] Among them, A and A' each independently comprise at least one of organic amines, Cs, K, Rb or Li, M comprises at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu, X and X' each independently comprise at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2, Q comprises at least one of Ag, Cs, K or Ru, and D comprises at least one of Bi, Sb, Ni, Fe, Cu or In. Thus, the stability of the perovskite solar cell can be improved on the premise of high efficiency of the perovskite solar cell.

[0031] According to some embodiments of the present application, the perovskite cell includes a first electrode, a first transport layer, the perovskite layer, the composite layer, a second transport layer, and a second electrode stacked in sequence. One of the first transport layer and the second transport layer includes an electron transport layer, and the other includes a hole transport layer. Thus, the stability of the perovskite cell can be improved on the premise of high efficiency of the perovskite cell.

[0032] According to some embodiments of the present application, the second transport layer includes the electron transport layer, and the electron transport layer includes at least one of fullerene and its derivatives, cyanide-containing poly(phenylene ethynylene), boron-containing polymer, bathocuproine, bathophenanthroline, aluminum hydroxyquinolate, oxadiazole compound, benzimidazole compound, naphthalenetetracarboxylic acid compound, perylene derivative, phosphine oxide compound, phosphine sulfide compound, fluorinated phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride, sodium fluoride, magnesium fluoride, calcium fluoride, or zinc sulfide. Thus, the stability of the perovskite cell can be improved on the premise of high efficiency of the perovskite cell.

[0033] According to some embodiments of the present application, the fullerene and its derivatives include [6,6]-phenyl-C 61 -isobutyl methacrylate, [6,6]-phenyl-C 71 -methyl butyrate, fullerene C 60 or fullerene C 70 at least one of them. Thus, the stability of the perovskite cell can be improved on the premise of high efficiency of the perovskite cell.

[0034] The second aspect of the present application provides a method for preparing a perovskite cell, including: preparing a perovskite layer;

[0035] preparing a composite layer on at least one side of the perovskite layer, the composite layer including a compound composed of at least one repeating unit, and the repeating unit includes:

[0036] (R3-R1-R2) d (M a X b ) c

[0037] Formula 1

[0038] Among them, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu; X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2; R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6 - 12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group; R2 includes at least one of a group containing O-C-O, a group containing O-P=O-O or a group containing S; R3 includes at least one of H, F, a carboxyl group, an amino group or an amide group, and 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

[0039] Thus, for the perovskite solar cell prepared in this application, a composite layer is provided on the perovskite layer. The composite layer includes a compound composed of at least one repeating unit, and the repeating unit includes an organic-inorganic hybrid composite compound shown in Formula 1, which can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0040] According to some embodiments of this application, the composite layer is prepared by the following method:

[0041] Mix R3-R1-R4 with a solvent, coat it on the surface of at least one side of the perovskite layer, and anneal at 105°C - 160°C to obtain the composite layer, where R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6 - 12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group, R4 includes at least one of a carboxyl group, a phosphoric acid group, a mercapto group or a sulfonic acid group, R3 includes at least one of H, F, a carboxyl group, an amino group or an amide group, and the surface of at least one side of the perovskite layer contains M a X b , 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20. Thus, the prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0042] According to some embodiments of this application, the solvent includes at least one of acetonitrile, isopropyl alcohol, isobutyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, water or dimethylacetamide. Thus, the prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0043] According to some embodiments of the present application, based on the total volume of the mixed solution of R3-R1-R4 and the solvent, the concentration of R3-R1-R4 is 1 mg / mL - 30 mg / mL. Thus, the prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0044] According to some embodiments of the present application, the annealing temperature is 110°C - 130°C. Thus, the prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0045] According to some embodiments of the present application, the annealing time is 6 min - 30 min. Thus, the prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0046] The third aspect of the present application provides a photovoltaic module, including the perovskite solar cell provided by the first aspect of the present application or the perovskite solar cell prepared by the method provided by the second aspect of the present application. Thus, the photovoltaic module has good long-term stability and a long service life.

[0047] The fourth aspect of the present application provides a tandem cell, including the perovskite solar cell provided by the first aspect of the present application or the perovskite solar cell prepared by the method provided by the second aspect of the present application. Thus, the tandem cell has good long-term stability and a long service life.

[0048] The fifth aspect of the present application provides a power generation device, including the perovskite solar cell provided by the first aspect of the present application or the perovskite solar cell prepared by the method provided by the second aspect of the present application. Thus, the power generation device has good long-term stability and a long service life.

[0049] The sixth aspect of the present application provides an electrical device, including the perovskite solar cell provided by the first aspect of the present application or the perovskite solar cell prepared by the method provided by the second aspect of the present application. Thus, the electrical device has good long-term stability and a long service life.

[0050] The additional aspects and advantages of the present application will be partly given in the following description, partly will become obvious from the following description, or be understood through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] By reading the following detailed description of the preferred embodiments, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present application. And in all the drawings, the same reference numerals are used to represent the same components. In the drawings:

[0052] Figure 1 is a schematic structural diagram of a perovskite solar cell according to an embodiment of the present application;

[0053] Figure 2 It is the spatial structure diagram of the complex shown in Embodiment 1-1 of the present application;

[0054] Figure 3 It is the scanning electron microscope image of the surface of the perovskite layer prepared in Example 1 of the present application;

[0055] Figure 4 It is the XRD pattern of the complex layer prepared in Example 1 of the present application.

[0056] Explanation of reference numerals:

[0057] 1: Perovskite solar cell; 10: First electrode; 11: First transport layer; 12: Perovskite layer; 13: Complex layer; 14: Second transport layer; 15: Second electrode. Detailed implementation manners

[0058] The embodiments of the technical solutions of the present application will be described in detail below. The following embodiments are only used to illustrate the technical solutions of the present application more clearly, so they are only examples and cannot be used to limit the protection scope of the present application.

[0059] Referring to "embodiment" herein means that the specific features, structures or characteristics described in connection with the embodiment may be included in at least one embodiment of the present application. The phrase appears in various places in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein may be combined with other embodiments.

