Perovskite battery and preparation method therefor, laminated battery, photovoltaic module, power generation apparatus and electric device

Abstract

A perovskite battery and a preparation method therefor, a laminated battery, a photovoltaic module, a power generation apparatus and an electric device. The perovskite battery comprises a perovskite layer and a passivation layer, which is arranged on at least one side of the perovskite layer, wherein the passivation layer comprises at least one of substances as shown in formula 1 or formula 2. M and M' each independently comprise at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni; 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; R and R' each independently comprise at least one of a substituted or unsubstituted anilino and a substituted or unsubstituted guanidyl, A and A' each independently comprise at least one of an organic amine, Li, Na, K, Rb or Cs; and n≥1, and m≥1. The perovskite battery has a high efficiency and high stability.

Description

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

[0001] Priority information

[0002] This application claims priority and benefits of patent application 202410171945.3 filed with the State Intellectual Property Office of China on February 6, 2024, and incorporates the entire text of it herein by reference. Technical Field

[0003] The present application relates to the field of batteries, and specifically, to perovskite batteries and preparation methods thereof, laminated batteries, photovoltaic modules, power generation devices and electrical equipment. Background Art

[0004] Perovskite cells have attracted widespread attention due to their excellent optoelectronic properties, including tunable band gaps, high light absorption coefficients, long carrier lifetimes and diffusion lengths, high defect tolerance, and low-cost, low-temperature liquid-phase fabrication methods. In just over a decade, the efficiency of perovskite cells has increased from 3.8% to over 25%, demonstrating enormous potential. However, existing perovskite cells suffer from limited stability and efficiency.

[0005] Summary of the Invention

[0006] In view of the technical problems existing in the background technology, the present application provides a perovskite battery that can improve the efficiency and stability of the perovskite battery.

[0007] A first aspect of the present application provides a perovskite cell, comprising a perovskite layer and a passivation layer provided on at least one side of the perovskite layer, wherein the passivation layer comprises at least one of the substances represented by Formula 1 or Formula 2:

[0008] wherein M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni; 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; R and R' each independently include at least one of a substituted or unsubstituted aniline group and a substituted or unsubstituted guanidine group; A and A' each independently include at least one of an organic amine, Li, Na, K, Rb or Cs; and n≥1, m≥1.

[0009] The perovskite cell proposed in this application provides a passivation layer composed of the material of Formula 1 and / or Formula 2 on the perovskite layer, which can improve the efficiency and stability of the perovskite cell.

[0010] According to some embodiments of the present application, R and R' each independently include at least one of a substituted or unsubstituted benzylamino group, a substituted or unsubstituted phenethylamino group, and a substituted or unsubstituted guanidino group, and the substituent includes at least one of a halogen and a haloalkyl group. This can improve the efficiency and stability of perovskite cells.

[0011] According to some embodiments of the present application, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6. Thus, the efficiency and stability of the perovskite battery can be improved.

[0012] According to some embodiments of the present application, one or more of the following conditions are met: n=1-10; m=1-10, M includes Pb; M' includes Pb; X includes at least one of I, Cl or Br; X' includes at least one of I, Cl or Br; R includes -C9H 11 F3N or -C8H 11 At least one of FN; R' includes CN3H6-; A includes at least one of Cs, -CH3NH3, or -CN2H5; and A' includes at least one of Cs, -CH3NH3, or -CN2H5. Thus, the efficiency and stability of the perovskite cell can be improved.

[0013] According to some embodiments of the present application, the perovskite grain size of the perovskite layer is 500 nm to 3000 nm, thereby improving the efficiency and stability of the perovskite cell.

[0014] According to some embodiments of the present application, the perovskite grain size of the perovskite layer is 800 nm to 2000 nm, thereby improving the efficiency and stability of the perovskite cell.

[0015] According to some embodiments of the present application, the passivation layer includes at least one of the following substances:

[0016] As a result, the efficiency and stability of perovskite cells can be improved.

[0017] According to some embodiments of the present application, the thickness of the passivation layer is 0.01 nm to 100 nm, thereby improving the efficiency and stability of the perovskite cell.

[0018] According to some embodiments of the present application, the thickness of the passivation layer is 1 nm to 10 nm, thereby improving the efficiency and stability of the perovskite cell.

[0019] According to some embodiments of the present application, the thickness of the perovskite layer is 300 nm to 1000 nm, thereby improving the efficiency and stability of the perovskite cell.

[0020] According to some embodiments of the present application, the perovskite layer includes at least one of the following chemical formulas:

[0021] Among them, A" and A ＊ Each independently comprises at least one of an organic amine, Li, Na, K, Rb or Cs, M" comprises at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, X" and X ＊ Each independently includes 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, Ni, Fe, Cu, Sb, or In. Thus, the efficiency and stability of the perovskite cell can be improved.

[0022] According to some embodiments of the present application, the perovskite cell includes a first electrode, a first transmission layer, the perovskite layer, the passivation layer, a second transmission layer, and a second electrode stacked in sequence, thereby improving the efficiency and stability of the perovskite cell.

[0023] A second aspect of the present application provides a method for preparing a perovskite battery, comprising:

[0024] A passivation layer is prepared on at least one side of the perovskite layer, wherein the passivation layer comprises at least one of the substances represented by Formula 1 or Formula 2:

[0025] Wherein, M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, 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, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, A and A' each independently include at least one of organic amine, Li, Na, K, Rb or Cs, n≥1, m≥1.

[0026] Therefore, the perovskite battery prepared in the present application can form a passivation layer on the perovskite layer, which can improve the efficiency and stability of the perovskite battery.

[0027] According to some embodiments of the present application, including:

[0028] A crystallization regulator is added to the precursor liquid of the perovskite layer to prepare the perovskite layer, wherein the crystallization regulator includes A # Y, A # including at least one of an organic amine, Pb, Cu, Li, Na, K, Rb, or Cs, and Y includes at least one of -SCN or -CH3COO;

[0029] At least one side of the perovskite layer is coated with a coating containing R"X # The passivation solution is annealed to form a passivation layer to obtain a perovskite cell, wherein R" includes C9H 11 F3N-、C8H 11 At least one of FN- or CN3H6-, X # The perovskite battery comprises at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2. Thus, the perovskite battery has excellent efficiency and stability.

