Perovskite cell and preparation method thereof, electrode for perovskite cell, photovoltaic module and power utilization device

Abstract

The invention provides a perovskite cell and a preparation method thereof, an electrode for the perovskite cell, a photovoltaic module and an electric device, the perovskite cell comprises a first electrode, a second electrode, a light absorption layer, a first charge transport layer and a second charge transport layer, the light absorption layer is located between the first electrode and the second electrode, and the first charge transport layer is located between the first electrode and the second electrode. The first charge transmission layer is located between the first electrode and the light absorption layer, the second charge transmission layer is located between the second electrode and the light absorption layer, the second electrode comprises a first conductive film layer and a second conductive film layer, and the first conductive film layer is arranged close to the second charge transmission layer; an electrode material of the first conductive film layer comprises one or more of a mixture of non-metal and first metal and an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal is 4-5.5 eV; and the electrode material of the second conductive film layer comprises one or more of second metal and second transparent conductive metal oxide.

Description

Perovskite solar cell, its preparation method, electrode for perovskite solar cell, photovoltaic module, and electrical device

[0001] This application relates to a perovskite solar cell, its preparation method, an electrode for a perovskite solar cell, a photovoltaic module, and an electrical device.

[0002] With the development of modern industry, the problems of global energy shortage and environmental pollution have become increasingly prominent. Perovskite solar cells, as ideal renewable energy sources, have received more and more attention. A perovskite solar cell is a solar cell that uses a perovskite material as the light-absorbing layer. How to improve the photoelectric conversion efficiency of perovskite solar cells while enhancing their stability is the direction of research efforts. The above statements are only used to provide background technical information related to this application and do not necessarily constitute prior art.

[0003] Summary of the Invention

[0004] This application provides a perovskite solar cell, its preparation method, an electrode for a perovskite solar cell, a photovoltaic module, and an electrical device, which can endow the perovskite solar cell with high stability and high photoelectric conversion efficiency.

[0005] In a first aspect of this application, a perovskite solar cell is provided, including a first electrode, a second electrode, a light-absorbing layer, a first charge transport layer, and a second charge transport layer. The light-absorbing layer is located between the first electrode and the second electrode. The first charge transport layer is located between the first electrode and the light-absorbing layer. The second charge transport layer is located between the second electrode and the light-absorbing layer. Among them, the second electrode includes a first conductive film layer and a second conductive film layer. The first conductive film layer is disposed close to the second charge transport layer. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal, and an alloy formed by a non-metal and a first metal. And the Fermi level of the non-metal is 4 - 5.5 eV. The electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide.

[0006] By introducing a non-metal with a Fermi level of 4 - 5.5 eV into the first conductive film layer of the second electrode, the tolerance of the perovskite solar cell device to halogen ions can be increased, and the stability of the perovskite solar cell device can be enhanced. At the same time, since the second conductive film layer of the second electrode is still a metal or metal oxide electrode, the perovskite solar cell device can also have a high photoelectric conversion efficiency. Therefore, the perovskite solar cell provided by the embodiments of this application can have high stability and high photoelectric conversion efficiency.

[0007] In any embodiment, the non-metal includes one or more of boron, carbon, silicon, and tellurium.

[0008] In any embodiment, the work function of the first metal is 4 - 5.5 eV. Optionally, the first metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0009] In any embodiment, the work function of the second metal is 4 - 5.5 eV. Optionally, the second metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0010] In any embodiment, the first metal is the same as the second metal. This can enable the first conductive film layer and the second conductive film layer to be in close contact, thereby helping to reduce the contact resistance and increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0011] In any embodiment, the second transparent conductive metal oxide includes one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, and indium-doped zinc oxide.

[0012] In any embodiment, the molar ratio of the non-metal to the first metal in the first conductive film layer is greater than 0 and less than or equal to 1:1, and can be optionally 1:15 - 1:5. By making the molar ratio of the non-metal to the first metal in the first conductive film layer within the above range, the work function of the contact surface between the second charge transport layer and the first conductive film layer can also be adjusted within a small range, thereby improving the carrier transport rate, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency while improving the stability of the perovskite solar cell device.

[0013] In any embodiment, the thickness of the first conductive film layer is greater than 0 and less than or equal to 30 nm, and can be optionally 5 - 20 nm. When the thickness of the first conductive film layer is within the above range, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0014] In any embodiment, the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is less than or equal to 1:2.6, and can be optionally 1:16 - 1:4. When the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is within the above range, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0015] In any embodiment, the total thickness of the second electrode is 60 - 120 nm, and can be optionally 70 - 90 nm.

[0016] In any embodiment, the thickness of the second conductive film layer is 50 - 79 nm, and optionally 60 - 75 nm.

[0017] In any embodiment, the electrode material of the first electrode includes an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material, and optionally includes one or more of a first transparent conductive metal oxide, carbon, and metal, and more optionally includes one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, and carbon.

[0018] In any embodiment, the light-absorbing layer includes a perovskite material. Optionally, the perovskite material includes one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material.

[0019] In any embodiment, the first charge transport layer is a hole transport layer, and the second charge transport layer is an electron transport layer; or, the first charge transport layer is an electron transport layer, and the second charge transport layer is a hole transport layer.

[0020] In any embodiment, the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer, the bottom energy level of the conduction band of the second charge transport layer is higher than the work function of the first conductive film layer, and the bottom energy level of the conduction band of the second charge transport layer is higher than the work function of the second conductive film layer. Thereby, the transport rate of carriers can be improved, and further, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0021] Optionally, the work function of the first conductive film layer is higher than the work function of the second conductive film layer. Thereby, the transport rate of carriers can be further improved.

[0022] Optionally, the first metal in the first conductive film layer includes one or more of silver, copper, aluminum, and tin, and the non-metal in the first conductive film layer includes one or more of boron, carbon, silicon, and tellurium.

[0023] Optionally, the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide, and the second metal includes one or more of silver, copper, aluminum, and tin.

[0024] In any embodiment, the first charge transport layer is an electron transport layer, the second charge transport layer is a hole transport layer, the valence band top energy level of the second charge transport layer is lower than the work function of the first conductive film layer, and the valence band top energy level of the second charge transport layer is lower than the work function of the second conductive film layer. Thereby, the carrier transport rate can be improved, and further, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0025] Optionally, the work function of the first conductive film layer is lower than the work function of the second conductive film layer. Thereby, the carrier transport rate can be further improved.

[0026] Optionally, the first metal in the first conductive film layer includes one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum, and the non-metal in the first conductive film layer includes one or more of boron, carbon, silicon, and tellurium.

[0027] Optionally, the electrode material of the second conductive film layer includes one or more of the second metals, and the second metals include one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum.

[0028] In any embodiment, the electron transport material in the electron transport layer includes one or more of an organic electron transport material, an inorganic electron transport material, and an organic-inorganic hybrid electron transport material.

[0029] In any embodiment, the hole transport material in the hole transport layer includes one or more of an organic small molecule hole transport material, an organic polymer hole transport material, and an inorganic hole transport material.

[0030] The second aspect of the present application provides a method for preparing a perovskite solar cell, including the following steps: providing a first electrode; forming a first charge transport layer on the first electrode; forming a light-absorbing layer on the first charge transport layer; forming a second charge transport layer on the light-absorbing layer; forming a first conductive film layer on the second charge transport layer; and forming a second conductive film layer on the first conductive film layer. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal and an alloy formed by a non-metal and a first metal, and the Fermi level of the non-metal is 4 - 5.5 eV; the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide.

[0031] In any embodiment, the method of forming the first conductive film layer on the second charge transport layer includes evaporation or sputtering.