[0060] The "scope" disclosed in this application is defined in the form of a lower limit and an upper limit. A given scope is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular scope. The scope defined in this way can include or exclude the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a scope. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, ranges of 60-110 and 80-120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise specified, the numerical range "a-b" represents an abbreviated representation of any real number combination between a and b, where both a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are fully listed herein, and "0-5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0061] If there is no special instruction, all embodiments and optional embodiments of this application can be combined with each other to form a new technical solution.

[0062] If there is no special instruction, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0063] If there is no special instruction, all steps of this application can be carried out sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) carried out sequentially, or can also include steps (b) and (a) carried out sequentially. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b), and (c), or can also include steps (a), (c), and (b), or can also include steps (c), (a), and (b), etc.

[0064] With the increasingly severe problems of the global ecological environment and energy shortage, solar photovoltaic power generation has received extensive attention. As the third-generation new solar cell, perovskite batteries have attracted much attention in the field of solar cells due to their advantages such as low cost, simple preparation process, and high efficiency.

[0065] However, in the preparation process of perovskite solar cells, due to the ionic nature of the organic-inorganic hybrid perovskite material in the perovskite layer of perovskite solar cells, one of the common defects on the perovskite surface is that the A-site cations in AMX3 leave the system, resulting in M on the perovskite surface a X b (such as the common PbI2 system) being in excess, which usually reduces the stability and efficiency of perovskite solar cells: First, the excess M a X b will damage the perovskite crystal structure and reduce the performance of perovskite solar cells. M a X b reacts too much with the perovskite crystal, resulting in a change in the perovskite crystal structure, thus affecting the photoelectric conversion efficiency of perovskite solar cells; Second, the excess M a X b will also lead to a decrease in the stability of perovskite solar cells, forming some unstable compounds or ions in the perovskite film. These compounds or ions may cause the migration of electrons or ions inside the perovskite solar cells, resulting in the performance decline or even damage of perovskite solar cells; In addition, the excess M a X b will also introduce trap states harmful to the performance of perovskite solar cells, accelerating the performance loss of perovskite solar cells. These trap states will capture photo-generated carriers, reducing the carrier mobility and lifetime, thus affecting the photoelectric conversion efficiency of perovskite solar cells. On the other hand, the perovskite layer is also easily eroded by water and oxygen in the air, resulting in the decomposition of the components of the perovskite layer and the reduction of the efficiency of perovskite solar cells containing it.

[0066] In this application, a perovskite solar cell is proposed. A composite layer is provided on the perovskite layer. The composite layer includes a compound composed of at least one repeating unit. The repeating unit includes an organic-inorganic hybrid composite compound shown in Formula 1. This composite is composed of a basic unit (R3-R1-R2) d (M a X b ) c periodically assembled along at least one spatial direction, and is a low-dimensional (one-dimensional or two-dimensional) metal framework organic material with good chemical stability. Covering it on the perovskite layer can reduce the excess amount of M a X b on the perovskite layer surface, and can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer, damage the structure of the perovskite layer, enhance the continuity of the perovskite layer, and modify the perovskite device into a continuous thin-film device. On the premise of high efficiency of perovskite solar cells, the stability of perovskite solar cells is improved.

[0067] The perovskite battery disclosed in this application belongs to a photovoltaic battery, and the perovskite battery disclosed in the embodiments of this application can be used as a power source for electrical equipment, or can be assembled into a photovoltaic power generation system and store electrical energy in an energy storage system composed of energy storage batteries. The electrical equipment can include street lights, signal lights, insecticidal lights, electric fans, electric toys, power tools, battery cars, electric vehicles, ships, spacecraft, etc. Among them, the electric toys can include fixed or mobile electric toys, such as game consoles, electric vehicle toys, electric ship toys, and electric aircraft toys, etc. The spacecraft can include airplanes, rockets, space shuttles, and spaceships, etc.; the photovoltaic power generation system can include large-scale ground photovoltaic power generation systems, distributed photovoltaic power generation and building-integrated photovoltaic power generation systems, etc.

[0068] In the first aspect of this application, a perovskite battery is provided. Referring to Figure 1 , the perovskite battery 1 includes a perovskite layer 12 and a composite layer 13 provided on the perovskite layer 12. The composite layer 13 includes a compound composed of at least one repeating unit. The repeating unit includes:

[0069] (R3-R1-R2) d (M a X b ) c

[0070] Formula 1

[0071] Wherein, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu, X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2, R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group, R2 includes at least one of a group containing O-C-O, a group containing O-P=O-O or a group containing S, R3 includes at least one of H, F, a carboxyl group, an amino group or an amide group, 0.1≤a≤10, 1≤b≤20, 1≤c≤50, 1≤d≤50.

[0072] In this application, a perovskite battery 1 is proposed. A composite layer 13 is provided on the perovskite layer 12. The composite layer 13 includes a compound composed of at least one repeating unit. The repeating unit is the organic-inorganic hybrid composite compound shown in Formula 1. This composite is composed of the basic unit (R3-R1-R2) d (M a X b )c It is periodically assembled along at least one spatial direction and is a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material with good chemical stability and electrical conductivity. It is arranged tightly and regularly. Covering it on the perovskite layer 12 can reduce the amount of M on the surface of the perovskite layer 12 a X b in excess, and can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer 12 and damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, modify the perovskite device into a continuous thin-film device, and improve the stability of the perovskite battery 1 on the premise of the high efficiency of the perovskite battery 1.

[0073] In the embodiments of the present application, the material of the composite layer 13 can be determined by XRD.

[0074] It can be understood that the basic unit (R3-R1-R2) of Formula 1 d (M a X b ) c In, a coordination bond is formed between R2 and M. For example, when R2 includes a group containing O-C-O, at least one O in O-C-O forms a coordination bond with M to form a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material (MOFs, Metal organic Framework). When R2 includes a group containing O-P=O-O, at least one O other than the O in the P=O double bond in O-P=O-O forms a coordination bond with M to form a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material.

[0075] It can be understood that X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2. When including at least one of -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2, taking -SCN as an example, the "-" in -SCN represents a bond linked to other groups. The same applies hereinafter and will not be repeated.

[0076] According to some embodiments of the present application, R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group. As the R3-R1-R2 main body of the organic group in the organic-inorganic hybrid composite compound (Formula 1), selecting the above groups can play a good supporting role, and R1 can separate R2 and R3, so that R2 and the inorganic group M a X bThrough coordination, R3 interacts with other layers of the perovskite cell 1. The two groups do not interfere with each other. On the premise of the high efficiency of the perovskite cell 1, the stability of the perovskite cell 1 is improved. In some other embodiments of the present application, R1 includes at least one of a straight-chain alkyl group with 3 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group.

