Composite electrodes and solar cells, methods for manufacturing them, electrical devices, and energy storage devices

Abstract

This application discloses a composite electrode, a solar cell, a method for manufacturing them, an electrical device, and an energy storage device. The composite electrode includes a conductive oxide substrate and a metal doped into the conductive oxide substrate. The composite electrode has high stability and functions as a matrix protecting the doped metal, thereby improving the chemical stability of the metal. By modifying the conductive oxide substrate with the doped metal, the conductivity of the composite electrode can be significantly improved. The back electrode of the solar cell includes the composite electrode. The photoelectric performance of the solar cell is improved and the photoelectric performance is stable.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to a Chinese patent application filed with the China National Intellectual Property Office on May 29, 2023, with application number 202310618013.4 and title "Composite electrodes and solar cells, methods for manufacturing the same, electrical devices and energy storage devices," the entire contents of which are incorporated into this application by reference. This application relates to the technical field of perovskite solar cells, and more specifically to composite electrodes and methods for manufacturing the same, solar cells and methods for manufacturing the same, electrical devices, and energy storage devices. [Background technology]

[0002] Perovskite solar cells (PSCs) are mainly composed of five parts: a transparent conductive glass, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a metal back electrode. The perovskite absorption layer uses perovskite-type organometallic halides (simply called perovskite materials) as the light-absorbing material, and under light irradiation conditions, this perovskite material can generate photogenerated carriers.

[0003] Currently, the back electrode material used in perovskite solar cells is generally a metal that is easily oxidized, which reduces the photoelectric conversion efficiency of the perovskite solar cell. Furthermore, because metal back electrodes have low light transmittance, the applications of perovskite solar cells are limited. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In view of the above-mentioned problems, the embodiments of this application provide a composite electrode and a solar cell, a method for manufacturing them, an electrical device and an energy storage device, in order to solve the technical problem of reduced photoelectric conversion efficiency of perovskite solar cells due to the susceptibility of metal back electrodes to oxidation. [Means for solving the problem]

[0005] In the first aspect, an embodiment of the present application provides a composite electrode. The composite electrode according to the embodiment of the present application includes a conductive oxide substrate and a metal, and the metal is doped into the conductive oxide substrate.

[0006] The conductive oxide substrate included in the composite electrode according to the embodiment of the present application imparts good stability performance to the composite electrode, plays a role in protecting the doped metal, reduces the probability of the metal being oxidized, and improves the operating stability of the composite electrode. When the conductive oxide substrate is used for the electrode of a perovskite solar cell, the stability of the operating performance of the perovskite solar cell can be effectively improved. For example, the stability of the photoelectric conversion efficiency of the perovskite solar cell can be improved.

[0007] In some embodiments, the volume content ratio of the metal doped in the composite electrode is 8% or less, and selectively 0.5 to 5%. By controlling and adjusting the doping amount of the metal in the composite electrode, the operating stability of the composite electrode and the stability of photoelectric conversion are improved.

[0008] In some embodiments, the metal includes at least one metal selected from Group IIIA elements, Group IB elements, and Group IIB elements. Here, the Group IIIA elements include at least one of aluminum, gallium, indium, and thallium, the Group IB elements include at least one of copper, gold, and silver, and the Group IIB elements include at least one of zinc and cadmium.

[0009] By doping the above metal into the conductive oxide substrate, the chemical stability and conductivity of the composite electrode can be further improved. In addition, some metals have a certain degree of light transmittance, which can improve the light transmittance of the composite electrode.

[0010] In some embodiments, in the thickness direction of the composite electrode, the metal is distributed so as to form a gradient in the composite electrode.

[0011] When the doped metal is controlled to have a gradient distribution, and such a metal is used as the back electrode of a perovskite solar cell, the surface with a lower amount of metal doping will have higher chemical stability, while the surface with a higher amount of metal doping will have better conductivity. This can further improve the chemical stability and conductivity of the composite electrode, thereby improving the photoelectric performance and stability of the perovskite solar cell.

[0012] In the embodiment, the composite electrode includes a first metal-doped layer, a second metal-doped layer, and a third metal-doped layer, wherein the first metal-doped layer, the second metal-doped layer, and the third metal-doped layer are provided in order in the thickness direction of the composite electrode.

[0013] In the example, the volume content of the metal in the first metal-doped layer is 0%, the volume content of the metal in the second metal-doped layer is 0.1-2%, and the volume content of the metal in the third metal-doped layer is 2-8%.

[0014] In the example, the ratio of the thicknesses of the first metal-doped layer, the second metal-doped layer, and the third metal-doped layer is 1:(1~3):(1~5).

[0015] By controlling the metals in the composite electrode to form a gradient distribution including three metal-doped layers, and further controlling the thickness of each metal-doped layer and the amount of metal doping, the metals are made to perform the aforementioned roles, thereby resulting in the composite electrode having excellent chemical stability and conductivity.

[0016] In some embodiments, the conductive oxide substrate includes a light-transmitting metal oxide. By using a metal oxide as the conductive oxide substrate, the composite electrode according to the embodiments of this application can achieve both excellent chemical stability and conductivity.

[0017] In the examples, the metal element contained in the metal oxide includes at least one of the group IIIA elements, group IVA elements, group IB elements, and group IIB elements, where the group IIIA element includes at least one of aluminum, gallium, indium, and thallium; in exemplary examples, the group IVA element includes tin; the group IB element includes at least one of copper, gold, and silver; and the group IIB element includes at least one of zinc and cadmium.

[0018] The above-mentioned conductive oxide substrate possesses both excellent chemical stability and conductivity, while also exhibiting high light transmittance. Therefore, the composite electrode according to the embodiment of this application combines excellent chemical stability, conductivity, and light transmittance.

[0019] In exemplary examples, the metals include aluminum, gallium, indium, and thallium, and the conductive oxide includes tin oxide. The composite electrode comprising a tin oxide substrate and the four doping metals of aluminum, gallium, indium, and thallium exhibits relatively superior chemical stability, conductivity, and light transmittance.

[0020] In some embodiments, the composite electrode includes at least one of the following (1) to (3). (1) The thickness is 60-200 nm, and selectively 80-100 nm. (2) The work function values ​​are between 4 and 5.5 eV, and selectively between 4.26 and 5.20 eV. (3) The sheet resistance is 5 to 15 ohms, and selectively 7 to 11 ohms.

[0021] If the composite electrode according to the embodiment of this application has at least one of the characteristics (1) to (3) above, the applicability of the composite electrode according to the embodiment of this application in perovskite solar cells will be increased.

[0022] In a second aspect, the embodiments of the present application further provide a method for manufacturing a composite electrode. The method for manufacturing a composite electrode of the present application is The process includes a step of forming a composite electrode by applying a film deposition treatment to a raw material containing a metal and a conductive oxide on the surface of a matrix.

[0023] The method for manufacturing a composite electrode according to the embodiments of this application effectively achieves metal doping of a conductive oxide substrate, thereby imparting excellent chemical and conductive properties to the manufactured composite electrode.

[0024] In some embodiments, the method for forming a film on the surface of the matrix, which includes a raw material containing a metal and a conductive oxide, includes at least one of magnetron sputtering, co-evaporation, atomic layer deposition, and ion plating.

[0025] In a third embodiment, embodiments of the present application further provide a solar cell. The solar cell according to embodiments of the present application includes a transparent electrode and a back electrode provided opposite each other, and further includes a first transport layer, a perovskite absorption layer and a second transport layer provided between the transparent electrode and the back electrode in order in the direction from the transparent electrode to the back electrode, Here, the back electrode includes a composite electrode according to the embodiment of this application, or a composite electrode manufactured by the method for manufacturing a composite electrode according to the embodiment of this application.

[0026] The back electrode included in the solar cell according to the embodiment of this application exhibits excellent chemical stability and operational stability, as well as high conductivity, thereby improving the photoelectric performance of the perovskite solar cell and ensuring stable photoelectric performance.

[0027] In some embodiments, the metal contained in the composite electrode is distributed in the thickness direction of the composite electrode so as to form a gradient, and the side of the composite electrode with a lower metal content is stacked toward the second transport layer. By having the surface of the back electrode with a lower metal doping amount face the second transport layer, excitons transported from the transport layer can be effectively collected, further improving the photoelectric performance and stability of the photoelectric performance of the perovskite solar cell.

[0028] In some embodiments, the second transport layer is a hole transport layer or an electron transport layer.

[0029] In the example, the hole transport material contained in the hole transport layer includes at least one of the following: the material shown in M, a derivative of the material shown in M, a material obtained by doping and modifying the material shown in M, and a material obtained by passivating the material shown in M.

[0030] The aforementioned M includes at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly-3-hexylthiophene, triptycene-cored triphenylamine, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-phenylamine)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), polythiophene, nickel oxide, molybdenum oxide, cuprous iodide, and cuprous oxide.

[0031] In the examples, the thickness of the hole transport layer is 0.1 to 30 nm.

[0032] In the example, the electron transport material included in the electron transport layer includes at least one of the following: the material shown in N, a derivative of the material shown in N, a material obtained by doping and modifying the material shown in N, and a material obtained by passivating the material shown in N.

[0033] The aforementioned N includes at least one of [6,6]-phenylC61 methyl butyrate, [6,6]-phenylC71 methyl butyrate, fullerene C60, fullerene C70, stannic oxide, and zinc oxide.

[0034] In the examples, the thickness of the electron transport layer is 10 to 80 nm.

