Composite electrode, perovskite battery and preparation method and application thereof

Abstract

The application provides a composite electrode, a perovskite battery and a preparation method and application thereof. The composite electrode comprises a buffer layer, a conductive layer and a protective layer which are sequentially stacked. The components of the buffer layer and the protective layer both comprise a transparent conductive oxide, and the component of the conductive layer comprises a conductive metal. The composite electrode can assist in passivating defects on the surface of a functional layer (for example, a hole transport layer) in contact therewith, and reduce kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering. At the same time, the probability of the conductive layer being directly eroded by water, oxygen and the like in the environment is reduced, so that the efficiency of the perovskite battery is improved.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and in particular to a composite electrode, a perovskite battery, its preparation method and application. Background Technology

[0002] Perovskite solar cells are solar cells that use perovskite-type organometal halide semiconductors as light-absorbing materials. The photoelectric conversion efficiency of perovskite solar cells with various structures has surpassed that of industrialized solar cell technologies such as crystalline silicon solar cells, which have been developed for many years, showing great potential for industrial development.

[0003] In existing technologies, precious metals such as gold and silver are commonly used as electrode materials for perovskite solar cells. However, iodine ions migrating from the perovskite layer can chemically react with the silver electrode, inducing chemical / electrochemical corrosion of the gold electrode under working or fabrication conditions (such as electric field, light, water, and oxygen). This leads to damage to the electrode interface, increased contact resistance, and accelerated degradation of battery performance. For example, a typical perovskite solar cell generally includes a transparent conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer, and a top electrode. When fabricating the top electrode of a typical perovskite solar cell, firstly, the organic hole transport layer is easily damaged by the top electrode, and secondly, the top electrode is easily corroded by water, oxygen, and other substances in the environment, which has a significant impact on the photoelectric conversion efficiency of the perovskite solar cell.

[0004] Therefore, traditional technologies still need further improvement. Summary of the Invention

[0005] Based on this, this application provides a composite electrode, a perovskite battery, and its preparation method and application, aiming to reduce the probability of the battery being corroded by water, oxygen and other elements in the environment, and improve the efficiency of the perovskite battery.

[0006] The technical solution of this application is as follows:

[0007] A first aspect of this application provides a composite electrode, the composite electrode comprising a buffer layer, a conductive layer and a protective layer stacked sequentially. The buffer layer and the protective layer are both composed of transparent conductive oxides, and the conductive layer is composed of conductive metals.

[0008] The composite electrode provided by this invention adopts a three-layer composite electrode structure of a specific material. By setting a buffer layer and a protective layer of a specific material on both sides of the conductive layer, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery during the preparation of the conductive layer by magnetron sputtering. On the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment, which is beneficial to improving battery efficiency and electrochemical performance.

[0009] In some embodiments, the thickness of the buffer layer is 20 nm to 60 nm, and / or The thickness of the conductive layer is 60 nm to 180 nm, and / or The thickness of the protective layer is 20 nm to 60 nm.

[0010] The thickness of each layer was further adjusted to optimize the protective function of the composite electrode while ensuring excellent conductivity.

[0011] In some embodiments, the components of the buffer layer and the protective layer are each independently selected from at least one of indium tin oxide, indium tungsten oxide, indium gallium oxide, zinc aluminum oxide, and indium gallium tin oxide.

[0012] It is understandable that the components of the buffer layer and the protective layer may be the same or different.

[0013] In some embodiments, the conductive metal includes at least one of aluminum, copper, gold, and nickel.

[0014] A second aspect of this application provides a method for preparing the composite electrode of the first aspect, comprising the following steps: The composite electrode is prepared by sequentially forming a buffer layer, a conductive layer, and a protective layer using physical vapor deposition.

[0015] In some embodiments, the physical vapor deposition method is magnetron sputtering.

[0016] When the above-mentioned composite electrode is formed, a three-layer composite electrode structure of a specific material is formed. By setting a buffer layer and a protective layer of a specific material on both sides of the conductive layer, on the one hand, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering; on the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment; which is beneficial to improving battery efficiency and electrochemical performance.

