Perovskite cell and preparation method thereof, photovoltaic module, photovoltaic system, power utilization device and power generation device

Abstract

The invention relates to a perovskite cell and a preparation method thereof, a photovoltaic module, a photovoltaic system, a power utilization device and a power generation device. The perovskite cell comprises a first electrode layer, a hole transport layer, a perovskite layer and a second electrode layer, wherein the hole transport layer is arranged on one side of the first electrode layer, and the hole transport layer comprises nickel oxide and reducing cations; the perovskite layer is arranged on the side, away from the first electrode layer, of the hole transport layer; the second electrode layer is arranged on the side, away from the hole transport layer, of the perovskite layer. The perovskite layer in the perovskite cell is good in long-term stability, and the perovskite cell is long in service life.

Description

Technical Field

[0001] The present application relates to the field of solar cells, and specifically to a perovskite cell and a preparation method thereof, a photovoltaic module, a photovoltaic system, an electrical device, and a power generation device. Background Art

[0002] With the rapid development of new energy, solar cells have been widely used in aerospace, industry, commerce, agriculture, and communications. Perovskite solar cells, currently the third generation of solar cells, utilize the photoelectric conversion mechanism of perovskite crystal materials to convert solar energy into electrical energy. They offer numerous advantages, including high photoelectric conversion efficiency, simple fabrication, and low production costs, and have been the subject of extensive research in recent years.

[0003] However, existing perovskite batteries often suffer from poor long-term stability of the perovskite layer, resulting in a short lifespan, which seriously restricts the industrial application of perovskite batteries. Therefore, how to improve the long-term stability of the perovskite layer and extend the battery life has become one of the important research directions in this field. Summary of the Invention

[0004] The present application is made in view of the above-mentioned problems, and one of its purposes is to provide a perovskite battery in which the perovskite layer has good long-term stability and the perovskite battery has a longer life.

[0005] In order to achieve the above objectives, the first aspect of the present application provides a perovskite battery, comprising:

[0006] a first electrode layer;

[0007] a hole transport layer, disposed on one side of the first electrode layer, the hole transport layer comprising nickel oxide and reducing cations;

[0008] a perovskite layer, disposed on a side of the hole transport layer facing away from the first electrode layer; and

[0009] The second electrode layer is disposed on a side of the perovskite layer away from the hole transport layer.

[0010] In the perovskite battery mentioned above in the present application, the reducing cation refers to a cation that has the ability to lose electrons in a chemical reaction. The reducing cation described in the present invention is preferably a reducing cation that can reduce high-valent nickel ions, wherein the valence of the high-valent nickel ions is greater than or equal to +3. The present application adds a reducing cation that can reduce high-valent nickel ions to the hole transport layer. The reducing cation can undergo an oxidation-reduction reaction with the high-valent nickel ions in the hole transport layer, converting the high-valent nickel ions into low-valent nickel ions, thereby alleviating the degradation problem of perovskite caused by contact between the high-valent nickel ions and the perovskite light-absorbing layer, improving the long-term stability of the perovskite layer, and thereby increasing the life of the perovskite battery.

[0011] In any embodiment, the reducing cation comprises a lanthanide metal ion.

[0012] In any embodiment, the lanthanide metal ion comprises Eu 2+ 、Yb 2+ 、Sm 2+ 、Ce 3+ 、Tb 3+ or Pr 3+ The lanthanide metal ions can effectively reduce the high-valent nickel ions in the hole transport layer to low-valent nickel ions, thereby effectively alleviating the degradation of perovskite.

[0013] In any embodiment, the concentration of reducing cations on the side of the hole transport layer facing away from the first electrode layer is greater than the concentration of reducing cations on the side of the hole transport layer facing the first electrode layer. In this way, the reducing cations are primarily located on the side of the hole transport layer facing the perovskite layer, which can better mitigate the degradation of the perovskite.

[0014] In any embodiment, the nickel oxide further includes doped cations. Doped cations can distort the nickel oxide lattice and create defects in the nickel oxide crystals, thereby increasing the hole mobility of the hole transport layer and thereby improving the photoelectric conversion efficiency and fill factor of the perovskite cell.

[0015] In any embodiment, the doping cation includes Li + 、Cs + , Rb + 、Ag + Mg 2+ , Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu+ 、Eu 3+ 、Yb 3+ 、Sm 2+ 、Ce 4+ , Tb 4+ 、Pr 4+ 、Cu 2+ or Nd 3+ The above-mentioned doping cations are added to the hole transport layer to effectively improve the hole mobility of the hole transport layer.

[0016] In any embodiment, the hole transport layer includes a direct contact layer facing the perovskite layer and an indirect contact layer away from the perovskite layer, the direct contact layer includes nickel oxide and the reducing cations, and the indirect contact layer includes nickel oxide. In this way, the reducing cations can reduce the high-valent nickel ions on the interface of the hole transport layer close to the perovskite layer without excessively affecting the high-valent nickel ions within the hole transport layer, thereby reducing the problem of perovskite degradation due to deprotonation reaction when the high-valent nickel ions at the interface contact the perovskite layer, while not affecting the promoting effect of the high-valent nickel ions within the hole transport layer on hole transport.

[0017] In any embodiment, at least 60% of the reducing cations are distributed in the direct contact layer. Thus, at least 60% of the reducing cations distributed in the direct contact layer can reduce high-valent nickel ions at the interface of the hole transport layer near the perovskite layer without excessively affecting the high-valent nickel ions within the hole transport layer.

[0018] In any embodiment, the thickness of the direct contact layer is 0.1 nm to 20 nm, optionally 0.1 nm to 10 nm, and further optionally 2 nm to 10 nm. In this way, the reducing cations can reduce the high-valent nickel ions at the interface to reduce their damage to the perovskite layer material, while not significantly affecting the high-valent nickel ions in the hole transport layer that promote hole transport.

[0019] In any embodiment, the molar ratio of the reducing cation to the nickel element in the direct contact layer is in the range of 0.0001 to 0.2:1, and can be optionally in the range of 0.002 to 0.05:1. Thus, controlling the molar ratio of the reducing cation to the nickel element within the above range can effectively mitigate perovskite degradation and improve the life of the perovskite battery.

[0020] In any embodiment, the hole transport layer further includes an indirect contact layer, the indirect contact layer being located between the direct contact layer and the indirect contact layer, the indirect contact layer comprising nickel oxide and the reducing cation, or the indirect contact layer comprising nickel oxide, the reducing cation, and the doped cation. Thus, the reducing cation can reduce the high-valent nickel ions in the nickel oxide. When the indirect contact layer includes the doped cation, the doped cation can distort the nickel oxide lattice and create defects in the nickel oxide crystals, thereby improving the hole mobility of the hole transport layer and, in turn, improving the photoelectric conversion efficiency and fill factor of the perovskite cell.

[0021] In any embodiment, the thickness of the indirect contact layer is 0.1 nm to 20 nm, optionally 0.1 nm to 10 nm, and more optionally 0.1 nm to 5 nm; and / or, in the indirect contact layer, the molar ratio of the reducing cation to the nickel element is in the range of 0.0001 to 0.2:1, optionally 0.002 to 0.05:1; and / or, in the indirect contact layer, when the indirect contact layer includes the dopant cation, the molar ratio of the dopant cation to the nickel element is in the range of 0.0001 to 0.2:1, optionally 0.001 to 0.1:1. In this way, while effectively improving the hole mobility of the hole transport layer and the photoelectric conversion efficiency of the perovskite cell, the indirect contact layer and the non-contact layer can maintain good crystallinity.

[0022] In any embodiment, the density of the direct contact layer, the indirect contact layer, and the indirect contact layer is independently 1% to 100%, and can be optionally 85% to 100%.

[0023] The second aspect of the present application provides a method for preparing the perovskite battery of the first aspect of the present application, comprising the following steps:

[0024] forming a first electrode layer, a hole transport layer, a perovskite layer, and a second electrode layer stacked in sequence;

[0025] Wherein, the hole transport layer includes nickel oxide and reducing cations.

[0026] The above-mentioned preparation method adds reducing cations to the hole transport layer, and the reducing cations can reduce high-valent nickel ions. In this way, the reducing cations can react with the high-valent nickel ions in the hole transport layer to convert the high-valent nickel ions into low-valent nickel ions, which can alleviate the degradation of perovskite caused by the reaction of high-valent nickel ions with the perovskite layer material, thereby improving the long-term stability of the perovskite layer and the life of the perovskite battery.

