Solar cell, power utilization device and power generation device

Abstract

The invention provides a solar cell, a power utilization device and a power generation device, a back electrode layer of the solar cell comprises a composite material, the solar cell comprises a groove penetrating through a functional layer, and the composite material is at least located in the groove and covers the side face, facing the groove, of the functional layer or fills the groove. The composite material comprises a metal organic framework material and metal simple substances located in the metal organic framework material or metal simple substances and metal salt located in the metal organic framework material, and due to the fact that the metal simple substances have good conductivity, after the metal organic framework material is filled with the metal simple substances, the metal simple substances not only can play a conductive role, but also can play a conductive role. And the defects in the metal organic framework material body can be overcome, and the formed composite material has high conductivity. When the composite material is applied to the back electrode layer of the solar cell, the conductive function can be realized, and the metal salt and / or the metal elementary substance cannot cause degradation of the functional layer, so that the stability of the solar cell can be improved.

Description

Technical Field

[0001] The present application relates to the technical field of solar cells, and in particular to a solar cell, an electrical device, and a power generation device. Background Art

[0002] Solar cells have a high theoretical photoelectric conversion efficiency and a bright future. However, improving the stability of solar cells is a technical problem that needs to be solved urgently. Summary of the Invention

[0003] In view of the above technical problems, the present application provides a solar cell, an electrical device and a power generation device with high stability.

[0004] The first technical solution adopted in the present application is: providing a solar cell, the solar cell including a back electrode layer, the back electrode layer including a composite material, the solar cell including a groove penetrating the functional layer, the composite material at least located in the groove, covering the side of the functional layer facing the groove or filling the groove, the composite material including a metal organic framework material and a metal element located in the metal organic framework material or a metal element and a metal salt located in the metal organic framework material.

[0005] In the technical solution of the embodiment of the present application, the metal organic framework material generally has high water, oxygen, chemical and high temperature stability. Since the metal organic framework material has electrical conductivity, the metal organic framework material contains a metal element or contains a metal element and a metal salt, that is, the metal element is used as the core or the metal element and the metal salt are used as the core, and the metal organic framework material is used as a protective framework with a core outer layer. Since the metal element has good electrical conductivity, after being filled into the metal organic framework material, it can not only play its own conductive role, but also fill the defects in the metal organic framework material body, and the composite material formed has high electrical conductivity. The composite material is applied to the back electrode layer of the solar cell, not only can the conductive function be achieved, but the metal salt and / or the metal element will not directly contact the functional layer in the solar cell, so that the metal salt and / or the metal element will not chemically react with the functional layer in the solar cell, and the metal salt and / or the metal element will not cause degradation of the functional layer, therefore, the stability of the solar cell can be improved.

[0006] In some embodiments, the conductivity of the metal organic framework material is 1 S·cm -1 ~100S·cm -1 .

[0007] In the technical solution of the embodiment of the present application, the electrical conductivity of the metal organic framework material is within the above range, so that the composite material has good electrical conductivity when applied to the back electrode layer.

[0008] In some embodiments, the pore size of the metal organic framework material is less than or equal to 100 nm.

[0009] In the technical solution of the embodiment of the present application, the pore size of the metal-organic framework material is within the above-mentioned range, which can make it easier for the metal salt to enter the interior of the metal-organic framework material. After entering the interior of the metal-organic framework material, at least part of the metal salt can be reduced to form a metal element inside the metal-organic framework material, thereby making the formed composite material have high conductivity.

[0010] In some embodiments, the particle size of the metal element is less than or equal to 100 nm.

[0011] In the technical solution of the embodiment of the present application, the particle size of the metal element is within the above-mentioned range, so that it can be effectively loaded inside the metal-organic framework material and effectively fill the defects in the metal-organic framework material body. The formed composite material has high conductivity and good structural stability.

[0012] In some embodiments, the metal-organic framework material includes a metal element and a ligand coordinated with the metal element, and the ligand includes an aromatic group.

[0013] In the technical solution of the embodiment of the present application, the metal organic framework material is within the above range, and the metal organic framework material has a conjugated structure, so that the metal organic framework material has conductivity.

[0014] In some embodiments, the metal-organic framework material is a two-dimensional structure or a one-dimensional structure.

[0015] In the technical solution of the embodiment of the present application, the metal organic framework material has conductivity within the above range.

[0016] In some embodiments, the metal organic framework material includes at least one of Cu-HHTP, Cu-THQ, and Ni3(HHTP)2.

[0017] In the technical solution of the embodiment of the present application, the composite material formed by using the above-mentioned metal organic framework material has high conductivity and good structural stability.