[0077] It can be understood that the five-membered aromatic heterocyclic group refers to a five-membered ring containing heteroatoms with aromaticity. As an example, the five-membered aromatic heterocyclic group can be a pyrrolyl group, a furyl group, a thiophenyl group, etc.; similarly, the six-membered aromatic heterocyclic group refers to a six-membered ring containing heteroatoms with aromaticity. As an example, the six-membered aromatic heterocyclic group can be pyridine, etc.

[0078] According to some embodiments of the present application, R1 includes a straight-chain alkyl group with a carbon atom number less than or equal to 6. For example, the carbon atom number of R1 can be 1 - 6, 2 - 5, 3 - 4, etc. Limiting the carbon atom number within the above range enables R1 to separate R2 and R3, enabling R2 to coordinate with the inorganic group M a X b Through coordination, it interacts with other layers of the perovskite cell 1. The two groups do not interfere with each other. On the premise of the high efficiency of the perovskite cell 1, the stability of the perovskite cell 1 is improved. In some other embodiments of the present application, R1 includes a straight-chain alkyl group with 3 to 6 carbon atoms.

[0079] According to some embodiments of the present application, R3 includes any one of F, a carboxyl group, an amino group, or an amide group. By using the above groups for R3, R1 can separate R2 and R3, enabling R2 to coordinate with the inorganic group M a X b Through coordination, R3 interacts with other layers of the perovskite cell 1 to form hydrogen bonds, strengthening the connection ability between the composite layer 13 and other layers, enhancing the bonding effect of each film layer of the perovskite cell 1, enhancing the upper limit value of interface filling. On the premise of the high efficiency of the perovskite cell 1, the stability of the perovskite cell 1 is improved. In some other embodiments of the present application, R1 includes a straight-chain alkyl group with 3 to 6 carbon atoms.

[0080] It can be understood that when R1 includes an aryl group with 6 carbon atoms and R3 includes H, R3 - R1 - can form a phenyl group.

[0081] According to some embodiments of the present application, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo, Eu. The inorganic group (M a X b)Combined with the organic group (R3-R1-R2), a coordination bond is formed between R2 and M to obtain a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material, which has good chemical stability and conductivity, is closely and regularly arranged. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , and an ion protection layer can also be formed to block the reaction of water vapor in the air with the perovskite layer 12 to damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, and modify the perovskite device into a continuous thin-film device. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved. In some other embodiments of the present application, M includes at least one of Pb or Sn.

[0082] According to some embodiments of the present application, 0.1 ≤ a ≤ 10. For example, a can be 0.1 - 9.9, 0.5 - 9.5, 1 - 9, 2 - 8, 3 - 7, 4 - 6. Controlling the range of a within the above range, the composite layer 13 has good chemical stability and conductivity, is closely and regularly arranged. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , and an ion protection layer can also be formed to block the reaction of water vapor in the air with the perovskite layer 12 to damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, and modify the perovskite device into a continuous thin-film device. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved. In some other embodiments of the present application, 0.5 ≤ a ≤ 6.

[0083] According to some embodiments of the present application, 1 ≤ b ≤ 20. For example, 1 ≤ b ≤ 19, 2 ≤ b ≤ 18, 3 ≤ b ≤ 17, 4 ≤ b ≤ 16, 5 ≤ b ≤ 15, 6 ≤ b ≤ 14, 7 ≤ b ≤ 13, 8 ≤ b ≤ 12, 9 ≤ b ≤ 11, etc. Controlling the range of b within the above range, the composite layer 13 has good chemical stability and conductivity, is closely and regularly arranged. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , and an ion protection layer can also be formed to block the reaction of water vapor in the air with the perovskite layer 12 to damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, and modify the perovskite device into a continuous thin-film device. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved. In some other embodiments of the present application, 1 ≤ b ≤ 12.

[0084] According to some embodiments of the present application, 1 ≤ c ≤ 50. For example, 1 ≤ c ≤ 49, 5 ≤ c ≤ 45, 10 ≤ c ≤ 40, 15 ≤ c ≤ 35, 20 ≤ c ≤ 30, 25 ≤ c ≤ 30, etc. By controlling the range of c within the above range, the inorganic group and the organic group have a good ratio, the composite layer 13 has good chemical stability and conductivity, and is arranged tightly and regularly. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , and can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer 12 to damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, and modify the perovskite device into a continuous thin-film device. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved. In some other embodiments of the present application, 1 ≤ c ≤ 25.

[0085] According to some specific embodiments of the present application, 1 ≤ d ≤ 50. For example, 1 ≤ d ≤ 49, 5 ≤ d ≤ 45, 10 ≤ d ≤ 40, 15 ≤ d ≤ 35, 20 ≤ d ≤ 30, 25 ≤ d ≤ 30, etc. By controlling the range of d within the above range, the inorganic group and the organic group have a good ratio, the composite layer 13 has good chemical stability and conductivity, and is arranged tightly and regularly. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , and can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer 12 to damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, and modify the perovskite device into a continuous thin-film device. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved. In some other embodiments of the present application, 1 ≤ d ≤ 25.

[0086] According to some embodiments of the present application, R3-R1-R2 includes at least one of the following structures:

[0087]

[0088] Thus, R3-R1-R2 with the above structure can be combined with the inorganic group (M a X b ), a coordination bond is formed between R2 and M to obtain a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material, which has good chemical stability and conductivity, and is arranged tightly and regularly. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b, an ion protection layer can also be formed to block the reaction between water vapor in the air and the perovskite layer 12 from damaging the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, modify the perovskite device into a continuous thin-film device, and improve the stability of the perovskite battery 1 on the premise of the high efficiency of the perovskite battery 1. That is, on the premise of the high efficiency of the perovskite battery, the stability of the perovskite battery can be improved.