[0035] In the case of the thickness and transport material of the hole transport layer and electron transport layer, the collection and transport of excitons generated by photoexcitation of the perovskite absorption layer are improved. When the hole transport layer and electron transport layer are second transport layers, these transport materials can be relatively matched to the energy levels of the back electrode.

[0036] In some embodiments, the perovskite absorption layer is further doped with quantum dots. Doping the perovskite absorption layer with quantum dots expands the spectral range of sunlight absorption by the perovskite absorption layer, improves the absorption capacity of the perovskite absorption layer, and increases the photoelectric conversion efficiency of the solar cell.

[0037] In some embodiments, the thickness of the perovskite absorption layer is 400 to 1000 nm. By setting the thickness within this range, the absorption capacity of the perovskite absorption layer can be further improved, thereby improving the photoelectric conversion efficiency and stability of the photoelectric conversion efficiency of the solar cell.

[0038] In a fourth aspect, embodiments of the present application further provide a method for manufacturing a solar cell. The method for manufacturing a solar cell according to embodiments of the present application is: The process includes a step of sequentially laminating a first transport layer, a perovskite absorption layer, and a second transport layer on the surface of a transparent electrode in a direction opposite to the surface of the transparent electrode.

[0039] The composite electrode is formed by applying a film deposition treatment to the surface of the second transport layer opposite to the perovskite absorption layer, according to the method for manufacturing a composite electrode according to the embodiment of this application described above.

[0040] The back electrode included in the solar cell manufactured by the solar cell manufacturing method according to the embodiment of this application has the above-mentioned high stability and conductivity, or furthermore, high light transmittance such as translucency.

[0041] In some embodiments, the perovskite absorption layer contains quantum dots, and the method for forming the perovskite absorption layer is A step of preparing a mixed solution of quantum dots and perovskite precursors, A step of applying a first film formation treatment to the mixed solution on the surface of the first transport layer opposite to the transparent electrode to obtain a perovskite precursor film layer, The process includes the step of annealing the perovskite precursor film layer to obtain the perovskite absorbance layer.

[0042] By preparing a mixed solution of quantum dots and perovskite precursors and fabricating a perovskite absorption layer, defects, absorption capacity, and photoexciton separation in the perovskite absorption layer can be effectively reduced.

[0043] In a fifth embodiment, embodiments of the present application further provide an electrical device. The electrical device according to embodiments of the present application includes a power supply unit or an energy storage unit, the power supply unit or energy storage unit includes a solar cell, the solar cell includes a solar cell according to embodiments of the present application, or a solar cell manufactured by a method for manufacturing a solar cell according to embodiments of the present application. The electrical device according to embodiments of the present application can effectively convert sunlight into electrical energy with relatively high efficiency and can improve the operational stability of the power supply unit or energy storage unit.

[0044] In a sixth embodiment, embodiments of the present application further provide an energy storage device. The energy storage device according to embodiments of the present application includes an energy storage unit, the energy storage unit includes a solar cell, the solar cell includes a solar cell according to embodiments of the present application, or a solar cell manufactured by a method for manufacturing a solar cell according to embodiments of the present application. The energy storage device according to embodiments of the present application can effectively convert sunlight into electrical energy with relatively high efficiency and can store it with stable conversion efficiency.

[0045] The above description is merely a general overview of the technical solution of this application. In order to more clearly understand the technical means of this application and to implement them based on the contents of the specification, and to make the above and other objectives, features, and benefits of this application easier to understand, specific embodiments of this application are given below. [Brief explanation of the drawing]

[0046] By reviewing the detailed description of the optional embodiments below, various other advantages and merits will become obvious to those skilled in the art. The drawings are for illustrative purposes only and should not be construed as limiting this application. Throughout the drawings, the same reference numerals indicate the same components. The description of the drawings is as follows.

[0047] [Figure 1] This is a schematic diagram showing some structures of composite electrodes according to embodiments of this application. [Figure 2] This is a schematic diagram showing some other structures of the composite electrode according to the embodiments of this application. [Figure 3] This is a schematic diagram of the structure of a composite electrode according to an embodiment of this application, in which the metals contained in the composite electrode are distributed to form a gradient having three metal-doped layers. [Figure 4] This is a schematic diagram showing some structures of a perovskite solar cell according to the embodiments of this application. [Figure 5] This is a schematic diagram showing some structures of a perovskite solar cell according to the embodiments of this application, where the back electrode is a composite electrode as shown in Figure 3.

[0048] The reference numerals in the attached drawings for specific embodiments are as follows: 5': Composite electrode, 51: Conductive oxide matrix, 52: Metal, 53: First metal-doped layer, 54: Second metal-doped layer, 55: Third metal-doped layer 1: Transparent electrode, 2: First transport layer, 3: Perovskite absorption layer, 4: Second transport layer, 5: Backside electrode [Modes for carrying out the invention]

[0049] The following examples of embodiments of the technical solution of this application will be described in detail with reference to the drawings. The following embodiments are used solely to illustrate the technical solution of this application more clearly and are merely examples; they should not limit the scope of protection of this application.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art. Terms used herein are for illustrative purposes only and are not intended to limit this application. Terms such as “includes,” “has,” and any variations thereof in the description, claims, and brief description of the drawings above are intended to cover the non-exclusive “includes.”

[0051] In the descriptions of the embodiments of this application, technical terms such as "first," "second," etc., are merely used to distinguish different subjects and should not be understood as indicating or implying relative importance, or implicitly indicating the number of technical features shown, a specific order, or a primary-secondary relationship. In the descriptions of the embodiments of this application, unless otherwise clearly and specifically limited, "multiple" means two or more.

[0052] Where the “Examples” are described herein, it means that the specific features, structures, or properties described by the Examples may be included in at least one Example of this Application. The phrase “Examples” appearing in different parts of the Specification does not necessarily refer to the same Example, nor does it refer to an Example that is exclusively independent or alternative to another Example. It will be understood expressly or implicitly by those skilled in the art that the Examples described herein may be combined with other Examples.

[0053] In the description of the embodiments of this application, the term "and / or" is merely used to describe the relationship between related objects, and indicates that there may be three such relationships. For example, A and / or B can represent the case where A exists alone, where A and B exist simultaneously, or where B exists alone. In addition, the symbol " / " in this specification generally means that the preceding and following related objects are in an "or" relationship.

[0054] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more sets (including two sets), and "multiple sheets" refers to two or more sheets (including two sheets).

[0055] In the description of the embodiments of this application, the orientations or positional relationships indicated by technical terms such as "center," "vertical direction," "horizontal direction," "length," "width," "thickness," "top," "bottom," "front," "back," "left," "right," "vertical," "horizontal," "top," "bottom," "inside," "outside," "clockwise," "counterclockwise," "axial direction," "radial direction," and "circumferential direction" are orientations or positional relationships shown based on the drawings, and are merely for the purpose of making the embodiments of this application easier to explain and simplifying the description. They do not explicitly or implicitly suggest that the shown devices or elements necessarily have a specific orientation, or are composed and operated in a specific orientation, and should not be understood as limiting the embodiments of this application.

[0056] In the descriptions of the embodiments of this application, unless otherwise explicitly specified or limited, technical terms such as "attach," "connect," "join," and "fix" should be understood in a broad sense. For example, they may refer to fixed connections, removable connections, or integration. They may also refer to mechanical or electrical connections. Furthermore, they may refer to direct connections, indirect connections via an intermediate mediator, internal communication between two elements, or interaction relationships between two elements. Those skilled in the art will be able to understand the specific meaning of the above terms in the embodiments of this application depending on the specific circumstances.

[0057] Perovskite solar cells (PSCs) are mainly composed of five parts: a transparent conductive glass, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a metal back electrode. The perovskite absorption layer uses a perovskite-type organometallic halide (simply called a perovskite material) as the light-absorbing material. When the energy of the incident photon is greater than the band gap of the material, the perovskite absorption layer absorbs the photon and becomes excited, generating excitons, i.e., electron-hole pairs. Here, electrons and holes are transported through the transport layer and collected by the transparent electrode and the metal back electrode, respectively.

[0058] Currently, metal back electrodes are generally made of metallic materials and are susceptible to environmental influences. For example, adverse effects such as water vapor and oxygen can cause oxidation reactions, reducing the conductivity of the metal back electrode and decreasing its ability to collect electrons and holes. Furthermore, currently used metal back electrodes generally have low light transmittance, for example, they are opaque. As greater applicability is required, and the metal back electrode solution limits the application of perovskite solar cells.

[0059] This application investigates how to effectively improve the chemical stability of back electrodes. Through research, it was found that using a conductive oxide as a substrate and doping this oxide substrate with a specific type of metal results in a composite electrode with high chemical stability and excellent conductivity. Furthermore, by selecting and controlling the types of oxide and metal, the light transmittance of the composite electrode can be adjusted. By using this composite electrode as the back electrode of a perovskite solar cell, the range of applications for perovskite solar cells is broadened. Based on this research, this application proposes the following solutions. composite electrode

[0060] In a first embodiment, the embodiments of the present application provide a composite electrode. The composite electrode according to the embodiments of the present application comprises a conductive oxide substrate and a metal, wherein the metal is doped into the conductive oxide substrate.

[0061] Here, the conductive oxide substrate is the main component included in the composite electrode according to the embodiment of this application; that is, the main component is the conductive oxide, and the metal is understood to be the doping component. Doping should be understood as the distribution of metal within the conductive oxide substrate. The metal can be understood as a monatomic metal or metal particles, etc.