[0030] According to some embodiments of the present application, A # Y and R"X # The molar ratio of the substance is 1:(0.0005-2000). Thus, the perovskite battery prepared has excellent efficiency and stability.

[0031] According to some embodiments of the present application, the precursor liquid of the perovskite layer includes a perovskite precursor, A # The molar ratio of Y to the perovskite precursor is (0.001-0.1): 1. Thus, the prepared perovskite battery has excellent efficiency and stability.

[0032] According to some embodiments of the present application, the precursor liquid of the perovskite layer includes a perovskite precursor, R"X # The amount ratio of the substance of the perovskite precursor is (0.001-0.1): 1. Thus, the prepared perovskite battery has excellent efficiency and stability.

[0033] The third aspect of the present application provides a laminated battery, comprising the perovskite battery provided in the first aspect of the present application or the perovskite battery prepared by the method provided in the second aspect of the present application. Thus, the laminated battery has good long-term stability and a long service life.

[0034] A fourth aspect of the present application provides a photovoltaic module, comprising the perovskite cell provided in the first aspect of the present application or the perovskite 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.

[0035] In a fifth aspect, the present application provides a power generation device comprising the perovskite cell provided in the first aspect of the present application or the perovskite 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.

[0036] In a sixth aspect, the present application provides an electrical device comprising the perovskite battery provided in the first aspect of the present application or the perovskite battery prepared by the method provided in the second aspect of the present application. Thus, the electrical device has good long-term stability and a long service life.

[0037] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become obvious from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present application. The same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0039] FIG1 is a schematic structural diagram of a perovskite battery according to an embodiment of the present application;

[0040] FIG2 is a scanning electron microscope image of the upper surface of the perovskite layer prepared in Example 1 of the present application;

[0041] FIG3 is a scanning electron microscope image of the upper surface of the perovskite layer prepared in Comparative Example 1 of the present application;

[0042] FIG4 is an XRD pattern of the passivation layer prepared in Example 1 of the present application;

[0043] FIG5 is an XRD diagram of the passivation layer prepared in Comparative Example 1 of the present application.

[0044] Explanation of reference numerals: 1: perovskite cell; 10: first electrode; 11: first transmission layer; 12: perovskite layer; 13: passivation layer; 14: second transmission layer; 15: second electrode. DETAILED DESCRIPTION

[0045] The following embodiments of the technical solution of the present application are described in detail. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only used as examples and are not intended to limit the scope of protection of the present application.

[0046] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0047] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0048] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0049] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0050] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0051] As global ecological and energy shortages become increasingly severe, solar photovoltaic power generation has attracted widespread attention. Perovskite cells, as a new third-generation solar cell, have attracted much attention in the solar cell field due to their low cost, simple preparation process, and high efficiency.

[0052] However, in the preparation process of perovskite cells, the perovskite layer of the perovskite cell has ionic properties. One of the more common defects on the perovskite surface is that the A-site cations in the perovskite layer leave the system, causing the M a X b (0.1≤a≤10, 1≤b≤20, such as the common PbI2) is excessive, which usually reduces the stability and efficiency of perovskite cells: First, excessive M a X b It will destroy the perovskite crystal structure and reduce the performance of perovskite cells. a X b Excessive reaction with perovskite crystals causes changes in the perovskite crystal structure, thereby affecting the photoelectric conversion efficiency of perovskite cells; secondly, excessive M a X b It will also lead to a decrease in the stability of the perovskite battery and the formation of some unstable compounds or ions in the perovskite film. These compounds or ions may cause the migration of electrons or ions inside the perovskite battery, resulting in the performance degradation or even damage of the perovskite battery. In addition, excessive M a X b It also introduces trap states that are harmful to the performance of perovskite cells, accelerating the performance loss of perovskite cells. These trap states capture photogenerated carriers, reducing the carrier mobility and lifetime, thereby affecting the photoelectric conversion efficiency of perovskite cells. On the other hand, the three-dimensional perovskite layer is also susceptible to corrosion by water and oxygen in the air, leading to the decomposition of the perovskite layer components and reducing the efficiency of the perovskite cell containing it.

[0053] In the present application, a perovskite cell is proposed. The perovskite cell proposed in the present application can reduce the defects of the perovskite layer by providing a passivation layer composed of the substances of Formula 1 and / or Formula 2 on the perovskite layer, thereby significantly improving the efficiency and stability of the perovskite cell.

[0054] The perovskite battery disclosed in this application is 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. Electrical equipment may include street lights, signal indicators, insect killer lamps, electric fans, electric toys, electric tools, battery cars, electric cars, ships, spacecraft, etc., wherein electric toys may include fixed or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc., and spacecraft may include airplanes, rockets, space shuttles, and spacecraft, etc.; photovoltaic power generation systems may include large-scale ground photovoltaic power generation systems, distributed photovoltaic power generation and building-integrated photovoltaic power generation systems, etc.

[0055] In a first aspect, the present application provides a perovskite cell 1. Referring to FIG1 , the perovskite cell 1 includes a perovskite layer 12 and a passivation layer 13 disposed on at least one side of the perovskite layer 12. The passivation layer 13 includes at least one of the substances represented by Formula 1 or Formula 2:

[0056] wherein M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni; 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; R and R' each independently include at least one of a substituted or unsubstituted aniline group and a substituted or unsubstituted guanidine group; A and A' each independently include at least one of an organic amine, Li, Na, K, Rb or Cs; and n≥1, m≥1.

[0057] In the present application, a perovskite cell 1 is proposed, in which a passivation layer 13 is provided on one side of a three-dimensional perovskite layer 12. The passivation layer 13 includes at least one of the substances represented by Formula 1 or Formula 2. The passivation layer 13 of the above structural formula is a layered two-dimensional structure that can passivate defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen from the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the performance degradation of the perovskite cell 1, improve its stability, and the efficiency of the perovskite cell 1 is high. In summary, the perovskite cell 1 proposed in the present application, in which the passivation layer 13 is provided on the perovskite layer 12, significantly improves the efficiency and stability of the perovskite cell 1.