[0089] According to some specific embodiments of the present application, the repeating unit includes at least one of the following chemical formulas:

[0090]

[0091] Wherein, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

[0092] Thus, the formation of the complex by the above repeating unit is a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material with good chemical stability and conductivity, arranged closely and regularly. Covering it on the perovskite layer 12 can reduce the excessive M on the surface of the perovskite layer 12 a X b , an ion protection layer can also be formed to block the reaction between water vapor in the air and the perovskite layer 12 from damaging the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, modify the perovskite device into a continuous thin-film device, and improve the stability of the perovskite battery 1 on the premise of the high efficiency of the perovskite battery 1.

[0093] Specifically, taking Formula 1-1 as an example, the repeating unit of the complex is shown as follows:

[0094]

[0095] In the chemical bond connecting the Pb atom and the I atom in the above formula, the solid line represents the connection bond between the Pb atom and the I atom in PbI2 in the smallest repeating unit, and the dotted line represents the bond formed when the Pb atom and the I atom are connected to the adjacent smallest repeating unit after the expansion of the smallest repeating unit. A coordination bond is formed between the Pb atom and the S atom. Each Pb atom is connected to 5 I atoms and one S sulfur atom. The spatial structure of the complex shown in Formula 1-1 is as Figure 2 shown. It can be seen that the complex shown in Formula 1-1 is periodically assembled along a spatial direction and is a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material.

[0096] According to some embodiments of the present application, the ratio of the thickness of the composite layer to the thickness of the perovskite layer is (0.1 - 50):100. For example, the thickness of the composite layer 13 can account for (0.1 - 49.9):100, (1 - 49):1, (5 - 45):1, (10 - 40):1, (15 - 35):1, (20 - 30):1, (25 - 28):1, etc. of the thickness of the perovskite layer 12. By limiting the thickness of the composite layer 13 within the above range, the composite layer 13 covers the perovskite layer 12 and consumes the excessive M on the surface of the perovskite layer 12. a X b It can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer 12 and damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, modify the perovskite device into a continuous thin-film device, and not be too thick to affect the efficiency of the perovskite solar cell 1. On the premise of the high efficiency of the perovskite solar cell 1, the stability of the perovskite solar cell 1 is improved. In some other embodiments of the present application, the ratio of the thickness of the composite layer to the thickness of the perovskite layer is (0.3 - 4):100.

[0097] According to some embodiments of the present application, the thickness of the composite layer 13 is 1 nm - 100 nm. For example, the thickness of the composite layer 13 can be 1 nm - 99 nm, 5 nm - 95 nm, 10 nm - 90 nm, 20 nm - 80 nm, 3 nm - 70 nm, 40 nm - 60 nm, etc. By limiting the thickness of the composite layer 13 within the above range, the composite layer 13 covers the perovskite layer 12 and consumes the excessive M on the surface of the perovskite layer 12. a X b It can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer 12 and damage the structure of the perovskite layer 12, enhance the continuity of the perovskite layer 12, modify the perovskite device into a continuous thin-film device, and not be too thick to affect the efficiency of the perovskite solar cell 1. On the premise of the high efficiency of the perovskite solar cell 1, the stability of the perovskite solar cell 1 is improved. In some other embodiments of the present application, the thickness of the composite layer 13 is 2 nm - 10 nm.

[0098] According to some embodiments of the present application, the thickness of the perovskite layer 12 is 200 nm - 800 nm. For example, it can be 200 nm - 790 nm, 250 nm - 750 nm, 300 nm - 700 nm, 350 nm - 650 nm, 400 nm - 600 nm, 500 nm - 600 nm, etc., or it can be a range composed of any of the above values. Thus, by controlling the thickness of the perovskite layer 12 within the above range, the excessive M on the surface of the perovskite layer 12 is made... a X bLess, on the premise of high efficiency of the perovskite cell 1, the stability of the perovskite cell 1 is improved. In some other embodiments of the present application, the thickness of the perovskite layer 12 is 300 nm - 600 nm.

[0099] It can be understood that the thicknesses of the perovskite layer 12 and the composite layer 13 are definitions well known in the art and can be measured by methods well known in the art. For example, they can be measured by the following method:

[0100] Measure using a Bruker DEKTAK-XT profilometer.

[0101] According to some embodiments of the present application, the perovskite layer 12 includes at least one of the following chemical formulas:

[0102]

[0103] Among them, A and A' each independently include at least one of organic amines, Cs, K, Rb or Li, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu, X and X' each independently include at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2, Q includes at least one of Ag, Cs, K or Ru, and D includes at least one of Bi, Sb, Ni, Fe, Cu or In. At least one of the above substances is used in the perovskite layer 12, and the excessive M on the surface of the perovskite layer 12 a X b is less, and on the premise of high efficiency of the perovskite cell 1, the stability of the perovskite cell 1 is improved.

[0104] According to some embodiments of the present application, the organic amine includes NR4R5R6R7-, R8R9N=CR 10 R 11 -, R 12 R 13 N-CR 14 =NR 15 R 16 - or R 17 R 18 N-C(N R19 R 20 )=R 21 R 22 - and at least one of them, where R4 to R 22 each independently include any one of a substituted or unsubstituted alkyl group with 1 - 20 carbon atoms, a substituted or unsubstituted aryl group or H. When R4 to R 22When each independently includes an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted, the number of carbon atoms may be 1 to 19, 2 to 18, 3 to 17, 4 to 16, 5 to 15, 7 to 14, 9 to 13, 10 to 12, etc. The organic amine uses at least one of the above groups, and the excess M on the surface of the perovskite layer 12 a X b is less. On the premise of the high efficiency of the perovskite battery 1, the stability of the perovskite battery 1 is improved.

[0105] It can be understood that the organic amine refers to an organic compound containing a nitrogen element. For example, the organic amine may include, but is not limited to, formamidine (FA), methylamine, etc.

[0106] According to some embodiments of the present application, please refer to Figure 1 , the perovskite battery 1 includes a first electrode 10, a first transport layer 11, a perovskite layer 12, a composite layer 13, a second transport layer 14, and a second electrode 15 arranged in sequence from bottom to top:

[0107] The first electrode 10 is a transparent electrode for light incidence and may include one or more mixtures of glass or transparent organic polymers. For example, it includes, but is not limited to, conductive glass, PET (polyethylene terephthalate), PI (polyimide), etc.

[0108] The material of the second electrode 15 may include at least one of an organic conductive material or an inorganic conductive material. Such as metal conductive materials Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, etc., conductive oxides FTO, ITO, IWO, AZO, IZO, BZO, MoO3, etc. or their mixtures.