[0032] In any embodiment, the method of forming the second conductive film layer on the first conductive film layer includes evaporation or sputtering.

[0033] In any embodiment, the non-metal and the first metal form the first conductive film layer by co-evaporation.

[0034] The third aspect of the present application provides an electrode for a perovskite solar cell, including a first conductive film layer and a second conductive film layer arranged in a stacked manner. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal, and an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal is 4 - 5.5 eV; the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide.

[0035] By introducing a non-metal with a Fermi level of 4 - 5.5 eV into the first conductive film layer, the tolerance of the perovskite solar cell device to halogen ions can be increased, and the stability of the perovskite solar cell device can be increased; at the same time, since the second conductive film layer is still a metal or metal oxide electrode, the perovskite solar cell device can also have a high photoelectric conversion efficiency. Therefore, the electrode provided by the embodiments of the present application can make the perovskite solar cell have high stability and high photoelectric conversion efficiency.

[0036] In any embodiment, the non-metal includes one or more of boron, carbon, silicon, and tellurium.

[0037] In any embodiment, the work function of the first metal is 4 - 5.5 eV. Optionally, the first metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0038] In any embodiment, the work function of the second metal is 4 - 5.5 eV. Optionally, the second metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0039] In any embodiment, the first metal is the same as the second metal. This can make the first conductive film layer and the second conductive film layer in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0040] In any embodiment, the second transparent conductive metal oxide includes one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, and indium-doped zinc oxide.

[0041] In any embodiment, the molar ratio of the non-metal to the first metal in the first conductive film layer is greater than 0 and less than or equal to 1:1, and may be optionally 1:15 - 1:5. By making the molar ratio of the non-metal to the first metal in the first conductive film layer within the above range, when applied to a perovskite solar cell, the work function of the contact surface between the charge transport layer and the second conductive film layer can also be adjusted within a small range, thereby improving the carrier transport rate. Furthermore, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0042] In any embodiment, the thickness of the first conductive film layer is greater than 0 and less than or equal to 30 nm, and may be optionally 5 - 20 nm. When the thickness of the first conductive film layer is within the above range and applied to a perovskite solar cell, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0043] In any embodiment, the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is less than or equal to 1:2.6, and may be optionally 1:16 - 1:4. When the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is within the above range and applied to a perovskite solar cell, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0044] In any embodiment, the total thickness of the electrode is 60 - 120 nm, and may be optionally 70 - 90 nm.

[0045] In any embodiment, the thickness of the second conductive film layer is 50 - 79 nm, and may be optionally 60 - 75 nm.

[0046] The fourth aspect of the present application provides a photovoltaic module, which includes the perovskite solar cell of the first aspect of the present application or the perovskite solar cell prepared by the method of the second aspect of the present application.

[0047] The fifth aspect of the present application provides an electrical device, which includes one or more of the perovskite solar cell of the first aspect of the present application, the perovskite solar cell prepared by the method of the second aspect of the present application, and the photovoltaic module of the fourth aspect of the present application. The perovskite solar cell and the photovoltaic module are used to supply power to the electrical device.

[0048] The electrical device of the present application includes the perovskite solar cell provided by the present application, and thus has at least the same advantages as the perovskite solar cell.

[0049] To more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings required for use in the embodiments of the present application. Obviously, the following described drawings are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on the drawings.

[0050] FIG. 1 is a schematic structural diagram of a perovskite battery provided by some embodiments of the present application.

[0051] In the drawings, the drawings are not necessarily drawn to actual scale. The reference numerals are explained as follows: 1, the first electrode; 2, the first charge transport layer; 3, the light absorption layer; 4, the second charge transport layer; 5, the second electrode; 51, the first conductive film layer; 52, the second conductive film layer.

[0052] Hereinafter, embodiments of the perovskite battery, its preparation method, the electrode for the perovskite battery, the photovoltaic module, and the electrical device of the present application are specifically disclosed with appropriate reference to the drawings. However, there may be cases where unnecessary details are omitted. For example, there are cases where the detailed description of well-known matters and the repeated description of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter recited in the claims.

[0053] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a specific range. The range defined in this way can include or not include the end values, and 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, ranges of 60-110 and 80-120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been fully listed herein, and "0-5" is only an abbreviated representation of these numerical combinations. In addition, when it is stated that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0054] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present application.

[0055] Unless otherwise specified, all technical features and optional technical features of the present application can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present application.

[0056] Unless otherwise specified, all steps of the present application can be carried out sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) carried out sequentially, or may also include steps (b) and (a) carried out sequentially. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may also include steps (a), (c) and (b), or may also include steps (c), (a) and (b), etc.

[0057] Unless otherwise specified, the terms "comprising" and "including" mentioned in the present application mean open-ended, and can also be closed-ended. For example, the "comprising" and "including" can mean that other components not listed may also be included or contained, or may only include or contain the listed components.

[0058] Unless otherwise specified, in the present application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0059] Unless otherwise specified, in the present application, terms such as "first", "second", etc. are used to distinguish different objects, rather than to describe a specific order or primary-secondary relationship.

[0060] Unless otherwise specified, the terms used in the present application have the well-known meanings commonly understood by those skilled in the art.

[0061] Unless otherwise specified, the numerical values of the various parameters mentioned in the present application can be determined by various commonly used testing methods in the art. For example, they can be determined according to the testing methods given in the present application. Unless otherwise specified, the testing temperature of each parameter is 25°C.

[0062] The working principle of a perovskite solar cell is generally as follows: under light illumination, the light-absorbing layer absorbs photon energy, generating electron-hole pairs at its valence band. The electrons are excited to the conduction band, leaving holes at the valence band. The conduction band energy level of the light-absorbing layer is usually higher than that of the electron transport layer. Thus, electrons can be transported from the conduction band position of the light-absorbing layer to the conduction band position of the electron transport layer and then to the conductive electrode. The valence band energy level of the light-absorbing layer is usually lower than that of the hole transport layer. Thus, holes can be transported through the hole transport layer to the conductive electrode. After connecting the external circuit, a complete circuit is formed, generating a photocurrent.

[0063] The light-absorbing layer includes a perovskite material, which is usually a halide perovskite material (e.g., inorganic halide perovskite material, organic halide perovskite material, organic-inorganic hybrid halide perovskite material, etc.). It has advantages such as a large carrier diffusion length, an easily adjustable bandgap, a high defect tolerance, and a low manufacturing cost, and thus has received wide attention.

[0064] Metal electrodes are commonly used conductive electrodes at present. However, for metal electrodes, they are prone to erosion caused by the migration of halogen ions inside the perovskite material, that is, the metal electrode material is likely to react with halogen ions to form metal halides, which will reduce the stability of the perovskite solar cell device and also affect the photoelectric conversion efficiency of the perovskite solar cell device.

[0065] In view of this, the inventor has improved the structure of the perovskite solar cell.

[0066] The embodiment of the present application provides a perovskite solar cell. FIG. 1 is a schematic structural diagram of a perovskite solar cell provided by some embodiments of the present application. As shown in FIG. 1, the perovskite solar cell includes a first electrode 1, a second electrode 5, a light-absorbing layer 3, a first charge transport layer 2, and a second charge transport layer 4. The light-absorbing layer 3 is located between the first electrode 1 and the second electrode 5. The first charge transport layer 2 is located between the first electrode 1 and the light-absorbing layer 3. The second charge transport layer 4 is located between the second electrode 5 and the light-absorbing layer 3. The second electrode 5 includes a first conductive film layer 51 and a second conductive film layer 52, and the first conductive film layer 51 is disposed close to the second charge transport layer 4.