[0058] It is understood that the passivation layer 13, which contains at least one of the substances represented by Formula 1 or Formula 2, can be viewed as a two-dimensional perovskite, forming a framework of M-position cations and X-position anions, with R and R' coordinated in the gaps between the frameworks. This protects the perovskite layer 12 and improves the stability of the perovskite cell 1, while also increasing the efficiency of the perovskite cell 1.

[0059] According to some embodiments of the present application, R and R' independently include at least one of a substituted or unsubstituted benzylamino group, a substituted or unsubstituted phenylethylamino group, and a substituted or unsubstituted guanidine group, and the substituent includes at least one of a halogen and a haloalkyl group. This facilitates the formation of a two-dimensional passivation layer 13 on the perovskite layer 12, which can passivate surface defects of the perovskite layer 12, block the intrusion of water and oxygen from the external environment, reduce damage to the perovskite layer 12 by water and oxygen, slow down the performance degradation of the perovskite cell 1, improve its stability, and achieve high efficiency of the perovskite cell 1.

[0060] According to some embodiments of the present application, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6. This facilitates the formation of a two-dimensional passivation layer 13 on the perovskite layer 12, which can passivate defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen from the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the attenuation of the performance of the perovskite cell 1, improve its stability, and increase the efficiency of the perovskite cell 1.

[0061] It is understood that in perovskite cells, in R and R' of formula 1 and formula 2, -C8H 11 FN is a fluorophenylethylamine cation. In this case, X or X' is an anion, -C8H 11 The structural formula of FN is as follows:

[0062] -C9H 11 The structural formula of F3N is:

[0063] -CN3H6 is a guanidine cation, and its structural formula is:

[0064] -C8H 11 FN, -C9H 11 F3N and -CN3H6 can act as large cations in the passivation layer 13. The radius of the group is larger than that of the cations formed by M and M' and the cations formed by A and A'. Compared with the three-dimensional perovskite layer, the large cations replace the A-site cations to form a two-dimensional perovskite structure (passivation layer).

[0065] In the embodiment of the present application, the material of the passivation layer 13 can be measured by GIXRD (grazing incidence X-ray diffraction) with an incident angle of 1° and 0.05°, using a Bruker D8 instrument. The position of the diffraction peak of the passivation layer is related to the specific material of the passivation layer. For example, when the passivation agent (C8H 11 FN)2(CN2H5)2CsPb4I 13When q=0.31A-1, a (020) characteristic diffraction peak appears, which is the characteristic peak of the passivation layer.

[0066] It can be understood that in Formula 1 and Formula 2, 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. 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 connected to other groups, and the following description is similar and will not be repeated.

[0067] According to some embodiments of the present application, n≥1. As an example, n can be 1-100, 2-80, 3-50, 4-40, 5-30, 6-20, 7-10, 8-9, etc. Specifically, controlling n within the above range is conducive to the formation of a two-dimensional layered structure of the passivation layer 13, which can passivate defects on the surface of the perovskite layer 12. Moreover, compared with the three-dimensional structure, the above two-dimensional structure is more stable and can better block the intrusion of water and oxygen in the external environment, further improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, n=1-10, for example, n=2-4.

[0068] According to some embodiments of the present application, m≥1. As an example, m can be 1-100, 2-80, 3-50, 4-40, 5-30, 6-20, 7-10, 8-9, etc. Specifically, controlling m within the above range is conducive to the formation of a two-dimensional layered structure of the passivation layer 13, which can passivate defects on the surface of the perovskite layer 12. Moreover, compared with the three-dimensional structure, the above two-dimensional structure is more stable and can better block the intrusion of water and oxygen in the external environment, further improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, m=1-10, for example, m=2-4.

[0069] According to some embodiments of the present application, M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu, or Ni. M and M' act as positive cations in the passivation layer, forming a two-dimensional layered structure in the passivation layer 13. This structure is more stable and can better block the intrusion of water and oxygen from the external environment, further improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, M includes Pb; M' includes Pb.

[0070] According to some embodiments of the present application, X and X' independently include at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3, or -NO2. X and X' act as negatively charged anions in the passivation layer, so that the passivation layer 13 forms a two-dimensional layered structure, which is more stable and can better block the intrusion of water and oxygen in the external environment, further improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, X includes at least one of I, Cl, or Br; and X' includes at least one of I, Cl, or Br.

[0071] According to some embodiments of the present application, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, R and R' act as large cations in the passivation layer, so that the passivation layer 13 forms a two-dimensional layered structure, which is more stable and can better block the intrusion of water and oxygen in the external environment, further improving the efficiency and stability of the perovskite battery 1. According to other embodiments of the present application, R includes -C9H 11 F3N and -C8H 11 At least one of FN; R' includes -CN3H6.

[0072] According to some embodiments of the present application, A and A' each independently include at least one of an organic amine, Li, Na, K, Rb, or Cs. A and A' act as positively charged cations in the passivation layer, forming a two-dimensional layered structure in the passivation layer 13. This structure is more stable and better able to block the intrusion of water and oxygen from the external environment, further improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, A includes at least one of Cs, -CH3NH3, or -CN2H5; and A' includes at least one of Cs, -CH3NH3, or -CN2H5.

[0073] It is understood that, in the optional groups of A and A', organic amine refers to an organic compound containing nitrogen. For example, the organic amine may include but is not limited to formamidine, methylamine, and the like.

[0074] It can be understood that, taking A including -CH3NH3 as an example, the "-" in -CH3NH3 represents a bond connecting to other groups.

[0075] 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 R16 or -R 17 R 18 NC(N R19 R 20 )=R 21 R 22 At least one of, wherein R4 to R 22 Each independently includes any one of a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, or H. 22 When each independently includes a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, the number of carbon atoms can 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.

[0076] According to some embodiments of the present application, the perovskite grain size of the perovskite layer 12 is 500 nm-3000 nm. For example, the perovskite grain size of the perovskite layer 12 can be 500nm-2999nm, 600nm-2900nm, 700nm-2800nm, 800nm-2700nm, 900nm-2600nm, 1000nm-2500nm, 1100nm-2400nm, 1200nm-2300nm, 1300nm-2200nm, 1400nm-2100nm, 1500nm-2000nm, 1600nm-1900nm, 1700nm-1800nm, etc. Specifically, the perovskite grain size of the perovskite layer 12 is controlled within the above range. The larger the perovskite grain size of the perovskite layer 12, the smaller the excess M at the grain boundary of the perovskite layer 12. a X b , thereby reducing defects in the perovskite layer 12, improving the crystallinity of the perovskite layer 12, and improving the stability and efficiency of the perovskite cell 1. According to other embodiments of the present application, the perovskite grain size of the perovskite layer 12 is 800nm-2000nm.