[0018] In some embodiments, the metal element in the metal salt and / or the metal element includes at least one of gold (Au), silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), and manganese (Mn).

[0019] In the technical solution of the embodiment of the present application, the metal element formed by the above-mentioned metal elements or the metal element and metal salt formed are loaded in the metal-organic framework material, so that it has excellent conductive properties.

[0020] In some embodiments, the thickness of the back electrode layer is 30 nm to 300 nm.

[0021] In the technical solution of the embodiment of the present application, the thickness of the back electrode layer can have good conductive properties within the above range.

[0022] In some embodiments, the solar cell includes at least a stacked bottom electrode layer, a functional layer, and a back electrode layer as described above; wherein the back electrode layer includes a first conductive layer or includes a first conductive layer and a second conductive layer, wherein the first conductive layer is located between the functional layer and the second conductive layer, the first conductive layer includes a composite material, and the second conductive layer includes a conductive material.

[0023] In the technical solution of the embodiment of the present application, the composite material has electrical conductivity and high stability. When the composite material is applied to the back electrode layer of a solar cell, it not only achieves the function of electrical conductivity, but also prevents the metal salt and / or metal element from directly contacting the functional layer in the solar cell, thereby preventing the metal salt and / or metal element from chemically reacting with the functional layer in the solar cell, weakening the degradation of the functional layer and improving the stability of the solar cell.

[0024] At the same time, when the back electrode layer includes the first conductive layer and the second conductive layer, the composite material is located between the functional layer and the second conductive layer, and the functional layer and the second conductive layer will not react with each other, which can improve the stability of the solar cell.

[0025] In some embodiments, the thickness of the first conductive layer is 30 nm to 300 nm.

[0026] In the technical solution of the embodiment of the present application, the thickness of the first conductive layer can have good conductive properties within the above range.

[0027] In some embodiments, when the back electrode layer includes a first conductive layer and a second conductive layer, the thickness of the first conductive layer accounts for less than or equal to 40% of the thickness of the back electrode layer.

[0028] In the technical solution of the embodiment of the present application, when the back electrode layer includes a first conductive layer and a second conductive layer, the first conductive layer is used as an interlayer between the second conductive layer and the functional layer, and the thickness of the first conductive layer accounts for less than or equal to 40% of the thickness of the back electrode layer, which can make the back electrode layer have better conductive properties and at the same time improve the stability of the solar cell.

[0029] The second technical solution adopted in this application is to provide an electrical device comprising the solar cell as described above.

[0030] Since the electric device of the present application includes the solar cell provided by the present application, it has at least the same advantages as the solar cell.

[0031] The third technical solution adopted in the present application is to provide a power generation device comprising the solar cell as described above.

[0032] Since the power generation device of the present application includes the solar cell provided by the present application, it has at least the same advantages as the solar cell.

[0033] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the optional embodiments below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present application. The same reference numerals are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0035] Figure 1 This is a schematic structural diagram of a solar cell according to some embodiments of the present application;

[0036] Figure 2 This is a schematic structural diagram of a solar cell according to some embodiments of the present application;

[0037] Figure 3 This is a schematic structural diagram of an electrical device according to some embodiments of the present application;

[0038] Figure 4 This is a schematic structural diagram of a power generation device according to some embodiments of the present application. DETAILED DESCRIPTION

[0039] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0041] In the description of the embodiments of this application, the technical terms "first" and "second" are used only to distinguish different objects and should not be understood to indicate or imply relative importance or implicitly specify the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise clearly and specifically defined.

[0042] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0043] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0044] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0045] In recent years, solar cells have become the most promising emerging photovoltaic devices due to their wide availability of low-cost raw materials, simple manufacturing process, and ability to be manufactured on flexible substrates. Usually, when forming a series or parallel structure of solar cells, it is necessary to scribe different film layers at different locations to form P1 grooves, P2 grooves, and P3 grooves. The scribing of the functional layer can be accomplished by masking, chemical etching, mechanical or laser scribing. Figure 1 , marking different film layers at different positions can be divided into:

[0046] P1 groove: The bottom electrode layer is separated by equipment. After the conductive layer is prepared, it is scribed by related equipment before the hole transport layer, light absorption layer and electron transport layer are prepared to form independent conductive layer substrates.

[0047] P2 groove: This exposes the conductive layer substrate, providing a channel for connecting the positive and negative electrodes of two adjacent sub-cells. After the hole transport layer, light absorption layer, and electron transport layer are prepared, they are etched using related equipment to expose the conductive layer, allowing the positive and negative electrodes of the sub-cells to be connected to each other during the next electrode deposition process. The P2 groove is created by cutting through the hole transport layer, light absorption layer, and electron transport layer above the conductive layer before the back electrode layer is deposited, ending at the conductive layer.

