A flexible perovskite battery based on full coating of silver nanowires

Abstract

The present invention provides a perovskite cell comprising a nanosilver layer. Furthermore, the perovskite cell comprises, from bottom to top, a flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a carbon layer, and a silver layer. The perovskite cell containing the nanosilver layer has advantages such as lower resistance than ITO / FTO, higher light transmittance, convenient preparation of large-area flexible perovskites, low internal resistance, and high efficiency. Furthermore, by coating the surface of the nanosilver layer with a polymer and electron transport composite layer, the electron transfer rate and battery stability can be effectively improved, thereby extending the service life.

Description

Technical Field

[0001] The present invention belongs to the field of solar energy technology, and in particular relates to a flexible perovskite battery fully coated with nano silver wires. Background Art

[0002] In line with my country's dual carbon strategy, clean and renewable energy will continue to grow its share of the country's energy market to achieve carbon peak and carbon neutrality. Solar energy utilization is a key area, and the photovoltaic power generation industry plays a crucial role in my country's new energy power generation industry. Perovskite solar cells are the third generation of solar cells, following crystalline silicon solar cells and thin-film solar cells. They offer advantages such as simple structure, high photoelectric conversion efficiency, and low cost. They have attracted attention from countries around the world, including China, Japan, South Korea, the United States, and the United Kingdom, and technological research is continuing to deepen.

[0003] Currently, most perovskite cells are based on glass substrates, which require complex equipment and are not suitable for applications in curved or flexible scenarios, such as car roofs. They also have low production efficiency and yield, and the ITO / FTO substrates have high resistance and low transmittance. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to provide a flexible perovskite battery based on full coating of nano silver wires, which has the advantages of low ITO / FTO resistance, high transmittance, high efficiency, good flexibility and corrosion resistance.

[0005] To achieve the above-mentioned purpose, the present invention adopts the following technical solutions.

[0006] A perovskite cell comprising a nanosilver layer.

[0007] In some embodiments, the sheet resistance of the nanosilver layer is 1 to 100 ohm / sq; preferably, the sheet resistance of the nanosilver layer is 5 to 20 ohm / sq.

[0008] In some embodiments, the nanosilver layer is prepared by coating a nanosilver ink comprising nanosilver wires and a solvent selected from at least one of an organic solvent, IPA, alcohol, and n-butanol.

[0009] In some embodiments, the silver nanowire has a diameter of 8 to 100 nm and a length of 5 to 80 um.

[0010] In some preferred embodiments, the diameter of the silver nanowire is 10-40 nm and the length is 20-50 um.

[0011] In some embodiments, the solid content of the nanosilver ink is 0.1-5%.

[0012] In some preferred embodiments, the solid content of the nanosilver ink is 0.1-2%.

[0013] In some embodiments, the perovskite cell comprises, from bottom to top, a flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a carbon layer, and a silver layer.

[0014] In some embodiments, the polymer and electron transport composite layer is prepared from raw materials comprising the following components: a metal oxide, a resin capable of undergoing polymerization reaction, an initiator and a solvent; the solid content of the metal oxide is 10 to 90%, the sum of the solid contents of the acrylic resin and the initiator is 10 to 90%, and the mass ratio of the acrylic resin to the initiator is (10 to 1000):1.

[0015] In some preferred embodiments, the solid content of the metal oxide is 50-80%, the sum of the solid contents of the acrylic resin and the initiator is 20-50%, and the mass ratio of the acrylic resin to the initiator is (50-300):1.

[0016] More preferably, the mass ratio of the acrylic resin to the initiator is (75-150):1

[0017] In some embodiments, the metal oxide is selected from at least one of titanium dioxide, zinc oxide, tin oxide, and tin dioxide;

[0018] And / or, the resin capable of undergoing polymerization reaction is selected from at least one of acrylic resin, polyurethane resin, and epoxy resin;

[0019] And / or, the initiator is selected from at least one of an organic peroxide compound, an inorganic peroxide compound, an azo initiator, and a redox initiator; the general structural formula of the organic peroxide compound is R—O—O—H or R—O—O—R; wherein R is selected from an alkyl group, an acyl group, and a carbonate group;

[0020] And / or, the solvent is selected from at least one of alcohol compounds and ester compounds.