[0077] It is understood that the perovskite grain size of the perovskite layer 12 refers to the average particle size of the perovskite polycrystalline particles. The perovskite grain size of the perovskite layer 12 is a well-known definition in the art and can be measured using methods well-known in the art. For example, the perovskite grain size can be obtained by scanning electron microscopy (SEM) by photographing different areas of the sample and extracting grain size information using nanomeasure software. The SEM equipment model is Gemini 360, with an accelerating voltage of 2 kV.

[0078] According to some embodiments of the present application, the passivation layer 13 includes at least one of the following substances:

[0079] Specifically, the passivation layer 13 includes at least one of the above compounds. The passivation layer 13 is a layered two-dimensional structure, which can passivate defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen in the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the performance decay of the perovskite battery 1, and significantly improve the efficiency and stability of the perovskite battery 1.

[0080] It can be understood that in perovskite cells, in the above formula, CN2H5 is the formamidinium ion CH(NH2)2 + (FA), CH3NH3 is methylamine ion CH3NH3 + (MA).

[0081] According to some embodiments of the present application, the thickness of the passivation layer 13 is 0.01nm-100nm. For example, the thickness of the passivation layer 13 can be 0.01nm-99nm, 0.03nm-90nm, 0.05nm-80nm, 0.07nm-50nm, 0.09nm-20nm, 0.1nm-18nm, 1nm-17nm, 3nm-15nm, 5nm-13nm, 8nm-11nm, etc. Specifically, controlling the thickness of the passivation layer 13 within the above range can not only passivate the defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen from the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the attenuation of the performance of the perovskite cell 1, but also have little effect on the function of the perovskite layer 12, thereby improving the efficiency and stability of the perovskite cell 1. According to other embodiments of the present application, the thickness of the passivation layer 13 is 1nm-10nm.

[0082] It is understood that the thickness of the passivation layer 13 is a well-known definition in the art and can be measured using methods well-known in the art. For example, it can be measured using the following method:

[0083] Using the GIXRD grazing-incidence X-ray diffraction method, the passivation layer signal gradually disappears as the incident angle increases from 0.1° to 1°. The absorption coefficient of the device's X-rays in the material is fixed, so the absorption depth L is determined. Based on the incident angle θ at which the diffraction peak signal disappears, the passivation layer thickness d = Lsinθ.

[0084] According to some embodiments of the present application, the thickness of the perovskite layer 12 is 300nm-1000nm. For example, the thickness of the perovskite layer 12 can be 300nm-999nm, 400nm-900nm, 500nm-800nm, 600nm-700nm, etc. Controlling the thickness of the perovskite layer 12 within the above range is conducive to the full play of the perovskite layer 12, and the perovskite grain size of the perovskite layer 12 is large, which can reduce the excess M at the grain boundary of the perovskite layer 12. a X b , thereby reducing the defects of the perovskite layer 12 , improving the crystallinity of the perovskite layer 12 , and improving the stability and efficiency of the perovskite cell 1 .

[0085] It is understood that the thickness of the perovskite layer 12 is a well-known definition in the art and can be measured using methods well-known in the art. For example, it can be measured using the following method:

[0086] Use TOF-SIMS time-of-flight secondary ion mass spectrometry to determine the thickness of the perovskite layer: select the elements contained in the perovskite component, and cyclically bombard the perovskite layer with an ion gun until the B-site elements of the perovskite component cannot be detected. The thickness of the perovskite layer can be obtained by multiplying the action time of the ion gun by the stripping speed.

[0087] According to some embodiments of the present application, the perovskite layer 12 includes at least one of the following chemical formulas:

[0088] Among them, A" and A ＊ Each independently comprises at least one of an organic amine, Li, Na, K, Rb or Cs, M" comprises at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, X" and X ＊ Each independently includes 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, Ni, Fe, Cu, Sb or In.

[0089] Specifically, the perovskite layer 12 has a large perovskite grain size, which can reduce the excess M a X b , thereby reducing the defects of the perovskite layer 12 , improving the crystallinity of the perovskite layer 12 , and improving the stability and efficiency of the perovskite cell 1 .

[0090] It is understood that the A-site cations in the perovskite layer 12 refer to A″ and A in Formula 3 and Formula 4. ＊corresponding to the ions formed.

[0091] 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 passivation layer 13, a second transport layer 14 and a second electrode 15, which are arranged in sequence from bottom to top. One of the first electrode 10 and the second electrode 15 includes a substrate, and the other includes an electrode layer. One of the first transport layer 11 and the second transport layer 14 includes an electron transport layer, and the other includes a hole transport layer.

[0092] According to some embodiments of the present application, the first electrode 10 includes a substrate, is a transparent electrode for light incidence, and may include one or more mixtures of glass or transparent organic polymers, for example, including but not limited to conductive glass, PET (polyethylene terephthalate), PI (polyimide), etc.

[0093] The second electrode 15 includes an electrode layer, and 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 such as Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, etc., conductive oxides such as FTO (F-doped tin oxide), ITO (In-doped tin oxide), IWO (W-doped In2O3), AZO (Al-doped zinc oxide), IZO (indium zinc oxide), BZO (zinc oxide doped with boron), MoO3, etc., or a mixture thereof.

[0094] According to some embodiments of the present application, one of the first transport layer 11 and the second transport layer 14 is an electron transport layer, and the other is a hole transport layer. The electron transport layer can effectively extract electrons and block holes, and the hole transport layer is responsible for transporting holes and blocking electrons. The materials may include at least one of the following materials and their derivatives: 2,2',7,7'-tetrakis(N,N-p-anisyl)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenyl)amino)-1,2-dimethyl-1,2-diphenylamine (DMSO-OMeTPA), and 1,2-dimethyl-1,2-diphenylamine (DMSO-OMeTPA). ) Carbazole-spirobifluorene (CzPAF-SBF), p-PY (polypyrrole), PPY2, Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid), MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly3-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.