[0048] P3 groove: After the back electrode layer is deposited, the hole transport layer, light absorption layer, electron transport layer and back electrode layer above the conductive layer are cut off until the conductive layer is reached.

[0049] Among them, the back electrode layer commonly uses metal electrodes such as Cu, Ag, etc. The P2 groove runs through the entire solar cell. The material of the back electrode layer will contact the various functional layers of the solar cell. If it directly contacts the light absorption layer or organic layer material, it will react with the light absorption layer ABX3 after a long time to generate CuX2, AgX, etc., increase the contact resistance, accelerate the degradation of the light absorption layer, reduce the stability of the solar cell, and shorten the service life.

[0050] The present application provides a solar cell, which includes a back electrode layer, which includes a composite material. The solar cell includes a groove that penetrates a functional layer. The composite material is at least located in the groove, covers the side of the functional layer facing the groove, or fills the groove. The composite material includes a metal-organic framework material and a metal element located in the metal-organic framework material, or a metal element and a metal salt located in the metal-organic framework material.

[0051] In the technical solution of the embodiment of the present application, the metal organic framework material generally has high water, oxygen, chemical and high temperature stability. Since the metal organic framework material has electrical conductivity, the metal organic framework material contains a metal element or contains a metal element and a metal salt, that is, the metal element is used as the core or the metal element and the metal salt are used as the core, and the metal organic framework material is used as a protective framework with a core outer layer. Since the metal element has good electrical conductivity, after being filled into the metal organic framework material, it can not only play its own conductive role, but also fill the defects in the metal organic framework material body, and the composite material formed has high electrical conductivity. The composite material is applied to the back electrode layer of the solar cell, not only can the conductive function be achieved, but the metal salt and / or the metal element will not directly contact the functional layer in the solar cell, so that the metal salt and / or the metal element will not chemically react with the functional layer in the solar cell, and the metal salt and / or the metal element will not cause degradation of the functional layer, therefore, the stability of the solar cell can be improved.

[0052] The metal organic framework material can be selected to be a metal organic framework material that can withstand temperatures above 100° C., humidity greater than or equal to 30% RH, and / or oxygen content greater than or equal to 10,000 ppm for more than 24 hours without degradation or collapse.

[0053] In some embodiments, the conductivity of the metal organic framework material is 1 S·cm -1 ~100S·cm -1 .

[0054] The electrical conductivity of metal-organic framework materials can reach 1 S·cm -1 、5S·cm -1 、10S·cm -1 、20S·cm -1 、30S·cm -1 、32S·cm -1 、40S·cm -1 、50S·cm -1 、55S·cm -1 、60S·cm -1 、70S·cm -1 、72.5S·cm -1 、80S·cm -1 、90S·cm -1 、100S·cm -1 etc.; or a range consisting of any two of the above values, for example, 1S·cm -1 ~50S·cm -1 、20S·cm -1 ~70S·cm -1 , 2S·cm -1 ~40S·cm -1 、55S·cm -1 ~100S·cm -1 In some embodiments, the conductivity of the metal organic framework material can be selected to be 2S·cm -1 ~40S·cm -1 .

[0055] Conductivity has a well-known definition and testing method in the industry. For example, it can be tested using a conductivity meter.

[0056] In the technical solution of the embodiment of the present application, the electrical conductivity of the metal organic framework material is within the above range, so that the composite material has good electrical conductivity when applied to the back electrode layer.

[0057] In some embodiments, the pore size of the metal organic framework material is less than or equal to 100 nm.

[0058] In the technical solutions of the embodiments of the present application, the pore size of the metal-organic framework material is within the above-mentioned range, which allows the metal salt to more easily enter the interior of the metal-organic framework material. Once inside the metal-organic framework material, at least a portion of the metal salt can be reduced to form a metal element within the metal-organic framework material, thereby making the formed composite material highly conductive. The pore size of the metal-organic framework material is less than or equal to 100 nm, and can be selected from 1 nm to 50 nm, for example, 1 nm, 10 nm, 20 nm, 28 nm, 35 nm, 50 nm, 68 nm, 94 nm, 100 nm, etc.; or a range consisting of any two of the above values, for example, 1 nm to 35 nm, 20 nm to 50 nm, 20 nm to 100 nm, 35 nm to 100 nm, etc.

[0059] In some embodiments, the particle size of the metal element is less than or equal to 100 nm.

