Precursor, perovskite light-absorbing layer and manufacturing method, perovskite battery, power consumption device

Abstract

The present application provides a precursor, a perovskite light-absorbing layer, a manufacturing method thereof, a perovskite battery, and a power consumption device. The precursor is used to manufacture a perovskite light-absorbing layer and includes a perovskite precursor solution and an organic additive added to the perovskite precursor solution, where the organic additive includes a six-membered heterocyclic compound, and the heteroatom of the six-membered heterocyclic compound includes one or more of S, N, and Se. In this embodiment, an organic additive, specifically a six-membered heterocyclic compound, is added to the perovskite precursor solution to form a precursor for manufacturing a perovskite light-absorbing layer, which is used to control the quality of the formed perovskite light-absorbing layer and inhibit interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, thereby improving the interfacial stability between the perovskite light-absorbing layer and the carrier transport layer, thereby improving the photoelectric conversion efficiency and stability of perovskite batteries containing this perovskite light-absorbing layer and extending the service life of the perovskite battery.

Description

[Technical Field]

[0001] The present application relates to the field of battery technology, in particular to precursors, perovskite light-absorbing layers and manufacturing methods, perovskite batteries, and power-consuming devices. [Background technology]

[0002] Perovskite solar cells are cells that use perovskite materials as the light-absorbing layer material. Due to the significant performance advantages of perovskite materials, such as a high optical absorption coefficient, long carrier mobility, and a direct and controllable optical band gap, perovskite solar cells have attracted widespread attention and are developing rapidly. Currently, the highest photoelectric conversion efficiency (PCE) of the latest internationally certified perovskite solar cells has already reached 25.7%, demonstrating their great application value. Summary of the Invention [Problem to be solved by the invention]

[0003] The technical problem that the present application mainly solves is the problem that reactions tend to occur at the interface between the perovskite light-absorbing layer and the carrier transport layer. [Means for solving the problem]

[0004] First aspect: A precursor for use in the manufacture of a perovskite light absorbing layer, comprising: a perovskite precursor liquid; and an organic additive added to the perovskite precursor liquid; Here, the organic additive comprises a six-membered heterocyclic compound, and the heteroatom of the six-membered heterocyclic compound comprises one or more of S, N, and Se.

[0005] In this embodiment, an organic additive, specifically a six-membered heterocyclic compound, is added to the perovskite precursor solution to form a precursor for producing a perovskite light-absorbing layer, which is used to control the quality of the formed perovskite light-absorbing layer and inhibit interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, thereby improving the interfacial stability between the perovskite light-absorbing layer and the carrier transport layer, and improving the photoelectric conversion efficiency and stability of perovskite batteries containing this perovskite light-absorbing layer, and prolonging the service life of the perovskite battery.

[0006] In some embodiments, the perovskite precursor solution contains Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) Contains a precursor solution of PbI3.

[0007] In one or more embodiments of the present application, by employing the above-mentioned perovskite materials, the quality of the formed perovskite light-absorbing layer is relatively high, and the perovskite cell containing this perovskite light-absorbing layer has relatively high photoelectric conversion efficiency and stability.

[0008] In some embodiments, Pb in the perovskite precursor solution 2+ The concentration is 1M to 2M.

[0009] In one or more embodiments of the present application, any concentration of Pb in the perovskite precursor solution that can improve the quality of the formed perovskite light-absorbing layer is within the scope of protection of the present application. 2+ The concentration of may be 1M to 2M, and when a perovskite precursor solution within this concentration range is used to manufacture a perovskite light-absorbing layer, organic additives and the like can be uniformly dispersed therein, making the performance of the formed perovskite light-absorbing layer more uniform, which is advantageous for demonstrating the performance of the perovskite battery.

[0010] In some embodiments, the molar fraction of the organic additive to the perovskite precursor is between 0.1% and 10%.

[0011] In one or more embodiments of the present application, the molar fraction of any one of the organic additives and the perovskite precursor solution that can improve the quality of the formed perovskite light-absorbing layer is within the scope of protection of the present application. In one or more embodiments, when the molar fraction of the organic additive relative to the perovskite precursor solution is within the range of 0.1% to 10%, the formed perovskite light-absorbing layer has a relatively high quality, and interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer are effectively inhibited, thereby improving the performance of the perovskite battery.

[0012] In some embodiments, the six-membered heterocyclic compound comprises a -R(=O)2- functional group and a -N + and one or two of the functional groups, where R includes S and / or Se.

[0013] When the six-membered heterocyclic compound of one or more embodiments of the present application contains the above functional group, it has an advantageous effect of preventing the occurrence of interfacial reactions such as oxidation-reduction at the interface between the formed perovskite light-absorbing layer and the carrier transport layer. Specifically, this is due to the -R(=O)2- functional group and / or -N + This may be because the functional groups react with the ions of the precursor material in the perovskite precursor solution, controlling the crystallization process of the perovskite material and causing modifications at the interface between the formed perovskite light-absorbing layer and the carrier transport layer, thereby inhibiting interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, and improving the photoelectric conversion efficiency and stability of perovskite cells containing this perovskite light-absorbing layer.

[0014] In some embodiments, the six-membered heterocyclic compound is [ka] It includes one or more of the following.

[0015] In one or more embodiments of the present application, the organic additives can effectively control the formation of the perovskite light-absorbing layer, improve the quality of the formed perovskite light-absorbing layer, and enhance the photoelectric conversion efficiency and stability of the perovskite cell containing this perovskite light-absorbing layer.

[0016] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0017] In this example, the organic additive is provided and added to the perovskite precursor solution to form a perovskite light-absorbing layer with a layered structure, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell containing this perovskite light-absorbing layer.