[0067] The electrode material of the first conductive film layer 51 includes one or more of a mixture of a non-metal and a first metal and an alloy formed by a non-metal and a first metal, and the Fermi level of the non-metal is 4 - 5.5 eV; the electrode material of the second conductive film layer 52 includes one or more of a second metal and a second transparent conductive metal oxide.

[0068] The second electrode of the perovskite battery provided by the embodiment of the present application includes a first conductive film layer and a second conductive film layer. The first conductive film layer is located between the second charge transport layer and the second conductive film layer, and the electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal, and an alloy formed by the non-metal and the first metal.

[0069] By introducing a non-metal with a Fermi level of 4 - 5.5 eV into the first conductive film layer of the second electrode, the tolerance of the perovskite battery device to halogen ions can be increased, and the stability of the perovskite battery device can be enhanced; at the same time, since the second conductive film layer of the second electrode is still a metal or metal oxide electrode, the perovskite battery device can thus have a high photoelectric conversion efficiency. Therefore, the perovskite battery provided by the embodiment of the present application can have high stability and high photoelectric conversion efficiency.

[0070] The Fermi level of the non-metal is 4 - 5.5 eV. Therefore, the Fermi level of the non-metal is close to the work function of the currently used metal or metal oxide electrode, which will not affect the carrier transport. Furthermore, while enhancing the stability of the perovskite battery device, the perovskite battery device can have a high photoelectric conversion efficiency. In some embodiments, the non-metal may include one or more of boron, carbon, silicon, and tellurium.

[0071] In some embodiments, the molar ratio of the non-metal to the first metal in the first conductive film layer 51 may be greater than 0 and less than or equal to 1:1.

[0072] By making the molar proportion of the non-metal in the first conductive film layer less than or equal to that of the first metal, it is beneficial to carrier transport. Furthermore, while enhancing the stability of the perovskite battery device, the perovskite battery device can have a high photoelectric conversion efficiency.

[0073] Optionally, the molar ratio of the non-metal to the first metal in the first conductive film layer 51 may be 1:15 - 1:5.

[0074] By making the molar ratio of the non-metal to the first metal in the first conductive film layer within the above range, the work function of the contact surface between the second charge transport layer and the first conductive film layer can also be adjusted within a small range. Thereby, the carrier transport rate can be increased, and furthermore, while enhancing the stability of the perovskite battery device, the perovskite battery device can have a high photoelectric conversion efficiency.

[0075] In some embodiments, the thickness of the first conductive film layer 51 may be greater than 0 and less than or equal to 30 nm, and may be optionally 5 - 20 nm.

[0076] When the thickness of the first conductive film layer is within the above range, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0077] In some embodiments, the ratio of the thickness of the first conductive film layer 51 to the total thickness of the second electrode 5 may be less than or equal to 1:2.6, and may be optionally 1:16 - 1:4.

[0078] When the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is within the above range, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material, thereby further improving the stability of the perovskite solar cell device and enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0079] In some embodiments, the total thickness of the second electrode 5 (i.e., the sum of the thicknesses of the first conductive film layer and the second conductive film layer) may be 60 - 120 nm, and may be optionally 65 - 100 nm, 70 - 90 nm.

[0080] In some embodiments, the thickness of the second conductive film layer 52 may be 50 - 115 nm, and may be optionally 50 - 79 nm, 60 - 75 nm.

[0081] In some embodiments, the work function of the first metal may be 4 - 5.5 eV. Optionally, the first metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0082] In some embodiments, the work function of the second metal may be 4 - 5.5 eV. Optionally, the second metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0083] In some embodiments, the first metal and the second metal may be the same. This can make the first conductive film layer and the second conductive film layer in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0084] In some embodiments, the second transparent conductive metal oxide may include one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).

[0085] The first electrode 1 is close to the light incident side. In some embodiments, the electrode material of the first electrode 1 may include an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material. As an example, the electrode material of the first electrode 1 may include one or more of a first transparent conductive metal oxide, carbon, and metal, optionally including one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium-doped zinc oxide (IZO), gold, silver, aluminum, copper, and carbon, and more optionally including one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).

[0086] The thickness of the first electrode is not specifically limited and can be selected according to actual requirements. For example, in some embodiments, the thickness of the first electrode 1 may be 10 - 700 nm.

[0087] The perovskite battery provided by the embodiments of the present application may be a normal structure battery or a reverse structure battery.

[0088] In some embodiments, the first charge transport layer 2 is a hole transport layer, and the second charge transport layer 4 is an electron transport layer, thereby forming a reverse structure battery.

[0089] In some embodiments, the first charge transport layer 2 is an electron transport layer, and the second charge transport layer 4 is a hole transport layer, thereby forming a normal structure battery.

[0090] In some embodiments, the first charge transport layer 2 is a hole transport layer, the second charge transport layer 4 is an electron transport layer, the conduction band bottom energy level (CBM) of the second charge transport layer 4 is higher than the work function of the first conductive film layer 51, and the conduction band bottom energy level (CBM) of the second charge transport layer 4 is higher than the work function of the second conductive film layer 52. Thereby, the carrier transport rate can be improved, and further, while improving the stability of the perovskite battery device, the perovskite battery device can have a high photoelectric conversion efficiency.

[0091] Optionally, the work function of the first conductive film layer 51 is higher than the work function of the second conductive film layer 52, thereby further improving the carrier transport rate.

[0092] Optionally, the first metal in the first conductive film layer 51 includes one or more of silver, copper, aluminum, and tin, and the non-metal in the first conductive film layer 51 includes one or more of boron, carbon, silicon, and tellurium.

[0093] Optionally, the electrode material of the second conductive film layer 52 includes one or more of a second metal and a second transparent conductive metal oxide, and the second metal includes one or more of silver, copper, aluminum, and tin.

[0094] In some embodiments, the first charge transport layer 2 is an electron transport layer, the second charge transport layer 4 is a hole transport layer, the valence band top energy level (VBM) of the second charge transport layer 4 is lower than the work function of the first conductive film layer 51, and the valence band top energy level (VBM) of the second charge transport layer 4 is lower than the work function of the second conductive film layer 52. Thereby, the transport rate of carriers can be improved, and further, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0095] Optionally, the work function of the first conductive film layer 51 is lower than the work function of the second conductive film layer 52, thereby further improving the transport rate of carriers.

[0096] Optionally, the first metal in the first conductive film layer 51 includes one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum, and the non-metal in the first conductive film layer 51 includes one or more of boron, carbon, silicon, and tellurium.

[0097] Optionally, the electrode material of the second conductive film layer 52 includes one or more of the second metals, and the second metals include one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum. Thereby, the transport rate of carriers can be improved.

[0098] The type of the electron transport material in the electron transport layer is not specifically limited and can be selected according to actual needs. For example, the electron transport material can include one or more of an organic electron transport material, an inorganic electron transport material, and an organic-inorganic hybrid electron transport material.

[0099] In some embodiments, the electron transport material can include one or more of the following materials, their derivatives, and the materials obtained by doping or passivating them: [6,6]-phenyl C 61 butyric acid methyl ester (abbreviated as PC 61 BM), [6,6]-phenyl C 71 butyric acid methyl ester (abbreviated as PC 71 BM), fullerene C60, fullerene C70, SnO 2 、TiO 2 、ZnO. When the electron transport material is within the above range, the conduction band bottom energy level of it can better match the conduction band bottom energy level of the light absorption layer, thereby facilitating the transport of electrons.

[0100] The thickness of the electron transport layer is not specifically limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the electron transport layer can be 1 - 300 nm.