[0109] The first transport layer 11 and the second transport layer 14, one of which is an electron transport layer and the other is a hole transport layer. In this application, taking the second transport layer 14 as the electron transport layer and the first transport layer 11 as the hole transport layer as an example, the electron transport layer can play a good role in extracting electrons and blocking holes, and the hole transport layer undertakes the role of transporting holes and blocking electrons. The hole transport layer may include at least one of the following materials and their derivatives: 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoromethylformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (CzPAF-SBF), p-PY (polypyrrole), Me-4PACz ([4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid), MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), imide compounds, quinone compounds, WO3, thiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, cuprous thiocyanate, copper iodide, fluorine-containing phosphonic acid, carbonyl-containing phosphonic acid, carbon nanotubes and graphene.

[0110] According to some embodiments of the present application, the second transport layer 14 includes the electron transport layer, and the electron transport layer includes at least one of fullerenes and their derivatives, cyanide-containing poly(phenylacetylene), boron-containing polymers, bathocuproine, bathophenanthroline, aluminum tris(8-hydroxyquinoline), oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorinated phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride, sodium fluoride, magnesium fluoride, calcium fluoride or zinc sulfide. The electron transport layer composed of the above substances can play a good role in extracting electrons and blocking holes, and improve the stability of the perovskite battery 1 on the premise of high efficiency of the perovskite battery 1.

[0111] According to some other embodiments of the present application, the electron transport layer includes fullerenes and their derivatives, such that R3 in the complex of Formula 1 interacts with the electron transport layer to form a hydrogen bond, strengthening the connection ability between the complex layer 13 and the electron transport layer, enhancing the bonding effect of each film layer of the perovskite battery 1, enhancing the upper limit value of interface filling, and improving the stability of the perovskite battery 1 on the premise of high efficiency of the perovskite battery 1.

[0112] According to some other embodiments of the present application, the fullerenes and their derivatives include [6,6]-phenyl-C 61 -isobutyl methacrylate (CAS No.: 160848-22-6), [6,6]-phenyl-C 71 -methyl butyrate (CAS No.: 609771-63-3), fullerene C 60 or fullerene C 70 or at least one of them. The electron transport layer made of the above fullerene-containing substance is more likely to interact with R3 in the complex of Formula 1 to form a hydrogen bond, strengthen the connection ability between the complex layer 13 and the electron transport layer, enhance the bonding effect of each film layer of the perovskite battery 1, enhance the upper limit value of interface filling, and improve the stability of the perovskite battery 1 on the premise of high efficiency of the perovskite battery 1.

[0113] The second aspect of the present application provides a method for preparing a perovskite battery, including:

[0114] S100: Prepare a perovskite layer;

[0115] S200: Prepare a complex layer on at least one side of the perovskite layer, the complex layer includes a compound composed of at least one repeating unit, and the repeating unit includes:

[0116] (R3-R1-R2) d (M a X b ) c

[0117] Formula 1

[0118] wherein, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu, X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2, R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group, R₂ includes at least one of a group containing O-C-O, a group containing O-P=O-O or a group containing S, R3 includes at least one of H, F, carboxyl group, amino group or amide group, 0.1≤a≤10, 1≤b≤20, 1≤c≤50, 1≤d≤50.

[0119] According to some embodiments of the present application, the complex layer is prepared by the following method:

[0120] S201: Mix R3-R1-R4 with a solvent, apply the mixture on the surface of one side of the perovskite layer, and anneal at 105°C - 160°C to obtain a composite layer, where R1 includes at least one of an alkyl group with 6 or fewer carbon atoms, an aryl group with 6 - 12 carbon atoms, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group; R4 includes at least one of a carboxyl group, a phosphate group, a mercapto group, or a sulfonic acid group; R3 includes at least one of H, F, a carboxyl group, an amino group, or an amide group, and the surface of at least one side of the perovskite layer contains M a X b , 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20.

[0121] Specifically, for the perovskite solar cell prepared by the above method, a composite layer is in-situ formed on the perovskite layer. On the one hand, it can consume the excessive M a X b on the upper surface of the perovskite layer. The composite layer is tightly combined with the perovskite layer. On the other hand, the composite layer includes an organic-inorganic hybrid composite compound shown in Formula 1. This composite is composed of basic units (R3-R1-R2) d (M a X b ) c periodically assembled along at least one spatial direction. It is a low-dimensional (one-dimensional or two-dimensional) metal-organic framework material. It not only has the activity of metal but also obtains the flexibility of organic ligands, the selectivity of functional groups, and other physical and chemical properties, as well as the special spatial structure formed by coordination. This makes the composite layer have good chemical stability and conductivity, and it is arranged tightly and regularly. Covering it on the perovskite layer can reduce the excessive M a X b on the perovskite layer surface. It can also form an ion protection layer to block the reaction of water vapor in the air with the perovskite layer and damage the structure of the perovskite layer, enhance the continuity of the perovskite layer, and modify the perovskite device into a continuous thin-film device, thereby improving the stability of the perovskite solar cell on the premise of high efficiency.

[0122] It can be understood that when the composite layer is prepared by the method of step S201, the perovskite layer prepared in the above step S100 will react. Since different degrees of M a X b excess will occur after the perovskite layer is prepared. Therefore, after mixing R3-R1-R4 with a solvent and applying the mixture on the surface of one side of the perovskite layer, annealing at 105°C - 160°C, R3-R1-R4 and the excessive M a X bA reaction will occur to form a complex composed of repeating units shown in Formula 1. The perovskite layer after annealing is different from the perovskite layer before annealing. There is a loss of the perovskite layer in the final product, and it is no longer the perovskite layer in Step S100.

[0123] Specifically, taking R4 including a carboxyl group as an example, R3-R1-R4 and M a X b During the reaction, the carbon-oxygen double bond in the carboxyl group opens, and at least one O atom forms a coordination bond with M a X b in M d (M a X b ) c n In the resulting metal-organic framework material [(R3-R1-R2) a X b , the carboxyl group correspondingly forms a group containing O-C-O. Since the phosphorus-oxygen double bond in the phosphate group is relatively stable, the phosphorus-oxygen double bond will not open during the formation of the complex. The phosphate group reacts with M a X b to form a group containing O-P=O-O, the mercapto group forms a group containing S, and the sulfonic acid group forms a group containing O=S=O-O.