[0062] The composite electrodes according to the embodiments of this application have high chemical stability, such as high oxidation resistance, by using a conductive oxide as the substrate. Furthermore, since the conductive oxide functions as a carrier for the metal, the conductive oxide substrate plays a role in isolating the metal from the environment and protecting the doped metal. As a result, the probability of the metal being oxidized is reduced, the chemical stability of the metal is improved, and the operational stability of the composite electrode is enhanced. When used as an electrode for a perovskite solar cell, it can effectively improve the operational stability of the perovskite solar cell, for example, by increasing its photoelectric conversion efficiency. In addition, metal doping modifies the conductive oxide substrate, significantly improving the conductive performance of the conductive oxide.

[0063] Therefore, a synergistic effect is achieved between the conductive oxide substrate and the metal in the composite electrode according to the embodiment of this application, resulting in extremely high chemical stability and excellent conductive performance of the composite electrode.

[0064] Based on the relationship between the conductive oxide substrate and the metal included in the composite electrode according to the embodiment of this application, the composite electrode according to the embodiment of this application may have a structure in which the conductive oxide substrate constitutes the conductive oxide matrix 51 of the composite electrode 5' according to the embodiment of this application, and the metal 52 is doped into this conductive oxide matrix 51, as shown in Figures 1 and 2.

[0065] Here, as shown in Figure 1, the metal 52 may be uniformly distributed in the conductive oxide matrix 51. By controlling the doping of metal 52 to be uniform, the uniformity of the composite electrode 5', including its chemical stability and conductivity, can be improved.

[0066] Of course, the metal 52 does not have to be uniformly distributed in the conductive oxide matrix 51. For example, in some embodiments, as shown in Figure 2, the metal 52 is distributed in the thickness direction of the composite electrode 5', or in other words, in the conductive oxide matrix 51, such that it forms a gradient.

[0067] Here, the thickness direction refers to the direction perpendicular to the surface of the conductive oxide matrix 51. The gradient distribution can be understood as the concentration of the metal content differing with depth in the thickness direction of the conductive oxide matrix 51. For example, in the thickness direction from one surface of the conductive oxide matrix 51 to the other, for example, as shown in Figure 2, the metal content 52 gradually increases, but of course it may also gradually decrease.

[0068] By controlling the distribution of metal 52 in the conductive oxide matrix 51 to have a gradient in the thickness direction, the amount of metal 52 doping on one surface layer of the conductive oxide matrix 51 can be made higher than on the opposing surface layer. When this is used as the back electrode of a perovskite solar cell, the surface with a lower amount of metal 52 doping has higher chemical stability, and the surface with a higher amount of metal 52 doping has better conductivity. This further improves the chemical stability and conductivity of the composite electrode 5', thereby improving the photoelectric performance and stability of the perovskite solar cell.

[0069] In the embodiment, if the metal 52 is distributed in the conductive oxide matrix 51 to form a gradient, the composite electrode 5' may include several metal-doped layers, each with a different amount of metal 52 doping, and the amount of metal 52 doping in each metal-doped layer may increase in a gradient in the thickness direction of the composite electrode 5', i.e., from one surface to the opposing other surface, or of course, may decrease in a gradient.

[0070] If the composite electrode 5' includes several metal-doped layers, as in the example shown in Figure 3, the composite electrode 5' includes a first metal-doped layer 53, a second metal-doped layer 54, and a third metal-doped layer 55, which are arranged sequentially in the thickness direction of the composite electrode 5'. It should be understood that the metal 52 content in the first metal-doped layer 53, the second metal-doped layer 54, and the third metal-doped layer 55 are different. For example, the amount of metal 52 doping in these three metal-doped layers may increase sequentially or decrease sequentially, forming a gradient distribution of metal 52.

[0071] In the examples, the volume content of metal 52 in the first metal-doped layer 53 is 0%, and the volume content of metal 52 in the second metal-doped layer 54 is 0.1-2%, specifically, it can be in the range of 0.1-1%, 1-1.5%, 1.5-2%, etc., but is not limited to these ranges. The volume content of metal 52 in the third metal-doped layer 55 is 2-8%, specifically, it can be in the range of 2-3%, 3-4%, 4-5%, 5-6%, 6-7%, 7-8%, etc., but is not limited to these ranges.

[0072] In another embodiment, the ratio of the thicknesses of the first metal-doped layer 53, the second metal-doped layer 54, and the third metal-doped layer 55 may be 1:(1~3):(1~5).

[0073] By controlling the gradient distribution of metal 52 in the composite electrode 5', for example by controlling the amount of metal 52 doping, a structure including a first metal-doped layer 53, a second metal-doped layer 54, and a third metal-doped layer 55 can be formed. By arranging these metal-doped layers in order of increasing or decreasing thickness, the role of metal 52 described above can be further improved, and the composite electrode 5' will have excellent chemical stability and conductivity.

[0074] In some embodiments, the metal 52 contained in the composite electrode in each of the above embodiments may include at least one of the group IIIA elements, group IB elements, and group IIB elements.

[0075] In the examples, if metal 52 is a Group IIIA metal, such metallic elements include at least one of aluminum, gallium, indium, and thallium. If metal 52 is a Group IB metal, such metallic elements include at least one of copper, gold, and silver. If metal 52 is a Group IIB metal, such metallic elements include at least one of zinc and cadmium.

[0076] The various metals 52 described above have high chemical stability and excellent conductivity. Doping these metals 52 into a conductive oxide substrate, i.e., a conductive oxide matrix 51, makes it possible to further improve the chemical stability and conductivity of the composite electrode. Furthermore, since some metals have a certain degree of light transmittance, the light transmittance of the composite electrode can be improved.

[0077] The metal 52 contained in the composite electrode in each of the above embodiments may be one type or a combination of two or more types. Whether the metal 52 doped into the conductive oxide matrix 51 is one type or two or more types, the purpose is to improve the chemical stability and conductivity of the composite electrode in cooperation with the conductive oxide substrate. Of course, the types of these metals 52 and the doping ratio of two or more types of metals 52 may be adjusted further, taking into consideration the economic cost and light transmittance of the composite electrode.

[0078] Based on the types of metal 52 described above, in the examples, the metal 52 included in the composite electrode in each of the above examples may include one or more types from among aluminum, gallium, indium, thallium, copper, gold, silver, zinc, cadmium, etc. Here, two or more types include combinations of two types of metals. When metal 52 is a combination of two or more types of metals, the doping of the conductive oxide substrate, i.e., conductive oxide matrix 51, of the metal 52 included in the composite electrode in each of the above examples may include at least the following methods.

[0079] In the examples, the metal 52 included in the composite electrode in each of the above examples may include, but is not limited to, two combinations such as Au and Ag, Au and Al, or Au and In. In the examples, the volume ratio of the two metals such as Au and Ag, Au and Al, or Au and In may be 0.1 to 0.9:1.

[0080] In the examples, the metals included in the composite electrodes in each of the above examples may include, but are not limited to, combinations of three metals such as Au, Ag, and Cd; three metals such as Au, Al, and Cu; three metals such as Ga, In, and Ti; or three metals such as Ag, Ga, and Zn.

[0081] In the exemplary examples, the metals included in the composite electrodes in each of the above embodiments may include, but are not limited to, combinations of four metals such as Al, Ga, In, and Tl, or four metals such as Ag, Zn, Cd, and Cu.

[0082] The types of metal 52 described above, the method of doping with only one type of metal, or the method of doping with a combination of two or more metals are merely examples of metal 52. When metal 52 is composed of two or more metals, the content of each metal can be adjusted as needed. Of course, other types of metals or combinations of two or more other metals may be selected and used, taking into consideration factors such as the light transmittance and economic cost of the composite electrode, while ensuring the stability and conductivity of the composite electrode.

[0083] In some embodiments, the volume content of metal 52 in the composite electrode in each of the above embodiments is greater than 0 and 8% or less, and selectively between 0.5% and 5%. In exemplary examples, the volume content of the doped metal can typically be, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc., but these are not the only limited volume content. The conductive performance of the composite electrode can be adjusted by controlling and adjusting the amount of metal doping in the composite electrode. For example, it was found that when the volume content of this metal 52 doped into the composite electrode 5' is greater than 0, 8% or less, and further controlled within the range of 0.5-5%, the amount of metal 52 doping can effectively improve the conductivity of the composite electrode compared to electrodes with different doping amounts, satisfying the conductivity requirements of the back electrode of the perovskite solar cell, improving the stability of this metal 52 in the composite electrode 5', and thereby improving the photoelectric performance and stability of the perovskite solar cell.

[0084] In some embodiments, the conductive oxide substrate included in the composite electrode in each of the embodiments described above contains a metal oxide. As the conductive oxide substrate used is a metal oxide that not only has excellent chemical stability and conductivity but also partially possesses light transmittance, the composite electrode according to the embodiments of this application combines excellent chemical stability, conductivity, and light transmittance. When the composite electrode according to the embodiments of this application is used as the back electrode of a perovskite solar cell, the photoelectric performance and stability of the photoelectric performance of the perovskite solar cell can be further improved, and its range of application can be expanded.

[0085] In the examples, when the conductive oxide substrate contains a metal oxide, the metal elements contained in this metal oxide include at least one of the group IIIA, group IVA, group IB, and group IIB elements.

[0086] In the examples, if the metal element of the metal oxide includes a Group IIIA element, this Group IIIA metal element may include at least one of aluminum, gallium, indium, and thallium. In the exemplary examples, this metal oxide may include at least one of aluminum oxide (Al2O3), gallium oxide (Ga2O3), indium oxide (In2O3), thallium oxide (Tl2O3), etc.