[0060] In the technical solution of the embodiment of the present application, the particle size of the metal element is within the above range, so as to achieve effective loading inside the metal organic framework material and effectively fill the defects in the metal organic framework material body, so that the composite material formed has high conductivity and good structural stability. The particle size of the metal element can be 0.02nm, 0.5nm, 2nm, 19nm, 20nm, 30nm, 35nm, 49nm, 50nm, 65nm, 80nm, 98nm, 100nm, etc.; or a range consisting of any two of the above values, for example, it can be 0.02nm~49nm, 30nm~65nm, 50nm~98nm, 49nm~100nm, etc.

[0061] In some embodiments, the metal-organic framework material includes a metal element and a ligand coordinated with the metal element, and the ligand includes an aromatic group.

[0062] In the technical solution of the embodiment of the present application, the metal organic framework material is within the above range, and the metal organic framework material has a conjugated structure, so that the metal organic framework material has conductivity.

[0063] In some embodiments, the metal-organic framework material is a two-dimensional structure or a one-dimensional structure.

[0064] In the technical solution of the embodiment of the present application, the metal organic framework material has conductivity within the above range.

[0065] In some embodiments, the metal organic framework material includes at least one of Cu-HHTP (CAS: 2257422-27-6), Cu-THQ (CAS: 2243781-38-4), and Ni3(HHTP)2 (CAS: 2271400-02-1).

[0066] Specifically, the structural formula of Cu-HHTP is: The structural formula of Cu-THQ is: The structural formula of Ni3(HHTP)2 is

[0067] In the technical solution of the embodiment of the present application, the composite material formed by using the above-mentioned metal organic framework material has high conductivity and good structural stability.

[0068] In some embodiments, the metal element in the metal salt and / or the metal element includes at least one of gold (Au), silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), and manganese (Mn).

[0069] In the technical solution of the embodiment of the present application, the metal element formed by the above-mentioned metal elements or the metal element and metal salt formed are loaded in the metal-organic framework material, so that it has excellent conductive properties.

[0070] In the present application, the method for preparing a composite material may include: preparing a metal salt solution; mixing a metal organic framework material with the metal salt solution to obtain a mixed solution; filtering the mixed solution, and vacuum drying to obtain a composite material; wherein the composite material includes any of the composite materials described above.

[0071] During the drying process, the metal salt loaded in the metal organic framework material can be reduced by controlling the atmosphere to form a metal element.

[0072] Before filtering the mixed solution, a reducing agent may be added to the mixed solution to reduce the metal salt in the metal organic framework material to form a metal element.

[0073] Specifically, the composite material is prepared by preparing a metal salt solution, which includes, but is not limited to, an aqueous solution or an alcohol solution of a salt of at least one of the metal elements gold (Au), silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), and manganese (Mn). For example, an aqueous solution or an alcohol solution of AgNO3, Cu(NO3)2, Ni(NO3)2, Co(NO3)2, etc. The metal organic framework material and the metal salt solution were mixed in a three-necked flask, sealed, and magnetically stirred at 50°C and 160 rpm for 24 hours. The mixture was filtered and vacuum dried at 50°C for 12 hours to obtain composite materials, such as Cu-HHTP@Ag, Cu-HHTP@Cu, Cu-HHTP@Ni, Cu-HHTP@Co, Cu-THQ@Ag, Cu-THQ@Cu, Cu-THQ@Ni, Cu-THQ@Co, Ni3(HHTP)2@Ag, Ni3(HHTP)2@Cu, Ni3(HHTP)2@Ni, Ni3(HHTP)2@Co, etc.

[0074] In some embodiments, after the metal organic framework material and the metal salt solution are mixed to obtain a mixed solution, the mixture is sealed and stirred for a period of time to fully mix the metal organic framework material and the metal salt solution, allowing more metal salt to enter the pores of the metal organic framework material.

[0075] In some embodiments, the concentration ratio of the metal organic framework material to the metal salt solution is 10:0.5 to 10:1.5.

[0076] In the technical solution of the embodiment of the present application, the composite material formed by the metal organic framework material and the metal salt solution with the concentration ratio within the above range is composed of a metal element or a metal element and a metal salt as the core, and the metal organic framework material as the protective framework of the core outer layer. Since the metal element has good conductivity, after being filled into the metal organic framework material, it can not only play its own conductive role, but also fill the defects in the metal organic framework material itself, and the composite material has high conductivity. The concentration ratio of the metal organic framework material to the nitrate aqueous solution can be 10:0.5, 10:0.6, 10:0.7, 10:0.85, 10:0.95, 10:1, 10:1.1, 10:1.5, etc.; or a range consisting of any two of the above values, for example, it can be 10:0.5-10:0.85, 10:0.7-10:1.1, 10:0.85-10:1, 10:0.85-10:1.5, etc.