[0124] According to some embodiments of the present application, after the R3-R1-R4 solution is coated into a wet film, solvent quenching (drying) is achieved by using an air knife or vacuum drying, and then the annealing temperature is 105°C - 160°C. For example, it can be 105°C - 159°C, 110°C - 155°C, 115°C - 150°C, 120°C - 145°C, 125°C - 140°C, 130°C - 135°C, etc. Specifically, controlling the annealing temperature within the above range enables the in-situ formation of the complex of Formula 1 on the perovskite layer, which can reduce the excessive M a X b on the surface of the perovskite layer, form an ion protection layer, enhance the continuity of the perovskite layer, and modify the perovskite device into a continuous thin-film device, thereby improving the stability of the perovskite battery on the premise of high efficiency of the perovskite battery. According to other embodiments of the present application, the annealing temperature is 110°C - 130°C.

[0125] It can be understood that after the R3-R1-R4 solution is coated into a wet film and annealed, there may be an excessive amount of R3-R1-R4 that does not participate in the reaction. After annealing, the excessive R3-R1-R4 may volatilize or decompose.

[0126] According to some embodiments of the present application, the annealing time is 6 min - 30 min. For example, the annealing time can be 6 min - 29 min, 10 min - 25 min, 15 min - 20 min, etc. Specifically, controlling the annealing time within the above range is beneficial to forming the complex of Formula 1 on the perovskite layer, which can reduce the excessive M on the surface of the perovskite layer a X b , forming an ion protection layer, enhancing the continuity of the perovskite layer. The prepared perovskite solar cell can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0127] According to some embodiments of the present application, the solvent includes at least one of acetonitrile, isopropanol, isobutanol, N,N-dimethylformamide, N,N-dimethylacetamide, water, or dimethylacetamide. Thus, the perovskite solar cell prepared with the above solvent can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0128] According to some embodiments of the present application, based on the total volume of the mixed solution of R3-R1-R4 and the solvent, the concentration of R3-R1-R4 is 1 mg / mL - 30 mg / mL. For example, the concentration of R3-R1-R4 can be 1 mg / mL - 29 mg / mL, 5 mg / mL - 25 mg / mL, 10 mg / mL - 20 mg / mL, 15 mg / mL - 18 mg / mL, etc. Thus, the perovskite solar cell prepared with the R3-R1-R4 solution of the above concentration has a moderate thickness and good uniformity of the complex layer, and can improve the stability of the perovskite solar cell on the premise of high efficiency of the perovskite solar cell.

[0129] The third aspect of the present application provides a tandem solar cell, including the perovskite solar cell provided in the first aspect of the present application or the perovskite solar cell prepared by the method provided in the second aspect of the present application. Thus, the tandem solar cell has good long-term stability and a long service life.

[0130] The fourth aspect of the present application provides a photovoltaic module, including the perovskite solar cell provided in the first aspect of the present application or the perovskite solar cell prepared by the method provided in the second aspect of the present application. Thus, the photovoltaic module has good long-term stability and a long service life.

[0131] The fifth aspect of the present application provides a power generation device, including the perovskite solar cell provided in the first aspect of the present application or the perovskite solar cell prepared by the method provided in the second aspect of the present application. Thus, the power generation device has good long-term stability and a long service life.

[0132] A power generation device refers to a power generation system that directly converts solar radiant energy into electrical energy using the photovoltaic effect, and is divided into a stand-alone PV system and a grid-connected PV system. The stand-alone PV system consists of a solar PV array composed of photovoltaic modules, a battery bank, a charge controller, a power electronic converter (inverter), a load, etc. The grid-connected PV system consists of a PV array, a high-frequency DC / DC boost circuit, a power electronic converter (inverter), and a system monitoring part.

[0133] A photovoltaic module refers to a solar cell module, that is, an overall module including multiple perovskite cells. Among them, it includes several cell strings, and each cell string includes multiple perovskite cells connected in series through connectors such as solder tapes.

[0134] In a photovoltaic module, in addition to the cell strings, it also includes a front glass, a front encapsulation film, a back encapsulation film, a back glass, etc. As an example, the photovoltaic module includes a front glass, a front encapsulation film, a cell string, a back encapsulation film, and a back glass that are stacked in sequence along the thickness direction.

[0135] The sixth aspect of this application provides an electrical device, including the perovskite cell provided in the first aspect of this application or the perovskite cell prepared by the method provided in the second aspect of this application. The electrical device can include lighting elements, display elements, mobile devices, etc. Specifically, it can include street lamps, signal indicators, insecticidal lamps, electric fans, electric toys, power tools, battery cars, electric vehicles, ships, spacecraft, etc. Among them, the electric toys can include fixed or mobile electric toys, for example, game consoles, electric vehicle toys, electric ship toys, and electric aircraft toys, etc. The spacecraft can include airplanes, rockets, space shuttles, and spaceships, etc.; the photovoltaic power generation system can include large-scale ground photovoltaic power generation systems, distributed photovoltaic power generation and building-integrated photovoltaic power generation systems, etc. Thus, the electrical device has good long-term stability and a long service life.

[0136] In order to make the technical problems, technical solutions, and beneficial effects solved by the embodiments of this application clearer, the following will be further described in detail in combination with embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way constitutes a limitation on this application and its application. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of this application.

[0137] Embodiment 1

[0138] 1. A set of FTO conductive glasses with a specification of 30 cm × 30 cm (fluorine-doped tin dioxide conductive glass) is etched with infrared laser at P1. The width of P1 is about 30 μm. The whole glass is divided into 44 sub-cells along the long side direction in turn. The series resistance of different sub-cells is greater than 10 MΩ. The upper and lower 10 mm are used as the areas for component welding. The etched conductive glass surface is cleaned with acetone and isopropanol twice in turn, immersed in deionized water for ultrasonic treatment for 10 min, then dried in a blast drying oven and placed in a drying room (humidity below 2%), which is used as the first electrode.

[0139] 2. The cleaned conductive glass is put into a magnetron sputtering to deposit a hole transport layer of nickel oxide, and the thickness of the nickel oxide layer film is about 15 nm.