[0087] In the examples, if the metal element of the metal oxide includes a group IVA element, this group IVA metal element may include tin. In the exemplary examples, this metal oxide may include, but is not limited to, tin oxide (SnO2).

[0088] In the examples, if the metal elements of the metal oxide include Group IB elements, these Group IB metal elements include at least one of copper, gold, and silver. In the exemplary examples, the metal oxide may include at least one of copper oxide (CuO), silver oxide (Ag2O), gold oxide (Au2O3), etc.

[0089] If the metal elements of a metal oxide include Group IIB elements, these Group IIB metal elements include at least one of zinc and cadmium. In exemplary examples, the metal oxide may include at least one of zinc oxide (ZnO), cadmium oxide (CdO), and the like.

[0090] Based on the types of metal oxides described above, the conductive oxide substrate may contain one or more of the following: aluminum oxide (Al2O3), gallium oxide (Ga2O3), indium oxide (In2O3), thallium oxide (Tl2O3), tin oxide (SnO2), copper oxide (CuO), silver oxide (Ag2O), gold oxide (Au2O3), zinc oxide (ZnO), cadmium oxide (CdO), etc. Here, "two or more" includes combinations of two metals. When the metal oxide is a combination of two or more metals, the conductive oxide substrate included in the composite electrode in each of the above examples may include at least the following configurations.

[0091] In the examples, the conductive oxide substrate may include combinations of two metal oxides, such as aluminum oxide (Al2O3) and thallium oxide (Tl2O3); combinations of two metal oxides, such as gold oxide (Au2O3) and zinc oxide (ZnO); and combinations of two metal oxides, such as aluminum oxide (Al2O3) and cadmium oxide (CdO).

[0092] In the examples, the conductive oxide substrate may include combinations of three metal oxides: aluminum oxide (Al2O3), silver oxide (Ag2O), and zinc oxide (ZnO); combinations of three metal oxides: tin oxide (SnO2), copper oxide (CuO), and silver oxide (Ag2O); and combinations of three metal oxides: thallium oxide (Tl2O3), tin oxide (SnO2), and copper oxide (CuO).

[0093] In the examples, the conductive oxide substrate may include a combination of four metal oxides: silver oxide (Ag2O), gold oxide (Au2O3), zinc oxide (ZnO), and cadmium oxide (CdO); or a combination of four metal oxides: copper oxide (CuO), silver oxide (Ag2O), gold oxide (Au2O3), and zinc oxide (ZnO).

[0094] The types of conductive oxide substrates of the metal oxides described above, the method of doping with only one type, or the method of doping with a combination of two or more metals are merely examples of conductive oxide substrates. When the conductive oxide substrate is composed of two or more metal oxides, the content of each conductive oxide substrate can be adjusted according to the requirements of conductivity and chemical stability. Of course, while ensuring the stability and conductivity of the composite electrode, other types of conductive oxide substrates or combinations of two or more other conductive oxide substrates may be selected and used, taking into consideration factors such as the light transmittance and economic cost of the composite electrode.

[0095] Depending on the type of conductive oxide substrate described above, or the combination of two more types, the conductive oxide substrate can achieve both excellent chemical stability and conductivity. Furthermore, some metal oxides have high light transmittance, so the composite electrode according to the embodiment of this application possesses excellent chemical stability, conductivity, and light transmittance.

[0096] Based on the types of metals and conductive oxide substrates included in the composite electrodes according to each of the above embodiments, in the exemplary example, the conductive oxide includes tin oxide, and the metal includes four types: aluminum, gallium, indium, and thallium. The composite electrode, comprising a tin oxide substrate and four doping metals (aluminum, gallium, indium, and thallium), exhibits relatively superior chemical stability, conductivity, and light transmittance. This improves the applicability of the composite electrode in perovskite solar cells, for example, by increasing its applicability as a back electrode, thereby improving the photoelectric performance and stability of the photoelectric performance of the perovskite solar cell and expanding its range of applications.

[0097] Based on the selection and control of the type and content of conductive oxide substrates and metals included in the composite electrodes according to each of the above embodiments, in some embodiments, the composite electrodes according to the embodiments of this application include at least one of the following (1) to (3). (1) The thickness is 60 to 200 nm, and may also be 80 to 100 nm, etc. In the exemplary examples, this thickness may typically be 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, etc., but these are not the only limiting thicknesses. (2) The value of the work function is between 4 and 5.5 eV, and may also be between 4.26 and 5.20 eV. In the example, this value of the work function may typically be 4.0 eV, 4.26 eV, 4.5 eV, 4.6 eV, 4.7 eV, 4.8 eV, 4.9 eV, 5.0 eV, 5.1 eV, 5.2 eV, 5.5 eV, etc., but these are not the only limited values ​​of the work function. (3) The sheet resistance may be 5 to 15 Ω, or even 7 to 11 Ω. In the example, this sheet resistance may be 5 Ω, 6 Ω, 7 Ω, 8 Ω, 9 Ω, 10 Ω, 11 Ω, 12 Ω, 13 Ω, 14 Ω, 15 Ω, etc., but these are not the only limited sheet resistances.

[0098] Therefore, if the composite electrode according to the embodiment of this application has at least one of the characteristics (1) to (3) above, the applicability of the composite electrode according to the embodiment of this application in perovskite solar cells is improved. Specifically, its applicability as a back electrode is improved, the photoelectric performance and stability of the photoelectric performance of the perovskite solar cell are improved, and its range of application can be expanded. Manufacturing method for composite electrodes

[0099] In a second embodiment, the embodiments of this application provide a method for manufacturing a composite electrode. The method for manufacturing a composite electrode according to the embodiments of this application includes the following steps. S10: A composite electrode is formed on the surface of the matrix by applying a film deposition treatment to a raw material containing a metal and a conductive oxide.

[0100] The metal-containing raw material in step S10 may be a metal element or an alloy, and of course, it may be a precursor of a metal element or alloy. Similarly, the conductive oxide raw material may be a conductive oxide, or a precursor of a conductive oxide.

[0101] The film deposition process can be selected according to the type of raw material containing metal and conductive oxide. In the examples, the film deposition method may include, but is not limited to, one or more combinations of film deposition methods such as spin coating and annealing, vapor deposition, sputtering, and atomic layer deposition. In the examples, if the raw material containing metal and conductive oxide is metal and conductive oxide, one or more combinations of film deposition methods such as co-evaporation, sputtering, and atomic layer deposition can be used.

[0102] Of course, a composite electrode manufactured by the method for manufacturing a composite electrode according to the embodiment of this application is the composite electrode according to the embodiment of this application described above.

[0103] Therefore, the method for manufacturing composite electrodes according to the embodiments of this application effectively achieves metal doping of a conductive oxide substrate, thereby imparting excellent chemical and conductive properties to the manufactured composite electrodes. Furthermore, the manufacturing process is easy to control, ensuring mass production of composite electrodes and guaranteeing the stability of the composite electrodes' performance, including quality.

[0104] The composite electrodes according to the embodiments of this application described above, and the composite electrodes manufactured by the method for manufacturing the composite electrodes, can be applied to perovskite solar cells, but of course, they can also be applied to other products. Based on the performance of the composite electrodes according to the embodiments of this application described above, perovskite solar cells and methods for manufacturing the same are further provided in the embodiments of this application described later. Perovskite solar cells

[0105] In a third embodiment, the embodiments of the present application provide a perovskite solar cell (hereinafter simply referred to as a solar cell). In some embodiments, the structure of the solar cell according to the embodiments of the present application includes a transparent electrode 1 and a back electrode 5 arranged opposite each other, as shown in Figure 4, and further includes a first transport layer 2, a perovskite absorption layer 3, and a second transport layer 4 between the transparent electrode 1 and the back electrode 5. That is, the transparent electrode 1, the first transport layer 2, the perovskite absorption layer 3, the second transport layer 4, and the back electrode 5 are stacked in order in the direction from the transparent electrode 1 to the back electrode 5.

[0106] The transparent electrode 1 and back electrode 5 included in the solar cell according to the embodiment of this application function as conductive members. One of the first transport layer 2 and the second transport layer 4 is a hole transport layer, and the other is an electron transport layer. The back electrode 5 includes a composite electrode according to the embodiment of this application described above. The fact that they are arranged in a stacked configuration should be understood as a coupling method for each layer of the solar cell, such as stack coupling.

[0107] Therefore, the back electrode 5 included in the solar cell according to the embodiment of this application has excellent chemical stability and operational stability, and high conductivity, which improves the photoelectric performance of the perovskite solar cell and stabilizes its photoelectric performance. Furthermore, since the composite electrode according to the embodiment of this application can also achieve light transmittance such as semi-transparency, the back electrode 5 can achieve even greater light transmittance such as semi-transparency, thereby expanding the application range of the solar cell according to the embodiment of this application.

[0108] Since the back electrode 5 includes a composite electrode according to the above-described embodiment of this application, in some embodiments, the back electrode 5 may have a structure as shown in Figure 1, i.e., the contained metal is uniformly doped into a conductive oxide matrix 51 formed by a conductive oxide substrate. In some embodiments, the back electrode 5 may have a structure as shown in Figure 2, i.e., the contained metal is doped in such a way that it forms a gradient in the conductive oxide matrix 51 formed by a conductive oxide substrate.