[0101] The type of the hole transporting material in the hole transporting layer is not specifically limited and can be selected according to actual needs. For example, the hole transporting material can include one or more of organic small molecule hole transporting materials, organic polymer hole transporting materials, and inorganic hole transporting materials.

[0102] In some embodiments, the hole transporting material can include one or more of the following materials and their derivatives and the materials obtained by doping or passivating them: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (abbreviated as PTAA), poly(3-hexylthiophene) (abbreviated as P3HT), triphenylamine with triptycene as the core (abbreviated as H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (abbreviated as EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (abbreviated as CzPAF-SBF), poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (abbreviated as PEDOT:PSS), 2,2',7,7'-tetrakis(N,N-p-methoxyanilino)-9,9'-spirobifluorene (abbreviated as Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (abbreviated as OMeTPA-FA), polythiophene, nickel oxide (NiO x , 0 < x < 1), molybdenum oxide (MoO 3 ), cuprous iodide (CuI), cuprous oxide (Cu 2 O), cuprous thiocyanate (CuSCN).

[0103] The thickness of the hole transporting layer is not specifically limited and can be selected according to actual needs. For example, in some embodiments, the thickness of the hole transporting layer can be 5 - 1000 nm.

[0104] In some embodiments, the light absorbing layer can include perovskite materials. The type of perovskite materials is not specifically limited and can be selected according to actual needs. In some embodiments, the perovskite materials in the light absorbing layer can include one or more of inorganic halide perovskite materials, organic halide perovskite materials, and organic-inorganic hybrid halide perovskite materials.

[0105] The perovskite materials can include ABX 3 , A 2 CDX 6 shown materials.

[0106] A represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation. By way of example, A can include CH 3 NH 3 + (abbreviated as MA + ), CH(NH 2 ) 2+ (abbreviated as FA + ), Li + , Na + , K + , Rb + , Cs + or one or more of them. Optionally, A may include CH 3 NH 3 + , CH(NH 2 ) 2 + , Cs + or one or more of them.

[0107] B represents an inorganic cation, an organic cation, or an organic-inorganic hybrid cation. Optionally, B may represent a divalent metal cation. As an example, B may include Pb 2+ , Sn 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , Ni 2+ or one or more of them. Optionally, B may include Pb 2+ , Sn 2+ or one or two of them.

[0108] C represents an inorganic cation, an organic cation, or an organic-inorganic hybrid cation. Optionally, C may represent a monovalent metal cation. As an example, C may include Li + , Na + , K + , Rb + , Cs + , Ag + or one or more of them.

[0109] D represents an inorganic cation, an organic cation, or an organic-inorganic hybrid cation. Optionally, D may represent a trivalent metal cation. As an example, D may include In 3+ , Bi 3+ or one or more of them.

[0110] X represents an inorganic anion, an organic anion, or an organic-inorganic hybrid anion. Optionally, X may represent a halide ion. As an example, X may include F - , Cl - , Br - , I -One or more of them. Optionally, X may include Cl - , Br - , I - One or more of them.

[0111] In some embodiments, the perovskite material in the light-absorbing layer may include, but is not limited to, CH 3 NH 3 PbI 3 (abbreviated as MAPbI 3 ), CH(NH 2 ) 2 PbI 3 (abbreviated as FAPbI 3 ), Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 (abbreviated as CsFAMA), CsPbI 3 , CsPbI 2 Br, CsPbIBr 2 , Cs 2 NaInCl 6 , Cs 2 KBiCl 6 , Cs 2 AgInCl 6 One or more of them.

[0112] In some embodiments, the bandgap of the light-absorbing layer may be 1.20 eV - 2.30 eV. The bandgap of the light-absorbing layer can be obtained by acquiring the ultraviolet absorption curve through ultraviolet absorption spectroscopy and then calculated by the Tauc equation.

[0113] The thickness of the light-absorbing layer is not particularly limited and can be selected according to actual needs. In some embodiments, the thickness of the light-absorbing layer can be 400 - 1000 nm.

[0114] In some embodiments, the perovskite cell further includes a substrate, such as a glass substrate, and a transparent metal conductive oxide can be provided on the surface of the substrate.

[0115] The perovskite cell provided by the embodiments of the present application is not limited to the above structure and may further include other functional layers. For example, it may further include a passivation layer provided between the first charge transport layer and / or the second charge transport layer and the light-absorbing layer.

[0116] In some embodiments, a perovskite solar cell may include a substrate, a first electrode 1, a first charge transport layer 2, a light-absorbing layer 3, a second charge transport layer 4, a first conductive film layer 51, and a second conductive film layer 52, which are sequentially stacked. The electrode material of the first conductive film layer 51 includes one or more of a mixture of a non-metal and a first metal, an alloy formed by a non-metal and a first metal, and the non-metal includes one or more of boron, carbon, silicon, and tellurium; the electrode material of the second conductive film layer 52 includes one or more of a second metal and a second transparent conductive metal oxide. Optionally, a passivation layer is further disposed between the first charge transport layer 2 and the light-absorbing layer 3, and / or between the second charge transport layer 4 and the light-absorbing layer 3.

[0117] In some embodiments, a perovskite solar cell may include a substrate, a first electrode 1, a first charge transport layer 2, a light-absorbing layer 3, a second charge transport layer 4, a first conductive film layer 51, and a second conductive film layer 52, which are sequentially stacked. The electrode material of the first conductive film layer 51 includes one or more of a mixture of a non-metal and a first metal, an alloy formed by a non-metal and a first metal, and the non-metal includes one or more of boron, carbon, silicon, and tellurium; the electrode material of the second conductive film layer 52 includes a second metal, and the first metal is the same as the second metal. Optionally, a passivation layer is further disposed between the first charge transport layer 2 and the light-absorbing layer 3, and / or between the second charge transport layer 4 and the light-absorbing layer 3.

[0118] This can enable the first conductive film layer and the second conductive film layer to be in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency while improving the stability of the perovskite solar cell device.

[0119] [Preparation Method]

[0120] The embodiments of the present application further provide a method for preparing the above-mentioned perovskite solar cell.

[0121] The method includes the following steps: providing a first electrode 1; forming a first charge transport layer 2 on the first electrode 1; forming a light-absorbing layer 3 on the first charge transport layer 2; forming a second charge transport layer 4 on the light-absorbing layer 3; forming a first conductive film layer 51 on the second charge transport layer 4; and forming a second conductive film layer 52 on the first conductive film layer 51. The electrode material of the first conductive film layer 51 includes one or more of a mixture of a non-metal and a first metal, an alloy formed by a non-metal and a first metal, and the Fermi level of the non-metal is 4 - 5.5 eV; the electrode material of the second conductive film layer 52 includes one or more of a second metal and a second transparent conductive metal oxide.

[0122] In some embodiments, the method of forming the first conductive film layer 51 on the second charge transport layer 4 may include evaporation or sputtering. In some embodiments, the evaporation may be vacuum evaporation. Optionally, the vacuum degree of the evaporation may be 10 -4 to 10 - 6 Pa, and the evaporation rate may be 0.1-5 Å / s. In some embodiments, the sputtering may be magnetron sputtering. Optionally, the operating pressure may be 10 -3 to 10 -7 Pa, and the sputtering power density may be 800-1200 W / cm 2 .

[0123] In some embodiments, the non-metal and the first metal may form the first conductive film layer by co-evaporation. By adjusting the evaporation rates of the non-metal and the first metal respectively, the molar ratio of the non-metal to the first metal can be adjusted, and the thickness of the first conductive film layer can also be adjusted.