[0021] In some embodiments, the flexible base material is selected from at least one of PC, PMMA, and PET; and / or the perovskite layer material is selected from at least one of CsPbI3, CsPbBr3, and MAPbI3; and / or the carbon layer material is selected from at least one of C60, carbon paste, and graphene.

[0022] In some embodiments, the thickness of the polymer and electron transport composite layer is 5 to 200 nm; and / or the thickness of the perovskite layer is 100 to 1000 nm; and / or the thickness of the carbon layer is 1 to 50 μm.

[0023] In some preferred embodiments, the thickness of the polymer and electron transport composite layer is 20 to 80 nm; and / or the thickness of the perovskite layer is 300 to 600 nm; and / or the thickness of the carbon layer is 20 to 30 μm.

[0024] In some embodiments, a hole transport layer is further contained between the perovskite layer and the carbon layer; the hole transport layer material is selected from at least one of triphenylamine, Spiro-OMeTAD, cuprous iodide, cuprous sulfide, cuprous oxide, and copper thiocyanate; and / or the hole transport layer has a thickness of 1 to 50 μm.

[0025] In some preferred embodiments, the hole transport layer has a thickness of 1 to 50 μm.

[0026] The present invention also provides a method for preparing the perovskite battery as described above, comprising the following steps: (1) coating nanosilver ink on the flexible base layer to obtain a nanosilver layer; (2) coating the polymer and electron transport composite layer on the nanosilver layer; (3) coating a perovskite layer on the polymer and electron transport composite layer; (4) coating a carbon layer on the perovskite layer; and (5) coating silver paste on the carbon layer to obtain a silver layer, thereby preparing the perovskite battery.

[0027] The present invention provides a perovskite battery, which contains a nanosilver layer. By coating the nanosilver layer on a flexible substrate layer, the perovskite battery can have a lower resistance relative to ITO / FTO, higher transmittance, convenient preparation of large-area perovskites, low internal resistance, and high efficiency. Furthermore, the inventors have found that when an electron transport layer containing a metal oxide is directly coated on the nanosilver layer, holes are easily formed and the migration of halogen ions cannot be completely prevented. Therefore, the nanosilver cannot be prevented from being corroded, and the charge transfer is not conducive. The performance of the battery device produced is poor. However, a polymer and electron transport composite layer made of a metal oxide and a non-conductive polymer is coated on the nanosilver layer. This solves the conductivity problem while providing density, preventing the perovskite layer from corroding the nanosilver wires, and optimizing the formula of the suitable polymer and electron transport composite layer. The surface of the polymer and electron transport composite layer is smoother, which is conducive to coating the perovskite layer, making the manufactured device more efficient. The polymer and electron transport composite layer can further block the diffusion of halogen ions and prevent nanosilver from being corroded, thereby improving the long-term stability of the battery device.

[0028] The preparation method of the perovskite battery of the present invention adopts full coating processing, simple equipment, high efficiency, and good flexibility, and can be applied to various application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is a comparison chart of the electron transfer rates of perovskite cells containing a polymer and electron transport composite layer and an electron transport layer.

[0030] Figure 2 These are the stability test results of perovskite cells containing polymer and electron transport composite layers and electron transport layers. DETAILED DESCRIPTION

[0031] The experimental methods in the following examples of the present invention, where specific conditions are not specified, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various commonly used chemical reagents used in the examples are all commercially available products.

[0032] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0033] The terms "comprise," "comprising," and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, product, or device comprising a series of steps is not limited to the listed steps or modules but may optionally include steps not listed, or other steps inherent to the process, method, product, or device.

[0034] In this application, "plurality" refers to two or more. "And / or" describes the relationship between related objects, indicating that three possible relationships exist. For example, "A and / or B" can mean: A exists alone, A and B exist simultaneously, or B exists alone. The character " / " generally indicates that the related objects are in an "or" relationship.

[0035] The following describes the details in conjunction with specific embodiments.

[0036] Example 1

[0037] This embodiment provides a perovskite cell, which comprises, from bottom to top, a PET film flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a C60 layer, and a silver layer.