[0109] When the back electrode 5 has a metal gradient doped structure as shown in Figures 2 and 3, in some embodiments, in the thickness direction of the composite electrode 5', the side (surface) of the composite electrode 5' with a lower metal content is close to the second transport layer 4, and is provided laminated with the second transport layer 4, for example. Specifically, when the back electrode 5 has the structure of the composite electrode 5' according to the above embodiment of this application as shown in Figure 3, and specifically includes a first metal doped layer 53, a second metal doped layer 54, and a third metal doped layer 55, the first metal doped layer 53 is close to the second transport layer 4, and specifically, as shown in Figure 5, is provided laminated with the surface of the second transport layer 4. In this way, the back electrode 5 not only has high chemical stability but also excellent conductivity, so that excitons transported from the second transport layer 4 are collected more effectively, thereby further improving the photoelectric conversion performance and stability of the photoelectric conversion performance of the perovskite solar cell.

[0110] Of course, if the back electrode 5 has a metal gradient doped structure as shown in Figures 2 and 3, the side with a higher metal content, for example, the third metal doped layer 55 as shown in Figure 3, may be placed closer to the second transport layer 4. In this way, the role of the composite electrode according to the above embodiment of this application can be fully utilized, while also reducing the movement of metal to the perovskite absorption layer 3, thereby improving the stability of the photoelectric conversion efficiency of the perovskite absorption layer 3.

[0111] The transparent electrode 1 included in the solar cell according to the embodiment of this application may be an electrode that allows light transmission. It should be understood that sunlight can pass through the transparent electrode 1 and reach the perovskite absorption layer 3.

[0112] In some embodiments, the transparent electrode 1 includes transparent conductive glass. Transparent conductive glass refers to a conductive material that can transmit light and collect electric charge. Transparent conductive glass (abbreviated as Transparent Conducting Oxide; TCO) is also called transparent conductive oxide coated glass, and is obtained by uniformly coating the surface of a glass plate with a transparent conductive oxide thin film by a physical or chemical coating method. The film material mainly includes oxides of In, Sn, Zn, and Cd, as well as composite multi-component oxide thin film materials thereof. By using transparent conductive glass for the transparent electrode 1, it is ensured that the transparent conductive glass conducts electricity while the solar cell sufficiently absorbs sunlight and converts it into photoelectric energy, thereby increasing the photoelectric conversion efficiency of the solar cell according to the embodiments of this application.

[0113] In exemplary examples, transparent conductive glass may contain at least one of FTO, ITO, AZO, BZO, IZO, etc. FTO refers to a fluorine-doped tin(II) oxide (SnO2) film. ITO refers to an indium tin oxide film. AZO refers to an aluminum-doped zinc oxide (ZnO) film. BZO refers to a boron-doped zinc oxide (ZnO) film. IZO refers to an indium-doped zinc oxide (ZnO) film. Transparent conductive glass manufactured by providing the above light-transmitting conductive films on the surface of glass has high conductivity and light transmittance.

[0114] The first transport layer 2 and the second transport layer 4 included in the solar cell according to the embodiment of this application are used to transport photoexcitons generated in the perovskite absorption layer 3 from the perovskite absorption layer 3. In the embodiment, when the first transport layer 2 is an electron transport layer, the second transport layer 4 becomes a hole transport layer. In this case, the solar cell according to the embodiment of this application is a positive-structure solar cell. In the embodiment, when the first transport layer 2 is a hole transport layer, the second transport layer 4 becomes an electron transport layer. In this case, the solar cell according to the embodiment of this application is an inverse-structure solar cell.

[0115] The hole transport layer refers to a component for collecting and transporting holes. In the examples, the thickness of this hole transport layer may be 0.1 to 30 nm. In the exemplary examples, this thickness may typically be 0.1 nm, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, etc., but these are not the only limiting thicknesses.

[0116] The hole transport layer contains a hole transport material. The hole transport material may be an organic hole transport material or an inorganic hole transport material. In the examples, this hole transport material may include at least one of the following: the material shown in M, a derivative of the material shown in M, a doped and modified material of the material shown in M, and a passivated material of the material shown in M. Here, M is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly-3-hexylthiophene (P3HT), triptycene-cored triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamine)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS), polythiophene, nickel oxide (NiO x ), may contain at least one of molybdenum oxide (MoO3), cuprous iodide (CuI), and cuprous oxide (CuO).

[0117] With these hole transport layer thicknesses and hole transport materials, the collection and transport of holes generated by photoexcitation of the perovskite absorption layer 3 are efficient. When the second transport layer 4 is a hole transport layer, these hole transport materials can be relatively matched to the energy levels of the back electrode 5, which is more advantageous for hole transport and collection.

[0118] An electron transport layer refers to a component used to extract and transport electrons. The thickness of the electron transport layer may be 10 to 80 nm. In illustrative examples, this thickness may typically be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, etc., but these are not the only limiting thicknesses.

[0119] In an embodiment, the electron transport material included in the electron transport layer may include at least one of the materials shown in N below, derivatives of the materials shown in N, materials obtained by doping and modifying the materials shown in N, and materials obtained by passivation treatment of the materials shown in N. Here, N includes at least one of methyl [6,6]-phenyl C61 butyrate (PC61BM), methyl [6,6]-phenyl C71 butyrate (PC71BM), fullerene C60 (C60), fullerene C70 (C70), stannic oxide (SnO2), and zinc oxide (ZnO).

[0120] For the thickness of these electron transport layers and the electron transport material, the collection and transport of electrons generated by photoexcitation of the perovskite light absorption layer 3 are good. When the second transport layer 4 is an electron transport layer, these electron transport materials can be relatively aligned according to the energy level of the back electrode 5, which is advantageous for electron transport and collection.

[0121] The perovskite light absorption layer 3 included in the solar cell according to the embodiment of the present application functions as a light absorption functional layer and includes a perovskite material. This perovskite material may be the perovskite material in the current perovskite light absorption layer. In some embodiments, this perovskite material may include a perovskite with the chemical formula ABX3 or A2CDX6. Here, A may include at least one of an inorganic cation and an organic cation. In an exemplary example, A is CH3NH3 + , HC(NH2)2 + , Li + , Na + , K + , Rb + , and Cs + and may include at least one of them.

[0122] B may include at least one of an inorganic cation and an organic cation. In an exemplary example, B is Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+Ba 2+ Zn 2+ , Ge 2+ Fe 2+ Co 2+ , and Ni 2+ It may include at least one of the following.

[0123] C may comprise at least one of an inorganic cation and an organic cation. In the exemplary example, C is Ag + It may include.

[0124] D may comprise at least one of inorganic and organic cations. In an exemplary example, D is Bi 3+ Sb 3+ , and In 3+ It may include at least one of the following.

[0125] X may contain at least one inorganic anion and an organic anion. In an exemplary example, X is Cl - , Br - , I - , and SCN - It may include at least one of the following.

[0126] Based on the above ABX3 or A2CDX6 perovskite, in exemplary examples, this perovskite is CH3NH3PbI3 (MAPbI3), CH(NH2)2PbI3 (FAPbI3), Cs 0.05 (Fa 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 )3(CsFAMA), CsPbI3, CsPbI2Br, and CsPbIBr2 may include at least one of these.

[0127] The perovskite material described above has a relatively strong absorption capacity for sunlight, and can effectively generate, separate, and transport photoexcitons. Furthermore, defects in the perovskite absorption layer 3 formed by depositing the perovskite material can be kept relatively low. Therefore, the perovskite material described above has relatively high absorption energy and relatively high stability.

[0128] In one embodiment, by selecting the type of perovskite material, the band gap of the perovskite absorption layer 3 in each of the above embodiments can be set to 1.20 to 2.30 eV, or selectively to 1.5 to 1.7 eV. In the exemplary examples, this band gap may typically be 1.20 eV, 1.30 eV, 1.40 eV, 1.50 eV, 1.60 eV, 1.70 eV, 1.80 eV, 1.90 eV, 2.00 eV, 2.10 eV, 2.20 eV, 2.30 eV, etc., but these are not the only limiting band gaps.

[0129] By further adjusting and controlling the bandgap of the perovskite absorption layer 3, the absorption capacity of the perovskite absorption layer 3 for sunlight can be improved, thereby increasing the photoelectric conversion efficiency of the solar cell. In addition, the passivation layer 5 can improve the stability of the photoelectric conversion efficiency of the solar cell.

[0130] In one embodiment, the thickness of the perovskite absorption layer 3 in each of the above embodiments may be 300 to 1000 nm, and moreover, 400 to 700 nm. In exemplary examples, this thickness may typically be 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, etc., but these are not the only limiting thicknesses.

[0131] By further adjusting and controlling the thickness of the perovskite absorption layer 3, the light absorption capacity of the perovskite absorption layer 3 can be further improved, thereby improving the photoelectric conversion efficiency and stability of the photoelectric conversion efficiency of the solar cell. Of course, the thickness of the perovskite absorption layer 3 may be in a range of other thicknesses.

[0132] In the examples, the perovskite absorption layer 3 according to each of the above examples further includes quantum dots in addition to the perovskite material. By doping the perovskite absorption layer 3 with quantum dots, the spectral range of sunlight absorption by the perovskite absorption layer 3 can be expanded and the absorption capacity of the perovskite absorption layer 3 can be improved. Furthermore, a synergistic effect with the perovskite material can be achieved to reduce defects in the perovskite absorption layer 3 and improve the photoelectric conversion efficiency of the solar cell.