[0095] According to some embodiments of the present application, the electron transport layer includes at least one of fullerene and its derivatives, cyanide-containing polyphenylene vinylene, boron-containing polymers, bathocuproin, bathophenanthroline, hydroxyquinoline aluminum, 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, thereby improving the stability of the perovskite battery 1 under the premise of high efficiency of the perovskite battery 1.

[0096] According to other embodiments of the present application, the fullerene and its derivatives include [6,6]-phenyl-C 61 -Isomethyl butyrate (CAS No. 160848-22-6), [6,6]-phenyl-C 71 -Methyl butyrate (CAS No.: 609771-63-3), Fullerene C 60 or fullerene C 70 At least one of .

[0097] A second aspect of the present application provides a method for preparing a perovskite cell 1, comprising:

[0098] S100: preparing a passivation layer 13 on at least one side of the perovskite layer 12, wherein the passivation layer 13 comprises at least one of the substances represented by Formula 1 or Formula 2:

[0099] Wherein, M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, 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, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, A and A' each independently include at least one of organic amine, Li, Na, K, Rb or Cs, n≥1, m≥1.

[0100] Specifically, the perovskite cell 1 prepared in the present application has a passivation layer 13 composed of a substance of Formula 1 and / or Formula 2 prepared on one side of the perovskite layer 12. The passivation layer 13 of the above-mentioned structural formula is a layered two-dimensional structure, which can passivate defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen from the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the performance degradation of the perovskite cell 1, and improve its stability. In summary, by controlling the perovskite grain size of the perovskite layer 12 and providing the passivation layer 13 on the perovskite layer 12, the efficiency and stability of the perovskite cell 1 are significantly improved.

[0101] According to some embodiments of the present application, the perovskite cell 1 is prepared by the following method:

[0102] S101: Adding a crystallization modifier to the precursor liquid of the perovskite layer 12 to prepare the perovskite layer 12, wherein the crystallization modifier includes A # Y, A # including at least one of an organic amine, Pb, Cu, Li, Na, K, Rb, or Cs, and Y includes at least one of -SCN or -CH3COO;

[0103] S102: Coating a film containing R"X on at least one side of the perovskite layer 12 # The passivation solution is annealed to form a passivation layer 13, thereby obtaining a perovskite cell 1, wherein R" includes -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, X #Including at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2.

[0104] Specifically, in step S101, the crystallization modifier A # The Y anions generated by Y can fill the X-site vacancy defects generated during the annealing and crystallization process when the perovskite layer 12 is prepared, reduce defects, stabilize the crystal structure of the perovskite surface, and maintain the perovskite grain size of the perovskite layer 12 at a large level, and the perovskite layer 12 has high crystallinity. After the perovskite layer 12 is prepared, during the annealing process, the Y anions will volatilize by combining with volatile cations (such as hydrogen ions) in the precursor liquid of the perovskite layer 12. # The cations remain in the perovskite layer 12. In step S102, the passivation solution includes R"X # , A # Cations can provide nucleation sites, making R"X # R" and A # The A in the Y # cations, X and / or X' anions in the perovskite layer 12, R"X # X in # The anions in the wet film before annealing slow down the crystallization speed of the passivation layer 13. # The anions combine with the light cations to volatilize and form a two-dimensional passivation layer 13 structure.

[0105] Furthermore, when the passivation layer 13 is formed, R"X # By reacting with the perovskite layer 12, the R" large cation partially replaces the A position in the three-dimensional structure of the perovskite layer 12, causing the chemical bonds between atoms in the product crystal to change, and finally forming a passivation layer 13 with a layered two-dimensional structure.

[0106] In summary, by the above-mentioned preparation method, the crystallization regulator is added during the preparation of the perovskite layer 12, so that the grain size of the perovskite in the perovskite layer 12 can be regulated, so that the grain size is larger, the crystallinity is higher, and the perovskite layer 12 has fewer defects. In addition, the crystallization regulator also provides nucleation sites when the passivation layer 13 is formed, thereby slowing down the crystallization speed of the passivation layer 13. After annealing, the crystallization regulator is annealed. # The anions combine with the light cations and volatilize, thereby forming a two-dimensional passivation layer 13 structure of Formula 1 and / or Formula 2. The prepared perovskite cell 1 controls the perovskite grain size of the perovskite layer 12 to be between 500 nm and 3000 nm, and provides the passivation layer 13 on the perovskite layer 12. This can reduce defects in the perovskite layer 12 and significantly improve the efficiency and stability of the perovskite cell 1.

[0107] Understandably, R”X #When R" is -C9H 11 F3N group, X # When it is 1, R"X # 4-trifluoromethylphenylethylamine hydroiodide (p-CF3PEAI, CAS: 2770278-13-0); when R" is -C8H 11 FN group, X # When it is 1, R"X # It can be m-fluorophenylethylamine iodine (mF-PEAI, CAS: 2810129-43-0) or p-fluorophenylethylamine iodine (pF-PEAI, CAS: 1413269-55-2); when R" is a -CN3H6 group, X # When it is 1, R"X # is guanidine iodide (CAS: 19227-70-4), when R" is a -CN3H6 group, X # When it is Cl, R"X # It is guanidine hydrochloride (CAS: 50-01-1).

[0108] It is understood that when the structural formula of the passivation layer 13 generated in this step includes Formula 1, R"X # R" is the same as R in formula 1, X # Same as X in Formula 1; when the structural formula of the passivation layer 13 generated in this step includes Formula 2, R"X # R" is the same as R' in formula 2, X # Same as X' in Formula 1; when the structural formula of the passivation layer 13 generated in this step includes both Formula 1 and Formula 2, X # The R" part is the same as R in Formula 1, and the part is the same as R' in Formula 2. # Part is the same as X in Formula 1, and part is the same as X' in Formula 2.

[0109] It is understandable that when the passivation layer 13 is prepared by the method of step S201, the perovskite layer 12 prepared in the above step S101 will react with the passivation solution to generate a passivation layer 13 containing at least one of the substances represented by Formula 1 or Formula 2. Therefore, the perovskite layer 12 after step S201 is different from the perovskite layer 12 prepared in step S101, and the perovskite layer 12 in the final product is lost.