[0077] In some embodiments, the thickness of the back electrode layer is 30 nm to 300 nm.

[0078] In the technical solution of the embodiment of the present application, when the back electrode layer includes a first conductive layer and a second conductive layer, the thickness of the back electrode layer is 30 nm to 300 nm, optionally 40 nm to 200 nm. The thickness of the back electrode layer can be 30 nm, 40 nm, 80 nm, 135 nm, 198 nm, 210 nm, 260 nm, 300 nm, etc.; or a range consisting of any two of the above values, for example, 30 nm to 135 nm, 40 nm to 80 nm, 80 nm to 210 nm, 210 nm to 300 nm, etc. The back electrode layer having a thickness within the above range can have good conductivity.

[0079] A scanning electron microscope (SEM) was used to obtain cross-sectional scanning electron microscope (SEM) images of the film layer, and thickness was measured based on the SEM images.

[0080] In some embodiments, the solar cell 100 includes at least a stacked bottom electrode layer, a functional layer, and a back electrode layer as described above; wherein the back electrode layer includes a first conductive layer or includes a first conductive layer and a second conductive layer, wherein the first conductive layer is located between the functional layer and the second conductive layer, the first conductive layer includes a composite material, and the second conductive layer includes a conductive material.

[0081] In the technical solution of the embodiment of the present application, the composite material has electrical conductivity and high stability. When the composite material is applied to the back electrode layer of a solar cell, it not only achieves the function of electrical conductivity, but also prevents the metal salt and / or metal element from directly contacting the functional layer in the solar cell, thereby preventing the metal salt and / or metal element from chemically reacting with the functional layer in the solar cell, weakening the degradation of the functional layer and improving the stability of the solar cell.

[0082] At the same time, when the back electrode layer includes the first conductive layer and the second conductive layer, the composite material is located between the functional layer and the second conductive layer, and the functional layer and the second conductive layer will not react with each other, which can improve the stability of the solar cell.

[0083] The substrate of the bottom electrode layer is glass or a transparent organic polymer, and includes at least one of an organic conductive material, an inorganic conductive material, or an organic-inorganic mixed conductive material, optionally including at least one of a transparent conductive metal oxide, carbon, a metal, and an alloy thereof, more optionally including at least one of indium tin oxide (ITO), lanthanide metal-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and alloys thereof, graphite, graphene, and carbon nanotubes; optionally including at least one of Ag, Cu, C, Au, Al, ITO, AZO, BZO, or IZO, and further optionally including at least one of Cu, Ag, and Au.

[0084] The bottom electrode layer is similar to the back electrode layer, except that the bottom electrode layer is a transparent electrode for light incidence.

[0085] In other embodiments, reference Figure 2 The functional layers of the solar cell 100 may further include a hole transport layer, a light absorption layer, and an electron transport layer.

[0086] The hole transport layer is responsible for transporting holes and blocking electrons, and may include but is not limited to a mixture of at least one or more of the following materials: 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), p-PY, PPY2, Me-4PACz, Me O-2PACz, poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS), poly-3-hexylthiophene (P3HT), triphenylamine with triptycene as the core, polythiophene, phosphate-based monomers, carbazole-based monomers, sulfonic acid-based monomers, triphenylamine-based monomers, aromatic monomers, imide compounds, quinone compounds, WO3, thiophene, phthalocyanine, porphyrin, metal oxides (which can be recorded as first metal oxides, such as molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide), molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, cuprous thiocyanate, copper iodide, fluorine-containing phosphonic acid, carbonyl-containing phosphonic acid, carbon nanotubes and graphene.

[0087] The light absorbing layer includes a perovskite-type metal halide, whose general chemical formula includes ABX3 or A2CDX6. Wherein, A includes a monovalent inorganic cation, an organic cation, or an organic-inorganic mixed cation, B includes a divalent inorganic cation, an organic cation, or an organic-inorganic mixed cation, C includes a monovalent inorganic cation, an organic cation, or an organic-inorganic mixed cation, D includes a trivalent inorganic cation, an organic cation, or an organic-inorganic mixed cation, and X includes a monovalent inorganic anion, an organic anion, or an organic-inorganic mixed anion.

[0088] Specifically, when A represents a monovalent inorganic cation, optionally, A includes Li + 、Na + , K + , Rb + and Cs + When A represents an organic cation, optionally, A includes at least one of methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, amidino and imidazolyl; more optionally, A includes organic amine ions and Cs + At least one of .

[0089] When B represents a divalent cation, optionally, B includes at least one of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium.