[0133] These quantum dots may be uniformly doped into the perovskite absorption layer 3, for example, forming a uniform mixture of quantum dots and perovskite material. Of course, these quantum dots may also be non-uniformly doped into the perovskite absorption layer 3. In the embodiment, the doping concentration of quantum dots in the perovskite absorption layer 3 is higher on the side closer to the sunlight incident surface than on the other side. By controlling the doping concentration of quantum dots on one side of the perovskite absorption layer 3 facing sunlight to be higher than the doping concentration of quantum dots on the other side of the perovskite absorption layer 3, the light absorption capability of the perovskite absorption layer 3 is further improved, defects in the perovskite absorption layer 3 are reduced, and the photoelectric conversion efficiency of the solar cell according to the embodiment of this application is further increased.

[0134] In the examples, the quantum dot may have a band gap smaller than the band gap of the perovskite. In the examples, the difference between the band gap of the quantum dot and the band gap of the perovskite may be 0.05 to 0.4 eV, selectively 0.1 to 0.4 eV, and further 0.1 to 0.35 eV. In the exemplary examples, for example, typically 0.05 eV, 0.1 eV, 0.15 eV, 0.2 eV, 0.25 eV, 0.3 eV, 0.35 eV, 0.4 eV, etc., but these are not the only limiting band gap differences. In the examples, the band gap of the quantum dot may be 1.0 to 1.6 eV, selectively 1.0 to 1.55 eV, and selectively 1.2 to 1.3 eV. In the illustrative examples, the band gap of a type A quantum dot may typically be, for example, 1 eV, 1.1 eV, 1.2 eV, 1.3 eV, 1.4 eV, 1.5 eV, 1.55 eV, 1.6 eV, etc., but these are not the only limited band gaps.

[0135] By selecting quantum dots with this band gap, the absorption capacity of the perovskite absorption layer 3 for long-wavelength sunlight can be effectively enhanced. The band gap of a quantum dot is also called the energy gap of a quantum dot, and thus the band gap of a perovskite is also called the energy gap of a perovskite.

[0136] In the examples, the ratio of the molar content of quantum dots to the molar content of perovskite may be 0.01% to 2%, and selectively 0.05% to 0.5%. In the exemplary examples, typically the ratio may be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.5%, 1.8%, 2%, etc., but these are not the only limited doped molar content. By adjusting and controlling the amount of quantum doping in the perovskite absorption layer 3, the light absorption capacity of the perovskite absorption layer 3 can be improved, defects in the perovskite absorption layer 3 can be reduced, and the photoelectric conversion efficiency of the solar cell can be increased.

[0137] In exemplary examples, the quantum dots may include at least one of modified or unmodified cadmium telluride (1.45 eV), modified or unmodified molybdenum selenide (MoSe2, 1.3 eV), modified or unmodified copper-indium-gallium-selenium (Ga adjustable from 1.04 to 1.68 eV), modified or unmodified copper-indium-sulfur (1.5 eV), and modified or unmodified rhenium disulfide (ReS2, 1.5 eV). Here, the modified quantum dots refer to quantum dots having a related modifying group on their surface, for example, at least one of a thioglycolic acid group, an aminoacetic acid group, and a cyanopropionic acid group, but are not limited to these. These quantum dots have a narrow band gap and can effectively absorb light in the non-visible light region, especially long-wavelength light, thereby improving the absorption capacity of the perovskite absorption layer 3, reducing or repairing defects in the perovskite absorption layer 3, further increasing the photoelectric conversion efficiency of the perovskite absorption layer 3, and reducing heat transfer and concentration of sunlight to the perovskite absorption layer 3, thereby improving the stability of the photoelectric conversion efficiency of the perovskite absorption layer 3. Method for manufacturing perovskite solar cells

[0138] In a fourth aspect, embodiments of the present application provide a method for manufacturing a perovskite solar cell (hereinafter simply referred to as a solar cell manufacturing method). Referring to Figure 3, the solar cell manufacturing method according to embodiments of the present application includes the following steps. S20: The first transport layer 2, the perovskite absorption layer 3, and the second transport layer 4 are sequentially laminated and formed on the surface of the transparent electrode 1 in the direction opposite to that of the transparent electrode surface. S30: A film deposition process is performed on the surface of the second transport layer 4 opposite to the perovskite absorption layer 3 to manufacture the back surface electrode 5.

[0139] The back electrode 5 manufactured in step S30 of the solar cell manufacturing method according to the embodiment of this application is a composite electrode according to the embodiment of this application described above. Therefore, the back electrode 5 included in the solar cell manufactured by the solar cell manufacturing method according to the embodiment of this application has the high stability and conductivity performance described above, or furthermore, high light transmittance such as semi-transparency. As a result, the manufactured solar cell will have a high and stable photoelectric conversion efficiency, and its range of application will be expanded. In addition, the conditions of the manufacturing method are easy to control, and the performance stability and efficiency of the manufactured solar cell can be improved.

[0140] Process S20: To increase the bonding strength between the first transport layer 2 and the transparent electrode 1, in the examples, the transparent electrode 1 may be pretreated before it forms the first transport layer 2. In exemplary examples, this pretreatment includes at least one of laser etching, plasma treatment, ultraviolet treatment, ozone treatment, etc. In exemplary examples, if the transparent electrode 1 is transparent conductive glass, this pretreatment includes laser etching of the transparent conductive glass, then ultrasonically cleaning the laser-etched transparent conductive glass with solvents such as water, acetone, and isopropyl alcohol in sequence, further drying the solvent on the transparent conductive glass with a nitrogen gun, and finally further cleaning the transparent conductive glass in an ultraviolet ozone machine.

[0141] The method for forming the first transport layer 2 and the second transport layer 4 on the transparent electrode 1 can be selected according to the types of materials used for the first transport layer 2 and the second transport layer 4. For example, if the first transport layer 2 is an electron transport layer and the second transport layer 4 is a hole transport layer, the material of the electron transport layer included in the solar cell according to the above-described embodiment of this application may be deposited on the surface of the transparent electrode 1, and the material of the hole transport layer included in the solar cell according to the above-described embodiment of this application may be deposited on the surface of the perovskite absorption layer 3. Here, the film deposition process includes, but is not limited to, one of spin coating, knife coating, and slit coating, and further includes post-treatment performed after one of spin coating, knife coating, and slit coating, and this post-treatment includes, but is not limited to, vacuum drying and annealing.

[0142] The method for forming the perovskite absorption layer 3 can be selected according to the type of material of the perovskite absorption layer 3. In some embodiments, a corresponding film deposition method can be selected according to the material of the perovskite absorption layer 3 included in the solar cell according to the embodiments of this application described above, and these perovskite material precursors can be subjected to film deposition. For example, after preparing the perovskite precursor in solution, a film deposition treatment can be performed on the surface of the first transport layer 2, and then an annealing treatment can be performed to form the perovskite absorption layer 3.

[0143] In some embodiments, when the perovskite absorption layer 3 contains the quantum dots described above, the method for forming the perovskite absorption layer 3 includes the following steps. S21: Prepare a mixed solution of quantum dots and perovskite precursors. S22: On the surface of the first transport layer opposite to the transparent electrode, the mixed solution is subjected to a film deposition treatment to obtain a perovskite precursor film layer. S23: The perovskite precursor film layer is subjected to annealing to obtain a perovskite thin film.

[0144] Here, the quantum dot in step S21 may be the type of quantum dot in the case where the perovskite absorption layer 3 of the solar cell according to the above-described embodiment of this application contains quantum dots, and the perovskite precursor is also the precursor material of the perovskite contained in the perovskite absorption layer 3 of the solar cell according to the above-described embodiment of this application. The mixing ratio of quantum dots and perovskite precursor can be converted to a ratio of quantum dots to perovskite precursor according to the ratio of the content of quantum dots to the content of perovskite contained in the perovskite absorption layer 3 of the solar cell according to the above-described embodiment of this application, where quantum dots are contained.

[0145] The solvent in the mixed solution may be a general solvent used when forming a perovskite absorption layer, and the concentration of the mixed solution can be adjusted according to the specific film formation method.

[0146] The film formation process in step S22 involves forming a perovskite precursor film on the substrate by, for example, applying a film formation process to the surface of the first transport layer 2 in order to form a film layer of the mixed solution on the substrate. In the examples, this film formation process may include one of spin coating, knife coating, and slit coating. Of course, it further includes drying the wet film after forming the wet film to remove the solvent.

[0147] The annealing process in step S23 is performed to form a perovskite layer using the perovskite precursor film layer formed in step S22. During this annealing process, quantum dots can be doped in situ into the film layer formed by the generated perovskite.

[0148] By preparing a mixed solution of quantum dots and a perovskite precursor and fabricating a perovskite absorption layer, defects in the perovskite absorption layer 3 can be effectively reduced, improving the absorption capacity and photoexciton separation and transport capabilities of the perovskite absorption layer 3.

[0149] The back electrode 5 in step S30 can be manufactured according to the method for manufacturing a composite electrode in the embodiment of this application described above. Due to space limitations, the method for manufacturing the back electrode 5 in step S30 will not be described again here. In this case, the structure of the back electrode 5 in step S30 may be as shown in Figures 1 and 2, and includes a conductive oxide matrix 51 formed from a conductive oxide substrate and a metal 52 doped into the conductive oxide matrix 51. Electrical equipment

[0150] In a fifth embodiment, embodiments of the present application further provide an electrical device. The electrical device according to embodiments of the present application includes a power supply unit or an energy storage unit, and may further include other auxiliary members and necessary members. This power supply unit or energy storage unit includes a solar cell according to embodiments of the present application described above. The number of solar cells included in this power supply unit or energy storage unit may be one or more. If there are multiple solar cells, the multiple solar cells can form a battery module. Since the electrical device according to embodiments of the present application includes a solar cell according to embodiments of the present application described above, sunlight can be converted into electrical energy relatively efficiently and effectively, and the operational stability of the power supply unit or energy storage unit can be improved.