[0018] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0019] This embodiment provides some organic additives to position the two-dimensional perovskite layer in the perovskite absorber layer formed by the precursor between the three-dimensional perovskite layer and the buried interface, and inhibits the occurrence of interfacial reactions between the perovskite absorber layer and the buried interface.

[0020] In some embodiments, the two-dimensional perovskite layer is located at a surface away from the buried interface B1 of the three-dimensional perovskite layer, and the organic additive is [ka] It includes one or more of the following.

[0021] This example provides some organic additives to position the two-dimensional perovskite layer in the perovskite light-absorbing layer formed by the precursor at a surface away from the buried interface of the three-dimensional perovskite layer, and inhibit the occurrence of interfacial reactions between the functional layer in contact with the two-dimensional perovskite layer and the three-dimensional perovskite layer.

[0022] In some embodiments, the formed perovskite light absorbing layer is a three-dimensional perovskite layer, and the organic additive is: [ka] It includes one or two of the following.

[0023] This example provides some organic additives to allow the precursor to form a perovskite light-absorbing layer containing only three-dimensional perovskite layers, thereby improving the photoelectric conversion efficiency of perovskite cells containing this perovskite light-absorbing layer.

[0024] Second aspect: A perovskite light-absorbing layer, which is manufactured by employing any one of the precursors according to the first aspect.

[0025] It is advantageous to manufacture and form a perovskite light-absorbing layer based on any one precursor according to the first aspect of one or more embodiments of the present application, and to improve the quality and stability of the formed perovskite light-absorbing layer.

[0026] Third aspect: A method for producing a perovskite light-absorbing layer, comprising coating any one of the precursors according to the first aspect onto the surface of the buried interface BI, and annealing the resulting product to form a perovskite light-absorbing layer.

[0027] One or more embodiments of the present application provide a method for manufacturing a perovskite light-absorbing layer, allowing any one precursor according to the first aspect to form a perovskite light-absorbing layer with good quality and stability.

[0028] Fourth aspect: a perovskite cell, comprising a perovskite absorber layer, wherein the perovskite absorber layer is a perovskite absorber layer according to the second aspect or a perovskite absorber layer produced employing a method according to the third aspect.

[0029] The perovskite cells according to one or more embodiments of the present application have relatively high photoelectric conversion efficiency and stability.

[0030] In some embodiments, the perovskite cell is a negative perovskite solar cell or a positive perovskite solar cell.

[0031] The perovskite light absorber layer according to one or more embodiments of the present application is applicable to positive type perovskite solar cells, and also to negative type perovskite solar cells.

[0032] In some embodiments, the perovskite cell further comprises a hole transport layer, and the perovskite light absorber layer comprises a two-dimensional perovskite layer and a three-dimensional perovskite layer, and the two-dimensional perovskite layer is formed between the three-dimensional perovskite layer and the hole transport layer.

[0033] In this embodiment, a negative perovskite solar cell is taken as an example, and a two-dimensional perovskite layer is formed between the hole transport layer and the three-dimensional perovskite layer to prevent the occurrence of an interfacial reaction between the three-dimensional perovskite layer and the hole transport layer, thereby improving the quality and stability of the formed perovskite light absorption layer.

[0034] In some embodiments, the hole transport layer is a metal oxide layer.

[0035] In this embodiment, the hole transport layer is a metal oxide layer, which is prone to reactions such as oxidation and reduction at the interface of the perovskite light absorption layer, which is likely to deteriorate the photoelectric conversion efficiency and stability of the perovskite cell.In this embodiment, by positioning a two-dimensional perovskite layer between the three-dimensional perovskite layer and the metal oxide hole transport layer, the interfacial reaction between the three-dimensional perovskite layer and the hole transport layer is further inhibited, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell.

[0036] In some embodiments, the metal oxide is nickel oxide.

[0037] In this embodiment, the two-dimensional perovskite layer is positioned between the three-dimensional perovskite layer and the nickel oxide hole transport layer, which further inhibits the interfacial reaction between the three-dimensional perovskite light absorption layer and the hole transport layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell.

[0038] In some embodiments, the perovskite absorber layer material is Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) Contains PbI3.

[0039] In this example, a specific material for the perovskite light-absorbing layer of a perovskite battery is provided.

[0040] In some embodiments, the materials of the two-dimensional perovskite layer and the three-dimensional perovskite layer are the same.

[0041] In this embodiment, by using the same material for the two-dimensional perovskite layer and the three-dimensional perovskite layer, the interfacial reaction between the perovskite light-absorbing layer and the carrier transport layer is inhibited, while the photoelectric conversion efficiency and stability of the perovskite cell are improved.

[0042] Fifth aspect: A power consuming device, the power consuming device comprising any one perovskite battery according to the fourth aspect.

[0043] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without exerting any creative efforts. [Brief explanation of the drawings]

[0044] [Figure 1] FIG. 1 is a first structural schematic diagram of a perovskite light-absorbing layer according to the present application. [Figure 2] FIG. 2 is a second structural schematic diagram of a perovskite light-absorbing layer according to the present application. [Figure 3] FIG. 1 is a third structural schematic diagram of a perovskite light-absorbing layer according to the present application. [Figure 4] 1 is a structural schematic diagram of a perovskite battery produced according to the present application. [Figure 5] FIG. 1 is a structural schematic diagram of a positive perovskite solar cell according to the present application. [Figure 6] FIG. 1 is a structural schematic diagram of a negative perovskite solar cell according to the present application. DETAILED DESCRIPTION OF THE INVENTION

[0045] In the drawings, the drawings are not necessarily drawn to scale.