[0027] In any embodiment, the preparation of the hole transport layer comprises the following steps:

[0028] Multiple hole transport monolayers are sequentially prepared on the first electrode layer, and the multiple hole transport monolayers are stacked on the first electrode layer, and at least the hole transport monolayer in direct contact with the perovskite layer includes the reducing cation. In this way, different cations can be doped into different hole transport monolayers as needed. Furthermore, the reducing cations can reduce the high-valent nickel ions at the interface of the hole transport layer close to the perovskite layer, reducing the problem of deprotonation reaction of the high-valent nickel ions at the interface when contacting the perovskite layer, thereby improving the long-term stability of the perovskite layer and thereby increasing the life of the perovskite battery.

[0029] In any embodiment, the molar ratio of the reducing cation to the nickel element in the hole transport monolayer adjacent to the perovskite layer is 0.0001 to 0.2:1, and can optionally be 0.002 to 0.05:1. This effectively mitigates perovskite degradation and improves the life of the perovskite battery while maintaining good crystallinity of the hole transport layer.

[0030] In any embodiment, each hole transport monolayer independently contains or does not contain a dopant cation capable of causing lattice distortion in nickel oxide. By doping the hole transport monolayer with a dopant cation capable of causing lattice distortion in nickel oxide, defects can be introduced into the nickel oxide crystals, thereby increasing the hole mobility in the hole transport layer and thereby improving the photoelectric conversion efficiency and fill factor of the perovskite cell.

[0031] In any embodiment, the molar ratio of the dopant cation to nickel in the hole transport monolayer containing the dopant cation is 0.0001 to 0.2:1, and can be optionally 0.001 to 0.1:1. This effectively improves the hole mobility of the hole transport layer and the photoelectric conversion efficiency of the perovskite cell while maintaining good crystallinity.

[0032] In any embodiment, the number of the hole transport single layer is 2 to 50 layers, and can be optionally 4 to 20 layers.

[0033] In any embodiment, the thickness of each hole transport single layer is 0.1 nm to 20 nm, and can be optionally 0.5 nm to 10 nm.

[0034] The third aspect of the present application provides a photovoltaic module, comprising the perovskite cell of the first aspect of the present application or the perovskite cell prepared by the preparation method of the second aspect of the present application.

[0035] A fourth aspect of the present application provides a photovoltaic system, comprising the photovoltaic assembly of the third aspect of the present application.

[0036] The fifth aspect of the present application provides an electrical device, including the photovoltaic system of the fourth aspect of the present application.

[0037] A sixth aspect of the present application provides a power generation device, comprising the photovoltaic system of the fourth aspect of the present application.

[0038] The details of one or more embodiments of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to better describe and illustrate the embodiments or examples of the applications disclosed herein, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered to limit the scope of the disclosed applications, the embodiments or examples currently described, and any of the best modes currently understood for these applications. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0040] Figure 1 Schematic diagram of the structure of a perovskite battery according to one embodiment of the present application;

[0041] Figure 2 This is a schematic structural diagram of an electrical device according to one embodiment of the present application.

[0042] Description of reference numerals:

[0043] 10. Perovskite cell; 11. First electrode layer; 12. Hole transport layer; 13. Perovskite layer; 14. Second electrode layer; 121. First hole transport monolayer; 122. Second hole transport monolayer; 123. Third hole transport monolayer. DETAILED DESCRIPTION

[0044] Below, some embodiments of the perovskite cell disclosed in the present application are described in detail, with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary length in the following description and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0045] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit. A given range 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 range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and if the maximum range values ​​listed are 3, 4, and 5, then the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, wherein a and b are both 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 merely an abbreviation for a combination of these values. Furthermore, stating that a parameter is an integer ≥ 2 is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and so on. For example, stating that a parameter is an integer selected from "2-10" is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0046] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0047] 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.

[0048] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0049] Unless otherwise specified, the term "or" is used in this application to be inclusive. For example, the phrase "A or B" means "A, B, or both A and B." Furthermore, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0050] In this application, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0051] In this application, "a plurality of" or "a plurality of" refers to a number greater than or equal to 2 unless otherwise specified. For example, "one or more" means one or more than or equal to two.

[0052] As used herein, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0053] Herein, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc. shall be based on the technical solution that can implement the present application.

[0054] Herein, the terms "preferred," "better," "more preferred," and "suitable" are used solely to describe preferred implementations or examples and should not be construed as limiting the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0055] In this application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0056] In this application, the terms "first," "second," "third," "fourth," etc. in "the first aspect," "the second aspect," "the third aspect," "the fourth aspect," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0057] In this application, the term "room temperature" generally refers to 4°C to 35°C, and may refer to 20°C ± 5°C. In some embodiments of this application, room temperature refers to 20°C to 30°C.

[0058] In this application, when referring to a data range, if the unit is only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3h~5h or 3h~5h both mean that the units of the left endpoint "3" and the right endpoint "5" are both hours.

[0059] The weights of the relevant components mentioned in the examples of this application may not only refer to the content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Furthermore, the weights mentioned in the examples of this application may be mass units known in the chemical industry, such as μg, mg, g, and kg.

[0060] Existing perovskite solar cells often suffer from poor long-term stability of the perovskite layer, resulting in a short lifespan for the perovskite cell, which severely restricts its industrial application. Therefore, improving the long-term stability of the perovskite layer and thus extending the battery life has become an important research direction in this field. To address this issue, the present application improves the hole transport layer in the perovskite cell, effectively improving the long-term stability of the perovskite layer and thereby extending the lifespan of the perovskite cell.

[0061] See also Figure 1 In a first aspect, the present application provides a perovskite battery 10, comprising a first electrode layer 11, a hole transport layer 12, a perovskite layer 13, and a second electrode layer 14. The hole transport layer 12 is disposed on the first electrode layer 11 and comprises nickel oxide and reducing cations. The reducing cations are capable of reducing high-valent nickel ions, the valence of which is greater than or equal to +3. The perovskite layer 13 is disposed on a side of the hole transport layer 12 facing away from the first electrode layer 11. The second electrode layer 14 is disposed on a side of the perovskite layer 13 facing away from the hole transport layer 12.

[0062] During the preparation of the perovskite cell 10, the hole transport layer 12 is made of nickel oxide (NiOx), which contains divalent nickel ions and high-valent nickel ions with a valence greater than or equal to +3. These high-valent nickel ions are Brønsted bases. When they come into contact with the perovskite layer 13, they cause a deprotonation reaction of the perovskite material, causing the perovskite to degrade. This results in poor long-term stability of the perovskite layer 13, thereby affecting the life of the perovskite cell 10. The reaction process of perovskite degradation is schematically shown below:

[0063] HAPbI3 PbI2+HA + +I -

[0064] HA+ A （g） +H +

[0065] I - 1 / 2I 2（g） +e -

[0066] Ni ≥3+ O x +e - +H + Ni ≥2+ O x H

[0067] HAPbI3+Ni ≥3+ O x Ni ≥2+ O x H+PbI2+A （g） +1 / 2I 2（g）

[0068] The perovskite battery 10 of the present application is characterized by adding reducing cations capable of reducing high-valent nickel ions into the hole transport layer 12. The reducing cations can undergo redox reactions with the high-valent nickel ions in the hole transport layer 12, converting the high-valent nickel ions into low-valent nickel ions (such as Ni 2+ ), thereby alleviating the degradation of the perovskite, improving the long-term stability of the perovskite layer 13, and further increasing the life of the perovskite cell 10.

[0069] It should be noted that although reducing cations capable of reducing high-valent nickel ions are added to the hole transport layer 12, the reducing cations react with the high-valent nickel ions and are consumed. However, since perovskites typically contain halide ions (such as iodide ions), the cations in the portion of the hole transport layer 12 that contacts the perovskite layer 13 after reacting with the high-valent nickel ions react with the halide ions in the perovskite and are reduced to reducing cations. In other words, reducing cations can still be detected in the hole transport layer 12 of the perovskite cell 10.

[0070] In some embodiments, the reducing cation comprises a lanthanide metal ion. In some specific examples, the lanthanide metal ion comprises Eu 2+ 、Yb 2+ 、Sm 2+ 、Ce 3+ 、Tb 3+ or Pr 3+The lanthanide metal ions have a half-filled F orbital outside their nuclei. They have good reducibility and can reduce high-valent nickel ions in the hole transport layer to low-valent nickel ions, thereby effectively alleviating the degradation of perovskite.