[0151] The electrical device may, but is not limited to, mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), trains, ships and satellites, energy storage systems, etc. Energy storage devices

[0152] In a sixth embodiment, the embodiment of the present application further provides an energy storage device that includes an energy storage unit and, of course, may further include other auxiliary members and necessary members. This energy storage unit includes a solar cell according to the embodiment of the present application described above. The number of solar cells included in this power supply unit or energy storage unit may be one or more. If there are multiple solar cells, the multiple solar cells can form a battery module. Since the energy storage device according to the embodiment of the present application includes a solar cell according to the embodiment of the present application described above, it can effectively convert sunlight into electrical energy and store it with stable conversion efficiency. Examples

[0153] Examples of the present application are described below. The examples described below are illustrative and are for interpretive purposes only, and should not be understood as limiting this application. Unless otherwise specified in the examples, specific techniques or conditions are followed in accordance with the techniques or conditions or product specifications described in the literature in the art. Unless otherwise specified, the reagents or equipment used are common commercially available products.

[0154] Example 1: This embodiment provides a solar cell comprising a transparent electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a passivation layer, and a back electrode, which are sequentially stacked. The transparent electrode material was ITO conductive glass, the hole transport layer material was PTAA with a thickness of 20 nm, the perovskite absorption layer material was CsFAMA with a thickness of 600 nm, and the electron transport layer material was PCBM with a thickness of 60 nm. The back electrode contained a tin oxide-based film and metallic aluminum doped into the tin oxide-based film, with a thickness of 80 nm. The volume ratio of metallic aluminum to (metallic aluminum + tin oxide) was 3%.

[0155] The manufacturing method for solar cells included the following steps: Twenty S1:2.0*2.0cm ITO conductive glass sheets were prepared, and 0.35cm of ITO was removed from each end by laser etching, exposing the glass substrate. The etched ITO conductive glass sheets were ultrasonically cleaned several times in sequence with water, acetone, and isopropanol. The solvents on the ITO conductive glass sheets were dried with a nitrogen gun, and then further cleaned in an ultraviolet ozone machine. S2: A 2 mg / mL poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) organic hole transport layer was spin-coated onto an ITO substrate treated with UV ozone at a speed of 5000 rpm / s, and then annealed on a hot plate at 100°C for 10 minutes. S3: On the surface of the hole transport layer, Cs 0.05 (Fa 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 A perovskite precursor solution of 3(CsFAMA) was subjected to a spin coating process at a rate of 5000 rpm / s to form a perovskite precursor film layer. Subsequently, the perovskite precursor film layer was annealed at 100°C for 30 minutes and cooled to room temperature to form a CsFAMA perovskite absorption layer. S4: An electron transport layer of [6,6]-phenyl C61-methyl butyrate (PCBM) was spin-coated onto the surface of the perovskite absorption layer at a spin-coating speed of 1500 rpm / s, and then annealed at 100°C for 10 minutes. S5: Using a sputtering apparatus, tin oxide was sputtered at a rate of 0.1 A / s until a thickness of 20 nm was achieved. Then, while sputtering tin oxide at a rate of 1 A / s, metallic aluminum was sputtered at a rate of 0.02 A / s until a total thickness of 40 nm was achieved. After that, while sputtering tin oxide at a rate of 5 A / s, metallic aluminum was sputtered at a rate of 0.25 A / s until a total thickness of 80 nm was achieved, and finally, a back electrode of tin oxide doped with metallic aluminum was formed.

[0156] Example 2: This embodiment provides a solar cell similar to the solar cell in Example 1, except that the content of metallic aluminum in the back electrode was adjusted to 1% aluminum and (metallic aluminum + tin oxide) by controlling the sputtering speed. S5: Using a sputtering apparatus, tin oxide was sputtered at a rate of 0.1 A / s until a thickness of 20 nm was achieved. Then, tin oxide was sputtered at a rate of 1 A / s until a thickness of 40 nm was achieved. Subsequently, while sputtering tin oxide at a rate of 5 A / s, metallic aluminum was sputtered at a rate of 0.15 A / s until a total thickness of 80 nm was achieved. Finally, a back electrode of tin oxide doped with metallic aluminum was formed.

[0157] Example 3: This embodiment provides a solar cell similar to the solar cell in Example 1, except that the content of metallic aluminum in the back electrode was adjusted to 5% aluminum and (metallic aluminum + tin oxide) by controlling the sputtering rate. S5: Using a sputtering apparatus, tin oxide was sputtered at a rate of 0.1 A / s until a thickness of 20 nm was achieved. Then, while sputtering tin oxide at a rate of 1 A / s, metallic aluminum was sputtered at a rate of 0.05 A / s until a total thickness of 40 nm was achieved. After that, while sputtering tin oxide at a rate of 5 A / s, metallic aluminum was sputtered at a rate of 0.35 A / s until a total thickness of 80 nm was achieved, and finally, a back electrode of tin oxide doped with metallic aluminum was formed.

[0158] Example 4: This embodiment provides a solar cell similar to the solar cell in Example 1, except that the metallic aluminum content in the back electrode was adjusted from 3% in Example 1 to 8%, as shown in Table 1.

[0159] Example 5: This embodiment provides a solar cell similar to the solar cell in Example 1, except that the metallic aluminum content in the back electrode was adjusted from 3% in Example 1 to 9%, as shown in Table 1.

[0160] Example 6: This embodiment provides a solar cell similar to the solar cell in Example 1, except that the perovskite absorption layer is doped with cadmium quantum dots, and the molar amount of cadmium telluride quantum dots is 0.05% of the molar amount of perovskite CsFAMA.

[0161] The method for manufacturing solar cells includes the following steps: Steps S1 to S2 and S4 to S5 were the same as steps S1 to S2 and S4 to S5 in Example 1. The difference was in step S3. Step S3 in this example was as follows: S3: Fabrication of the perovskite absorption layer: S31: Cadmium Telluride Quantum Dots and Cs 0.05 (Fa 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 A perovskite precursor of 3(CsFAMA) was prepared as a mixed solution in which the molar amount of cadmium telluride quantum dots was 0.05% of the molar amount of perovskite CsFAMA. S32: On the surface of the hole transport layer, a perovskite precursor film layer was formed by applying a film deposition treatment to this mixed solution at a spin coating speed of 5000 rpm / s. S33: This perovskite precursor film layer was annealed at 100°C for 30 minutes and cooled to room temperature to form a perovskite absorption layer.

[0162] Example 7: This embodiment provides a solar cell similar to the solar cell in Example 1, except that metallic thallium is used instead of metallic aluminum in the back electrode.

[0163] Example 8: This embodiment provides a solar cell similar to the solar cell in Example 1, except that metallic gold is used instead of metallic aluminum in the back electrode.

[0164] Example 9: This embodiment provides a solar cell similar to the solar cell in Example 1, except that metallic zinc is used instead of metallic aluminum in the back electrode.

[0165] Example 10: This embodiment provides a solar cell similar to the solar cell in Example 1, except that, compared to the solar cell in Example 1, both metallic aluminum and gold are used instead of metallic aluminum in the back electrode, where the volume ratio of aluminum to gold is 1:1.

[0166] Example 11: This embodiment provides a solar cell similar to the solar cell in Example 1, except that zinc oxide was used instead of tin oxide in the back electrode.

[0167] Example 12: This embodiment provides a solar cell similar to the solar cell in Example 1, except that a combination of tin oxide and zinc oxide is used instead of tin oxide in the back electrode, where the volume ratio of tin oxide to zinc oxide is 1:1, and the volume ratio of aluminum to gold is 1:1.

[0168] Example 13: This embodiment provides a solar cell similar to the solar cell in Example 1, except that, compared to the solar cell in Example 1, a combination of tin oxide, copper oxide, and indium oxide is used instead of tin oxide in the back electrode, and a combination of metallic gallium, indium, and thallium is used instead of metallic aluminum. Here, the volume ratio of tin oxide, copper oxide, and indium oxide is 1:1:1, and the volume ratio of gallium, indium, and thallium is 1:1:1.

[0169] Example 14; This embodiment provides a solar cell similar to the solar cell in Example 1, except that it uses indium-doped tin oxide (purchased target material directly sputtered) as the back electrode material.

[0170] Comparative Example 1: This embodiment provides a solar cell similar to the solar cell in Example 1, except that copper was used as the back electrode.

[0171] Comparative Example 2: This embodiment provides a solar cell similar to the solar cell in Example 1, except that it uses tin oxide as the material for the back electrode (i.e., does not contain metallic aluminum).

[0172] Tests and results of performance-related aspects of solar cells: To verify the inventiveness of the solar cells according to the embodiments of this application, the solar cells provided in Examples 1 to 14 and the solar cells provided in Comparative Examples 1 to 2 were tested, including the relevant performance shown in Table 1.