[0110] According to some embodiments of the present application, A # Y and R"X #The amount ratio of the substance is 1: (0.0005-2000), for example, it can be 1: (0.0005-1999), 1: (0.005-1900), 1: (0.05-1800), 1: (0.5-1700), 1: (1-1600), 1: (100-1500), 1: (200-1400), 1: (300-1300), 1: (400-1200), 1: (500-1100), 1: (600-1000), 1: (700-900), etc. Specifically, A # Y and R"X # The amount ratio of the substances is controlled within the above range, which is beneficial to controlling the perovskite grain size of the perovskite layer 12 and generating a uniformly arranged two-dimensional passivation layer 13, thereby reducing the defects of the perovskite layer 12, improving the crystallinity of the perovskite layer 12, and improving the stability and efficiency of the perovskite battery 1; the passivation layer 13 can passivate the defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen in the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the attenuation of the performance of the perovskite battery 1, and improve its stability. According to other embodiments of the present application, A # Y and R"X # The ratio of the amount of substance is 1:(2-10).

[0111] According to some embodiments of the present application, the precursor liquid of the perovskite layer 12 includes a perovskite precursor, A # The ratio of the amount of Y to the amount of the perovskite precursor is (0.001-0.1):1. For example, A # The ratio of the amount of Y to the perovskite precursor can be (0.001-0.099):1, (0.01-0.09):1, (0.02-0.08):1, (0.03-0.07):1, (0.04-0.06):1, etc. Specifically, A # Controlling the amount ratio of Y to the perovskite precursor within the above range is beneficial to controlling the perovskite grain size of the perovskite layer 12 and generating a uniformly distributed two-dimensional passivation layer 13, thereby reducing the defects of the perovskite layer 12, improving the crystallinity of the perovskite layer 12, and improving the stability and efficiency of the perovskite battery 1; the passivation layer 13 can passivate the defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen in the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the attenuation of the performance of the perovskite battery 1, and improve its stability.

[0112] According to some embodiments of the present application, the precursor liquid of the perovskite layer 12 includes a perovskite precursor, R"X # The ratio of the amount of the substance of the perovskite precursor is (0.001-0.1): 1. For example, R"X #The molar ratio to the perovskite precursor can be (0.001 - 0.099):1, (0.01 - 0.09):1, (0.02 - 0.08):1, (0.03 - 0.07):1, (0.04 - 0.06):1, etc. Thus, R”X # Controlling the molar ratio to the perovskite precursor within the above range is beneficial to controlling the perovskite grain size of the perovskite layer 12, and generating a two-dimensional passivation layer 13 with uniform arrangement, thereby reducing the defects of the perovskite layer 12, improving the crystallinity of the perovskite layer 12, and enhancing the stability and efficiency of the perovskite solar cell 1; the passivation layer 13 can passivate the defects on the surface of the perovskite layer 12, block the intrusion of water and oxygen in the external environment, reduce the damage of water and oxygen to the perovskite layer 12, slow down the performance decay of the perovskite solar cell 1, and enhance its stability.

[0113] According to some embodiments of the present application, in the perovskite precursor solution, the perovskite precursor can be FA 1-x Cs x Pb(I 1-y Br y ), 0 < x, y < 1, x can be 0.1 - 0.9, 0.2 - 0.8, 0.3 - 0.7, 0.4 - 0.6, etc., y can be 0.1 - 0.9, 0.2 - 0.8, 0.3 - 0.7, 0.4 - 0.6, etc., in the perovskite precursor solution, the molar concentration of the perovskite precursor is 0.8 mol / L - 1.5 mol / L, for example, it can be 0.8 mol / L - 1.4 mol / L, 0.9 mol / L - 1.3 mol / L, 1 mol / L - 1.2 mol / L, etc., and the solvent used in the perovskite precursor solution is one or two of DMF (N,N-dimethylacetamide) / DMSO (dimethyl sulfoxide) / NMP (1-methyl-2-pyrrolidone) mixed in a certain volume ratio. The perovskite solution is formed into a film by the vacuum pumping method (the time of the vacuum degree is 0.5 min - 10 min, for example, 0.5 min - 9 min, 1 min - 8 min, 2 min - 7 min, 3 min - 6 min, 4 min - 5 min, etc.) or other methods, and the perovskite film is annealed (3 min - 60 min) under the condition of 70 °C - 200 °C. The annealing temperature can be 70 °C - 190 °C, 80 °C - 180 °C, 90 °C - 170 °C, 100 °C - 160 °C, 110 °C - 150 °C, 120 °C - 140 °C, etc., and the annealing time can be 3 min - 59 min, 5 min - 55 min, 10 min - 50 min, 20 min - 40 min, etc.

[0114] According to some embodiments of the present application, the passivation solution further includes a solvent, and the solvent includes at least one of isopropyl alcohol (IPA), chlorobenzene (CB), toluene, o-xylene, chloroform, and ethyl acetate.

[0115] The third aspect of the present application provides a laminated battery, comprising the perovskite battery provided in the first aspect of the present application or the perovskite battery prepared by the method provided in the second aspect of the present application. Thus, the laminated battery has good long-term stability and a long service life.

[0116] According to some embodiments of the present application, a stacked cell includes a sub-cell, and the sub-cell includes a perovskite cell.

[0117] A fourth aspect of the present application provides a photovoltaic module, comprising the perovskite cell provided in the first aspect of the present application or the perovskite 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.

[0118] In a fifth aspect, the present application provides a power generation device comprising the perovskite cell provided in the first aspect of the present application or the perovskite 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.

[0119] A power generation device refers to a power generation system that uses the photovoltaic effect to directly convert solar radiation energy into electrical energy. It is divided into a stand-alone photovoltaic power generation system (Stand-alone PV System) and a grid-connected photovoltaic power generation system (Grid-connected PV System). A stand-alone photovoltaic power generation system consists of a solar photovoltaic array composed of photovoltaic modules, a battery pack, a charge controller, a power electronic converter (inverter), a load, etc. A grid-connected photovoltaic power generation system consists of a photovoltaic array, a high-frequency DC / DC boost circuit, a power electronic converter (inverter), and a system monitoring system.