[0071] In some embodiments, the reducing cation concentration on the side of the hole transport layer 12 facing the perovskite layer 13 is greater than the reducing cation concentration on the side of the hole transport layer 12 facing the first electrode layer 11. In the perovskite battery 10, since the side of the hole transport layer 12 in contact with the perovskite layer 13 contains high-valent nickel ions, which will come into contact with the perovskite and cause degradation of the perovskite, by making the reducing cation concentration on the side of the hole transport layer 12 in contact with the perovskite layer 13 greater than the reducing cation concentration on the side of the hole transport layer 12 facing the first electrode layer 11, the reducing cations mainly reduce the high-valent nickel ions in the hole transport layer 12 on the side of the hole transport layer 12 in contact with the perovskite layer 13, thereby reducing the content of the high-valent nickel ions and thereby reducing the contact between the high-valent nickel ions and the perovskite material, thereby better alleviating the degradation of the perovskite.

[0072] In some embodiments, the nickel oxide in the hole transport layer 12 also includes doped cations that can cause lattice distortion in the nickel oxide. Due to the low intrinsic mobility of nickel oxide, when it is used as the hole transport layer 12 in the perovskite cell 10, there is a problem of low hole mobility, resulting in poor photovoltaic conversion efficiency (PCE) and fill factor (FF) of the perovskite cell 10. To address this issue, the present application adds doped cations that can cause lattice distortion in the nickel oxide to the hole transport layer 12. After these doped cations are added to the nickel oxide lattice, the difference in radius between the doped cations and the nickel ion radius causes the nickel oxide lattice to be distorted, resulting in defects in the nickel oxide crystals, thereby improving the hole mobility of the hole transport layer 12 and, in turn, improving the photovoltaic conversion efficiency and fill factor of the perovskite cell 10.

[0073] In some embodiments, the doping cation includes Li + 、Cs + , Rb + 、Ag + Mg 2+ , Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu +、Eu 3+ 、Yb 3+ 、Sm 2+ 、Ce 4+ 、Tb 4+ 、Pr 4+ 、Cu 2+ or Nd 3+ The ionic radius of these ions is different from that of nickel ions in nickel oxide. Adding them as doping cations to the hole transport layer 12 can effectively improve the hole mobility of the hole transport layer 12.

[0074] In some embodiments, the hole transport layer 12 includes a direct contact layer on the side facing the perovskite layer 13 and an indirect contact layer on the side away from the perovskite layer 13, wherein the direct contact layer includes nickel oxide and reducing cations, and the indirect contact layer includes nickel oxide. In this configuration, the reducing cations can reduce the high-valent nickel ions on the interface of the hole transport layer 12 close to the perovskite layer 13 without excessively affecting the high-valent nickel ions within the hole transport layer 12. This can reduce the problem of perovskite degradation caused by deprotonation reaction when the high-valent nickel ions at the interface contact the perovskite layer 13, while not affecting the role of the high-valent nickel ions within the hole transport layer 12 in promoting hole transport.

[0075] In some embodiments, the direct contact layer refers to the portion of the hole transport layer closest to the perovskite layer.

[0076] In some embodiments, the non-direct contact layer refers to a portion of the hole transport layer that is at least separated from the perovskite layer by the direct contact layer.

[0077] In some embodiments, not less than 60% by mass of the reducing cations in the hole transport layer 12 are distributed in the direct contact layer. Not less than 60% of the reducing cations distributed in the direct contact layer can reduce the high-valent nickel ions on the interface of the hole transport layer close to the perovskite layer without excessively affecting the high-valent nickel ions inside the hole transport layer.

[0078] It can be understood that the reducing cation content in the direct contact layer can be 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, 98%, 100% of the total mass of the reducing cations in the hole transport layer 12, and any value within the range formed by any two of the above values.

[0079] In some embodiments, the thickness of the direct contact layer is 0.1 nm to 20 nm; further, the thickness of the direct contact layer is 0.1 nm to 10 nm; by controlling the thickness of the direct contact layer within the above range, the reducing cations in the direct contact layer can effectively reduce the high-valent nickel ions at the interface to reduce their damage to the perovskite layer 13 material, while not affecting the promoting effect of the high-valent nickel ions in the hole transport layer 12 on hole transport.

[0080] It can be understood that the thickness of the direct contact layer can be 0.1nm, 0.5nm, 0.8nm, 1nm, 1.5nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm and any value within the range formed by any two of the above values.

[0081] In some embodiments, the thickness of the direct contact layer is 2 nm to 10 nm. This enables the perovskite cell to have both a high initial photoelectric conversion efficiency and a long lifespan, resulting in better overall performance.

[0082] In some embodiments, the molar ratio of reducing cations to nickel in the direct contact layer ranges from 0.0001 to 0.2:1; further, from 0.002 to 0.05:1. Controlling the molar ratio of reducing cations to nickel in the direct contact layer within the above range can effectively alleviate perovskite degradation and increase the life of the perovskite battery 10. It is understood that the molar ratio of reducing cations to nickel in the direct contact layer can be 0.0001:1, 0.0005:1, 0.001:1, 0.002:1, 0.005:1, 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, and any ratio within the range formed by any two of the above ratios.

[0083] In some embodiments, the hole transport layer 12 further includes an indirect contact layer, which is located between the direct contact layer and the indirect contact layer, and the indirect contact layer includes nickel oxide and reducing cations. The indirect contact layer refers to the portion of the hole transport layer located between the direct contact layer and the indirect contact layer. The thickness of the indirect contact layer is 0.1 nm to 20 nm; further, it can be optionally 0.1 nm to 10 nm; further, it can be optionally 0.1 nm to 5 nm. It is understandable that the thickness of the indirect contact layer can be 0.1 nm, 0.5 nm, 0.8 nm, 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 13 nm, 15 nm, 16 nm, 18 nm, 20 nm, and any value within the range formed by any two of the above values.

[0084] In some embodiments, the hole transport layer 12 further includes an indirect contact layer, which is located between the direct contact layer and the indirect contact layer, and the indirect contact layer includes nickel oxide, reducing cations, and doped cations. The thickness of the indirect contact layer is 0.1 nm to 20 nm; further, it can be 0.1 nm to 10 nm; further, it can be 0.1 nm to 5 nm. It is understood that the thickness of the indirect contact layer can be 0.1 nm, 0.5 nm, 0.8 nm, 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 13 nm, 15 nm, 16 nm, 18 nm, 20 nm, and any value within the range formed by any two of the above values.

[0085] In some embodiments, the molar ratio of the reducing cation to the nickel element in the indirect contact layer ranges from 0.0001 to 0.2:1, and can further be 0.002 to 0.05:1; the molar ratio of the doping cation to the nickel element ranges from 0.0001 to 0.2:1, and can further be 0.001 to 0.1:1. This arrangement can effectively improve the hole mobility of the hole transport layer 12 and the photoelectric conversion efficiency of the perovskite cell 10 while maintaining good crystallinity in the indirect contact layer and the non-contact layer.

[0086] It is understood that the molar ratio of reducing cations to nickel in the indirect contact layer can be 0.0001:1, 0.0005:1, 0.001:1, 0.002:1, 0.005:1, 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1 and the range formed by any two of the above ratios. the molar ratio of the doping cation to the nickel element can be 0.0001:1, 0.0005:1, 0.001:1, 0.002:1, 0.005:1, 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, and any ratio within the range formed by any two of the above ratios.

[0087] The second aspect of the present application provides a method for preparing the perovskite cell 10 of the first aspect of the present application, the method comprising the following steps S100 to S400:

[0088] Step S100: providing a first electrode layer 11 .

[0089] The first electrode layer 11 can serve as a substrate, and other functional layers of the perovskite cell 10 can be formed on the first electrode layer 11 .

[0090] In some embodiments, the first electrode layer 11 may be made of transparent conductive glass. The transparent conductive glass includes one or more of fluorine-doped tin dioxide (FTO), indium tin oxide (ITO), tungsten-doped indium oxide (IWO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), or indium zinc oxide (IZO).

[0091] Step S200 : preparing a hole transport layer 12 on the first electrode layer 11 .