[0046] The following describes in more detail the embodiments of the present application in conjunction with the drawings and examples. The detailed description of the embodiments and the drawings are for illustrative purposes only to explain the principles of the present application, but are not intended to limit the scope of the present application, i.e., the present application is not limited to the described embodiments.

[0047] In the description of this application, it should be explained that, unless otherwise specified, "plurality" means two or more, and the orientations or positional relationships indicated by terms such as "up," "down," "left," "right," "inside," and "outside" are merely for the convenience and simplification of the description of this application and do not indicate or imply that the referenced devices or elements must have a particular orientation or be configured and operated in a particular orientation, and should not be understood as limitations on this application. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and should not be understood as indicating or implying relative importance. "Perpendicular" does not mean strictly perpendicular, but has a margin of error. "Parallel" does not mean strictly parallel, but has a margin of error.

[0048] All directional terms appearing in the following description refer to the directions shown in the drawings and do not limit the specific structure of the present application. It should be further explained that in the description of the present application, unless otherwise clearly defined or limited, the terms "attached," "connected," and "coupled" should be understood in a broad sense, and may refer to, for example, a fixed connection, a detachable connection, or an integral connection, or may be a direct connection or an indirect connection via an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in the present application according to the specific circumstances.

[0049] Currently, in order to improve the photoelectric conversion efficiency and stability of perovskite solar cells, researchers have conducted a great deal of research into the device structure, functional layer materials and modifications, and interface modifications of perovskite solar cells.

[0050] During the research and development process, the inventors noticed that oxidation-reduction reactions are likely to occur at the interface between the perovskite light-absorbing layer and the carrier transport layer, which will significantly affect the properties of the perovskite light-absorbing layer, and further affect the photoelectric conversion efficiency and stability of the perovskite solar cell, as well as the service life of the perovskite solar cell.

[0051] To solve the above problems, the inventors of the present application provide a precursor and add an organic additive containing a six-membered heterocyclic compound to the perovskite precursor solution, thereby inhibiting the occurrence of interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell.

[0052] Furthermore, the inventors of the present application have provided a perovskite light-absorbing layer that forms a layered structure, whereby the layered layer close to the carrier transport layer inhibits the occurrence of interfacial reactions between the layered layer farther from the carrier transport layer and the carrier transport layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell. At the same time, the layered structure of the present application uses the same material, which can further improve the photoelectric conversion efficiency of the perovskite cell.

[0053] Furthermore, the inventors of the present application have provided a perovskite battery in which the stacking of the perovskite light-absorbing layer close to the hole transport layer inhibits the occurrence of interfacial reactions between the stacking layer away from the hole transport layer and the hole transport layer, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery.

[0054] The technical solutions described in the examples of this application are applicable to precursors, perovskite light-absorbing layers and manufacturing methods, perovskite batteries, and power-consuming devices. The perovskite batteries disclosed in this application may be used in perovskite stacked batteries or silicon-perovskite stacked batteries, and are not limited thereto in this application.

[0055] The present application will be described in detail below in conjunction with the drawings and examples.

[0056] According to a first aspect, the present application provides a precursor, which is used in the manufacture of a perovskite light absorbing layer, a perovskite precursor liquid; and an organic additive added to the perovskite precursor liquid; Here, the organic additive comprises a six-membered heterocyclic compound, and the heteroatom of the six-membered heterocyclic compound comprises one or more of S, N, and Se.

[0057] In one or more embodiments of the present application, the "precursor" refers to a precursor product prior to obtaining a perovskite light-absorbing layer. The "perovskite light-absorbing layer" is the core of a perovskite cell, absorbing photon energy from sunlight, generating electron-hole pairs, and separating the electron-hole pairs into free electrons and holes through the action of a built-in electric field. The holes are collected by the conductive substrate via the hole-transport layer, and the electrons are collected by the metal electrode. The conductive substrate and the metal electrode are connected to a circuit to generate photocurrent. The material of the "perovskite light-absorbing layer" is a perovskite material, which has the same crystal structure as CaTiO3 and exhibits a cubic phase in a stable state. The "perovskite precursor solution" refers to a precursor raw material for forming a perovskite material. The "organic additive" is added to the perovskite precursor solution to form a precursor, improving the quality of the formed perovskite light-absorbing layer, inhibiting interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, and enhancing the photoelectric conversion efficiency and stability of the perovskite cell. The "carrier transport layer" may be an electron transport layer or a hole transport layer. The "six-membered heterocyclic compound" refers to an organic compound containing a heterocyclic ring structure in the molecule, where the ring contains six elements and further contains at least one heteroatom in addition to carbon. In one or more embodiments of the present application, the heteroatom may include one or more of S, N, and Se.

[0058] In this embodiment, an organic additive, specifically a six-membered heterocyclic compound, is added to the perovskite precursor solution to form a precursor for producing a perovskite light-absorbing layer, which is used to control the quality of the formed perovskite light-absorbing layer and inhibit interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, thereby improving the interfacial stability between the perovskite light-absorbing layer and the carrier transport layer, and improving the photoelectric conversion efficiency and stability of perovskite batteries containing this perovskite light-absorbing layer, and prolonging the service life of the perovskite battery.

[0059] In one or more embodiments of the present application, the organic additive is a six-membered heterocyclic compound, and the heteroatoms of the six-membered heterocyclic compound include one or more of S, N, and Se.

[0060] In some embodiments, the perovskite precursor solution contains Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) A precursor solution of PbI3 may be included.

[0061] In this embodiment, Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) PbI3 represents a perovskite material, where Cs represents elemental cesium, FA represents formamidine, MA represents methylamine, Pb represents elemental lead, and I represents elemental iodine.