[0124] In some embodiments, the method of forming the second conductive film layer 52 on the first conductive film layer 51 may include evaporation or sputtering. In some embodiments, the evaporation may be vacuum evaporation. Optionally, the vacuum degree of the evaporation may be 10 -4 to 10 -6 Pa, and the evaporation rate may be 0.1-5 Å / s. In some embodiments, the sputtering may be magnetron sputtering. Optionally, the operating pressure may be 10 -3 to 10 -7 Pa, and the sputtering power density may be 800-1200 W / cm 2 .

[0125] In some embodiments, the method includes the following steps: providing a first electrode 1; forming a first charge transport layer 2 on the first electrode 1; forming a light-absorbing layer 3 on the first charge transport layer 2; forming a second charge transport layer 4 on the light-absorbing layer 3; co-evaporating a non-metal and a first metal on the second charge transport layer 4 to form a first conductive film layer 51; and continuously evaporating the first metal on the first conductive film layer 51 to form a second conductive film layer 52. The electrode material of the first conductive film layer 51 includes one or more of a mixture of a non-metal and a first metal, an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal is 4-5.5 eV; the electrode material of the second conductive film layer 52 includes the first metal. This can make the first conductive film layer and the second conductive film layer in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further can improve the stability of the perovskite solar cell device while enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0126] The film-forming methods of the first charge transport layer 2, the light-absorbing layer 3, and the second charge transport layer 4 are not particularly limited and can adopt film-forming methods known in the art, such as chemical bath deposition, chemical vapor deposition, electrochemical deposition, physical epitaxial growth, thermal evaporation, atomic layer deposition, magnetron sputtering, spin coating of precursor solution, slot coating of precursor solution, doctor blade coating of precursor solution, mechanical pressing, sol-gel method, pulsed laser deposition, etc.

[0127] The perovskite solar cell provided by the embodiment of the present application can be used alone as a single-junction perovskite solar cell, or can be made into a tandem solar cell with a perovskite-type or other type of perovskite solar cell, such as a perovskite-perovskite tandem solar cell or a perovskite-silicon tandem solar cell, etc.

[0128] The embodiment of the present application also provides an electrode for a perovskite solar cell.

[0129] The electrode provided by the embodiment of the present application includes a first conductive film layer and a second conductive film layer arranged in a stacked manner. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal and an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal is 4-5.5 eV; the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide.

[0130] The electrode provided by the embodiment of the present application includes a first conductive film layer and a second conductive film layer arranged in a stacked manner. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal and an alloy formed by the non-metal and the first metal.

[0131] By introducing a non-metal with a Fermi level of 4-5.5 eV into the first conductive film layer, the tolerance of the perovskite solar cell device to halogen ions can be increased, and the stability of the perovskite solar cell device can be increased; at the same time, since the second conductive film layer is still a metal or metal oxide electrode, the perovskite solar cell device can also have a high photoelectric conversion efficiency. Therefore, the electrode provided by the embodiment of the present application can make the perovskite solar cell have high stability and high photoelectric conversion efficiency.

[0132] The Fermi level of the non-metal is 4-5.5 eV. Therefore, the Fermi level of the non-metal is close to the work function of the currently used metal or metal oxide electrode, which will not affect the carrier transport. Furthermore, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency. In some embodiments, the non-metal may include one or more of boron, carbon, silicon, and tellurium.

[0133] In some embodiments, the molar ratio of the non-metal to the first metal in the first conductive film layer may be greater than 0 and less than or equal to 1:1.

[0134] When the molar proportion of non-metal in the first conductive film layer is less than or equal to that of the first metal, when applied to a perovskite solar cell, it is beneficial for carrier transport. Furthermore, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0135] Optionally, the molar ratio of the non-metal to the first metal in the first conductive film layer can be 1:15 - 1:5.

[0136] When the molar ratio of the non-metal to the first metal in the first conductive film layer is within the above range, when applied to a perovskite solar cell, the work function of the contact surface between the charge transport layer and the second conductive film layer can also be adjusted within a small range. Thereby, the carrier transport rate can be increased. Furthermore, while improving the stability of the perovskite solar cell device, the perovskite solar cell device can have a high photoelectric conversion efficiency.

[0137] In some embodiments, the thickness of the first conductive film layer can be greater than 0 and less than or equal to 30 nm, and can be optionally 5 - 20 nm.

[0138] When the thickness of the first conductive film layer is within the above range, when applied to a perovskite solar cell, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material. Thus, the stability of the perovskite solar cell device can be further improved, and the perovskite solar cell device can also have a high photoelectric conversion efficiency.

[0139] In some embodiments, the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode 5 can be less than or equal to 1:2.6, and can be optionally 1:16 - 1:4.

[0140] When the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is within the above range, when applied to a perovskite solar cell, it can effectively block the erosion of the second conductive film layer by the migration of halogen ions inside the perovskite material. Thus, the stability of the perovskite solar cell device can be further improved, and the perovskite solar cell device can also have a high photoelectric conversion efficiency.

[0141] In some embodiments, the total thickness of the electrode (i.e., the sum of the thicknesses of the first conductive film layer and the second conductive film layer) can be 60 - 120 nm, and can be optionally 65 - 100 nm, 70 - 90 nm.

[0142] In some embodiments, the thickness of the second conductive film layer can be 50 - 115 nm, and can be optionally 50 - 79 nm, 60 - 75 nm.

[0143] In some embodiments, the work function of the first metal can be 4 - 5.5 eV. Optionally, the first metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0144] In some embodiments, the work function of the second metal can be 4 - 5.5 eV. Optionally, the second metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt.

[0145] In some embodiments, the first metal and the second metal can be the same. This can enable the first conductive film layer and the second conductive film layer to be in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency.

[0146] In some embodiments, the second transparent conductive metal oxide can include one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium-doped zinc oxide (IZO).

[0147] In some embodiments, the electrode includes a first conductive film layer and a second conductive film layer arranged in a stack. The electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal, and an alloy formed by a non-metal and a first metal, and the non-metal includes one or more of boron, carbon, silicon, and tellurium; the electrode material of the second conductive film layer includes a second metal, and the first metal and the second metal are the same.

[0148] This can enable the first conductive film layer and the second conductive film layer to be in close contact, thereby helping to reduce the contact resistance, increase the fill factor of the perovskite solar cell device, and further enabling the perovskite solar cell device to have a high photoelectric conversion efficiency while improving the stability of the perovskite solar cell device.

[0149] The embodiments of the present application further provide a photovoltaic module. The photovoltaic module includes the perovskite solar cell provided by the embodiments of the present application or the perovskite solar cell prepared by the preparation method provided by the embodiments of the present application. The perovskite solar cell can be used as the power source of the photovoltaic module after processes such as series-parallel connection and encapsulation.

[0150] In some embodiments, the photovoltaic module includes the single-junction perovskite solar cell, perovskite-perovskite tandem cell, or perovskite-silicon tandem cell provided by the embodiments of the present application.

[0151] The embodiments of the present application further provide an electrical device. The electrical device includes one or more of the perovskite solar cell provided by the embodiments of the present application, the perovskite solar cell prepared by the method provided by the embodiments of the present application, and the photovoltaic module provided by the embodiments of the present application. The above perovskite solar cell and photovoltaic module can be used to supply power to the electrical device.

[0152] In some embodiments, the electrical device may be a common device including the perovskite battery or photovoltaic module provided by the embodiments of the present application, such as devices applied in the fields of communication, transportation, industry and agriculture, lighting, etc. As an example, the electrical device may include satellites, communication devices, traffic lights, lighthouses, wireless phone booths, monitoring devices in the oil drilling field, power systems, camping lights, electric vehicles, electronic device chargers, etc.