[0090] When C represents a monovalent inorganic cation, optionally, C includes Cs + 、Ag + , K + and Ru + At least one of .

[0091] When D represents a trivalent metal cation, optionally, D includes Bi 3+ 、Ni 3+ 、Fe 3+ 、Sb 3+ 、In 3+ At least one of, more optionally, D includes In 3+ 、Bi 3+ 、Sb 3+ At least one of .

[0092] X represents a halogen ion, optionally, X includes F - 、Cl - Br - , I - At least one of, more optionally, X includes Cl - Br - and I - At least one of .

[0093] The electron transport layer is responsible for extracting electrons and blocking holes, and may include but is not limited to a mixture of at least one or more of the following materials: fullerene and its derivatives (such as [6,6]-phenyl-C61-butyric acid isomethyl ester (PC61BM), [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), fullerene C60, fullerene C70), cyano-containing polyphenylene vinylene, boron-containing polymers, bathocuproin, bathophenanthroline, hydroxyquinoline aluminum, oxadiazole compounds, imide compounds, quinone compounds, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), benzimidazole compounds, naphthalene tetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluorine-containing phthalocyanine, calcium titanate (CaTiO3), strontium titanate (SrTiO3), tin sulfide, indium sulfide, lithium fluoride (LiF), sodium fluoride, magnesium fluoride ( MgF2), calcium fluoride (CaF2) and zinc sulfide, poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), poly 3-hexylthiophene (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, cuprous thiocyanate (CuSCN), metal oxide (which can be recorded as the second metal oxide, wherein the metal element can include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr, such as titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, silicon oxide (SiO2).

[0094] In other embodiments, the light absorbing layer may further include silicon material, copper indium gallium selenide material, copper indium gallium sulfide material, etc.

[0095] In some embodiments, the solar cell may not include a hole transport layer and / or an electron transport layer.

[0096] The first conductive layer comprises the composite material described above, and the second conductive layer can be an organic, inorganic, or a mixture of organic and inorganic materials in varying proportions, including transparent conductive oxides and metals. Transparent conductive oxides include at least one of indium tin oxide (ITO), lanthanide metal-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and indium tungsten oxide (IWO). Metals include at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, and Mg.

[0097] In some embodiments, the thickness of the first conductive layer is 30 nm to 300 nm.

[0098] In the technical solution of the embodiment of the present application, when the back electrode layer includes a first conductive layer, the thickness of the first conductive layer is 30 nm to 300 nm, optionally 40 nm to 200 nm. The thickness of the first conductive layer can be 30 nm, 40 nm, 85 nm, 120 nm, 189 nm, 200 nm, 250 nm, 300 nm, etc.; or a range consisting of any two of the above values, for example, 30 nm to 120 nm, 40 nm to 85 nm, 85 nm to 200 nm, 200 nm to 300 nm, etc. The thickness of the first conductive layer within the above range can provide good electrical conductivity.

[0099] In some embodiments, when the back electrode layer includes a first conductive layer and a second conductive layer, the thickness of the first conductive layer accounts for less than or equal to 40% of the thickness of the back electrode layer.

[0100] In the technical solution of the embodiment of the present application, when the back electrode layer includes a first conductive layer and a second conductive layer, the first conductive layer is used as a spacer between the second conductive layer and the functional layer. The thickness of the first conductive layer accounts for less than or equal to 40% of the thickness of the back electrode layer. This can make the back electrode layer have better conductivity and improve the stability of the solar cell. The thickness of the first conductive layer can account for 1%, 5%, 10%, 15%, 20%, 28%, 35%, or 40% of the thickness of the back electrode layer.

[0101] When preparing a perovskite solar cell, the following steps may be included:

[0102] (1) preparing a bottom electrode on a transparent substrate;

[0103] (2) preparing an electron transport layer or a hole transport layer on a transparent substrate coated with a bottom electrode;

[0104] (3) preparing a light absorbing layer (i.e., a perovskite layer) on the electron transport layer or the hole transport layer;

[0105] (4) preparing an electron transport layer or a hole transport layer on the light absorbing layer;

[0106] (5) Prepare the back electrode.

[0107] If it is prepared as a perovskite solar panel, several laser processes P1 / P2 / P3 will be added to the steps to divide the large-area battery into different small batteries for series or parallel connection.

[0108] See Figure 3 The present application also provides an electrical device 1000, which includes the perovskite solar cell as described above or a perovskite solar cell prepared by the method for preparing a perovskite solar cell as described above.

[0109] In the present application, the perovskite solar cell serves as a power source for the electrical device 1000; alternatively, the perovskite solar cell can serve as an energy storage unit for the electrical device 1000. By way of example, the electrical device 1000 can be a lighting element, a display element, or a car.