[0173] Photoelectric conversion efficiency (PCE) of perovskite solar cells 初期 (Notation) Exam: Standard simulated sunlight (AM1.5G, 100mW / cm²) 2 The battery performance was tested under irradiation of ) and an IV curve was obtained. From the IV curve and the data fed back from the test equipment, the short-circuit current Jsc (unit: mA / cm) was determined.2 The open-circuit voltage Voc (unit: V), maximum optical output current Jmpp (unit: mA), and maximum optical output voltage Vmpp (unit: V) were obtained. The curve factor FF (unit: %) of the battery was calculated using the formula FF = Jsc × Voc / (Jmpp × Vmpp). The photoelectric conversion efficiency PCE (unit: %) of the battery was calculated using the formula PCE = Jsc × Voc × FF / Pw. Pw represents the input power, and its unit was mW.

[0174] Stability testing of perovskite solar cells: The manufactured battery devices were subjected to accelerated testing in a drying chamber at approximately 5% humidity, placed on a hot plate at 65°C. After 10 days, the device efficiency (PCE) was measured. 10 (as indicated) Test again and improve PCE efficiency 10 and initial efficiency PCE 初期 Ratio (PCE 10 / PCE 初期 ) is calculated, and here this initial efficiency is the "Photoelectric conversion efficiency (PCE) of the perovskite solar cell" as described above. 初期 The efficiency was obtained by conducting tests according to the "Test" section (indicated as "Test"). The specific experimental results are shown in Table 2.

[0175] Following the process described above, the perovskite solar cells obtained in the above examples and comparative examples were tested, and the specific values ​​are shown in Table 1. [Table 1]

[0176] As can be seen from Table 1, the initial efficiency of the devices provided in Examples 1-14 is clearly higher than that of Comparative Example 2, indicating that metal doping of the metal oxide effectively improved the extraction and transport of internal carriers. Furthermore, the PCE of Examples 1-14 10 / PCE 初期 The value is the PCE of Comparative Example 2. 10 / PCE 初期This value is significantly higher than the previous value, indicating a clear improvement in the stability of the composite electrode containing metal-doped oxides.

[0177] The initial efficiency of the devices provided in Examples 1-14 is lower than that of Comparative Example 1, but the PCE of Examples 1-14 10 / PCE 初期 The value is PCE for Comparative Example 1 10 / PCE 初期 This value is significantly higher than the previous value, indicating that the stability of the composite electrode containing metal-doped oxide was clearly higher than that of the pure metal electrode.

[0178] The batteries of Examples 1, 3, and 6 exhibit superior overall performance. In these cases, the manufactured perovskite solar cells demonstrate superior efficiency and stability, resulting in overall superior performance.

[0179] Further comparison of Examples 1-14 revealed that the efficiencies of the devices provided in Examples 1-13 were all higher than those of the device using uniformly indium-doped tin oxide in Example 14. This indicates that gradient doping, appropriate doping ratios, and doping of multiple metal compositions to multiple oxide compositions can clearly improve carrier transport between device layers.

[0180] Further comparison of Examples 1-5 revealed that in the devices provided in Examples 1-3, the initial efficiency of the devices increased as the amount of metal doping increased. However, as the amount of metal doping increased further, the initial efficiency of the devices actually decreased. For example, the initial efficiency of the device in Example 4 was lower than that of the device in Example 3, and the initial efficiency of the device in Example 5 was lower than that of the device in Example 4. For this reason, the volume content of the metal doped into the composite electrode was kept below 8%, and selectively within the range of 0.5-5%.

[0181] Finally, it should be noted that the above embodiments are used solely to illustrate the technical solutions of this application and are not limiting. While this application has been described in detail with reference to the embodiments described above, those skilled in the art should understand that they may modify the technical solutions described in the embodiments described above, or make equivalent substitutions to some or all of their technical features, and that such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application, and will all be included within the scope of the claims and specification of this application. In particular, any technical features described in each embodiment can be combined in any way, provided there is no structural inconsistency. This application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the claims.

Claims

1. A composite electrode comprising a conductive oxide substrate and a metal, wherein the metal is doped into the conductive oxide substrate.

2. The composite electrode according to claim 1, wherein the volume content of the metal doped into the composite electrode is 8% or less, and selectively 0.5 to 5%.

3. The composite electrode according to claim 1, wherein the metal comprises at least one metal from among the Group IIIA elements, Group IB elements, and Group IIB elements, the Group IIIA element comprises at least one from among aluminum, gallium, indium, and thallium, the Group IB element comprises at least one from among copper, gold, and silver, and the Group IIB element comprises at least one from among zinc and cadmium.

4. The composite electrode according to claim 1, wherein the metal is distributed in the thickness direction of the composite electrode such that it forms a gradient in the composite electrode.

5. The composite electrode according to claim 4, wherein the composite electrode includes a first metal-doped layer, a second metal-doped layer, and a third metal-doped layer, and the first metal-doped layer, the second metal-doped layer, and the third metal-doped layer are provided in order in the thickness direction of the composite electrode.

6. The volume content of the metal in the first metal-doped layer is 0%, the volume content of the metal in the second metal-doped layer is 0.1% to 2%, the volume content of the metal in the third metal-doped layer is 2% to 8%, and / or The composite electrode according to claim 5, wherein the ratio of the thicknesses of the first metal-doped layer, the second metal-doped layer, and the third metal-doped layer is 1:(1-3):(1-5).

7. The composite electrode according to claim 1, wherein the conductive oxide substrate contains a metal oxide.

8. The composite electrode according to claim 7, wherein the metal element contained in the metal oxide includes at least one of the group IIIA elements, group IVA elements, group IB elements, and group IIB elements, the group IIIA element includes at least one of aluminum, gallium, indium, and thallium, the group IVA element includes tin, the group IB element includes at least one of copper, gold, and silver, and the group IIB element includes at least one of zinc and cadmium.

9. The composite electrode according to claim 1, wherein the metal comprises four elements: aluminum, gallium, indium, and thallium, and the conductive oxide comprises tin oxide.

10. The composite electrode according to claim 1, comprising at least one of the following (1) to (3): (1) The thickness is 60 nm to 200 nm, and selectively 80 to 100 nm. (2) The work function values ​​are between 4 eV and 5.5 eV, and selectively between 4.26 and 5.20 eV. (3) The sheet resistance is 5Ω to 15Ω, and selectively 7Ω to 11Ω.

11. A method for manufacturing a composite electrode, comprising the step of forming a composite electrode by applying a film deposition treatment to a raw material containing a metal and a conductive oxide on the surface of a matrix.

12. The manufacturing method according to claim 11, wherein the method for the step of applying a film deposition treatment to a raw material containing the metal and a conductive oxide on the surface of the matrix includes at least one of magnetron sputtering, co-evaporation, atomic layer deposition, and ion plating.

13. It includes a transparent electrode and a back electrode provided opposite each other, and further includes a first transport layer, a perovskite absorption layer, and a second transport layer provided between the transparent electrode and the back electrode, sequentially laminated in the direction from the transparent electrode to the back electrode. The solar cell wherein the back electrode includes a composite electrode according to any one of claims 1 to 10.

14. The solar cell according to claim 13, wherein the metal contained in the composite electrode is distributed in the thickness direction of the composite electrode so as to form a gradient in the composite electrode, and the side of the composite electrode with a lower metal content is stacked toward the second transport layer.

15. The second transport layer is a hole transport layer or an electron transport layer. The hole transport material contained in the hole transport layer includes at least one of the following: the material shown in M, a derivative of the material shown in M, a material obtained by doping and modifying the material shown in M, and a material obtained by passivating the material shown in M. The aforementioned M includes at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly-3-hexylthiophene, triptycene-cored triphenylamine, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-phenylamine)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), polythiophene, nickel oxide, molybdenum oxide, cuprous iodide, and cuprous oxide. The solar cell according to claim 13, wherein the thickness of the hole transport layer is 0.1 nm to 30 nm.

16. The electron transport material contained in the electron transport layer includes at least one of the following: the material shown in N, a derivative of the material shown in N, a material obtained by doping and modifying the material shown in N, and a material obtained by passivating the material shown in N. The aforementioned N comprises at least one of [6,6]-phenylC61methyl butyrate, [6,6]-phenylC71methyl butyrate, fullerene C60, fullerene C70, stannic oxide, and zinc oxide. The solar cell according to claim 15, wherein the thickness of the electron transport layer is 10 nm to 80 nm.

17. The perovskite absorption layer is further doped with quantum dots, and / or The solar cell according to claim 13, wherein the thickness of the perovskite absorption layer is 400 nm to 1000 nm.

18. A step of sequentially laminating a first transport layer, a perovskite absorption layer, and a second transport layer on the surface of the transparent electrode in a direction opposite to the surface of the transparent electrode, A method for manufacturing a solar cell, comprising the step of forming a composite electrode by performing a film deposition treatment on the surface of the second transport layer opposite to the perovskite absorption layer using the manufacturing method described in claim 11 or 12.

19. The perovskite absorption layer contains quantum dots, and the method for forming the perovskite absorption layer is: A step of preparing a mixed solution of quantum dots and perovskite precursors, A step of applying a first film formation treatment to the mixed solution on the surface of the first transport layer opposite to the transparent electrode to obtain a perovskite precursor film layer, The manufacturing method according to claim 18, comprising the step of annealing the perovskite precursor film layer to obtain the perovskite absorbance layer.

20. An electrical device comprising a power supply unit or an energy storage unit, wherein the power supply unit or energy storage unit includes a solar cell, and the solar cell includes the solar cell described in claim 13.

21. An energy storage device comprising an energy storage unit, wherein the energy storage unit comprises a solar cell, and the solar cell comprises the solar cell described in claim 13.

Images