[0092] With the first electrode layer 11 as a substrate, a hole transport layer 12 can be prepared on the first electrode layer 11 by magnetron sputtering or solution method. The hole transport layer 12 includes nickel oxide and reducing cations.

[0093] During the preparation process of the perovskite battery 10, high-valent nickel ions with a nickel valence greater than or equal to +3 are usually distributed in the hole transport layer 12. The high-valent nickel ions inside the hole transport layer 12 are conducive to hole transport, but the high-valent nickel ions at the interface between the hole transport layer 12 and the perovskite layer 13 will cause the perovskite to deprotonate when in contact with the perovskite layer 13, thereby degrading the perovskite and affecting the long-term stability of the perovskite layer 13 and the life of the perovskite battery 10. By adding reducing cations that can reduce high-valent nickel ions to the hole transport layer 12, the reducing cations can undergo redox reactions with the high-valent nickel ions in the hole transport layer 12, so that the high-valent nickel ions are converted into low-valent nickel ions (such as Ni 2+ ), thereby alleviating the degradation of the perovskite, improving the long-term stability of the perovskite layer 13, and further increasing the life of the perovskite cell 10.

[0094] In some embodiments, the reducing cation comprises a lanthanide metal ion. Specifically, the lanthanide metal ion comprises Eu 2+ 、Yb 2+ 、Sm 2+ 、Ce 3+ 、Tb 3+ or Pr 3+ The lanthanide metal ions have an F orbital outside the nucleus, and the F orbital is half-filled. They have good reducing properties and can reduce the high-valent nickel ions in the hole transport layer 12 to low-valent nickel ions, thereby effectively alleviating the degradation of the perovskite.

[0095] In some embodiments, the hole transport layer 12 also includes doped cations that can cause lattice distortion in nickel oxide. Nickel oxide has a low intrinsic mobility, resulting in poor photoelectric conversion efficiency and fill factor in the perovskite cell 10 using nickel oxide as the hole transport layer 12. The present application adds doped cations that can cause lattice distortion in nickel oxide when preparing the hole transport layer 12. After these doped cations are added to the nickel oxide lattice, the difference in radius between the doped cations and the nickel ion radius causes the nickel oxide lattice to be distorted, resulting in defects in the nickel oxide crystals, thereby improving the hole mobility of the hole transport layer 12 and further improving the photoelectric conversion efficiency and fill factor of the perovskite cell 10.

[0096] In some embodiments, the doping cation includes Li + 、Cs + , Rb + 、Ag + Mg 2+ , Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu + 、Eu 3+ 、Yb 3+ 、Sm 2+ 、Ce 4+ , Tb 4+ 、Pr 4+ 、Cu 2+ or Nd 3+ The ionic radius of these ions is different from that of nickel ions in nickel oxide. Adding them as doping cations to the hole transport layer 12 can effectively improve the hole mobility of the hole transport layer 12.

[0097] In some embodiments, the hole transport layer 12 is formed by forming a multi-layer hole transport monolayer by magnetron sputtering on the first electrode layer 11 through multiple cycles of film deposition. The multi-layer hole transport monolayer is stacked on the first electrode layer 11 to form the hole transport layer 12. The use of magnetron sputtering to form each hole transport monolayer facilitates doping of reducing cations and doping cations at different locations in the hole transport layer 12.

[0098] In some embodiments, when depositing each hole transport monolayer by magnetron sputtering, reducing cations are doped into the hole transport monolayer in the hole transport layer 12 near the perovskite layer 13. Since the high-valent nickel ions within the hole transport layer 12 are conducive to hole transport, the high-valent nickel ions at the interface between the hole transport layer 12 and the perovskite layer 13 cause the perovskite to undergo a deprotonation reaction, thereby degrading the perovskite. By doping the hole transport monolayer in the hole transport layer 12 in contact with the perovskite layer 13 with reducing cations, the degradation of the perovskite can be better alleviated, and the hole transport layer 12 can have better hole transport performance.

[0099] In one specific example, the hole transport layer 12 is formed by a single-target magnetron sputtering method as follows:

[0100] A single-target magnetron sputtering method is used to deposit a direct contact layer, an indirect contact layer, and an indirect contact layer; wherein the direct contact layer refers to a hole transport single layer that is in direct contact with the perovskite layer 13; the indirect contact layer refers to a hole transport single layer that is only separated from the perovskite layer by the direct contact layer; and the indirect contact layer refers to other hole transport single layers except the direct contact layer and the indirect contact layer.

[0101] First, a first hole transport monolayer 121 is deposited on the first electrode layer 11 by magnetron sputtering as a non-direct contact layer. In the process of preparing the non-direct contact layer, doped cations may be selectively introduced or not introduced into the nickel oxide target material selected, so that the prepared non-direct contact layer contains or does not contain a certain amount of doped cations; a second hole transport monolayer 122 is deposited on the non-direct contact layer by magnetron sputtering as an indirect contact layer. In the process of preparing the indirect contact layer, reducing cations and doped cations may be selectively introduced or not introduced into the nickel oxide target material selected, so that the prepared indirect contact layer contains or does not contain a certain amount of doped cations; then, a third hole transport monolayer 123 is deposited on the indirect contact layer as a direct contact layer. In the process of preparing the direct contact layer, reducing cations are introduced into the nickel oxide target material selected, so that the prepared direct contact layer contains a certain amount of reducing cations.

[0102] It should be noted that since the indirect contact layer is in contact with the direct contact layer and the direct contact layer contains reducing cations; based on factors such as ion diffusion, even if reducing cations are not introduced into the indirect contact layer during preparation, a certain amount of reducing cations will still exist in the indirect contact layer of the finally formed perovskite battery 10.

[0103] In some embodiments, the direct contact layer, indirect contact layer, and non-contact layer are all prepared by radio frequency sputtering. The working gases used in the radio frequency sputtering process are argon and oxygen, and the ratio of oxygen flow / (oxygen flow + argon flow) ranges from 0.001 to 0.5:1. The temperature range of the deposition table during sputtering is 20°C to 300°C. The vacuum degree of the reaction chamber during sputtering ranges from 1.0 -3 Pa~1.0 -1 Pa. Sputtering power density range is 5W / cm 2 ~50W / cm 2 The deposition time range is 5s~180s.

[0104] It can be understood that the ratio of oxygen intake / (oxygen intake + argon intake) can be 0.001:1, 0.005:1, 0.008:1, 0.01:1, 0.015:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1 and any ratio within the range formed by any two of the above ratios. The temperature of the deposition table can be 20°C, 50°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, 260°C, 280°C, 300°C, or any value within the range formed by any two of the above values. The vacuum degree of the reaction chamber can be 1.0 -3 Pa, 5.0 -3 Pa, 8.0 -3 Pa, 1.0 -2 Pa, 5.0 -2 Pa, 8.0 -2 Pa, 1.0 -1 Pa, and any value within the range formed by any two of the above values. The sputtering power density can be 5W / cm 2 , 8W / cm 2 , 10W / cm 2 、12W / cm 2 、14W / cm 2 , 15W / cm 2 、16W / cm 2 、18W / cm 2 , 20W / cm 2 , 22W / cm 2 , 24W / cm 2 , 25W / cm 2 , 26W / cm 2 , 28W / cm 2 、30W / cm 2 、32W / cm 2 、34W / cm 2 、35W / cm 2 、36W / cm 2 、38W / cm 2 , 40W / cm 2 , 42W / cm 2 , 44W / cm 2 、45W / cm 2 、46W / cm 2 , 48W / cm 2 , 50W / cm 2The deposition time may be 5 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, 180 s, or any value within the range formed by any two of the above values.

[0105] In some embodiments, the molar ratio of reducing cations to nickel in the direct and indirect contact layers doped with reducing cations ranges from 0.0001 to 0.2:1, and can optionally range from 0.002 to 0.05:1. Controlling the molar ratio of reducing cations to nickel within this range effectively mitigates perovskite degradation and improves the lifespan of perovskite cells while maintaining good crystallinity in the direct and indirect contact layers. It will be appreciated that the molar ratio of the reducing cation to the nickel element may be 0.0001:1, 0.0006:1, 0.002:1, 0.008:1, 0.01:1, 0.015:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, and any value within the range formed by any two of the above values.