[0062] In this embodiment, Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) The precursor liquid of PbI3 is methylammonium (CH3NH3 + , M.A. + ), inorganic cations (Cs + or Rb + ), divalent metal cations (Pb 2+ , Sn 2+ or Ge 2+ ), halide anions (I - ) may be composed of

[0063] In one or more embodiments of the present application, by employing the above-mentioned perovskite materials, the formed perovskite light-absorbing layer has relatively high quality, and the perovskite cell containing this perovskite light-absorbing layer has relatively high photoelectric conversion efficiency and relatively high stability.

[0064] In some embodiments, Pb in the perovskite precursor solution 2+ The concentration of Pb in the perovskite precursor solution 2+ To provide a specific concentration, it is 1M to 2M.

[0065] In one or more embodiments of the present application, any concentration of Pb in the perovskite precursor solution that can improve the quality of the formed perovskite light-absorbing layer is within the scope of protection of the present application. 2+ The concentration of may be 1M to 2M, and when a perovskite precursor solution within this concentration range is used to manufacture a perovskite light-absorbing layer, organic additives and the like can be uniformly dispersed therein, making the performance of the formed perovskite light-absorbing layer more uniform, which is advantageous for demonstrating the performance of the perovskite battery.

[0066] In one or more embodiments of the present application, the concentration of the perovskite precursor liquid is the ratio of the molar amount of the perovskite precursor material to the molar volume of the perovskite precursor solvent.

[0067] For example, Pb in the perovskite precursor solution 2+ The concentration of may be 1M, 1.2M, 1.4M, 1.6M, 1.8M, 2M, or may be 1.1M, 1.3M, 1.5M, 1.7M, 1.9M, etc., and is reasonably set as needed.

[0068] In some embodiments, the molar fraction of the organic additive to the perovskite precursor solution is between 0.1% and 10%.

[0069] In one or more embodiments of the present application, the molar fraction of any one of the organic additives and the perovskite precursor solution that can improve the quality of the formed perovskite light-absorbing layer is within the scope of protection of the present application. In one or more embodiments, when the molar fraction of the organic additive relative to the perovskite precursor solution is within the range of 0.1% to 10%, the formed perovskite light-absorbing layer has a relatively high quality, and interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer are effectively inhibited, thereby improving the performance of the perovskite battery.

[0070] In one or more embodiments, the molar fraction of the organic additive to the perovskite precursor liquid is the ratio of the molar amount of the organic additive to the molar amount of the perovskite precursor liquid.

[0071] In some embodiments, the six-membered heterocyclic compound comprises a -R(=O)2- functional group and a -N + and one or two of the functional groups, where R includes S and / or Se.

[0072] The six-membered heterocyclic compound according to this embodiment further defines the specific molecular structure of the six-membered heterocyclic compound by combining the -R(=O)2- functional group and the -N + It may further comprise a functional group.

[0073] When the six-membered heterocyclic compound of one or more embodiments of the present application contains the above functional group, it has an advantageous effect of preventing the occurrence of interfacial reactions such as oxidation-reduction at the interface between the formed perovskite light-absorbing layer and the carrier transport layer. Specifically, this is due to the -R(=O)2- functional group and / or -N + When a six-membered heterocyclic compound containing functional groups is added to the perovskite precursor solution, the -R(=O)2- functional group and / or -N + This may be because the functional groups react with the ions of the precursor material in the perovskite precursor solution, thereby controlling the crystallization process of the perovskite material (e.g., grain growth orientation, grain size, etc.), and modifying the interface between the formed perovskite light-absorbing layer and the carrier transport layer (e.g., passivation effect), thereby inhibiting interfacial reactions such as oxidation-reduction between the formed perovskite light-absorbing layer and the carrier transport layer, thereby improving the photoelectric conversion efficiency and stability of perovskite cells containing this perovskite light-absorbing layer.

[0074] Illustratively, the six-membered heterocyclic compounds of one or more embodiments of the present application may include a -S(=O)2- functional group, a -Se(=O)2- functional group, or a -N + It may contain only one functional group, or it may contain two functional groups, for example, an -S(=O)2- functional group and an -N + functional group, or Se(=O)2- functional group and -N +It may contain functional groups.

[0075] In some embodiments, the six-membered heterocyclic compound is [ka] It includes one or more of the following.

[0076] In one or more embodiments of the present application, the organic additives can effectively control the formation of the perovskite light-absorbing layer, improve the quality of the formed perovskite light-absorbing layer, and enhance the photoelectric conversion efficiency and stability of the perovskite cell containing this perovskite light-absorbing layer.

[0077] As can be seen from the above six-membered heterocyclic compounds according to one or more embodiments of the present application, the six-membered heterocyclic compounds may contain only one heteroatom, such as S, N, or Se. They may also contain only two heteroatoms, and the two heteroatoms may be the same element, such as two S, two N, one S and one N, or one Se and one N.

[0078] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0079] This embodiment provides the above organic additive and adds it to a perovskite precursor solution to form a perovskite absorber layer having a layered structure, thereby improving the photoelectric conversion efficiency and stability of perovskite cells containing this perovskite absorber layer. This may be because one or more embodiments of the present application can further form a perovskite absorber layer comprising a three-dimensional perovskite layer and a two-dimensional perovskite layer, thereby reducing crystal defects in the perovskite absorber layer and interfacial defects that may occur during the formation of the layered structure, thereby improving the quality of the perovskite absorber layer. In addition, the two-dimensional perovskite layer formed in situ can protect the buried interface, inhibiting interfacial reactions between the perovskite absorber layer and the carrier transport layer, and improving the interfacial stability of the carrier transport layer between the conductive substrate and the perovskite absorber layer.