[0017] A third aspect of this application provides a perovskite battery, the perovskite battery comprising the composite electrode described in the first aspect.

[0018] In some embodiments, the perovskite solar cell includes, in sequence, a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode, wherein the second electrode is the composite electrode.

[0019] The composite electrode of the present invention is used in the above perovskite battery. By setting a buffer layer and a protective layer of specific materials on both sides of the conductive layer, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering. On the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment. This is beneficial to improving the battery efficiency and electrochemical performance.

[0020] In some embodiments, the perovskite solar cell further includes a passivation layer disposed between the perovskite layer and the hole transport layer.

[0021] A fourth aspect of this application provides a photovoltaic module, the photovoltaic module comprising the perovskite cell of the third aspect. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell in one embodiment.

[0023] 10. First electrode; 20. Electron transport layer; 30. Perovskite layer; 40. Passivation layer; 50. Hole transport layer; 60. Composite electrode; 61. Buffer layer; 62. Conductive layer; 63. Protective layer. Detailed Implementation

[0024] To facilitate understanding of this application, a more complete description is provided below, along with preferred embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0026] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0027] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be independently included or excluded, and they can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0028] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0029] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0030] One embodiment of this application provides a composite electrode, which includes a buffer layer, a conductive layer and a protective layer stacked sequentially.

[0031] The buffer layer and the protective layer are both composed of transparent conductive oxides, and the conductive layer is composed of conductive metals.

[0032] The composite electrode provided by this invention adopts a three-layer composite electrode structure of a specific material. By setting a buffer layer and a protective layer of a specific material on both sides of the conductive layer, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery during the preparation of the conductive layer by magnetron sputtering. On the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment, which is beneficial to improving battery efficiency and electrochemical performance.

[0033] It should be noted that the specific components of the buffer layer and the protective layer may be the same or different, and various known transparent conductive oxides in this field are acceptable.

[0034] In some embodiments, the thickness of the buffer layer is 20 nm to 60 nm.

[0035] In some embodiments, the thickness of the conductive layer is 60 nm to 180 nm.

[0036] In some embodiments, the thickness of the protective layer is 20 nm to 60 nm.

[0037] The thickness of each layer was further adjusted to optimize the protective function of the composite electrode while ensuring excellent conductivity.

[0038] For example, the thickness of the buffer layer can be 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm or 60 nm, or any range of two values.

[0039] For example, the thickness of the conductive layer can be 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm or 180 nm, or any range of two values.

[0040] For example, the thickness of the protective layer can be 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm or 60 nm, or any range of two values.

[0041] In some embodiments, the components of the buffer layer and the protective layer are each independently selected from at least one of indium tin oxide, indium tungsten oxide, indium gallium oxide, zinc aluminum oxide, and indium gallium tin oxide.

[0042] It is understandable that the components of the buffer layer and the protective layer may be the same or different.

[0043] In some embodiments, the conductive metal includes at least one of aluminum, copper, gold, and nickel.

[0044] One embodiment of this application provides a method for preparing the above-mentioned composite electrode, including the following step S1.

[0045] Step S1: A buffer layer, a conductive layer, and a protective layer are sequentially formed using physical vapor deposition to prepare a composite electrode.

[0046] In some embodiments, the physical vapor deposition method described above is magnetron sputtering.

[0047] When the above-mentioned composite electrode is formed, a three-layer composite electrode structure of a specific material is formed. By setting a buffer layer and a protective layer of a specific material on both sides of the conductive layer, on the one hand, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering; on the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment; which is beneficial to improving battery efficiency and electrochemical performance.

[0048] One embodiment of this application provides a perovskite battery comprising the aforementioned composite electrode.

[0049] In some embodiments, the perovskite solar cell includes, in sequence, a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode, wherein the second electrode is a composite electrode.

[0050] The composite electrode of the present invention is used in the above perovskite battery. By setting a buffer layer and a protective layer of specific materials on both sides of the conductive layer, it can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it and reduce the kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering. On the other hand, it can effectively prevent the conductive layer from being directly corroded by water, oxygen and other substances in the environment. This is beneficial to improving the battery efficiency and electrochemical performance.

