Preparation method of transparent spacer layer in printable mesoscopic perovskite solar cells

Abstract

The present invention discloses a method for preparing a transparent spacer layer in a printable mesoscopic perovskite solar cell, which belongs to the field of photovoltaic devices. The raw materials of the zirconium dioxide slurry for preparing the mesoporous zirconium dioxide spacer layer of the present invention include yttrium-stabilized cubic phase zirconium dioxide nanoparticles, a pore-forming agent, a surfactant and a solvent. The transparent spacer layer of the printable mesoscopic perovskite solar cell prepared with the zirconium dioxide slurry designed by the present invention has a higher degree of transparency, greatly increases the light transmittance of the device, and thus can significantly improve the photoelectric conversion efficiency of the device. The present invention aims to solve the transparency problem of the mesoporous zirconium dioxide spacer layer. The method successfully achieves a significant improvement in the light transmittance of the spacer layer, effectively promotes the enhancement of the photoelectric conversion efficiency of the device, and provides strong support for optimizing the performance of printable mesoscopic perovskite solar cells.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic devices, and in particular to a method for preparing a transparent spacer layer in a printable mesoscopic perovskite solar cell. Background Art

[0002] In recent years, the field of perovskite solar cells has shown a rapid development trend. Its energy conversion efficiency has achieved a significant leap from about 3.8% to 26.9% in less than a decade, indicating that this technology has extremely broad application potential in the field of energy conversion. Among the many perovskite cell structures, printable mesoscopic perovskite solar cells have attracted widespread attention due to their excellent stability characteristics. The typical structure of this type of cell includes a fluorine-doped tin oxide conductive glass (FTO) substrate, a dense titanium dioxide layer, a mesoporous titanium dioxide layer, a mesoporous zirconium dioxide spacer layer, and a mesoporous carbon layer. In this multilayer structure, the mesoporous zirconium dioxide spacer layer, as a key spacer layer, plays a vital role in the overall performance of the cell.

[0003] However, mesoporous zirconium dioxide spacers prepared using current technology generally suffer from insufficient transparency and high light-blocking properties. This deficiency severely hinders the effective utilization of incident light by perovskite solar cells, thereby affecting the improvement of their photoelectric conversion efficiency, and has become one of the key factors restricting the large-scale commercial application of printable mesoscopic perovskite solar cells. Given the urgency of the transparency issue of mesoporous zirconium dioxide spacers, it is particularly important to explore and develop new preparation technologies to significantly improve their light transmission performance. Summary of the Invention

[0004] The object of the present invention is to provide a method for preparing a transparent spacer layer in a printable mesoscopic perovskite solar cell to solve the above-mentioned problems in the background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention is to provide a zirconium dioxide slurry for preparing a mesoporous zirconium dioxide spacer layer, wherein the raw materials, calculated by weight, include:

[0007] 8-12 parts of yttrium-stabilized cubic zirconium dioxide nanoparticles, 3-6 parts of a pore-forming agent, 0.1-4 parts of a surfactant, and 30-45 parts of a solvent.

[0008] The conventional spacer layer composed of tetragonal zirconium dioxide appears white. In order to prepare a transparent mesoporous zirconium dioxide spacer layer, the present invention uses yttrium-stabilized cubic zirconium dioxide nanoparticles to prepare the zirconium dioxide slurry.

[0009] Preferably, the particle size of the yttrium-stabilized cubic zirconia nanoparticles is 20-60 nm.

[0010] Preferably, the pore-forming agent is one or more of ethyl cellulose, hydroxypropyl cellulose and propyl cellulose.

[0011] The pore-forming agent of the present invention not only has a pore-forming function, but also can function as a binder.

[0012] Preferably, the surfactant is one or more of glacial acetic acid, dodecanoic acid and ethyl acetate.

[0013] Preferably, the solvent is one or more of n-butanol, terpineol, ethylene glycol and isopropyl alcohol.

[0014] Preferably, the zirconium dioxide slurry further contains 0.5-1.5 parts by mass of a binder.

[0015] More preferably, the binder is 300°C low-melting-point glass powder.