[0080] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0081] This embodiment provides some organic additives to position the two-dimensional perovskite layer in the perovskite absorber layer formed by the precursor between the three-dimensional perovskite layer and the buried interface, and inhibits the occurrence of interfacial reactions between the perovskite absorber layer and the buried interface.

[0082] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0083] This example provides some organic additives to position the two-dimensional perovskite layer in the perovskite light-absorbing layer formed by the precursor at a surface away from the buried interface of the three-dimensional perovskite layer, and inhibit the occurrence of interfacial reactions between the functional layer in contact with the two-dimensional perovskite layer and the three-dimensional perovskite layer.

[0084] In some embodiments, the organic additive is: [ka] It includes one or two of the following.

[0085] This example provides some organic additives to allow the precursor to form a perovskite light-absorbing layer containing only three-dimensional perovskite layers, thereby improving the photoelectric conversion efficiency of perovskite cells containing this perovskite light-absorbing layer. This may be because the functional groups of the organic additives added to the perovskite precursor liquid react with the precursor ions in the perovskite precursor liquid to control the crystallization process of the perovskite material (e.g., grain growth orientation, grain size, etc.), thereby improving the quality of the formed perovskite light-absorbing layer, and thereby improving the photoelectric conversion efficiency of the formed perovskite cells.

[0086] Referring to Figures 1 to 3, Figure 1 is a first structural schematic diagram of a perovskite light-absorbing layer according to the present application, Figure 2 is a second structural schematic diagram of a perovskite light-absorbing layer according to the present application, and Figure 3 is a third structural schematic diagram of a perovskite light-absorbing layer according to the present application.

[0087] According to a second aspect, one or more embodiments of the present application provide a perovskite light-absorbing layer 30, made from any one of the precursors according to the first aspect.

[0088] Referring to FIG. 1, this embodiment provides a perovskite light-absorbing layer 30, which includes a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, and the two-dimensional perovskite layer 31 is located between the three-dimensional perovskite layer 32 and the buried interface BI, and prevents the occurrence of an interfacial reaction between the three-dimensional perovskite layer 32 and the buried interface BI.

[0089] Referring to FIG. 2, this embodiment provides a perovskite light-absorbing layer 30, which includes a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, where the two-dimensional perovskite layer 31 is located on a surface away from the buried interface BI of the three-dimensional perovskite layer 32.

[0090] Referring to FIG. 3, this embodiment provides a perovskite light-absorbing layer 30, which includes only a three-dimensional perovskite layer 32, and an organic additive 60 is dispersed in the three-dimensional perovskite layer 32, as shown in FIG.

[0091] Any one of the precursors according to the first aspect of one or more embodiments of the present application is used to manufacture and form the perovskite light absorbing layer 30, and improves the quality and stability of the formed perovskite light absorbing layer 30.

[0092] According to a third aspect, one or more embodiments of the present application provide a method for manufacturing a perovskite light absorber layer 30, comprising coating any one of precursors according to the first aspect onto the surface of the buried interface BI, and annealing the resulting product to form the perovskite light absorber layer 30.

[0093] In one or more embodiments of the present application, the "buried interface BI" refers to a support structure on which the perovskite light-absorbing layer 30 is formed. In one or more embodiments of the present application, the buried interface BI may be an electron transport layer ETL or a hole transport layer HTL. "Annealing" refers to a heat treatment process in which a material is exposed to a high temperature for a certain period of time and then slowly cooled. In some embodiments, the process parameters for the annealing treatment in one or more embodiments of the present application are a temperature of 100°C to 150°C and an incubation time of 10 minutes to 30 minutes.

[0094] One or more embodiments of the present application provide a method for manufacturing a perovskite light-absorbing layer 30, allowing any one precursor according to the first aspect to form a perovskite light-absorbing layer 30 with good quality and stability.

[0095] In one or more embodiments of the present application, the provided precursors are used to prepare a perovskite light absorbing layer, a perovskite precursor liquid; and an organic additive added to the perovskite precursor liquid; Here, the organic additive is a six-membered heterocyclic compound, and the heteroatoms of the six-membered heterocyclic compound include one or more of S, N, and Se.

[0096] In some embodiments, the concentration of the perovskite precursor is 1M to 2M.

[0097] In some embodiments, the molar fraction of the organic additive to the perovskite precursor solution is between 0.1% and 10%.

[0098] In some embodiments, the perovskite precursor solution contains Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) A precursor solution of PbI3 may be included.

[0099] In some embodiments, the six-membered heterocyclic compound comprises a -R(=O)2- functional group and a -N + and one or two of the functional groups, where R is S and / or Se.

[0100] In some embodiments, the six-membered heterocyclic compound is [ka] It includes one or more of the following.

[0101] The perovskite light-absorbing layer 30 formed by oxidation with the six-membered heterocyclic compound according to this embodiment has a structure as shown in Figures 1 to 3, and a perovskite battery containing the perovskite light-absorbing layer 30 has good photoelectric conversion efficiency and / or stability.

[0102] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0103] The perovskite light-absorbing layer 30 formed with the organic additive according to this embodiment has a structure as shown in Figure 1 or 2, in which the perovskite light-absorbing layer 30 is divided into a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, and the two-dimensional perovskite layer 31 is located between the three-dimensional perovskite layer 32 and the buried interface B1, or is located on the surface of the three-dimensional perovskite layer 32 away from the buried interface B1. A perovskite cell containing the perovskite light-absorbing layer 30 has good photoelectric conversion efficiency and / or stability.

[0104] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0105] The perovskite light-absorbing layer 30 formed with the organic additive according to this embodiment has a structure as shown in Figure 1, which is divided into a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, with the two-dimensional perovskite layer 31 located between the three-dimensional perovskite layer 32 and the buried interface BI. The perovskite cell containing the perovskite light-absorbing layer 30 has good photoelectric conversion efficiency and stability.