[0051] In some embodiments, the composite electrode is in direct contact with the hole transport layer.

[0052] In other words, at least one surface of the composite electrode is in direct contact with the surface of the hole transport layer.

[0053] Furthermore, in the composite electrode, the buffer layer is closer to the hole transport layer than the protective layer.

[0054] In some embodiments, the perovskite solar cell further includes a passivation layer disposed between the perovskite layer and the hole transport layer.

[0055] Please refer to the details. Figure 1One embodiment of the perovskite includes: a first electrode 10, an electron transport layer 20, a perovskite layer 30, a perovskite protective layer 40, a hole transport layer 50, and a composite electrode 60, which are stacked in sequence; wherein, the composite electrode 60 includes: a buffer layer 61, a conductive layer 62, and a protective layer 63, which are stacked in sequence.

[0056] In some embodiments, the first electrode can be made of various commonly used electrode materials in the art, such as any one or more composite materials of conductive oxides and conductive metals. Further, the conductive oxide includes at least one of FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), and IWO (tungsten-doped indium oxide); the conductive metal includes at least one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), and chromium (Cr).

[0057] In some embodiments, the hole transport material of the hole transport layer of this application is a common hole transport layer material in the art, and this application does not limit its type.

[0058] The hole transport material of the hole transport layer may include, but is not limited to, one or more of the following materials and their derivatives: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (abbreviated as: PTAA), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (abbreviated as: Spiro-OMeTAD), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (abbreviated as: PEDOT:PSS), poly3-hexylthiophene (abbreviated as: P3HT), triphenylamine with a triphenylene core (abbreviated as: H101), 3,4-ethylenedioxythiazole-methoxytriphenylamine (abbreviated as: EDOT-OMeTPA), N-(4-aniline)carbazole-spirodifluorene (abbreviated as: CzPAF-SBF), polythiazole, triphenylamine monomers and their polymers, carbazole monomers and their polymers, and other materials that can transport holes and block electrons.

[0059] In some embodiments, the electron transport material of the electron transport layer of this application is a common electron transport layer material in the art, and this application does not limit its type, such as SnO2.

[0060] In some embodiments, the perovskite active material in the perovskite layer of this application is a common perovskite active material in the art. This application does not limit its type, such as FAxMAyCs(1-xy)Pb(IzBr(1-z))3 (often simply referred to as FAMACs), 0 ≤ x ≤ 1, 0 ≤ y ≤ 1 and x + y ≤ 1; 0 ≤ z ≤ 1.

[0061] In some embodiments, the passivation layer of this application uses perovskite passivation agents commonly used in the art, and this application does not limit the type of them, such as trifluoromethylphenethylamine hydroiodide (CF3-PEAI).

[0062] In some embodiments, the perovskite solar cell of this application may be prepared using commonly used methods in the art, and this application does not limit this to such methods, for example, step S2 as follows.

[0063] Step S2: An electron transport layer, a perovskite layer, a passivation layer, a hole transport layer, and a second electrode are sequentially formed on one side of the first electrode to obtain a perovskite solar cell. The second electrode is prepared using the same method as the composite electrode described above.

[0064] In some embodiments, the methods for forming the perovskite layer, hole transport layer, and electron transport layer may also employ conventional methods in the art, and this application does not impose any particular limitation on them, including but not limited to: any one of spin coating, blade coating, and slot coating.

[0065] According to one embodiment of this application, a photovoltaic module is provided, the photovoltaic module including the perovskite cell as described above.

[0066] The photovoltaic module of this application, by employing the perovskite cell of this application, has high photoelectric conversion efficiency and good stability.

[0067] In some embodiments, the photovoltaic module is a solar panel.

[0068] The present application will be described below with reference to specific embodiments, but the present application is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present application. Under the guidance of the concept of the present application, those skilled in the art should realize that certain changes made to the various embodiments of the present application will be covered by the spirit and scope of the claims of the present application.

[0069] The following are specific examples.

[0070] The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0071] Example 1 The fabrication of perovskite solar cells includes the following steps: (1) Preparation of the first electrode (substrate): Commercially purchased FTO glass with PI lines in the size of 30cm×30cm was ultrasonically cleaned for 15 minutes each with detergent, deionized water, acetone and isopropanol, dried with nitrogen and UV treated for 15 minutes, and used as the first electrode (substrate) for later use.