[0106] In some embodiments, the molar ratio of the dopant cation to nickel in the indirect contact layer and the indirect contact layer doped with the dopant cation is in the range of 0.0001 to 0.2:1, and can optionally be in the range of 0.001 to 0.1:1. Controlling the molar ratio of the dopant cation to nickel within this range effectively improves the hole mobility of the hole transport layer 12 and the photoelectric conversion efficiency of the perovskite cell 10 while maintaining good crystallinity in the indirect contact layer. It can be understood that the molar ratio range of the doping cation to the nickel element is 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1 and any value within the range formed by any two of the above values.

[0107] Specifically, the total number of hole transport monolayers in the hole transport layer 12 can range from 1 to 50 layers, and can optionally be 4 to 20 layers. Depending on the effect of magnetron sputtering, the thickness of each hole transport monolayer ranges from 0.1 nm to 20 nm, and can optionally be 0.5 nm to 10 nm. Depending on the effect of magnetron sputtering, the density of the hole transport monolayer ranges from 1% to 100%, and can optionally be 85% to 100%. It is understood that the number of hole transport monolayers can be 1 layer, 4 layers, 6 layers, 8 layers, 10 layers, 12 layers, 14 layers, 15 layers, 16 layers, 18 layers, 20 layers, 25 layers, 28 layers, 30 layers, 32 layers, 35 layers, 38 layers, 40 layers, 42 layers, 45 layers, 48 ​​layers, 50 layers, and any integer value within the range formed by any two of the above values. The thickness of each hole transport monolayer can be 0.1 nm, 0.5 nm, 1 nm, 2 nm, 4 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 15 nm, 16 nm, 18 nm, 20 nm, or any value within the range formed by any two of the aforementioned values. The density of each hole transport monolayer can be 1%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any value within the range formed by any two of the aforementioned values.

[0108] In some embodiments, the hole transport layer 12 is formed by a multi-target magnetron co-sputtering method as follows:

[0109] First, a first hole transport monolayer 121 is deposited on the first electrode layer 11 by magnetron sputtering as an indirect contact layer. In the process of preparing the indirect contact layer, the nickel oxide target material selected can be selectively introduced or not introduced with doped cations, so that the prepared indirect contact layer contains or does not contain a certain amount of doped cations; a second hole transport monolayer 122 is deposited on the indirect contact layer by magnetron sputtering as an indirect contact layer. In the process of preparing the indirect contact layer, the nickel oxide target material containing doped cations and the AO target material can be simultaneously selected. n Target; Among them, AO n represents the oxide corresponding to the reducing cation, and n represents the number of oxygen atoms; the prepared indirect contact layer contains a certain amount of reducing cations and doped cations; then, a third hole transport monolayer 123 is deposited on the indirect contact layer by magnetron sputtering as a direct contact layer. In the preparation process of the direct contact layer, nickel oxide target and AO can be selected at the same time. n target material, so that the prepared direct contact layer contains a certain amount of reducing cations.

[0110] In some embodiments, the direct contact layer, indirect contact layer, and indirect contact layer are all prepared by radio frequency sputtering. The working gases used in the radio frequency sputtering process are argon and oxygen, and the ratio of oxygen flow / (oxygen flow + argon flow) ranges from 0.001 to 0.5:1. The temperature range of the deposition table during co-sputtering is 20°C to 300°C. The vacuum range of the reaction chamber during co-sputtering is 1.0 -3 Pa~1.0 -1 Pa. The power density range of the cation-doped nickel oxide target during co-sputtering is 5W / cm 2 ~50W / cm 2 AO during co-sputtering n The power density of the target is in the range of 2W / cm 2 ~40W / cm 2 The deposition time range is 5s~180s.

[0111] It can be understood that the ratio of oxygen intake / (oxygen intake + argon intake) can be 0.001:1, 0.005:1, 0.008:1, 0.01:1, 0.015:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1 and any ratio within the range formed by any two of the above ratios. The temperature of the deposition table can be 20°C, 50°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, 260°C, 280°C, 300°C, or any value within the range formed by any two of the above values. The vacuum degree of the reaction chamber can be 1.0 -3 Pa, 5.0 -3 Pa, 8.0 -3 Pa, 1.0 -2 Pa, 5.0 -2 Pa, 8.0 -2 Pa, 1.0 -1 Pa, and any value within the range formed by any two of the above values. The power density of the nickel oxide target doped with cations during co-sputtering can be 5W / cm 2 , 8W / cm 2 , 10W / cm 2 、12W / cm 2 、14W / cm 2 , 15W / cm 2 、16W / cm 2 、18W / cm 2 , 20W / cm 2, 22W / cm 2 , 24W / cm 2 , 25W / cm 2 , 26W / cm 2 , 28W / cm 2 、30W / cm 2 、32W / cm 2 、34W / cm 2 、35W / cm 2 、36W / cm 2 、38W / cm 2 , 40W / cm 2 , 42W / cm 2 , 44W / cm 2 、45W / cm 2 、46W / cm 2 , 48W / cm 2 , 50W / cm 2 And any value within the range formed by any two of the above values. n The power density of the target can be 2W / cm 2 , 5W / cm 2 , 10W / cm 2 , 15W / cm 2 , 20W / cm 2 , 25W / cm 2 、30W / cm 2 、35W / cm 2 , 40W / cm 2 The deposition time may be 5 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, 180 s, or any value within the range formed by any two of the above values.

[0112] In some embodiments, the molar ratio of the reducing cations to nickel in the direct and indirect contact layers doped with reducing cations ranges from 0.0001 to 0.2:1, and may optionally range from 0.002 to 0.05:1. Controlling the molar ratio of the reducing cations to nickel within this range effectively mitigates perovskite degradation and improves the lifespan of the perovskite cell 10 while maintaining good crystallinity in the direct and indirect contact layers. It will be appreciated that the molar ratio of the reducing cation to the nickel element may be 0.0001:1, 0.0006:1, 0.002:1, 0.008:1, 0.01:1, 0.015:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, and any value within the range formed by any two of the above values.

[0113] In some embodiments, the molar ratio of the dopant cation to nickel in the indirect contact layer and the indirect contact layer doped with the dopant cation is in the range of 0.0001 to 0.2:1, and can optionally be in the range of 0.001 to 0.1:1. Controlling the molar ratio of the dopant cation to nickel within this range effectively improves the hole mobility of the hole transport layer 12 and the photoelectric conversion efficiency of the perovskite cell 10 while maintaining good crystallinity in the indirect contact layer. It can be understood that the molar ratio range of the doping cation to the nickel element is 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1 and any value within the range formed by any two of the above values.

[0114] Specifically, the total number of hole transport monolayers in the hole transport layer 12 can range from 1 to 30 layers, and can optionally range from 4 to 20 layers. Depending on the effect of magnetron sputtering, the thickness of the hole transport monolayer can range from 0.2 nm to 20 nm, and can optionally range from 1 nm to 10 nm. Depending on the effect of magnetron sputtering, the density of the hole transport monolayer can range from 1% to 100%, and can optionally range from 85% to 100%.

[0115] It is understood that the thickness of the second hole transport monolayer 122, serving as an indirect contact layer, is 0.1-20 nm, further preferably 0.1-10 nm, and further preferably 0.1-5 nm; the thickness of the third hole transport monolayer 123, serving as a direct contact layer, is 0.1-20 nm, further preferably 0.1-10 nm, and further preferably 0.1-5 nm. The total number of hole transport monolayers can be 1, 4, 6, 8, 10, 12, 14, 15, 16, 18, 20, 25, 28, 30, or any integer within the range formed by any two of the aforementioned values. The thickness of each hole transport monolayer may be 0.2 nm, 0.5 nm, 1 nm, 2 nm, 4 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 15 nm, 16 nm, 18 nm, 20 nm, or any value within the range formed by any two of the foregoing values. The density of each hole transport monolayer may be 1%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any value within the range formed by any two of the foregoing values.

[0116] Step S300 : forming a perovskite layer 13 on the surface of the hole transport layer 12 facing away from the first electrode layer 11 .

[0117] After the hole transport layer 12 is formed on the first electrode layer 11 , a perovskite layer 13 is prepared on the surface of the hole transport layer 12 facing away from the first electrode layer 11 as a light absorption layer of the perovskite cell 10 .