[0153] Embodiment

[0154] The following embodiments more specifically describe the content disclosed in the present application. These embodiments are only for illustrative purposes, because various modifications and changes within the scope of the present application disclosure are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on weight, and all reagents used in the embodiments are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the embodiments are all commercially available.

[0155] Example 1-1

[0156] Prepare the first electrode

[0157] Take 20 pieces of ITO-coated conductive glass with a specification of 2.0 cm × 2.0 cm, and remove 0.35 cm of the ITO layer at both ends by laser etching to expose the glass substrate; then ultrasonically clean with water, acetone, and isopropyl alcohol in sequence, dry the solvent under a nitrogen gun, and then put it into an ultraviolet ozone machine for further cleaning to obtain the first electrode.

[0158] Prepare the hole transport layer

[0159] Spin-coat a 2 mg / mL PTAA-chlorobenzene solution on the first electrode at a rate of 5000 rpm, and then anneal it on a hot plate at 100 °C for 10 min to obtain a hole transport layer with a thickness of about 20 nm.

[0160] Prepare the light-absorbing layer

[0161] Spin-coat the precursor solution of the perovskite material on the hole transport layer at a rate of 1000 - 5000 rpm, and then anneal it at 100 °C for 30 min and cool it to room temperature to obtain an absorption layer with a thickness of about 680 nm. The perovskite material is CsFAMA, the solvent is N,N-dimethylformamide, and the concentration of the precursor solution is 1.5 mol / L.

[0162] Prepare the electron transport layer

[0163] Spin-coat a solution of [6,6]-phenyl C71 butyric acid methyl ester (PC71BM)-chlorobenzene on the light-absorbing layer at a rate of 1000 - 1500 rpm, then anneal it at 100 °C for 10 min, and then spin-coat the bathocuproine (BCP) passivation layer at a rate of 5000 rpm. The thickness of the PC71BM layer is about 60 nm, and the thickness of the BCP passivation layer is about 6 nm. 61 BM)-chlorobenzene solution, and then anneal it at 100 °C for 10 min, and then spin-coat the bathocuproine (BCP) passivation layer at a rate of 5000 rpm. The thickness of the PC71BM layer is about 60 nm, and the thickness of the BCP passivation layer is about 6 nm. 61 Put the aforementioned sample into an evaporation machine, co-evaporate copper and silicon at rates of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm, thus completing the preparation of the perovskite solar cell device.

[0164] Prepare the second electrode

[0165] The perovskite solar cell device finally prepared in Example 1-1 has a structure of ITO / PTAA / CsFAMA / PC71BM / BCP / Cu+Si / Cu.

[0166] The perovskite solar cell device finally prepared in Example 1-1 has a structure of ITO / PTAA / CsFAMA / PC71BM / BCP / Cu+Si / Cu. 61 BM / BCP / Cu+Si / Cu.

[0167] Example 1-2

[0168] The preparation of the perovskite solar cell is the same as that in Example 1-1 except for the different preparation process of the second electrode.

[0169] Prepare the second electrode

[0170] Put the aforementioned sample into an evaporation machine, co-evaporate copper and boron at rates of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm, thus completing the preparation of the perovskite solar cell device.

[0171] The perovskite solar cell device finally prepared in Example 1-2 has a structure of ITO / PTAA / CsFAMA / PC71BM / BCP / Cu+B / Cu. 61 BM / BCP / Cu+B / Cu.

[0172] Example 1-3

[0173] The preparation of the perovskite solar cell is the same as that in Example 1-1 except for the different preparation process of the second electrode.

[0174] Prepare the second electrode

[0175] Put the aforementioned sample into an evaporation coater, co-evaporate copper and tellurium at rates of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer with a total thickness of 80 nm for the preparation of the perovskite solar cell device.

[0176] The perovskite solar cells finally obtained in Examples 1-3 have the structure of ITO / PTAA / CsFAMA / PC 61 BM / BCP / Cu+Te / Cu.

[0177] Examples 1-4

[0178] Except for the different preparation processes of the second electrode, the preparation of the perovskite solar cell is the same as that in Examples 1-1.

[0179] Prepare the second electrode

[0180] Put the aforementioned sample into an evaporation coater, co-evaporate copper and carbon at rates of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer with a total thickness of 80 nm for the preparation of the perovskite solar cell device.

[0181] The perovskite solar cells finally obtained in Examples 1-4 have the structure of ITO / PTAA / CsFAMA / PC 61 BM / BCP / Cu+C / Cu.

[0182] Examples 1-5 to 1-9

[0183] Except for the different molar ratio of non-metal to the first metal in the first conductive film layer of the second electrode, the preparation of the perovskite solar cell is the same as that in Examples 1-1. Specific parameters are shown in Table 1. The molar ratio of non-metal to the first metal can be adjusted by regulating the evaporation rates of copper and silicon.

[0184] Examples 1-10 to 1-16

[0185] Except for the different thickness of the first conductive film layer of the second electrode, the preparation of the perovskite solar cell is the same as that in Examples 1-1. Specific parameters are shown in Table 1.

[0186] Examples 1-17 to 1-18

[0187] Except for the different type of the second conductive film layer of the second electrode, the preparation of the perovskite solar cell is the same as that in Examples 1-1. Specific parameters are shown in Table 1.

[0188] Comparative Example 1-1

[0189] Except for the different preparation processes of the second electrode, the preparation of the perovskite solar cell is the same as that of Example 1-1.

[0190] Prepare the second electrode

[0191] Put the aforementioned sample into an evaporation coater and evaporate the copper electrode at a rate of 1 A / s to 80 nm to complete the preparation of the perovskite solar cell device.

[0192] The structure of the perovskite solar cell finally obtained in Comparative Example 1-1 is ITO / PTAA / CsFAMA / PC 61 BM / BCP / Cu.

[0193] Comparative Example 1-2

[0194] Except for the different preparation processes of the second electrode, the preparation of the perovskite solar cell is the same as that of Example 1-1.

[0195] Prepare the second electrode

[0196] Put the aforementioned sample into an evaporation coater, evaporate 5.5 nm of ITO to complete the preparation of the first conductive film layer; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm to complete the preparation of the perovskite solar cell device.

[0197] The structure of the perovskite solar cell finally obtained in Comparative Example 1-2 is ITO / PTAA / CsFAMA / PC 61 BM / BCP / ITO / Cu.

[0198] Comparative Example 1-3

[0199] Except for the different preparation processes of the second electrode, the preparation of the perovskite solar cell is the same as that of Example 1-1.

[0200] Prepare the second electrode

[0201] Put the aforementioned sample into an evaporation coater, evaporate the Bi electrode at a rate of 1 A / s to 5.5 nm to complete the preparation of the first conductive film layer; then evaporate the copper electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm to complete the preparation of the perovskite solar cell device.

[0202] The structure of the perovskite solar cell finally obtained in Comparative Example 1-3 is ITO / PTAA / CsFAMA / PC 61 BM / BCP / Bi / Cu.

[0203] Test the performance of the perovskite solar cells provided in the above Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-3. The results are shown in Table 1.

[0204] (1) Initial photoelectric conversion efficiency (PCE 0 ) test

[0205] Under the irradiation of standard simulated sunlight (AM 1.5G, 100 mW / cm 2 ), the performance of the perovskite solar cell is tested to obtain the I-V curve. According to the I-V curve and the data fed back by the test equipment, the short-circuit current Jsc (unit: mA / cm 2 ), open-circuit voltage Voc (unit: V), maximum optical output current Jmpp (unit: mA), and maximum optical output voltage Vmpp (unit: V) are obtained. The fill factor FF of the perovskite solar cell is calculated by the formula FF = Jsc×Voc / (Jmpp×Vmpp), unit: %. The photoelectric conversion efficiency PCE of the perovskite solar cell is calculated by the formula PCE = (Jsc×Voc×FF) / Pw, unit: %; Pw represents the input power, unit: mW.