[0072] (2) Preparation of electron transport (ETL) layer: The commercially purchased SnO2 colloidal diluent was diluted with deionized water at a volume ratio of deionized water: SnO2 = 4:1 and filtered before use to obtain ETL solution; the substrate obtained in step (1) was cut into 5cm×5cm size, and the prepared ETL solution was spin-coated on one side of the substrate. The spin-coating program was 4000 revolutions per minute for 30 seconds, and the substrate was annealed at 180°C for 15 minutes to obtain electron transport (ETL) layer.

[0073] (3) Preparation of perovskite layer: 22.1 mg cesium iodide, 27 mg methyl iodide, 8 mg chloromethyl iodide, 248.5 mg methyl ammonium iodide and 806.8 mg lead iodide were dissolved in 1 mL of DMF / NMP mixed solvent (volume ratio 6:1), stirred at 60 °C for 2 h, filtered, and prepared as perovskite precursor solution; then, perovskite film was prepared on the ETL layer obtained in step (2) by blade coating method. The specific method is as follows: 55 μL of precursor was dropped between the blade and the substrate, and coated at a gap of 300 μm and a speed of 5.0 mm / s; after coating, it was transferred to a vacuum chamber and treated at 10 Pa for 35 s, and then air annealed at 150 °C for 15 min to obtain perovskite layer.

[0074] (4) Passivation layer preparation: Dissolve 5 mg of trifluoromethylphenethylamine hydroiodide (CF3-PEAI) in 1 mL of isopropanol to prepare a passivation solution. Spin coat the passivation solution onto the perovskite layer obtained in step (3) at a spin coating speed of 3000 rpm for 30 s to prepare the passivation layer.

[0075] (5) Hole transport layer (HTL) preparation: 90 mg of 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD) was dissolved in 1 mL of chlorobenzene. After complete dissolution, 29 μL of 4-tert-butylpyridine and 23 μL of lithium bis(trifluoromethanesulfonylimide) in acetonitrile solution were added to prepare Spiro-OMeTAD solution. Spiro-OMeTAD solution was spin-coated onto the passivation layer obtained in step (4) at a spin-coating speed of 3000 rpm for 30 s. After standing for 30 min, it was etched with a green laser to complete the preparation of the hole transport layer (HTL).

[0076] (6) Preparation of composite (second) electrode: Place the hole transport layer obtained in step (5) upward on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: The equipment base vacuum reaches 5×E -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 10 min, to prepare a 60 nm thick ITO buffer layer.

[0077] Then, without breaking the vacuum, the equipment's background vacuum reached 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 20 min, to prepare a Cu conductive layer with a thickness of 90 nm.

[0078] Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, the formal sputtering was 10 min, and a 60 nm thick ITO protective layer was prepared, thus completing the preparation of the ITO-Cu-ITO three-layer composite electrode and obtaining the perovskite solar cell.

[0079] Example 2 Example 2 is basically the same as Example 1, except that the conditions for step (6) are as follows: (6) Preparation of composite (second) electrode: Place the hole transport layer obtained in step (5) upward on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: The equipment base vacuum reaches 5×E -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 10 min, to prepare a 60 nm thick ITO buffer layer.

[0080] Then, without breaking the vacuum, the equipment's background vacuum reached 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Al target RF power was 50 W, the pre-sputtering was 3 min, and the formal sputtering was 25 min to complete the 110 nm thick Al conductive layer in the middle layer.

[0081] Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was performed for 3 min, and the formal sputtering was performed for 10 min to prepare a 60 nm thick ITO protective layer, thus completing the preparation of the ITO-Al-ITO three-layer composite electrode and obtaining the perovskite solar cell.

[0082] The remaining conditions are the same as in Example 1.

[0083] Example 3 Example 3 is basically the same as Example 1, except that the conditions for step (6) are as follows: Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 6 min, to prepare a 35 nm thick ITO buffer layer.

[0084] Then, without breaking the vacuum, the equipment's background vacuum reached 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 40 min, to prepare a Cu conductive layer with a thickness of 180 nm.