[0106] In some embodiments, the organic additive is: [ka] It includes one or more of the following.

[0107] The perovskite light-absorbing layer 30 formed with the organic additive according to this embodiment has a structure as shown in Figure 2, which is divided into a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, with the two-dimensional perovskite layer 31 located on the surface away from the buried interface B1 of the three-dimensional perovskite layer 32. This is advantageous for improving the stability of perovskite cells containing the perovskite light-absorbing layer 30.

[0108] In some embodiments, the organic additive is: [ka] It includes one or two of the following.

[0109] The perovskite light-absorbing layer 30 formed by adding the organic additive 60 according to this embodiment has a structure as shown in Figure 3, in which the perovskite light-absorbing layer 30 is only a three-dimensional perovskite layer 32. This is advantageous for improving the photoelectric conversion efficiency and stability of perovskite cells containing the perovskite light-absorbing layer 30.

[0110] Referring to FIG. 4, FIG. 4 is a structural schematic diagram of a perovskite battery according to the present application.

[0111] According to a fourth aspect, and referring to Figure 4, one or more embodiments of the present application provide a perovskite cell 100, which includes a perovskite absorber layer 30. Here, the perovskite absorber layer 30 is the perovskite absorber layer 30 according to the second aspect or the perovskite absorber layer 30 manufactured by employing the method according to the third aspect.

[0112] Continuing to refer to Figure 4, a perovskite cell 100 according to one or more embodiments of the present application includes, in order, a conductive substrate 10, a first transport layer 20, a perovskite absorber layer 30, a second transport layer 40, and a metal electrode 50. One of the first transport layer 20 and the second transport layer 40 is a hole transport layer HTL, and the other is an electron transport layer ETL.

[0113] In one or more embodiments of the present application, the "conductive substrate 10" represents an electrode with high conductivity and high visible light transmittance as one output terminal of the perovskite battery 100, such as ITO conductive glass or FTO conductive glass. The "first transport layer 20" and the "second transport layer 40" represent structural layers that transport electrons or holes generated upon photon excitation of the perovskite light-absorbing layer 30. The "metal electrode 50" represents an electrode made of a metal material that is required to have high conductivity and stability as another output terminal of the perovskite battery 100 device.

[0114] The perovskite cell 100 according to one or more embodiments of the present application has good photoelectric conversion efficiency and stability.

[0115] Referring to Figures 5 and 6, Figure 5 is a schematic structural diagram of a positive-type perovskite solar cell according to the present application, and Figure 6 is a schematic structural diagram of a negative-type perovskite solar cell according to the present application.

[0116] In some embodiments, perovskite cell 100 is a negative perovskite solar cell or a positive perovskite solar cell.

[0117] In this example, combining Figures 4 and 5, the first transport layer 20 is an electron transport layer ETL, and the second transport layer 40 is a hole transport layer HTL, and the perovskite cell 100 including them is a positive type perovskite solar cell.

[0118] In this example, combining Figures 4 and 6, the first transport layer 20 is a hole transport layer HTL, the second transport layer 40 is an electron transport layer ETL, and the perovskite cell 100 including them is a negative-type perovskite solar cell.

[0119] The perovskite light absorber layer 30 according to one or more embodiments of the present application is applicable to positive-type perovskite solar cells, and also to negative-type perovskite solar cells.

[0120] 6, in some embodiments, the perovskite cell 100 further includes a hole transport layer HTL. The perovskite light absorber layer 30 includes a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32. The two-dimensional perovskite layer 31 is formed between the three-dimensional perovskite layer 32 and the hole transport layer HTL.

[0121] In this embodiment, a negative-type perovskite solar cell is taken as an example, and a two-dimensional perovskite layer 31 is formed between the hole transport layer HTL and the three-dimensional perovskite layer 32 to prevent an interfacial reaction between the three-dimensional perovskite layer 32 and the hole transport layer HTL, thereby improving the quality and stability of the formed perovskite light-absorbing layer 30.

[0122] In some embodiments, the hole transport layer HTL is a metal oxide layer.

[0123] In this embodiment, the hole transport layer HTL is a metal oxide layer, which is prone to reactions such as oxidation-reduction at the interface with the perovskite light-absorbing layer 30, which is likely to deteriorate the photoelectric conversion efficiency and stability of the perovskite cell 100. In this embodiment, the two-dimensional perovskite layer 31 is positioned between the three-dimensional perovskite layer 32 and the metal oxide hole transport layer HTL, which further inhibits the interfacial reaction between the three-dimensional perovskite layer 32 and the hole transport layer HTL, thereby improving the photoelectric conversion efficiency and stability of the perovskite cell 100.

[0124] In some embodiments, the metal oxide is nickel oxide.

[0125] In this embodiment, the nickel oxide is NiOx, a commonly used material for the hole transport layer (HTL). In this embodiment, the two-dimensional perovskite layer 31 is positioned between the three-dimensional perovskite layer 32 and the nickel oxide hole transport layer (HTL), which further inhibits the interfacial reaction between the three-dimensional perovskite light-absorbing layer 30 and the hole transport layer (HTL), thereby improving the photoelectric conversion efficiency and stability of the perovskite cell 100.

[0126] In some embodiments, the perovskite absorber layer material is Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) Contains PbI3.

[0127] In this example, a specific material for the perovskite light-absorbing layer 30 of the perovskite cell 100 is provided.

[0128] In some embodiments, the materials of the two-dimensional perovskite layer and the three-dimensional perovskite layer are the same.