[0118] In some embodiments, the material of the perovskite layer 13 may include one or more of ABX3 or A2CDX6, wherein A includes organic cations, Li + 、Na + , K + , Rb + or Cs + One or more of; B includes Pb 2+ 、Sn 2+ 、Be 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ 、Zn 2+ 、Ge 2+ 、Fe 2+ 、Co 2+ 、Cu 2+ or Ni 2+ One or more of; C includes Cs+ 、Ag + 、K + or Ru + one or more of; D includes Bi 3+ 、Ni 3+ 、Fe 3+ 、Cu 3+ 、Sb 3+ or In 3+ one or more of; X includes Br - or I - one or more of. For example, the material of the perovskite layer 13 can be CH3NH3PbI3, CH3NH3SnI3, CH3NH3PbI2Br or CH3NH3Pb(I 1- x Br x 3 (where 0 < x < 1) one or more of.

[0119] Step S400: Prepare the second electrode layer 14 on the side of the perovskite layer 13 facing away from the hole transport layer 12.

[0120] After the perovskite layer 13 is prepared and formed, the second electrode layer 14 can be prepared on the surface of the perovskite layer 13 facing away from the hole transport layer 12 by a vacuum thermal evaporation coating process, thereby forming the perovskite solar cell 10.

[0121] In some embodiments, the material of the second electrode layer 14 can include one or more of silver, copper, carbon, gold, aluminum, indium tin oxide, indium oxide doped with tungsten, zinc oxide doped with aluminum, zinc oxide doped with boron or indium zinc oxide.

[0122] In some embodiments, an electron transport layer can also be provided between the perovskite layer 13 and the second electrode layer 14 for transporting electrons and suppressing electron backflow.

[0123] In some embodiments, the perovskite solar cell 10 can also include functional layers such as a blocking layer and a passivation layer. The blocking layer includes a hole blocking layer or an electron blocking layer; the passivation layer is used to passivate the perovskite interface defects.

[0124] In some embodiments, the perovskite solar cell 10 can also be a tandem solar cell containing a perovskite solar cell. The tandem perovskite solar cell includes, but is not limited to, a perovskite-perovskite tandem solar cell, a perovskite-crystalline silicon tandem solar cell, a perovskite-heterojunction tandem solar cell, etc.

[0125] The third aspect of the present application provides a photovoltaic module, including the perovskite solar cell 10 of the first aspect of the present application or the perovskite solar cell 10 prepared by the preparation method of the second aspect of the present application. By adopting the perovskite solar cell 10 as described above in the present application, the photovoltaic module has a long lifespan.

[0126] The above-mentioned photovoltaic module includes one or more perovskite cells 10, which can be selected according to the specific application scenario; further, the above-mentioned photovoltaic module includes multiple perovskite cells 10, and the multiple perovskite cells 10 are connected in series or in parallel to form a cell sheet.

[0127] In some embodiments, the photovoltaic module further includes a photovoltaic glass layer, a bonding layer, and a back sheet.

[0128] Adhesive layers are provided on both surfaces of the cell, a back plate is provided on the surface of one of the adhesive layers away from the cell, and a photovoltaic glass layer is provided on the surface of the other adhesive layer away from the cell.

[0129] The photovoltaic glass layer and the back panel are used to protect the perovskite cell 10, and have the functions of sealing, insulation and waterproofing; the adhesive layer plays the role of bonding the photovoltaic glass layer and the cell, and bonding the back panel and the cell.

[0130] Optionally, the photovoltaic glass layer is made of tempered glass, the back panel is made of TPT (polyvinyl fluoride) or TPE (thermoplastic elastomer), and the adhesive layer is made of EVA (polyethylene-polyvinyl acetate copolymer).

[0131] Furthermore, the photovoltaic module further includes a junction box and an outer frame.

[0132] The junction box is used to protect the power generation system of the entire photovoltaic module. It is equivalent to a current transfer station. When a battery cell short-circuits, the junction box will automatically disconnect the short-circuited battery string.

[0133] The outer frame can support and protect the entire photovoltaic module. The frame can be made of aluminum alloy, which has excellent strength and corrosion resistance.

[0134] Furthermore, silicone is used to bond and seal the connection between the frame and other parts of the photovoltaic module. Photovoltaic modules can convert solar energy into electrical energy, which can be stored in batteries or used to drive loads.

[0135] In some embodiments, the photovoltaic component is a solar panel.

[0136] A fourth aspect of the present application provides a photovoltaic system, comprising the photovoltaic assembly of the third aspect of the present application.

[0137] The photovoltaic system utilizes the perovskite cell 10 in the above photovoltaic module to directly convert solar radiation energy into electrical energy with high efficiency and good stability; further, the above photovoltaic system is a photovoltaic power generation system.

[0138] Photovoltaic modules are the core part of photovoltaic power generation systems. The above photovoltaic system includes one or more photovoltaic modules, which can be selected according to the specific application scenario; further, when the above photovoltaic system includes multiple photovoltaic modules, the multiple photovoltaic modules form a photovoltaic array.

[0139] The above photovoltaic system can be an independent photovoltaic power generation system or a grid-connected photovoltaic power generation system.

[0140] An independent photovoltaic power generation system consists of a photovoltaic array, a battery pack, a charge controller, a power electronic converter (inverter), and a load. Its operating principle is that solar radiation energy is first converted into electrical energy by the photovoltaic array, then converted by the power electronic converter to power the load. Meanwhile, excess electrical energy passes through the charge controller and is stored as chemical energy in an energy storage device. In periods of insufficient sunlight, the energy stored in the battery is converted to 220V, 50Hz AC power after being boosted by the power electronic inverter, filtering, and power frequency transformer to supply the AC load.

[0141] 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 system monitoring. Its operating principle is that solar radiation energy is converted by the photovoltaic array, then converted to high-voltage DC through high-frequency DC conversion. This is then inverted by a power electronic inverter and output to the grid as a sinusoidal AC current with a frequency consistent with the grid voltage.

[0142] The above two photovoltaic power generation systems have their own characteristics and can be selected according to specific application scenarios.

[0143] See also Figure 2 The fifth aspect of the present application provides an electrical device, including the photovoltaic system of the fourth aspect of the present application.

[0144] In some embodiments, the power-consuming device is a common device that includes the solar cell of the present application, such as those used in the fields of communications, transportation, industry, agriculture, and lighting. Examples of the power-consuming device include satellites, communications equipment, traffic lights, lighthouses, wireless phone booths, monitoring equipment for oil drilling, power supply systems, camping lanterns, electric vehicles, electronic device chargers, and building curtain walls.

[0145] The sixth aspect of the present application provides a power generation device, which includes the photovoltaic system of the fourth aspect of the present application. It can be understood that in the above-mentioned power generation device, the photovoltaic system is a photovoltaic power generation system.

[0146] Below, the embodiment of the present application is described. The embodiment described below is exemplary and is only used to explain the present application, and is not to be construed as limiting the present application. Where specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used that do not specify the manufacturer are conventional products that can be obtained commercially.

[0147] Example 1:

[0148] 1) Take a set of 10cm*10cm FTO conductive glass and use a laser marking machine to etch away the 0.5cm area on both sides of the FTO conductive glass. After cleaning with a detergent, ultrasonicate the FTO conductive glass in deionized water, ethanol, and acetone for 10 minutes in sequence. After ultrasonication, blow dry with nitrogen gas before use.

[0149] 2) The dried FTO conductive glass was used as the first electrode layer. Three first hole transport monolayers with a thickness of 3 nm were prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers. Then, one second hole transport monolayer with a thickness of 3 nm was prepared as an indirect contact layer. Finally, one third hole transport monolayer with a thickness of 3 nm was prepared as a direct contact layer.

[0150] Among them, the non-direct contact layer is made of doped cations Li + Nickel oxide target, Li in the target + The molar ratio of nickel to nickel is 0.02:1; the indirect contact layer contains reducing cation Eu 2+ and doped cation Li + Nickel oxide target, Eu in the target 2+ The molar ratio of Li to nickel is 0.005:1. + The molar ratio of nickel to nickel is 0.0001:1; the direct contact layer contains reducing cation Eu 2+ Nickel oxide target, Eu in the target 2+ The molar ratio of argon to nickel is 0.005:1. The working gas used in the sputtering process is a mixture of argon and oxygen, with the ratio of oxygen flow: (oxygen flow + argon flow) being 2:300. The temperature of the deposition table during sputtering is controlled at 100°C~150°C. The vacuum degree of the reaction chamber during sputtering is controlled at 1.0*10 -2 Pa~1.0*10 -1 Pa. Sputtering power density is 10W / cm 2 The deposition time for each layer was 20 s.