[0038] The preparation method of the perovskite battery is as follows: (1) Toray's UV-resistant PET film is selected and roll-to-roll coated with a nanosilver wire conductive ink; the nanosilver wire conductive ink is prepared by dispersing nanosilver wires in an IPA solvent, the nanosilver wires having a diameter of 20 nanometers and a length of 35 micrometers; the nanosilver wire conductive ink has a solid content of 0.1%. The wet film coating thickness is 30 micrometers, the baking temperature is 100 degrees, and the square resistance is 10 ohm / sq to obtain a nanosilver layer; (2) 8 kg of nanosilver is added to a 10L container. 35% oxalic acid solution is heated to 70 degrees, and 200g of hydrogen peroxide and 100g of metallic zinc are slowly added (added over 10 minutes), and then the temperature is raised to 100 degrees and reacted for 40 minutes to obtain a zinc oxide aqueous solution with a diameter of 10 to 20nm; after the zinc oxide aqueous solution is cooled, 50g of isopropylamine is added thereto, and then 1g of dipentaerythritol hexaacrylate and 0.1g of initiator 184 are added, and mixed evenly to obtain a polymer and electron transport composite layer coating liquid, which is coated on the nanosilver layer, dried and cured by UV, with a dry film thickness of 50 nanometers, to obtain a polymer and electron transport composite layer; (3) a CsPbI3 perovskite layer is coated on the polymer and electron transport composite layer with a thickness of 500nm; (4) a C60 layer is coated on the CsPbI3 perovskite layer with a thickness of 25μm; (5) a silver paste layer is coated on the C60 layer to obtain the perovskite battery.

[0039] Example 2

[0040] This embodiment provides a perovskite cell, which comprises, from bottom to top, a PET film flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a C60 layer, and a silver layer.

[0041] The preparation method of the perovskite battery is as follows: (1) Toray's UV-resistant PET film is selected and roll-to-roll coated with a nanosilver wire conductive ink; the nanosilver wire conductive ink is prepared by dispersing nanosilver wires in an IPA solvent, the diameter of the nanosilver wires is 20 nanometers, and the length is 35 microns; the solid content of the nanosilver wire conductive ink is 0.1%. The wet film coating thickness is 30 microns, the baking temperature is 100 degrees, and the square resistance is 10 ohm / sq to obtain a nanosilver layer; (2) ZnC2O4, C2H2O4, ethanol and water are mixed in a mass and volume ratio of 4g:6g:40ml:50ml to form a suspension, and the suspension is stirred for one day to obtain a zinc dioxide sol; after the zinc dioxide sol is cooled, 50g of isopropylamine is added thereto, and then 1g of dipentaerythritol hexaacrylate and 0.1g of initiator 18 are added. 4. Mixing uniformly to obtain a polymer and electron transport composite layer coating liquid, coating the coating liquid on the nanosilver layer, drying and UV curing, with a dry film thickness of 50 nm, to obtain a polymer and electron transport composite layer; (3) coating a CsPbI3 perovskite layer on the polymer and electron transport composite layer with a thickness of 500 nm; (4) coating a C60 layer on the CsPbI3 perovskite layer with a thickness of 25 μm; (5) coating a silver paste layer on the C60 layer to obtain the perovskite battery.

[0042] Example 3

[0043] This embodiment provides a perovskite cell, which comprises, from bottom to top, a PET film flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a hole transport layer, a C60 layer, and a silver layer.