[0129] In this embodiment, by using the same material for the two-dimensional perovskite layer 31 and the three-dimensional perovskite layer 32, the interfacial reaction between the perovskite light-absorbing layer 30 and the carrier transport layer is inhibited, while the photoelectric conversion efficiency and stability of the perovskite cell 100 are improved, compared to when an interface structure layer made of a non-perovskite material is provided between the three-dimensional perovskite layer 32 and the carrier transport layer.

[0130] Fifth aspect: One or more embodiments of the present application provide a power consuming device, comprising any one of the perovskite cells 100 according to the fourth aspect.

[0131] Example The present application provides organic additives Nos. 1 to 12 for producing corresponding negative perovskite solar cells, and the molecular structures of the organic additives Nos. 1 to 12 are shown in Table 1.

[0132] [Table 1]

[0133] Example 1 This embodiment provides a method for manufacturing a negative perovskite solar cell, which includes the following steps:

[0134] (1) The conductive substrate 10 is cleaned, and a nickel oxide layer is formed on the surface of the cleaned conductive substrate 10 by magnetron sputtering. The nickel oxide layer is used as the hole transport layer HTL and as the first transport layer 20. The thickness of the first transport layer 20 in this example is 30 nm.

[0135] (2) The organic additive No. 1 is Cs (0~0.05) FA (0.8~0.95) MA (0~0.10) The organic additive No. 1 was added to a 1.4M perovskite precursor solution to form a PbI3 material, and the resulting perovskite precursor solution was spin-coated onto the surface of the first transport layer 20. The resulting product was annealed to form a 450 nm-thick perovskite light-absorbing layer 30. In this example, the molar fraction of the organic additive No. 1 relative to the perovskite precursor solution was 5%. The annealing treatment in this example specifically involved 30 minutes of incubation at a temperature of 120°C.

[0136] (3) PCBM (fullerene) and BCP (bathocuproine, a hole-blocking material) were spin-coated on the surface of the perovskite light-absorbing layer 30 to form an electron transport layer ETL having a thickness of 30 nm as the second transport layer 40.

[0137] (4) On the surface of second transport layer 40 away from conductive substrate 10, a 100 nm thick silver metal electrode was thermally evaporated as metal electrode 50.

[0138] The perovskite light-absorbing layer 30 formed in this embodiment has a stacked structure. Referring to FIG. 1, the stacked structure includes a two-dimensional perovskite layer 31 and a three-dimensional perovskite layer 32, and the two-dimensional perovskite layer 31 is disposed between the first transport layer 20 and the three-dimensional perovskite layer 32.

[0139] Example 2 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is the second one.

[0140] The rest is the same as in the first embodiment.

[0141] Example 3 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used was number 3.

[0142] The rest is the same as in the first embodiment.

[0143] Example 4 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used was number 4.

[0144] The rest is the same as in the first embodiment.

[0145] Example 5 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is number 5.

[0146] The rest is the same as in the first embodiment.

[0147] In the negative perovskite solar cell formed in this example, referring to FIG. 2, the two-dimensional perovskite layer 31 is provided between the three-dimensional perovskite layer 32 and the second transport layer 40 (which is the electron transport layer ETL in this example).

[0148] Example 6 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 5 is as follows: (2) The organic additive used is number 6.

[0149] The rest of the procedure is the same as in Example 5.

[0150] Example 7 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 5 is as follows: (2) The organic additive used is number 7.

[0151] The rest of the procedure is the same as in Example 5.

[0152] Example 8 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is number 8.

[0153] The rest is the same as in the first embodiment.

[0154] Example 9 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is number 9.

[0155] The rest is the same as in the first embodiment.

[0156] Example 10 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is number 10.

[0157] The rest is the same as in the first embodiment.

[0158] Example 11 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 1 is as follows: (2) The organic additive used is number 11.

[0159] The rest is the same as in the first embodiment.

[0160] In the negative perovskite solar cell formed in this example, referring to FIG. 3, the perovskite light absorption layer 30 is composed of only a three-dimensional perovskite layer 32.

[0161] Example 12 The difference between the manufacturing method of the negative perovskite solar cell according to this example and the manufacturing method according to Example 11 is as follows: (2) The organic additive used is number 12.

[0162] All other aspects are the same as in Example 11.

[0163] Example 13 The difference between the manufacturing method of the positive perovskite solar cell according to this example and the manufacturing method according to Example 5 is as follows: (2) The organic additive used is number 5.

[0164] The rest of the procedure is the same as in Example 5.

[0165] In the positive perovskite solar cell formed in this example, as shown in FIG. 5, a two-dimensional perovskite layer 31 is provided between a three-dimensional perovskite layer 32 and a second transport layer 40 (which is a hole transport layer HTL in this example).

[0166] Example 14 The difference between the manufacturing method of the positive perovskite solar cell according to this example and the manufacturing method according to Example 6 is as follows: (2) The organic additive used is number 6.

[0167] All other aspects are the same as in Example 6.

[0168] In the positive perovskite solar cell formed in this example, as shown in FIG. 5, a two-dimensional perovskite layer 31 is provided between a three-dimensional perovskite layer 32 and a second transport layer 40 (which is a hole transport layer HTL in this example).

[0169] Example 15 The difference between the manufacturing method of the positive perovskite solar cell according to this example and the manufacturing method according to Example 7 is as follows: (2) The organic additive used is number 7.

[0170] All other aspects are the same as in Example 7.

[0171] In the positive perovskite solar cell formed in this example, as shown in FIG. 5, a two-dimensional perovskite layer 31 is provided between a three-dimensional perovskite layer 32 and a second transport layer 40 (which is a hole transport layer HTL in this example).

[0172] Comparative Example 1 This comparative example provides a method for manufacturing a negative perovskite solar cell, and the differences from the manufacturing method in Example 1 are as follows: (2) No organic additives are added.