[0151] 3) After laser scribing, the FTO conductive glass with the nickel oxide hole transport layer deposited was placed in an ultrasonic cleaning device for 1 minute and dried at 100°C for 10 minutes. A layer of Cs with a thickness of about 500 nm was coated on the surface of the nickel oxide hole transport layer facing away from the FTO conductive glass. 0.1 FA 0.85 MA 0.05 PbI 2.7 Br 0.3 The perovskite film was continuously blown on the film surface with an air knife for 30 seconds, and then the film was transferred to a heating stage and annealed at 100°C for 10 minutes to form a perovskite layer.

[0152] 4) Using vacuum thermal evaporation coating process, in 1*10 -6 Torr, and then evaporate 50nm thick C 60 , 20nm thick BCP and 80nm thick Cu electrode, laser scribing followed by evaporation of 100nm thick Cu electrode;

[0153] 5) Through laser scribing, large-area perovskite devices are formed into a series structure to complete the preparation of perovskite cells.

[0154] Example 2:

[0155] This embodiment is basically the same as embodiment 1 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cations Li + The molar ratio of nickel to nickel is 0.001:1.

[0156] Example 3:

[0157] This embodiment is basically the same as embodiment 1 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cations Li + The molar ratio of nickel to nickel is 0.02:1.

[0158] Example 4:

[0159] This embodiment is basically the same as embodiment 1 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cations Li + The molar ratio of nickel to nickel is 0.1:1.

[0160] Example 5:

[0161] This embodiment is basically the same as embodiment 1 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cations Li + The molar ratio of nickel to nickel is 0.15:1.

[0162] Example 6:

[0163] This embodiment is basically the same as embodiment 1 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cations Li + The molar ratio of nickel to nickel is 0.2:1.

[0164] Example 7:

[0165] This embodiment is basically the same as embodiment 1, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Eu 2+ The molar ratio of nickel to nickel is 0.0001:1.

[0166] Example 8:

[0167] This embodiment is basically the same as embodiment 1, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Eu 2+ The molar ratio of nickel to nickel is 0.002:1.

[0168] Example 9:

[0169] This embodiment is basically the same as embodiment 1, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Eu 2+ The molar ratio of nickel to nickel is 0.05:1.

[0170] Example 10:

[0171] This embodiment is basically the same as embodiment 1, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Eu 2+ The molar ratio of nickel to nickel is 0.1:1.

[0172] Example 11:

[0173] This embodiment is basically the same as embodiment 1, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Eu 2+ The molar ratio of nickel to nickel is 0.2:1.

[0174] Example 12:

[0175] This embodiment is basically the same as embodiment 1, except that the reducing cations in the indirect contact layer and the direct contact layer in the hole transport layer are Yb 2+ , and Yb 2+ The molar ratio of Mg to nickel is 0.008:1; in the indirect contact layer and the indirect contact layer, the doped cation is Mg 2+ , Mg 2+ The molar ratio of nickel to nickel is 0.015:1.

[0176] Example 13:

[0177] This embodiment is basically the same as embodiment 12 except that the indirect contact layer and the indirect contact layer in the hole transport layer are doped with cationic Mg. 2+ The molar ratio of nickel to nickel is 0.12:1.

[0178] Example 14:

[0179] This embodiment is basically the same as embodiment 12 except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Yb 2+ The molar ratio of nickel to nickel is 0.1:1.

[0180] Example 15:

[0181] This embodiment is basically the same as embodiment 1, except that the reducing cations in the indirect contact layer and the direct contact layer in the hole transport layer are Ce. 3+ , and Ce 3+ The molar ratio of Sr to nickel is 0.006:1; in the indirect contact layer and the indirect contact layer, the doped cation is Sr 2+ , Sr 2+ The molar ratio of nickel to nickel is 0.05:1.

[0182] Example 16:

[0183] This embodiment is basically the same as embodiment 15, except that the doping cations in the indirect contact layer and the indirect contact layer in the hole transport layer are Sr 2+ The molar ratio of nickel to nickel is 0.15:1.

[0184] Example 17:

[0185] This embodiment is basically the same as embodiment 15, except that: in the indirect contact layer and the direct contact layer in the hole transport layer, the reducing cation Ce 3+ The molar ratio of nickel to nickel is 0.1:1.

[0186] Example 18:

[0187] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are first prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, then one second hole transport monolayer with a single layer thickness of 3 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 2 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as those in Example 1.

[0188] Example 19:

[0189] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are first prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, then one second hole transport monolayer with a single layer thickness of 3 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 0.1 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as in Example 1.

[0190] Example 20:

[0191] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are firstly prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, and then one second hole transport monolayer with a single layer thickness of 3 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 5 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as those in Example 1.

[0192] Example 21:

[0193] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are firstly prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, and then one second hole transport monolayer with a single layer thickness of 3 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 10 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as those in Example 1.

[0194] Example 22:

[0195] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are first prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, then one second hole transport monolayer with a single layer thickness of 3 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 20 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as in Example 1.

[0196] Example 23:

[0197] This embodiment is basically the same as embodiment 18, except that in step 2), no doping cations are introduced into the indirect contact layer, and only doping cations Li are introduced into the indirect contact layer. + , the rest is the same as Example 18.

[0198] Example 24:

[0199] This embodiment is basically the same as embodiment 18, except that: in step 2), the dried FTO conductive glass is used as the first electrode layer, and five nickel oxide layers with a single layer thickness of 3 nm are first prepared on the FTO conductive glass by magnetron sputtering as an indirect contact layer, and then a nickel oxide layer with a thickness of 3 nm is prepared as an indirect contact layer, and then a third hole transport layer with a single layer thickness of 5 nm is prepared as a direct contact layer (the direct contact layer is doped with Eu 2+ nickel oxide layer), the doping ratio of the direct contact layer is the same as that of Example 18.

[0200] Example 25:

[0201] This embodiment is basically the same as Example 1, with the only difference being that in step 2), the dried FTO conductive glass is used as the first electrode layer, and three first hole transport monolayers with a single layer thickness of 3 nm are first prepared on the FTO conductive glass by magnetron sputtering as indirect contact layers, then one second hole transport monolayer with a single layer thickness of 2 nm is prepared as an indirect contact layer, and finally one third hole transport monolayer with a single layer thickness of 3 nm is prepared as a direct contact layer. The doping materials and proportions of each layer are the same as in Example 1.

[0202] Comparative Example 1:

[0203] This comparative example is basically the same as Example 1, with the only difference being that the hole transport layer is not doped with reducing cations and doped cations; that is, when preparing the indirect contact layer, indirect contact layer, and direct contact layer in the hole transport layer, nickel oxide targets are used, and the targets are not doped with reducing cations and doped cations.

[0204] Comparative Example 2:

[0205] This comparative example is basically the same as Example 1, except that the hole transport layer is not doped with reducing cations; that is, when preparing the indirect contact layer and the direct contact layer in the hole transport layer, the target material is not doped with reducing cations.

[0206] Test method:

[0207] 1) Cation type and content test:

[0208] X-ray photoelectron spectroscopy (XPS) was used to characterize the prepared direct contact layer, indirect contact layer, and indirect contact layer. After collecting the photoelectron pulse signal, an energy spectrum was drawn with the photoelectron binding energy as the horizontal coordinate and the relative intensity as the vertical coordinate. After correction and fitting, the positions of the peaks related to nickel ions, doped cations, and reducing cations were determined by standard cards, and the valence states of nickel ions, doped cations, and reducing cations were confirmed (the photoelectron binding energy of elements is different in different valence states). According to the peak intensity, the values ​​of doped cations: nickel ions and reducing cations: nickel ions can be obtained.

[0209] 2) Photovoltaic conversion efficiency test of perovskite cells:

[0210] Using a solar simulator under standard test conditions (total irradiance 100 mW / cm 2 The photoelectric conversion efficiency of the perovskite cell device was tested at a temperature of 25°C and a spectral distribution of AM1.5G. The readings were recorded using a Keithley 2400 series digital multimeter. The photoelectric conversion efficiency of the perovskite cell was calculated as follows:

[0211] PCE = P OUT / P OPT

[0212] =V OC ×J SC ×(V MPP ×J MPP ) / (V OC ×J SC )

[0213] =V OC ×J SC ×FF

[0214] Among them, P OUT 、P OPT 、V MPP (V), J MPP (mA / cm 2 ), V OC (V) and J SC (mA / cm 2 ) are the output power of the perovskite cell, incident light power, cell maximum power point voltage, cell maximum power point current, open circuit voltage and short circuit current respectively. OUT 、P OPT 、V MPP (V), J MPP (mA / cm 2 ), V OC (V) and J SC (mA / cm 2 ) was obtained using a digital multimeter.