[0206] (2) Stability test of perovskite solar cell

[0207] The perovskite solar cell is placed on a 65 °C hot stage in a dry room for accelerated testing with a humidity of about 5%. After 10 days, the photoelectric conversion efficiency is retested and denoted as PCE 10 . PCE 10 / PCE 0 represents the stability of the perovskite solar cell.

[0208] Table 1

[0209] It can be seen from the test results in Table 1 that by making the second electrode include a first conductive film layer and a second conductive film layer, the first conductive film layer is located between the electron transport layer and the second conductive film layer, and the electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal, an alloy formed by a non-metal and a first metal, and the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide, the stability of the perovskite solar cell can be greatly improved, and the photoelectric conversion efficiency of the perovskite solar cell can also be improved.

[0210] Example 2-1

[0211] Prepare the first electrode

[0212] Take 20 pieces of ITO-coated conductive glass with a specification of 2.0 cm × 2.0 cm. Remove 0.35 cm of the ITO layer at both ends by laser etching to expose the glass substrate. Then, ultrasonically clean it successively with water, acetone, and isopropyl alcohol, dry the solvent under a nitrogen gun, and further clean it in an ultraviolet ozone machine to obtain the first electrode.

[0213] Prepare the electron transport layer

[0214] Spin-coat a solution of tin dioxide nanoparticles (purchased commercially and can be diluted before use) on the first electrode at a speed of 1000 - 3000 rpm. Then, anneal it at 150 °C for 30 min. After cooling to room temperature, obtain an electron transport layer with a thickness of about 20 nm.

[0215] Prepare the light-absorbing layer

[0216] Spin-coat a precursor solution of perovskite material on the hole transport layer at a rate of 1000 - 5000 rpm. Then, anneal it at 100 °C for 30 min. After cooling to room temperature, obtain an absorbent layer with a thickness of about 680 nm. The perovskite material is CsFAMA, the solvent is N,N-dimethylformamide, and the concentration of the precursor solution is 1.5 mol / L.

[0217] Prepare the hole transport layer

[0218] Spin-coat Spiro solution (purchased commercially, with a concentration of 72.3 mg / ml, the solvent is chlorobenzene, and it contains additives such as lithium salt) dynamically on the absorbent layer at a speed of 4000 - 4000 rpm. Without annealing, directly obtain a hole transport layer with a thickness of about 180 nm.

[0219] Prepare the second electrode

[0220] Put the aforementioned sample into an evaporation coater, co-evaporate gold and silicon at a rate of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm. Then, evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer. The total thickness of the second electrode is 80 nm, and the preparation of the perovskite solar cell device is completed.

[0221] The perovskite solar cell structure finally obtained in Example 2-1 is ITO / SnO 2 / CsFAMA / Spiro / Au+Si / Au.

[0222] Example 2-2

[0223] The preparation of the perovskite solar cell is the same as that in Example 2-1 except for the preparation process of the second electrode.

[0224] Prepare the second electrode

[0225] Put the aforementioned sample into an evaporation coater, and co-evaporate gold and boron at a rate of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm, thus completing the preparation of the perovskite solar cell device.

[0226] The perovskite solar cell structure finally obtained in Example 2-2 is ITO / SnO 2 / CsFAMA / Spiro / Au+B / Au.

[0227] Example 2-3

[0228] Except for the different preparation process of the second electrode, the preparation of the perovskite solar cell is the same as that in Example 2-1.

[0229] Prepare the second electrode

[0230] Put the aforementioned sample into an evaporation coater, and co-evaporate gold and tellurium at a rate of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm, thus completing the preparation of the perovskite solar cell device.

[0231] The perovskite solar cell structure finally obtained in Example 2-3 is ITO / SnO 2 / CsFAMA / Spiro / Au+Te / Au.

[0232] Example 2-4

[0233] Except for the different preparation process of the second electrode, the preparation of the perovskite solar cell is the same as that in Example 2-1.

[0234] Prepare the second electrode

[0235] Put the aforementioned sample into an evaporation coater, and co-evaporate gold and carbon at a rate of 1 A / s and 0.1 A / s respectively to complete the preparation of the first conductive film layer with a thickness of 5.5 nm; then evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm, thus completing the preparation of the perovskite solar cell device.

[0236] The perovskite solar cell structure finally obtained in Example 2-4 is ITO / SnO 2 / CsFAMA / Spiro / Au+C / Au.

[0237] Examples 2-5 to 2-6

[0238] The preparation of the perovskite solar cell is the same as that in Example 2-1 except that the type of the second conductive film layer of the second electrode is different. For specific parameters, see Table 2.

[0239] Comparative Example 2-1

[0240] The preparation of the perovskite solar cell is the same as that in Example 2-1 except that the preparation process of the second electrode is different.

[0241] Prepare the second electrode

[0242] Put the aforementioned sample into an evaporation machine and evaporate the gold electrode at a rate of 1 A / s to 80 nm to complete the preparation of the perovskite solar cell device.

[0243] The structure of the finally prepared perovskite solar cell in Comparative Example 2-1 is ITO / SnO 2 / CsFAMA / Spiro / Au.

[0244] Comparative Example 2-2

[0245] The preparation of the perovskite solar cell is the same as that in Example 2-1 except that the preparation process of the second electrode is different.

[0246] Prepare the second electrode

[0247] Put the aforementioned sample into an evaporation machine, evaporate ITO 5.5 nm to complete the preparation of the first conductive film layer; then evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm to complete the preparation of the perovskite solar cell device.

[0248] The structure of the finally prepared perovskite solar cell in Comparative Example 2-2 is ITO / SnO 2 / CsFAMA / Spiro / ITO / Au.

[0249] Comparative Example 2-3

[0250] The preparation of the perovskite solar cell is the same as that in Example 2-1 except that the preparation process of the second electrode is different.

[0251] Prepare the second electrode

[0252] Put the aforementioned sample into an evaporation machine, evaporate the Bi electrode at a rate of 1 A / s to 5.5 nm to complete the preparation of the first conductive film layer; then evaporate the gold electrode at a rate of 2 A / s to obtain the second conductive film layer, and the total thickness of the second electrode is 80 nm to complete the preparation of the perovskite solar cell device.

[0253] The structure of the finally prepared perovskite solar cell in Comparative Example 2-3 is ITO / SnO 2 / CsFAMA / Spiro / Bi / Au.

[0254] The performance test methods of the perovskite solar cells of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3 are the same as those of the above Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-3. The results are shown in Table 2.

[0255] Table 2

[0256] It can be seen from the test results in Table 2 that by making the second electrode include a first conductive film layer and a second conductive film layer, the first conductive film layer is located between the hole transport layer and the second conductive film layer, and the electrode material of the first conductive film layer includes one or more of a mixture of a non-metal and a first metal and an alloy formed by the non-metal and the first metal, and the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide, the stability of the perovskite solar cell can be greatly improved, and the photoelectric conversion efficiency of the perovskite solar cell can also be improved.

[0257] It can also be seen from the test results in Table 2 that in the formal structure solar cell, when the second conductive film layer includes a second metal, the photoelectric conversion efficiency can be further improved.