[0173] The rest is the same as in the first embodiment.

[0174] Experimental example The perovskite cells 100 produced in Examples 1 to 15 were tested for photoelectric conversion efficiency and stability, and the test results are shown in Table 2.

[0175] [Table 2]

[0176] The following conclusions can be drawn from the test results in Table 2.

[0177] (1) As can be seen from the test results of Examples 1 to 4 and Examples 8 to 10 and Comparative Example 1, the addition of organic additives 1 to 4 or 8 to 10 during the manufacturing process of the perovskite light-absorbing layer 30 significantly improved the photoelectric conversion efficiency and stability of the corresponding negative-type perovskite solar cell. This may be related to the inclusion of at least one S or Se heteroatom in the six-membered heterocycle of the organic additives 1 to 4 or 8 to 10. By adding organic additives in this configuration, the formed perovskite light-absorbing layer 30 has a stacked structure, and the two-dimensional perovskite layer 31 is positioned between the three-dimensional perovskite layer 32 and the hole transport layer HTL. This forms a functional layer in one step that inhibits the occurrence of interfacial reactions between the three-dimensional perovskite layer 32 and the hole transport layer HTL, thereby improving the photoelectric conversion efficiency and stability of the negative-type perovskite solar cell.

[0178] (2) As can be seen from the test results of Examples 5 to 7 and Examples 13 to 15, the photoelectric conversion efficiency and stability of the positive-type perovskite solar cell in which the two-dimensional perovskite layer 31 is provided between the three-dimensional perovskite layer 32 and the hole-transporting layer HTL are higher than those of the negative-type perovskite solar cell in which the two-dimensional perovskite layer 31 is provided between the three-dimensional perovskite layer 32 and the electron-transporting layer ETL.

[0179] (3) As can be seen from the test results of Examples 11 and 12 and Comparative Example 1, the addition of organic additives 11 and 12 in the manufacturing process of the perovskite light-absorbing layer 30 can improve the stability of the corresponding negative-type perovskite solar cells to a certain extent, which may be related to the improvement in the film layer quality of the perovskite light-absorbing layer 30 formed by the addition of organic additives 11 and 12.

[0180] Although the present application has been described with reference to preferred embodiments, various modifications may be made thereto and equivalents may be substituted for the components therein without departing from the scope of the present application. In particular, the technical features recited in each embodiment may be combined in any manner unless there is a structural conflict. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims. [Explanation of symbols]

[0181] 10 - conductive substrate, BI - buried interface, 20 - first transport layer, 30 - perovskite absorber layer, 31 - two-dimensional perovskite layer, 32 - three-dimensional perovskite layer, 40 - second transport layer, 50 - metal electrode, 60 - organic additive, 100 - perovskite cell, HTL - hole transport layer, ETL - electron transport layer.

Claims

1. A precursor used in the manufacture of a perovskite light absorbing layer, comprising: A perovskite precursor liquid and an organic additive added to the perovskite precursor liquid, The organic additive comprises a six-membered heterocyclic compound, and the heteroatom of the six-membered heterocyclic compound comprises one or more of S, N, and Se.

2. The perovskite precursor solution contains Cs （０～０．０５） FA （０．８～０．９５） MA （０～０．１０） PbI ３ 2. The precursor of claim 1, comprising a precursor solution of:

3. Pb in the perovskite precursor solution ２＋ 3. The precursor according to claim 2, wherein the concentration of is 1M to 2M.

4. 2. The precursor of claim 1, wherein the molar fraction of the organic additive to the perovskite precursor solution is 0.1% to 10%.

5. The six-membered heterocyclic compound is —R(═O) ２ -functional group and -N ＋ 2. The precursor of claim 1, wherein R comprises one or two of the following functional groups: S and / or Se.

6. The six-membered heterocyclic compound is 【Chemistry 1】 6. The precursor of claim 5, comprising one or more of:

7. The organic additive is 【Chemistry 2】 2. The precursor of claim 1, comprising one or more of:

8. The organic additive is 【Transformation 3】 8. The precursor of claim 7, comprising one or more of:

9. The organic additive is 【Chemistry 4】 8. The precursor of claim 7, comprising one or more of:

10. The organic additive is 【Transformation 5】 2. The precursor of claim 1, comprising one or two of:

11. A perovskite light-absorbing layer, characterized in that it is produced by employing the precursor according to any one of claims 1 to 10.

12. 11. A method for producing a perovskite light-absorbing layer, comprising: coating a precursor according to any one of claims 1 to 10 on a surface of an embedded interface BI; and annealing the resulting product to form a perovskite light-absorbing layer.

13. A perovskite battery, comprising a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is manufactured using the perovskite light-absorbing layer according to claim 11.

14. 14. The perovskite battery according to claim 13, wherein the perovskite battery is a negative perovskite solar cell or a positive perovskite solar cell.

15. 14. The perovskite battery of claim 13, further comprising a hole transport layer, wherein the perovskite light absorption layer comprises a two-dimensional perovskite layer and a three-dimensional perovskite layer, and the two-dimensional perovskite layer is formed between the three-dimensional perovskite layer and the hole transport layer.

16. 16. The perovskite battery of claim 15, wherein the hole transport layer is a metal oxide layer.

17. 17. The perovskite battery of claim 16, wherein the metal oxide is nickel oxide.

18. The material of the perovskite light absorption layer is Cs （０～０．０５） FA （０．８～０．９５） MA （０～０．１０） PbI ３ 14. The perovskite battery of claim 13, comprising:

19. 16. The perovskite battery of claim 15, wherein the two-dimensional perovskite layer and the three-dimensional perovskite layer are made of the same material.

20. 14. An electrical power consuming device comprising the perovskite battery of claim 13.

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