[0120] Photovoltaic modules refer to solar cell modules, i.e., integrated modules that include multiple perovskite cells. These modules include several cell strings, each of which includes multiple perovskite cells connected in series via connectors such as solder ribbons.

[0121] In a photovoltaic module, in addition to the cell string, it also includes front glass, front packaging film, back packaging film, back glass, etc. As an example, a photovoltaic module includes front glass, front packaging film, cell string, back packaging film and back glass stacked in sequence along the thickness direction.

[0122] The sixth aspect of the present application provides an electrical device, including the perovskite battery 1 provided in the first aspect of the present application or the perovskite battery 1 prepared by the method provided in the second aspect of the present application. The electrical device may include lighting elements, display elements, mobile devices, etc., and may specifically include street lights, signal indicators, insect killers, electric fans, electric toys, electric tools, battery vehicles, electric vehicles, ships, spacecraft, etc., wherein electric toys may include fixed or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc., and spacecraft may include airplanes, rockets, space shuttles, and spacecraft, etc.; photovoltaic power generation systems may include large-scale ground photovoltaic power generation systems, distributed photovoltaic power generation and building integrated photovoltaic power generation systems, etc. As a result, the electrical device has good long-term stability and a long service life.

[0123] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail with reference to the embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present application and its applications. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0124] Example 1

[0125] Take a 2cm x 2cm piece of FTO conductive glass and laser etch it to leave an insulating area. Then, ultrasonicate it with deionized water, detergent, ethanol, isopropyl alcohol, acetone, ethanol, and deionized water for 20 minutes, then blow dry with nitrogen.

[0126] NiO x The nanoparticle solution (volume average particle size Dv50 of 20 nm) was spin-coated at 3000 rpm on a clean 2 cm × 2 cm FTO substrate, annealed at 200 °C for 15 min, and naturally cooled to obtain a hole transport layer with a thickness of 20 nm.

[0127] NiO after UV ozone treatment for 15 min x The substrate surface was cleaned by blowing, and a perovskite precursor solution with a molar concentration of 1.25 mol / L was taken and spin-coated at a speed of 4000 rpm for 20 seconds to prepare a wet film. The solution was vacuumed for 30 seconds and annealed on a hot plate at 120°C for 45 minutes. After natural cooling, a perovskite layer CN2H5PbI3 was obtained. The perovskite precursor solution contained a crystallization modifier CH3NH3OOCCH3 (CAS: 6998-30-7). The thickness of the perovskite layer was 500 nm.

[0128] Take the C8H 11 FNI (CAS: 1583-88-6) passivation solution, CH3NH3OOCCH3 and C8H 11 The molar ratio of FNI (CAS: 1413269-55-2) was 1:2, the solvent was isopropyl alcohol, and the perovskite light absorbing layer was dynamically spin-coated at a speed of 5000 rpm / s and annealed at 100 ° C for 10 min to obtain a passivation layer (C8H 11 FN)2(CN2H5)Pb2I7, the thickness of the passivation layer is 5nm;

[0129] A PCBM solution and a BCP (fullerene derivative / 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) solution were spin-coated on the passivation layer at a speed of 3000 rpm to prepare a PCBM layer and a BCP layer, respectively, to form an electron transport layer. The thickness of the PCBM layer was 25 nm, and the thickness of the BCP layer was 7 nm.

[0130] A Cu counter electrode having the same pattern as the mask is deposited on the electron transport layer using a thermal evaporation method. The thickness of the Cu counter electrode is 100 nm, thereby obtaining a perovskite solar cell.

[0131] The preparation methods of the perovskite cells in Examples 2 to 20 and Comparative Examples 1 to 3 are the same as those in Example 1. The differences are detailed in Table 1.

[0132] The material of the passivation layer of Comparative Example 1 is C4H 12 I2N2 (CAS: 58464-47-4).

[0133] Table 1

[0134] Parameter test:

[0135] 1. Determination of passivation layer composition

[0136] The measurement was performed using GIXRD (grazing incidence X-ray diffraction) with incident angles of 1° and 0.05° using a Bruker D8 instrument.

[0137] 2. Determination of the thickness of the passivation layer and the perovskite layer

[0138] The thickness of the perovskite layer is measured using TOF-SIMS time-of-flight secondary ion mass spectrometry: the elements contained in the perovskite component are selected, and the ion gun is bombarded cyclically until the B-site elements of the perovskite component can no longer be detected. The thickness of the perovskite layer can be obtained by multiplying the ion gun action time by the stripping speed.

[0139] 3. Determination of perovskite grain size in the perovskite layer

[0140] The grain size was determined using a scanning electron microscope (SEM). The grain size information was extracted using the nanomeasure software. The SEM was a Gemini 360 with an accelerating voltage of 2 kV.

[0141] Performance testing:

[0142] 1. Photoelectric conversion efficiency determination

[0143] At room temperature and pressure, under standard simulated sunlight (AM 1.5G, 100mW / cm 2 ) and tested in accordance with the national standard IEC61215. A crystalline silicon solar cell was used to calibrate the light intensity to reach the intensity of one sun. A four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the solar cell under the light source, and the energy conversion efficiency (Eff) of the perovskite cell was obtained.

[0144] 2. Device stability measurement

[0145] After being placed in a dark state at 85°C for 200 hours in an environment with room temperature and 85% humidity, the energy conversion efficiency (Eff) of the perovskite cell was tested again using the same method as the photoelectric conversion efficiency test. The test results of Examples 1-20 and Comparative Examples 1-3 are shown in Table 2.

[0146] Scanning electron microscope images of the upper surfaces of the perovskite layers obtained in Example 1 and Comparative Example 1 were taken to obtain Figures 3 and 4. It can be seen that the perovskite grain size of the perovskite layer in Example 1 is 1000 nm, and the perovskite grain size of the perovskite layer in Comparative Example 1 is 600 nm. Further according to EDS element distribution analysis, it can be seen that the bright area at the grain boundary is PbI2. Using nanomeasure software, the bright area in the EDS image is selected to obtain the area, which is divided by the image area. It can be obtained that the proportion of excess PbI2 in the upper surface of the perovskite layer in Example 1 is 1%, and the excess PbI2 at the grain boundary in the upper interface of the perovskite layer is less; the proportion of excess PbI2 in the upper surface of the perovskite layer in Comparative Example 1 is 8%, and the excess PbI2 at the grain boundary in the upper surface of the perovskite layer in Comparative Example 1 is more.