[0110] See Figure 4 The present application also provides a power generation device 2000, comprising the aforementioned perovskite solar cell or a perovskite solar cell prepared by the aforementioned method for preparing a perovskite solar cell. The power generation device 2000 may include a perovskite solar cell and an energy storage device, which may be a secondary battery.

[0111] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail with reference to the embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present application and its applications. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0112] The features and performance of the present application are further described in detail below with reference to the embodiments.

[0113] Example 1:

[0114] (1) A set of FTO conductive glass with a size of 30cm×30cm was etched with P1 grooves using an infrared laser. The width of the P1 grooves was about 30μm. The entire conductive glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the solar cell welding area. The etched conductive glass surface was cleaned twice with acetone and isopropyl alcohol, immersed in deionized water for ultrasonic treatment for 10min, and then dried in a forced air drying oven. It was placed in a drying room (humidity less than 2%) and used as the bottom electrode layer.

[0115] (2) Preparation of hole transport layer: The cleaned conductive glass is placed in a magnetron sputtering device to deposit a layer of nickel oxide. The thickness of the nickel oxide layer is about 15 nm.

[0116] (3) Preparation of light absorbing layer: a layer of FA is coated by slit coating 0.95 Cs 0.05The PbI3 perovskite main layer was then transferred to a vacuum equipment and vacuumed for 60 seconds with a vacuum degree of 15 Pa. It was annealed at 150°C for 10 minutes using a non-contact closed space annealing process. After annealing, the perovskite dry film thickness was about 500nm.

[0117] (4) Preparation of electron transport layer: Place the device after preparing the light absorption layer in a vacuum thermal evaporation device and evacuate to 4×10 -4 Pa, C60 with a thickness of 30 nm and BCP with a thickness of 8 nm were deposited.

[0118] (5) Preparation of back electrode layer:

[0119] ① Preparation of composite materials:

[0120] Prepare a 1 mol / L AgNO3 aqueous solution.

[0121] 0.1 mol / L of the metal organic framework material Cu-HHTP was mixed with the above-mentioned AgNO3 aqueous solution in a three-necked flask, sealed, and magnetically stirred at 50°C and 160 rpm for 24 h.

[0122] The mixed solution was filtered and dried in vacuum at 50°C for 12 h to obtain the composite material: Cu-HHTP@Ag.

[0123] ② The first preparation stage of the first conductive layer of the back electrode layer: After depositing the electron transport layer in the vacuum thermal evaporation equipment, Ni3(HHTP)2@Ag with a thickness of 10nm is deposited on its surface by thermal evaporation.

[0124] ③ The second preparation stage of the first conductive layer of the back electrode layer: the device with the back electrode layer I deposited above was taken out of the vacuum, and the P2 groove was etched by laser. The width of the P2 groove was 150 μm and the depth was etched to the surface of the FTO layer. The gap between the P2 groove and the P1 groove was 20 μm. Then the substrate was placed in the evaporation equipment again and vacuumed to 4×10 -4 After Pa, a layer of Ni3(HHTP)2@Ag with a thickness of about 20 nm was deposited by thermal evaporation.

[0125] ④ Preparation of the second conductive layer of the back electrode layer: Continue to evaporate a layer of Cu with a thickness of 70 nm by thermal evaporation.

[0126] The reason for depositing Ni3(HHTP)2@Ag in two stages in steps ② and ③ is that laser scribing of the P2 trench is typically performed in oxygen, requiring a vacuum environment. The electron transport layer is typically an organic layer, such as BCP, which can aggregate or crystallize when exposed to air, leading to a sharp decline in solar cell performance. Therefore, a layer of Ni3(HHTP)2@Ag is deposited first in step ② to protect the electron transport layer from the oxygen in step ③ and to minimize laser damage.

[0127] (6) After cooling, the vacuum is broken and the sample is taken out. The P3 groove is etched by picosecond green laser. The width of the P3 groove is 15 μm and the depth is etched to the surface of the FTO layer. The interval between the P3 groove and the P2 groove is 20 μm.

[0128] (7) Then, infrared edge cleaning is used on the component, that is, 10 mm is etched on each side of the component to obtain a solar cell.

[0129] (8) At 1000W / m 2 The energy conversion efficiency of solar cells is tested under a solar simulator.

[0130] Example 2 to Example 30, Comparative Examples 1 to 3:

[0131] Examples 2 to 30 and Comparative Examples 1 to 3 are similar to Example 1, except that the formula and process parameters in step (5) are adjusted. Please see Table 1 for details.