[0044] The preparation method of the perovskite battery is as follows: (1) Toray's UV-resistant PET film is selected and roll-to-roll coated with a nanosilver wire conductive ink; the nanosilver wire conductive ink is prepared by dispersing nanosilver wires in an IPA solvent, the nanosilver wires having a diameter of 20 nanometers and a length of 35 micrometers; the nanosilver wire conductive ink has a solid content of 0.1%. The wet film coating thickness is 30 micrometers, the baking temperature is 100 degrees, and the square resistance is 10 ohm / sq to obtain a nanosilver layer; (2) 8 kg of nanosilver is added to a 10L container. 35% oxalic acid solution is heated to 70 degrees, and 200g of hydrogen peroxide and 100g of metallic tin are slowly added (addition is completed in 10 minutes), and then the temperature is raised to 100 degrees to react for 40 minutes to obtain a tin oxide aqueous solution with a diameter of 10 to 20nm; after the tin oxide aqueous solution is cooled, 50g of isopropylamine is added thereto, and then 1g of dipentaerythritol hexaacrylate and 0.1g of initiator 184 are added and mixed to obtain a polymer and electron transport composite layer coating liquid, which is coated on the nanosilver layer and baked. After drying, UV curing is adopted, and the dry film thickness is 80 nanometers to obtain a polymer and electron transport composite layer; (3) a CsPbI3 perovskite layer is coated on the polymer and electron transport composite layer, and the thickness is 600 nm; (4) Spiro-OMeTAD is coated on the CsPbI3 perovskite layer to form a hole transport layer, and the thickness is 50 nm; (5) carbon paste is coated on the hole transport layer to form a carbon layer, and the thickness is 30 μm; (6) a silver paste layer is coated on the carbon layer to obtain the perovskite battery.

[0045] Comparative Example 1

[0046] This comparative example provides a perovskite cell. The perovskite cell is the same as Example 1 except that the polymer and electron transport composite layer is replaced by an electron transport layer. The details are as follows:

[0047] The perovskite cell comprises, from bottom to top, a PET film flexible base layer, a nanosilver layer, an electron transport layer, a perovskite layer, a C60 layer, and a silver layer.

[0048] The preparation method of the perovskite battery is as follows: (1) Toray's UV-resistant PET film is selected and roll-to-roll coated with nanosilver wire conductive ink; the nanosilver wire conductive ink is prepared by dispersing nanosilver wires in IPA solvent, the diameter of the nanosilver wires is 20 nanometers and the length is 35 microns; the solid content of the nanosilver wire conductive ink is 0.1%. The wet film coating thickness is 30 microns, the baking temperature is 100 degrees, and the square resistance is 10 ohm / sq to obtain a nanosilver layer; (2) 8 kg of 35% oxalic acid solution is added to a 10L container, heated to 70 degrees, and 200 g of hydrogen peroxide solution and 100 g of metal zinc are slowly added (added over 10 minutes), and then the temperature is raised to 100 degrees and reacted for 40 minutes to obtain a zinc oxide aqueous solution with a diameter of 10 to 20 nm; the solution is coated on the nanosilver layer, dried and then UV cured to a dry film thickness of 50 nanometers to obtain a polymer and electron transport composite layer; (3) a CsPbI3 perovskite layer is coated on the polymer and electron transport composite layer with a thickness of 500 nm; (4) a C60 layer is coated on the CsPbI3 perovskite layer with a thickness of 25 μm; (5) a silver paste layer is coated on the C60 layer to obtain the perovskite battery.

[0049] The electron transfer rate and stability of the perovskite cells prepared in Example 1 and Comparative Example 1 were tested.

[0050] Electron transfer rate: The photoelectric conversion efficiency (PCE) is tested by the IV curve, and the electron transfer rate of the battery can be obtained.

[0051] The stability detection method is as follows: the life of the battery device can be tested by the change of the photoelectric conversion efficiency (PCE) over time, thereby evaluating the stability of the battery device.

[0052] like Figure 1 As shown in the figure, the electron transfer rate of the perovskite cell containing a polymer and an electron transport composite layer in Example 1 (represented by "ZnO-OC" in the figure) is faster than that of the perovskite cell containing only an electron transport layer in Comparative Example 1 (represented by "ZnO" in the figure). This is because the surface of the electron transport composite layer formed by directly coating the metal oxide on the nanosilver layer has many defects, which is not conducive to the transfer of charge. The surface of the polymer and electron transport composite layer formed by combining the metal oxide with the polymer is smoother and has better density, which is more conducive to the transfer of charge.

[0053] like Figure 2As shown, a perovskite cell device based on a composite polymer and electron transport layer (represented by "ZnO-OC" in the figure) can still maintain 91% of its initial value after being placed in an environment with a humidity of 85% for 600 hours after packaging. However, a perovskite cell device based on only an electron transport layer can only maintain 75% of its initial value under the same conditions. This shows that the present invention can effectively improve the stability of perovskite cells and extend their service life by combining polymers and metal oxides.