[0147] XRD was performed on the perovskite layers of Example 1 and Comparative Example 1, and Figures 4 and 5 were obtained. It can be seen that the intensity of the strongest peak in Example 1 is significantly higher than that in Comparative Example 1, which shows that the perovskite layer of Example 1 has high crystallinity, while the perovskite layer of Comparative Example 1 has low crystallinity.

[0148] Table 2

[0149] Conclusion: As can be seen from Table 2, in Examples 1-20 of the present application, a passivation layer composed of a substance of Formula 1 and / or Formula 2 is provided on the perovskite layer, and the efficiency and stability of the perovskite battery are excellent. Comparative Example 1 uses an existing passivation layer material, and Comparative Examples 2 and 3 do not provide a passivation layer. The efficiency and stability of the perovskite battery are significantly lower than those of Examples 1-20. It can be seen that the perovskite battery of the embodiments of the present application can improve the efficiency and stability of the perovskite battery.

[0150] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A perovskite battery, wherein: The perovskite cell includes a perovskite layer and a passivation layer provided on at least one side of the perovskite layer, wherein the passivation layer includes at least one of the substances represented by Formula 1 or Formula 2: wherein M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni; 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; R and R' each independently include at least one of a substituted or unsubstituted aniline group and a substituted or unsubstituted guanidine group; A and A' each independently include at least one of an organic amine, Li, Na, K, Rb or Cs; and n≥1, m≥1.

2. The perovskite cell according to claim 1, wherein R and R' each independently include at least one of a substituted or unsubstituted benzylamino group, a substituted or unsubstituted phenethylamino group, and a substituted or unsubstituted guanidino group, and the substituent includes at least one of a halogen and a halogenated alkyl group.

3. The perovskite cell according to claim 1 or 2, wherein: R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6.

4. The perovskite cell according to any one of claims 1 to 3, wherein One or more of the following conditions are met: n＝1-10； m＝1-10； M includes Pb; M' includes Pb; X comprises at least one of I, Cl or Br; X' comprises at least one of I, Cl or Br; R-C9H 11 F3N or -C8H 11 At least one of FN; R' includes -CN3H6; A includes at least one of Cs, -CH3NH3 or -CN2H5; A' includes at least one of Cs, -CH3NH3 or -CN2H5.

5. The perovskite cell according to any one of claims 1 to 4, wherein The perovskite grain size of the perovskite layer is 500nm-3000nm.

6. The perovskite cell according to any one of claims 1 to 5, wherein The perovskite grain size of the perovskite layer is 800nm-2000nm.

7. The perovskite cell according to any one of claims 1 to 6, wherein The passivation layer includes at least one of the following substances:

8. The perovskite cell according to any one of claims 1 to 7, wherein The thickness of the passivation layer is 0.01 nm-100 nm.

9. The perovskite cell according to any one of claims 1 to 8, wherein The thickness of the passivation layer is 1 nm-10 nm.

10. The perovskite cell according to any one of claims 1 to 9, wherein The thickness of the perovskite layer is 300nm-1000nm.

11. The perovskite cell according to any one of claims 1 to 10, wherein: The perovskite layer comprises at least one of the following chemical formulas: Among them, A" and A ＊ Each independently comprises at least one of an organic amine, Li, Na, K, Rb or Cs, M" comprises at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, X" and X ＊ Each independently includes 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, Ni, Fe, Cu, Sb or In.

12. The perovskite cell according to any one of claims 1 to 11, wherein The perovskite cell includes a first electrode, a first transmission layer, the perovskite layer, the passivation layer, a second transmission layer, and a second electrode stacked in sequence.

13. A method for preparing a perovskite battery, wherein: include: A passivation layer is prepared on at least one side of the perovskite layer, wherein the passivation layer comprises at least one of the substances represented by Formula 1 or Formula 2: Wherein, M and M' each independently include at least one of Pb, Sn, Be, Mg, Ca, Sr, Ba, Zn, Ge, Fe, Co, Cu or Ni, 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, R and R' each independently include -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, A and A' each independently include at least one of organic amine, Li, Na, K, Rb or Cs, n≥1, m≥1.

14. The method according to claim 13, wherein include: A crystallization regulator is added to the precursor liquid of the perovskite layer to prepare the perovskite layer, wherein the crystallization regulator includes A # Y, A # including at least one of an organic amine, Pb, Cu, Li, Na, K, Rb, or Cs, and Y includes at least one of -SCN or -CH3COO; At least one side of the perovskite layer is coated with a coating containing R"X # The passivation solution is annealed to form a passivation layer to obtain a perovskite battery, wherein R" includes -C9H 11 F3N, -C8H 11 At least one of FN or -CN3H6, X # Including at least one of F, Cl, Br, I, -SCN, -CNO, -OCN, -OSCN, -SH, -OH, -CP, -CN, -SeCN, -N3 or -NO2.

15. The method according to claim 14, wherein A # Y and R"X # The amount of substance ratio is 1:(0.0005-2000).

16. The method according to claim 14 or 15, wherein: The precursor liquid of the perovskite layer includes a perovskite precursor, A # The amount ratio of Y to the perovskite precursor is (0.001-0.1):

1.

17. The method according to any one of claims 14 to 16, wherein: The precursor liquid of the perovskite layer includes a perovskite precursor, R"X # The amount ratio of the substance to the perovskite precursor is (0.001-0.1):

1.

18. A stacked battery, wherein: A perovskite battery comprising the perovskite battery according to any one of claims 1 to 12 or a perovskite battery prepared by the method according to any one of claims 13 to 17.

19. A photovoltaic module, wherein: A perovskite battery comprising the perovskite battery according to any one of claims 1 to 12 or a perovskite battery prepared by the method according to any one of claims 13 to 17.

20. A power generation device, wherein: A perovskite battery comprising the perovskite battery according to any one of claims 1 to 12 or a perovskite battery prepared by the method according to any one of claims 13 to 17.

21. An electrical device, wherein: A perovskite battery comprising the perovskite battery according to any one of claims 1 to 12 or a perovskite battery prepared by the method according to any one of claims 13 to 17.

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