[0085] Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, the formal sputtering was 3.5 min, and a 20 nm thick ITO protective layer was prepared, thus completing the preparation of the ITO-Cu-ITO three-layer composite electrode and obtaining the perovskite solar cell.

[0086] The remaining conditions are the same as in Example 1.

[0087] Example 4 Example 4 is basically the same as Example 1, except that the conditions for step (6) are as follows: Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 3.5 min, to prepare a 20 nm thick ITO buffer layer.

[0088] Then, without breaking the vacuum, the equipment's background vacuum reached 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 13.5 min, to prepare a Cu conductive layer with a thickness of 60 nm.

[0089] Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the ITO target RF power was 30 W, the pre-sputtering was 3 min, the formal sputtering was 7 min, and a 40 nm thick ITO protective layer was prepared, thus completing the preparation of the ITO-Cu-ITO three-layer composite electrode and obtaining the perovskite solar cell.

[0090] The remaining conditions are the same as in Example 1.

[0091] Example 5 Example 5 is basically the same as Example 1, except that step (6) is as follows: Step (6): Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the RF power of the indium gallium tin oxide IGTO target was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 4 min, to prepare a 35 nm thick IGTO buffer layer.

[0092] Then, without breaking the vacuum, the equipment's background vacuum reached 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 40 min, to prepare a Cu conductive layer with a thickness of 180 nm.

[0093] Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the indium tungsten oxide (IWO) target RF power was 30 W, pre-sputtering was performed for 3 min, and formal sputtering was performed for 7 min to prepare a 20 nm thick IWO protective layer, thus completing the preparation of the IGTO-Cu-IWO three-layer composite electrode and obtaining the perovskite solar cell.

[0094] The remaining conditions are the same as in Example 1.

[0095] Comparative Example 1 Comparative Example 1 is basically the same as Example 1, except that: the second electrode uses a copper layer, and the specific conditions of step (6) are as follows: Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 20 min to complete the preparation of the 90 nm thick Cu layer in the middle layer.

[0096] The remaining steps and conditions are the same as in Example 1.

[0097] Comparative Example 2 Comparative Example 2 is basically the same as Example 1, except that: the composite electrode only has a buffer layer and a conductive layer, and the conditions for step (6) are as follows: Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E. -4 At a pressure of 1 Pa, 200 sccm of argon gas was introduced, the substrate rotation speed was set to 10 rpm, the ITO target RF power was 30 W, pre-sputtering was performed for 3 min, and formal sputtering was performed for 10 min to prepare a 60 nm thick ITO buffer layer; without breaking the vacuum, the equipment's base vacuum was once again reached 5 × E -4 At time P, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was performed for 3 min, and the formal sputtering was performed for 20 min to prepare a Cu conductive layer with a thickness of 90 nm, thus obtaining an ITO-Cu composite electrode.

[0098] The remaining steps and conditions are the same as in Example 1.

[0099] Comparative Example 3 Comparative Example 3 is basically the same as Example 1, except that the composite electrode only has a conductive layer and a protective layer, and the conditions for step (6) are as follows: Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 20 min, to prepare a Cu conductive layer with a thickness of 90 nm.

[0100] Without breaking the vacuum, the equipment's background vacuum can be restored to 5×E. -4 At Pa, 200 sccm was introduced. Argon gas was used, with a pressure of 1 Pa, a substrate rotation speed of 10 rpm, and an ITO target RF power of 30 W. Pre-sputtering was performed for 3 min, followed by formal sputtering for 10 min, to prepare a 60 nm thick ITO protective layer and complete the fabrication of the Cu-ITO composite electrode.

[0101] The remaining conditions are the same as in Example 1.

[0102] Comparative Example 4 Comparative Example 4 is basically the same as Example 5, except that step (6) is as follows: Step (6): Place the hole transport layer obtained in step (5) upwards on the tray of the PVD magnetron sputtering equipment and send it into the magnetron sputtering equipment: the equipment's base vacuum reaches 5×E -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the RF power of the indium gallium tin oxide IGTO target was 30 W, the pre-sputtering was 3 min, and the formal sputtering was 4 min, to prepare a 35 nm thick IGTO buffer layer.