[0054] In summary, the present invention provides a perovskite cell containing a nanosilver layer, which has advantages such as lower resistance than ITO / FTO, higher transmittance, convenient preparation of large-area perovskite, low internal resistance, and high efficiency. Furthermore, by coating the nanosilver layer with a polymer and electron transport composite layer, the electron transport rate and cell stability can be effectively improved.

[0055] The technical features of the above-described embodiments can be combined arbitrarily. To make the description concise, 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.

[0056] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A perovskite battery, characterized in that: The perovskite cell comprises a nanosilver layer; The sheet resistance of the nanosilver layer is 1 to 100 ohm / sq; The perovskite cell comprises, from bottom to top, a flexible base layer, a nanosilver layer, a polymer and electron transport composite layer, a perovskite layer, a carbon layer, and a silver layer; The polymer and electron transport composite layer is prepared from raw materials comprising the following components: a metal oxide, a resin capable of undergoing polymerization, an initiator, and a solvent; The resin capable of undergoing polymerization reaction is selected from acrylic resin; the acrylic resin is dipentaerythritol hexaacrylate; The solid content of the metal oxide is 10-90%, the sum of the solid contents of the acrylic resin and the initiator is 10-90%, and the mass ratio of the acrylic resin to the initiator is (10-1000):1; The metal oxide is selected from zinc oxide; And / or, the initiator is selected from at least one of an organic peroxide compound, an inorganic peroxide compound, an azo initiator, and a redox initiator; the general structural formula of the organic peroxide compound is R—O—O—H or R—O—O—R; wherein R is selected from an alkyl group, an acyl group, and a carbonate group; And / or, the solvent is selected from at least one of an alcohol compound and an ester compound; The solid content of the metal oxide is 50-80%, the sum of the solid contents of the acrylic resin and the initiator is 20-50%, and the mass ratio of the acrylic resin to the initiator is (50-300):1; The preparation method of the polymer and electron transport composite layer is as follows: A 35% oxalic acid solution is added to a container, heated to 70 degrees, and then hydrogen peroxide and metallic zinc are added. The temperature is then raised to 100 degrees and reacted for 40 minutes to obtain a zinc oxide aqueous solution with a diameter of 10 to 20 nm. After the zinc oxide aqueous solution is cooled, isopropylamine is added thereto, followed by dipentaerythritol hexaacrylate and an initiator, and the mixture is evenly mixed to obtain a polymer and electron transport composite layer coating liquid, which is then coated on the nanosilver layer, dried, and then cured using UV light to obtain a polymer and electron transport composite layer.

2. The perovskite battery according to claim 1, wherein The sheet resistance of the nanosilver layer is 5 to 20 ohm / sq.

3. The perovskite battery according to claim 1, wherein The flexible base material is selected from at least one of PC, PMMA, and PET; and / or the perovskite layer material is selected from at least one of CsPbI3, CsPbBr3, and MAPbI3; and / or the carbon layer material is selected from at least one of C60, carbon paste, and graphene.

4. The perovskite battery according to claim 1, wherein The thickness of the polymer and electron transport composite layer is 5 to 200 nm; and / or the thickness of the perovskite layer is 100 to 1000 nm; and / or the thickness of the carbon layer is 1 to 50 μm.

5. The perovskite battery according to any one of claims 1 to 4, wherein A hole transport layer is further contained between the perovskite layer and the carbon layer; the hole transport layer material is selected from at least one of triphenylamine, Spiro-OMeTAD, cuprous iodide, cuprous sulfide, cuprous oxide, and copper thiocyanate; and / or the hole transport layer has a thickness of 1 to 50 μm.

6. The method for preparing a perovskite battery according to any one of claims 1 to 4, wherein: The following steps are involved: (1) coating nanosilver ink on the flexible base layer to obtain a nanosilver layer; (2) coating the polymer and electron transport composite layer on the nanosilver layer; (3) coating a perovskite layer on the polymer and electron transport composite layer; (4) coating a carbon layer on the perovskite layer; (5) coating silver paste on the carbon layer to obtain a silver layer, thereby preparing the perovskite battery.

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