[0215] The hole transport layer parameters and photoelectric conversion efficiency test results of the perovskite cells of the above embodiments and comparative examples are shown in Table 1. In Table 1, "A ion type" represents the type of reducing cations in the direct contact layer and the indirect contact layer; "A / Ni molar ratio" represents the molar ratio of reducing cations to nickel in the direct contact layer and the indirect contact layer; "B ion type" represents the type of doped cations in the indirect contact layer and the indirect contact layer; "B / Ni molar ratio" represents the molar ratio of doped cations to nickel in the indirect contact layer and the indirect contact layer; "normalized efficiency after 30 days of storage" is the relative efficiency of the perovskite cell relative to the initial state, that is, the efficiency of the perovskite cell in the initial state is 100%.

[0216] Table 1

[0217]

[0218]

[0219] As shown in Table 1, the normalized photoelectric conversion efficiency of the perovskite cells of each embodiment of the present application after 30 days of storage is higher than that of the initial state of the cell, indicating that the perovskite cells have good stability and lifespan. At the same time, the perovskite cells have high photoelectric conversion efficiency.

[0220] The perovskite cells of Comparative Examples 1 and 2, in which no reducing cations were added to the hole transport layer, exhibited significantly lower normalized efficiencies after 30 days of storage than the perovskite cells of the present invention. Furthermore, the perovskite cell of Comparative Example 2, in which no doping cations were added to the hole transport layer, exhibited a further decrease in photoelectric conversion efficiency compared to Comparative Example 1.

[0221] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0222] The above-described embodiments merely represent several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make several modifications and improvements without departing from the concept of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be based on the appended claims, and the description and drawings may be used to interpret the content of the claims.

Claims

1. A perovskite battery, characterized in that: include: a first electrode layer; a hole transport layer, disposed on one side of the first electrode layer, the hole transport layer comprising nickel oxide and reducing cations; a perovskite layer, disposed on a side of the hole transport layer facing away from the first electrode layer; as well as The second electrode layer is disposed on a side of the perovskite layer away from the hole transport layer.

2. The perovskite battery according to claim 1, characterized in that The reducing cations include lanthanide metal ions.

3. The perovskite battery according to claim 2, characterized in that The lanthanide metal ions include Eu 2+ 、Yb 2+ 、Sm 2+ 、Ce 3+ 、Tb 3+ or Pr 3+ One or more of .

4. The perovskite battery according to any one of claims 1 to 3, characterized in that The reducing cation concentration on the side of the hole transport layer facing away from the first electrode layer is greater than the reducing cation concentration on the side of the hole transport layer close to the first electrode layer.

5. The perovskite battery according to any one of claims 1 to 3, characterized in that The nickel oxide also includes doped cations.

6. The perovskite cell according to claim 5, characterized in that The doping cations include Li + 、Cs + , Rb + 、Ag + Mg 2+ , Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu + 、Eu 3+ 、Yb 3+ 、Sm 2+ 、Ce 4+ 、Tb 4+ 、Pr 4+ 、Cu 2+ or Nd 3+ One or more of .

7. The perovskite battery according to any one of claims 1 to 6, characterized in that: The hole transport layer includes a direct contact layer facing the perovskite layer and an indirect contact layer away from the perovskite layer, the direct contact layer includes nickel oxide and the reducing cations, and the indirect contact layer includes nickel oxide.

8. The perovskite cell according to claim 7, characterized in that No less than 60% of the reducing cations are distributed in the direct contact layer.

9. The perovskite cell according to claim 7 or 8, characterized in that: The thickness of the direct contact layer is 0.1 nm to 20 nm.

10. The perovskite cell according to claim 9, characterized in that The thickness of the direct contact layer is 0.1 nm to 10 nm.

11. The perovskite cell according to claim 10, characterized in that The thickness of the direct contact layer is 2 nm to 10 nm.

12. The perovskite battery according to any one of claims 7 to 11, characterized in that: The molar ratio of the reducing cation to the nickel element in the direct contact layer is in the range of 0.0001 to 0.2:

1.

13. The perovskite cell according to claim 12, characterized in that: The molar ratio of the reducing cation to the nickel element in the direct contact layer is in the range of 0.002 to 0.05:

1.

14. The perovskite battery according to any one of claims 7 to 13, characterized in that: The hole transport layer further includes an indirect contact layer, which is located between the direct contact layer and the indirect contact layer, and the indirect contact layer includes nickel oxide and the reducing cations, or the indirect contact layer includes nickel oxide, the reducing cations and the doped cations.

15. The perovskite cell according to claim 14, characterized in that The indirect contact layer meets one or more of the following conditions: (1) The thickness of the indirect contact layer is 0.1 nm to 20 nm; (2) In the indirect contact layer, the molar ratio of the reducing cation to the nickel element is in the range of 0.0001 to 0.2:1; (3) When the indirect contact layer includes the doped cations, the molar ratio of the doped cations to the nickel element in the indirect contact layer is in the range of 0.0001 to 0.2:

1.

16. The perovskite cell according to claim 15, characterized in that The thickness of the indirect contact layer is 0.1 nm to 10 nm.

17. The perovskite cell according to claim 16, characterized in that The thickness of the indirect contact layer is 0.1 nm to 5 nm.

18. The perovskite cell according to claim 15, characterized in that In the indirect contact layer, the molar ratio of the reducing cation to the nickel element is in the range of 0.002 to 0.05:

1.

19. The perovskite cell according to claim 18, characterized in that In the indirect contact layer, the molar ratio of the doping cation to the nickel element is in the range of 0.001 to 0.1:

1.

20. The perovskite battery according to any one of claims 14 to 19, characterized in that: The densities of the direct contact layer, the indirect contact layer, and the indirect contact layer are each independently 1% to 100%.

21. A method for preparing a perovskite battery according to any one of claims 1 to 20, characterized in that: The following steps are involved: forming a first electrode layer, a hole transport layer, a perovskite layer, and a second electrode layer stacked in sequence; Wherein, the hole transport layer includes nickel oxide and reducing cations.

22. The method for preparing a perovskite battery according to claim 21, wherein: The preparation of the hole transport layer comprises the following steps: Multiple hole transport monolayers are sequentially prepared on the first electrode layer. The multiple hole transport monolayers are stacked on the first electrode layer, and at least the hole transport monolayer in direct contact with the perovskite layer includes the reducing cation.

23. The method for preparing a perovskite battery according to claim 22, wherein: In the hole transport monolayer close to the perovskite layer, the molar ratio of the reducing cation to the nickel element is 0.0001-0.2:

1.

24. The method for preparing a perovskite battery according to claim 23, wherein: In the hole transport monolayer close to the perovskite layer, the molar ratio of the reducing cation to the nickel element is 0.002-0.05:

1.

25. The method for preparing a perovskite battery according to claim 22, wherein: Each hole transporting single layer independently contains or does not contain doping cations.

26. The method for preparing a perovskite battery according to claim 25, wherein: In the hole transport monolayer containing the doped cations, the molar ratio of the doped cations to the nickel element is 0.0001-0.2:

1.

27. The method for preparing a perovskite battery according to claim 26, wherein: In the hole transport monolayer containing the doped cations, the molar ratio of the doped cations to the nickel element is 0.001-0.1:

1.

28. The method for preparing a perovskite battery according to any one of claims 22 to 27, wherein: The number of the hole transport single layer is 2 to 50 layers.

29. The method for preparing a perovskite battery according to any one of claims 22 to 27, wherein: The thickness of each hole transport single layer is 0.1 nm to 20 nm.

30. A photovoltaic module, characterized in that: A perovskite battery comprising the perovskite battery according to any one of claims 1 to 20 or a perovskite battery prepared by the preparation method according to any one of claims 21 to 29.

31. A photovoltaic system, characterized in that: A photovoltaic module comprising the photovoltaic module according to claim 30.

32. An electrical device, characterized in that: A photovoltaic system comprising the photovoltaic system of claim 31.

33. A power generation device, characterized in that: A photovoltaic system comprising the photovoltaic system of claim 31.

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