[0258] As described above, the above are only specific embodiments of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should be covered within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

A perovskite solar cell, comprising: a first electrode; a second electrode; a light-absorbing layer located between the first electrode and the second electrode; a first charge transport layer located between the first electrode and the light-absorbing layer; and a second charge transport layer located between the second electrode and the light-absorbing layer, wherein the second electrode comprises a first conductive film layer and a second conductive film layer, and the first conductive film layer is disposed close to the second charge transport layer; the electrode material of the first conductive film layer comprises one or more of a mixture of a non-metal and a first metal, an alloy formed by a non-metal and a first metal, and the Fermi level of the non-metal is 4 - 5.5 eV; the electrode material of the second conductive film layer comprises one or more of a second metal, a second transparent conductive metal oxide. The perovskite solar cell according to claim 1, wherein, the non-metal comprises one or more of boron, carbon, silicon, tellurium; and / or, the work function of the first metal is 4 - 5.5 eV, optionally, the first metal comprises one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, cobalt; and / or, the work function of the second metal is 4 - 5.5 eV, optionally, the second metal comprises one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, cobalt; and / or, the second transparent conductive metal oxide comprises one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide. The perovskite solar cell according to claim 1 or 2, wherein, the first metal is the same as the second metal. The perovskite solar cell according to any one of claims 1 - 3, wherein, the molar ratio of the non-metal to the first metal in the first conductive film layer is greater than 0 and less than or equal to 1:1, and may be 1:15 - 1:

5. The perovskite solar cell according to any one of claims 1 - 4, wherein, the thickness of the first conductive film layer is greater than 0 and less than or equal to 30 nm, and may be 5 - 20 nm; and / or, the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is less than or equal to 1:2.6, and may be 1:16 - 1:

4. The perovskite solar cell according to claim 5, wherein, the total thickness of the second electrode is 60 - 120 nm, and may be 70 - 90 nm; and / or, the thickness of the second conductive film layer is 50 - 79 nm, and may be 60 - 75 nm. The perovskite solar cell according to any one of claims 1 - 6, wherein, The electrode material of the first electrode includes an organic conductive material, an inorganic conductive material, or an organic-inorganic hybrid conductive material, optionally including one or more of a first transparent conductive metal oxide, carbon, and metal, and more optionally including one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, indium-doped zinc oxide, gold, silver, aluminum, copper, and carbon; and / or, the light-absorbing layer includes a perovskite material, optionally, the perovskite material includes one or more of an inorganic halide perovskite material, an organic halide perovskite material, and an organic-inorganic hybrid halide perovskite material. The perovskite solar cell according to any one of claims 1-7, wherein, the first charge transport layer is a hole transport layer, and the second charge transport layer is an electron transport layer; or, the first charge transport layer is an electron transport layer, and the second charge transport layer is a hole transport layer. The perovskite solar cell according to any one of claims 1-8, wherein, the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer, the bottom energy level of the conduction band of the second charge transport layer is higher than the work function of the first conductive film layer, and the bottom energy level of the conduction band of the second charge transport layer is higher than the work function of the second conductive film layer; optionally, the work function of the first conductive film layer is higher than the work function of the second conductive film layer. The perovskite solar cell according to claim 9, wherein, the first metal in the first conductive film layer includes one or more of silver, copper, aluminum, and tin, and the non-metal in the first conductive film layer includes one or more of boron, carbon, silicon, and tellurium; and / or, the electrode material of the second conductive film layer includes one or more of a second metal and a second transparent conductive metal oxide, and the second metal includes one or more of silver, copper, aluminum, and tin. The perovskite solar cell according to any one of claims 1-8, wherein, the first charge transport layer is an electron transport layer, the second charge transport layer is a hole transport layer, the top energy level of the valence band of the second charge transport layer is lower than the work function of the first conductive film layer, and the top energy level of the valence band of the second charge transport layer is lower than the work function of the second conductive film layer; optionally, the work function of the first conductive film layer is lower than the work function of the second conductive film layer. The perovskite solar cell according to claim 11, wherein, the first metal in the first conductive film layer includes one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum, and the non-metal in the first conductive film layer includes one or more of boron, carbon, silicon, and tellurium; and / or, the electrode material of the second conductive film layer includes one or more of a second metal, and the second metal includes one or more of gold, platinum, beryllium, cobalt, silver, and molybdenum. The perovskite solar cell according to any one of claims 8-12, wherein, The electron transport material in the electron transport layer includes one or more of an organic electron transport material, an inorganic electron transport material, and an organic-inorganic hybrid electron transport material; and / or, the hole transport material in the hole transport layer includes one or more of an organic small molecule hole transport material, an organic polymer hole transport material, and an inorganic hole transport material. A method for preparing a perovskite solar cell according to any one of claims 1-13, comprising the following steps: providing a first electrode; forming a first charge transport layer on the first electrode; forming a light-absorbing layer on the first charge transport layer; forming a second charge transport layer on the light-absorbing layer; forming a first conductive film layer on the second charge transport layer; and forming a second conductive film layer on the first conductive film layer, the electrode material of the first conductive film layer including one or more of a mixture of a non-metal and a first metal and an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal being 4-5.5 eV; the electrode material of the second conductive film layer including one or more of a second metal and a second transparent conductive metal oxide. The method according to claim 14, wherein, the method of forming the first conductive film layer on the second charge transport layer includes evaporation or sputtering; and / or, the method of forming the second conductive film layer on the first conductive film layer includes evaporation or sputtering; and / or, the first conductive film layer is formed by co-evaporation of the non-metal and the first metal. An electrode for a perovskite solar cell, comprising a first conductive film layer and a second conductive film layer stacked, the electrode material of the first conductive film layer including one or more of a mixture of a non-metal and a first metal and an alloy formed by the non-metal and the first metal, and the Fermi level of the non-metal being 4-5.5 eV; the electrode material of the second conductive film layer including one or more of a second metal and a second transparent conductive metal oxide. The electrode according to claim 16, wherein, the non-metal includes one or more of boron, carbon, silicon, and tellurium; and / or, the work function of the first metal is 4-5.5 eV, optionally, the first metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt; and / or, the work function of the second metal is 4-5.5 eV, optionally, the second metal includes one or more of gold, silver, copper, aluminum, tin, molybdenum, platinum, beryllium, and cobalt; and / or, the second transparent conductive metal oxide includes one or more of fluorine-doped tin oxide, indium tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, and indium-doped zinc oxide. The electrode according to claim 16 or 17, wherein, the first metal is the same as the second metal. The electrode according to any one of claims 16-18, wherein, the molar ratio of the non-metal to the first metal in the first conductive film layer is greater than 0 and less than or equal to 1:1, and is optionally 1:15-1:

5. The electrode according to any one of claims 16-19, wherein, The thickness of the first conductive film layer is greater than 0 and less than or equal to 30 nm, and can be optionally 5 - 20 nm; and / or, the ratio of the thickness of the first conductive film layer to the total thickness of the second electrode is less than or equal to 1:2.6, and can be optionally 1:16 - 1:

4. The electrode according to claim 20, wherein, the total thickness of the electrode is 60 - 120 nm, and can be optionally 70 - 90 nm; and / or, the thickness of the second conductive film layer is 50 - 79 nm, and can be optionally 60 - 75 nm. A photovoltaic module, comprising the perovskite cell according to any one of claims 1 - 13, or the perovskite cell prepared by the method according to any one of claims 14 - 15. An electrical device, comprising one or more of the perovskite cells according to any one of claims 1 - 13, the perovskite cells prepared by the method according to any one of claims 14 - 15, and the photovoltaic module according to claim 22, wherein the perovskite cells and the photovoltaic module are used to supply power to the electrical device.

Images