[0132] 1. Photoelectric conversion rate test method

[0133] At room temperature and pressure, the test was conducted using a standard AM1.5G sunlight simulation light source in compliance with the national standard IEC61215. A crystalline silicon solar cell was used to calibrate the light intensity to the intensity of one sun. A four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the solar cell under the light source, and the open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and energy conversion efficiency (Eff) of the solar cell were obtained.

[0134] 2. Battery stability test method

[0135] After the test, the battery was placed in an atmospheric environment (relative humidity of 65%-85%, ambient temperature of approximately 15°C-40°C), and after being placed in the dark for 500 hours, the energy conversion efficiency was tested again (each test was performed until there was no hysteresis in the forward and reverse scans, and the energy conversion efficiency was recorded). The ratio of the solar cell efficiency after 500 hours of atmospheric placement to the initial efficiency was calculated as the normalized efficiency of the solar cell after 500 hours of placement.

[0136] Initial normalized efficiency = retest efficiency / initial efficiency × 100%

[0137] The battery devices 1 to 33 obtained in the above Examples 1 to 30 and Comparative Examples 1 to 3 were subjected to battery performance tests, and the results are shown in Table 1.

[0138]

[0139]

[0140] It can be seen from the relevant data in Table 1 that the battery devices 1 to 34 of Examples 1 to 34 all use composite materials in the back electrode layer, and their efficiency after 500 hours of placement is higher than that of devices 35 to 37 of Comparative Examples 1 to 3. In devices 35 to 37 of Comparative Examples 1 to 3, no composite material is used in the back electrode layer. The back electrode layer of Comparative Examples 1 to 3 reacts with the light absorption layer, or the back electrode layer accelerates agglomeration with the electron transport layer in the air, resulting in low efficiency after 500 hours of placement and poor device stability. This shows that the present application uses a composite material in the back electrode layer of the solar cell. The composite material can not only achieve the conductive function, but also the metal salt and / or metal element will not directly contact the functional layer in the solar cell, so that the metal salt and / or metal element will not chemically react with the functional layer in the solar cell, and the metal salt and / or metal element will not cause degradation of the functional layer. Therefore, the stability of the solar cell can be improved.

[0141] The above description is only an implementation method of the present application and does not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the description and drawings of this application, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A solar cell, characterized in that: The solar cell includes a back electrode layer, the back electrode layer includes a composite material, the solar cell includes a groove penetrating the functional layer, the composite material is at least located in the groove, covers the side of the functional layer facing the groove, or fills the groove, and the composite material includes a metal organic framework material and a metal element located in the metal organic framework material, or a metal element and a metal salt located in the metal organic framework material.

2. The solar cell according to claim 1, wherein The conductivity of the metal organic framework material is 1S·cm -1 ~100S·cm -1 .

3. The solar cell according to claim 1 or 2, wherein: The pore diameter of the metal organic framework material is less than or equal to 100 nm.

4. The solar cell according to any one of claims 1 to 3, wherein The particle size of the metal element is less than or equal to 100 nm.

5. The solar cell according to any one of claims 1 to 4, wherein The metal organic framework material includes a metal element and a ligand coordinated with the metal element, and the ligand includes an aromatic group.

6. The solar cell according to any one of claims 1 to 5, wherein The metal organic framework material has a two-dimensional structure or a one-dimensional structure.

7. The solar cell according to any one of claims 1 to 6, wherein: The metal organic framework material includes at least one of Cu-HHTP, Cu-THQ, and Ni3(HHTP)2.

8. The solar cell according to any one of claims 1 to 7, wherein The metal element in the metal salt and / or metal element includes at least one of gold (Au), silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe) and manganese (Mn).

9. The solar cell according to any one of claims 1 to 8, wherein The thickness of the back electrode layer is 30 nm to 300 nm.

10. The solar cell according to any one of claims 1 to 9, wherein The solar cell comprises at least a bottom electrode layer, the functional layer and the back electrode layer which are stacked; The back electrode layer includes a first conductive layer or a first conductive layer and a second conductive layer, wherein the first conductive layer is located between the functional layer and the second conductive layer, the first conductive layer includes the composite material, and the second conductive layer includes a conductive material.

11. The solar cell according to claim 10, wherein The thickness of the first conductive layer is 30 nm to 300 nm.

12. The solar cell according to claim 10 or 11, wherein: When the back electrode layer includes a first conductive layer and a second conductive layer, the thickness of the first conductive layer accounts for less than or equal to 40% of the thickness of the back electrode layer.

13. An electrical device, characterized in that: The solar cell according to any one of claims 1 to 12 is included.

14. A power generation device, characterized in that: The solar cell according to any one of claims 1 to 12 is included.

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