[0140] 3. A layer of FA 0.92 Cs 0.08 PbI3 perovskite main layer is coated by slit coating, and then it is transferred to a vacuum equipment for vacuuming for 60 s with a vacuum degree of 15 Pa. It is annealed at 150 °C for 10 min by a non-contact closed-space annealing process, and the thickness of the perovskite layer is 500 nm.

[0141] 4. 3-mercapto-1,2,4-triazole (CAS: 3179-31-5) is configured into a 20 mg / mL solution according to the volume ratio of acetonitrile: IPA (isopropanol) = 1:9, and is coated above the perovskite by slit coating with a wet film thickness of 2.697 μm. It is dried in vacuum for 60 s and then annealed at 120 °C for 10 min to obtain a composite layer. The repeating unit of the composite layer is

[0142] 5. The above-prepared device is put into a vacuum thermal evaporation equipment, evacuated to 4 × 10 -4 Pa, and a 30 nm-thick fullerene C 60 and 8 nm BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) are deposited as the electron transport layer of the device.

[0143] 6. After depositing the electron transport layer in the vacuum thermal evaporation equipment, continue to deposit 10 nm of Ag on its surface and then break the vacuum and take it out. Laser etch P2 with a width of 150 μm and etch the depth to the surface of the FTO conductive glass. The interval between P2 and P1 is 20 μm. Then the substrate is put into the evaporation equipment again and evacuated to 4 × 10 -4 Pa and continue to deposit a layer of Ag with a thickness of about 80 nm.

[0144] 7. After cooling down, break the vacuum and take out the P-second green laser etching of P3. The width of P3 is 15 μm, and the depth is etched to the surface of the FTO conductive glass. The interval between P3 and P2 is 20 μm (the positions of the etching lines are P1 / P2 / P3 in sequence);

[0145] 8. Then use infrared edge cleaning on the component, that is, etch 10 mm on both sides of the component;

[0146] 9. Test the energy conversion efficiency of the component under a solar simulator of 1000 W / m 2 .

[0147] After testing the initial energy conversion efficiency, place the battery in the atmospheric environment (relative humidity is 65 - 85%, ambient temperature is about 15 - 40 °C), and place it without light shielding for 500 hours. Then, test the energy conversion efficiency again, and calculate the ratio of the energy conversion efficiency of the solar cell after being placed in the atmosphere for 500 hours to the initial energy conversion efficiency as the normalized efficiency of the solar cell.

[0148] The preparation methods of the perovskite batteries in Example 2 - Example 21 and Comparative Example 1 are the same as those in Example 1, and the differences are shown in Table 1 for details.

[0149] Among them, in step 4, the wet film thickness of Example 2 is 6.742 μm, the wet film thickness of Example 3 is 13.483 μm, the wet film thickness of Example 4 is 67.416 μm, the wet film thickness of Example 5 is 134.831 μm, and the wet film thicknesses of Example 1 and Examples 5 - 21 are all 2.697 μm.

[0150] Table 1

[0151]

[0152]

[0153]

[0154] Performance test:

[0155] 1. Photovoltaic conversion efficiency

[0156] Under normal temperature and pressure, use a standard light source with a solar light simulation source of AM1.5G, and conduct the test in accordance with the national standard IEC61215. Calibrate the intensity of the light with a crystalline silicon solar cell to make it reach one sun intensity, and use a four-channel digital source meter (Keithley 2440) to measure the volt-ampere characteristic curve of the solar cell under the light source irradiation to obtain the energy conversion efficiency Eff (Efficiency) of the solar cell;

[0157] 2. Device stability determination

[0158] After the test, the battery is placed in an atmospheric environment (relative humidity of 65%-85%, ambient temperature of about 15°C-40°C) and left without light shielding for 500 hours. Then, the energy conversion efficiency is measured again (each measurement is carried out until there is no hysteresis phenomenon during the forward and reverse scans, and the energy conversion efficiency is recorded). Calculate the ratio of the solar cell efficiency after being placed in the atmosphere for 500 hours to the initial efficiency, which is used as the normalized efficiency of the solar cell after being placed for 500 hours.

[0159] Normalized efficiency = re-measured efficiency / initial efficiency × 100%. The test results are shown in Table 2.

[0160] A scanning electron microscope image is taken of the surface of the perovskite layer obtained in Step 3 of Example 1, and Figure 3 it can be seen that there is excessive PbI2 at the grain boundaries on the surface of the perovskite layer.

[0161] XRD is performed on the composite layer obtained in Step 4 of Example 1, and Figure 4 it can be seen that the composite layer is prepared in Example 1.

[0162] Table 2

[0163] Energy conversion efficiency Normalized efficiency after 500 h of placement Example 1 21.5％ 94.34％ Example 2 23.2％ 94.66％ Example 3 21.7％ 99.83％ Example 4 21.2％ 88.62％ Example 5 19.5％ 83.20％ Example 6 19.3％ 89.29％ Example 7 18.4％ 81.70％ Example 8 18.5％ 82.55％ Example 9 18.5％ 77.61％ Example 10 20.9％ 92.54％ Example 11 22.3％ 96.78％ Example 12 20.5％ 97.76％ Example 13 19.7％ 91.61％ Example 14 19.8％ 92.35％ Example 15 18.6％ 95.42％ Example 16 18.1％ 98.11％ Example 17 22.4％ 93.87％ Example 18 21.8％ 94.17％ Example 19 19.5％ 92.11％ Example 20 18.9％ 90.88％ Example 21 20.7％ 91.57％ Comparative Example 1 17.8％ 45.78％

[0164] Conclusion: As can be seen from Table 2, for the perovskite batteries of Examples 1-21 of the present application, a composite layer composed of an organic-inorganic hybrid composite compound is provided on at least one side of the perovskite layer, which can improve the stability of the perovskite battery on the premise of high efficiency. Compared with Examples 1-21, in Comparative Example 1, no composite layer is provided, and the efficiency of the perovskite battery is low and the stability is significantly reduced. It can be seen that the perovskite batteries of the examples of the present application can improve the stability of the perovskite battery on the premise of high efficiency.

[0165] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be covered within the scope of the claims and the description of the present application. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way. The present application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions falling within the scope of the claims.