[0103] Then, without breaking the vacuum, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the indium tungsten oxide (IWO) target RF power was 30 W, the pre-sputtering was 3 min, the formal sputtering was 7 min, and a 20 nm thick IWO protective layer was prepared. Finally, without breaking the vacuum, the equipment's background vacuum once again reached 5×E. -4 At Pa, the equipment's background vacuum reaches 5×E again. -4 At Pa, 200 sccm of argon gas was introduced, the gas pressure was set to 1 Pa, the substrate rotation speed was 10 rpm, the Cu target RF power was 60 W, the pre-sputtering was 3 min, and the formal sputtering was 40 min, to prepare a Cu conductive layer with a thickness of 180 nm, thus completing the preparation of the IGTO-IWO-Cu three-layer composite electrode and obtaining the perovskite solar cell.

[0104] The remaining conditions are the same as in Example 5.

[0105] test Using a sunlight simulator, an area of ​​8.50 cm² was observed. 2 The perovskite solar cells obtained in the above embodiments and comparative examples were subjected to IV testing. The solar simulator used for IV testing was set to a standard AM 1.5G, 1000 W / m² light intensity. 2 Simulated sunlight was used to scan a voltage range of -0.1V to 4.8V at a scan rate of 0.01V / s. The photoelectric conversion efficiency (η), fill factor (FF), open-circuit voltage (Voc), and short-circuit current (Jsc) were measured and the results were rounded to two decimal places. The test results are shown in Table 1.

[0106] Table 1

[0107] Note: Voc: Open-circuit voltage; Jsc: Short-circuit current density; FF: Fill factor; Rs: Series resistance; Rsh: Parallel resistance; η: Photoelectric conversion efficiency; Comparative analysis of the data in Table 1 shows that the composite electrode of the present invention, through the cooperation of the buffer layer, conductive layer and protective layer, can help passivate the defects on the surface of the functional layer (such as the hole transport layer) in contact with it, and reduce the kinetic energy damage to the battery when the conductive layer is prepared by magnetron sputtering; at the same time, it reduces the probability of the conductive layer being directly corroded by water, oxygen and other substances in the environment, thereby improving the efficiency of the perovskite battery.

[0108] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0109] The above embodiments merely illustrate several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent should be determined by the appended claims.

Claims

1. A composite electrode, characterized in that, The composite electrode includes a buffer layer stacked sequentially. Conductive layer and protective layer; The buffer layer and the protective layer are both composed of transparent conductive oxides, and the conductive layer is composed of conductive metals.

2. The composite electrode as described in claim 1, characterized in that, The thickness of the buffer layer is 20 nm to 60 nm, and / or The thickness of the conductive layer is 60 nm to 180 nm, and / or The thickness of the protective layer is 20 nm to 60 nm.

3. The composite electrode as described in claim 1 or 2, characterized in that, The components of the buffer layer and the protective layer are each independently selected from at least one of the following: indium tin oxide, indium tungsten oxide, indium gallium oxide, zinc aluminum oxide, and indium gallium tin oxide.

4. The composite electrode as described in claim 1 or 2, characterized in that, The conductive metal includes at least one of aluminum, copper, gold, and nickel.

5. The method for preparing the composite electrode according to any one of claims 1 to 4, characterized in that, Includes the following steps: The composite electrode is prepared by sequentially forming a buffer layer, a conductive layer, and a protective layer using physical vapor deposition.

6. The method for preparing the composite electrode as described in claim 5, characterized in that, The physical vapor deposition method is magnetron sputtering.

7. A perovskite battery, characterized in that, The perovskite solar cell includes the composite electrode as described in any one of claims 1 to 4.

8. The perovskite solar cell as described in claim 7, characterized in that, The perovskite solar cell comprises, in sequence, a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode, wherein the second electrode is the composite electrode.

9. The perovskite solar cell according to any one of claims 7 to 8, characterized in that, The perovskite solar cell further includes a passivation layer disposed between the perovskite layer and the hole transport layer.

10. A photovoltaic module, characterized in that, The photovoltaic module includes a perovskite cell as described in any one of claims 7-9.

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