Claims

1. A perovskite solar cell, characterized in that, The perovskite solar cell includes a perovskite layer and a composite layer disposed on at least one side of the perovskite layer. The composite layer includes a compound composed of at least one repeating unit, and the repeating unit includes: (R3-R1-R2) d (M a X b ) c Formula 1 wherein M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu; X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2; R1 includes at least one of an alkyl group with a carbon atom number less than or equal to 6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group; R2 includes at least one of a group containing O-C-O, a group containing O-P=O-O or a group containing S; R3 includes at least one of H, F, a carboxyl group, an amino group or an amide group; 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

2. The perovskite cell according to claim 1, characterized in that, Meet one or more of the following conditions: R1 includes at least one of a straight-chain alkyl group with a carbon atom number of 3-6, an aryl group with a carbon atom number of 6-12, a five-membered aromatic heterocyclic group or a six-membered aromatic heterocyclic group; R3 includes any one of F, a carboxyl group, an amino group or an amide group; M includes at least one of Pb or Sn; 0.5≤a≤6； 1≤b≤12； 1≤c≤25； 1≤d≤25。 3. The perovskite solar cell according to claim 1 or 2, characterized in that, R3-R1-R2 includes at least one of the following structures:

4. The perovskite solar cell according to any one of claims 1-3, characterized in that The repeating unit includes at least one of the following chemical formulas: wherein, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

5. The perovskite cell according to any one of claims 1-4, characterized in that The ratio of the thickness of the composite layer to the thickness of the perovskite layer is (0.1-50):

100.

6. The perovskite cell according to any one of claims 1-5, characterized in that, The thickness of the composite layer is 1 nm - 100 nm.

7. The perovskite cell according to any one of claims 1-6, characterized in that, The thickness of the composite layer is 2 nm - 10 nm.

8. The perovskite solar cell according to any one of claims 1-7, characterized in that, The thickness of the perovskite layer is 200 nm - 800 nm.

9. The perovskite cell according to any one of claims 1-8, characterized in that, The perovskite layer includes at least one of the following chemical formulas: wherein A and A' each independently include at least one of an organic amine, Cs, K, Rb or Li; M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo or Eu; X and X' each independently include at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2; Q includes at least one of Ag, Cs, K or Ru; D includes at least one of Bi, Sb, Ni, Fe, Cu or In.

10. The perovskite cell according to any one of claims 1-9, characterized in that, The perovskite solar cell includes a first electrode, a first transport layer, the perovskite layer, the composite layer, a second transport layer and a second electrode stacked in sequence. One of the first transport layer and the second transport layer includes an electron transport layer, and the other includes a hole transport layer.

11. The perovskite battery according to claim 10, characterized in that, The second transport layer includes the electron transport layer, and the electron transport layer includes at least one of fullerene and its derivatives, cyano-containing poly(phenylacetylene), boron-containing polymers, bathocuproine, bathophenanthroline, tris(8-hydroxyquinoline)aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorinated phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, lithium fluoride, sodium fluoride, magnesium fluoride, calcium fluoride, or zinc sulfide.

12. The perovskite cell according to claim 11, characterized in that, The fullerenes and their derivatives include [6,6]-phenyl-C 61 -isobutyl methacrylate, [6,6]-phenyl-C 71 -methyl butyrate, fullerene C 60 or fullerene C 70 at least one of them.

13. A method for preparing a perovskite solar cell, characterized in that, Comprising: Preparing a perovskite layer; Preparing a composite layer on at least one side of the perovskite layer, the composite layer comprising a compound composed of at least one repeating unit, and the repeating unit comprising: (R3 - R1 - R2) d (M a X b ) c Formula 1 Wherein, M includes at least one of Pb, Sn, Zn, Ti, Sb, Bi, Ni, Fe, Co, Ag, Cu, Ga, Ge, Mg, Ca, In, Al, Mn, Cr, Mo, or Eu; X includes at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3, or -NO2; R1 includes at least one of an alkyl group having 6 or fewer carbon atoms, an aryl group having 6-12 carbon atoms, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group; R2 includes at least one of a group containing O-C-O, a group containing O-P=O-O, or a group containing S; R3 includes at least one of H, F, a carboxyl group, an amino group, or an amide group; 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20, 1 ≤ c ≤ 50, 1 ≤ d ≤ 50.

14. The method according to claim 13, wherein The composite layer is prepared by the following method: Mix R3-R1-R4 with a solvent, apply it to the surface of at least one side of the perovskite layer, and anneal it at 105°C - 160°C to obtain a composite layer, where R1 includes at least one of an alkyl group with 6 or fewer carbon atoms, an aryl group with 6 - 12 carbon atoms, a five-membered aromatic heterocyclic group, or a six-membered aromatic heterocyclic group, R4 includes at least one of a carboxyl group, a phosphate group, a mercapto group, or a sulfonic acid group, R3 includes at least one of H, F, a carboxyl group, an amino group, or an amide group, and the surface of at least one side of the perovskite layer contains M a X b , 0.1 ≤ a ≤ 10, 1 ≤ b ≤ 20.

15. The method according to claim 14, wherein The solvent includes at least one of acetonitrile, isopropanol, isobutanol, N,N-dimethylformamide, N,N-dimethylacetamide, water, or dimethylacetamide.

16. The method according to claim 14 or 15, characterized in that, Based on the total volume of the mixed solution of R3-R1-R4 and the solvent, the concentration of R3-R1-R4 is 1 mg / mL - 30 mg / mL.

17. The method according to any one of claims 14 - 16, characterized in that, Satisfying one or more of the following conditions: The temperature of the annealing is 110°C - 130°C; The time of the annealing is 6 min - 30 min.

18. A stacked battery, characterized in that, Comprising the perovskite cell according to any one of claims 1-12 or the perovskite cell prepared by the method according to any one of claims 13-17.

19. A photovoltaic module, characterized in that, Comprising the perovskite cell according to any one of claims 1-12 or the perovskite cell prepared by the method according to any one of claims 13-17.

20. A power generation device, characterized in that, Comprising the perovskite cell according to any one of claims 1-12 or the perovskite cell prepared by the method according to any one of claims 13-17.

21. An electrical device, characterized in that, Comprising the perovskite cell according to any one of claims 1-12 or the perovskite cell prepared by the method according to any one of claims 13-17.

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