[0016] The second technical solution of the present invention is to provide a method for preparing the above-mentioned zirconium dioxide slurry, comprising the following steps:

[0017] The raw materials are mixed to obtain the zirconium dioxide slurry.

[0018] The third technical solution of the present invention: provides an application of the above-mentioned zirconium dioxide slurry in the field of printable mesoscopic perovskite solar cells.

[0019] Technical solution 4 of the present invention: provides a method for preparing a transparent spacer layer of a printable mesoscopic perovskite solar cell, comprising the following steps:

[0020] The zirconium dioxide slurry is printed on the mesoporous titanium dioxide layer of the perovskite solar cell and dried to complete the preparation of the transparent spacer layer.

[0021] Preferably, the drying temperature is 80°C.

[0022] The beneficial technical effects of the present invention are as follows:

[0023] The transparent spacer layer of the printable mesoscopic perovskite solar cell made from the zirconium dioxide slurry designed by the present invention has a higher degree of transparency, greatly increases the light transmittance of the device, and thus can significantly improve the photoelectric conversion efficiency of the device.

[0024] The present invention aims to solve the transparency problem of the mesoporous zirconium dioxide spacer layer. The method successfully achieves a significant improvement in the transmittance of the spacer layer, effectively promotes the enhancement of the device's photoelectric conversion efficiency, and provides strong support for optimizing the performance of printable mesoscopic perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0026] Figure 1 Schematic diagram of the structure of the printable mesoscopic perovskite solar cell of Examples 1-3 of the present invention.

[0027] Figure 2 Macroscopic pictures of zirconium oxide films prepared using the zirconium dioxide slurries of Example 1 and Comparative Example 1.

[0028] Figure 3 This is the efficiency curve of the perovskite solar cell in Example 1. DETAILED DESCRIPTION

[0029] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0030] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or stated range, and any other stated value or intervening value in the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0031] Unless otherwise specified, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention pertains. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. It should be noted that any details not described herein are conventional procedures in the art and are not the focus of the present invention.

[0032] The terms “include,” “including,” “have,” “contain,” etc. used in the present invention are open-ended terms, meaning including but not limited to.

[0033] The particle size of the yttrium-stabilized cubic zirconium dioxide nanoparticles used in the present invention is 30 nm.

[0034] The present invention has no particular limitation on the preparation methods used in the processes of spraying a dense titanium dioxide layer, printing mesoporous titanium dioxide, printing mesoporous carbon, and one-step drop coating, and methods well known to those skilled in the art may be used.

[0035] All raw materials used in the following examples of the present invention are commercially available products.

[0036] Example 1

[0037] A method for preparing a printable mesoscopic perovskite solar cell, comprising the following steps:

[0038] (1) Preparation of zirconium dioxide slurry: Weigh 12 g of yttrium-stabilized cubic zirconium dioxide nanoparticles, 6 g of ethyl cellulose, 2 g of glacial acetic acid, 0.7 g of low-melting-point glass powder, and 36 g of pine alcohol, mix them with 150 g of ethanol, and then place these materials in a clean zirconium dioxide ball mill. After ball milling at a speed of 600 r / min for 48 h, take them out, and then remove the ethanol by rotary evaporation to obtain a white mesoporous titanium dioxide slurry.

[0039] (2) Preparation of perovskite solar cells: a dense titanium dioxide layer (c-TiO2) is sprayed on a FTO substrate at 450°C, mesoporous titanium dioxide is printed on the dense titanium dioxide layer and sintered at 500°C to form an electron transport layer (mesoporous titanium dioxide layer, m-TiO2); the zirconium dioxide slurry prepared in step (1) is printed on the mesoporous titanium dioxide layer and dried at 80°C to form a mesoporous zirconium dioxide layer (m-ZrO2); mesoporous carbon is printed on the mesoporous zirconium dioxide layer and sintered at 400°C to form a carbon electrode (mC); a perovskite solution is dripped from the surface of the carbon electrode using a one-step drop coating method, annealed, and a perovskite solar cell is formed.

[0040] Example 2

[0041] A method for preparing a printable mesoscopic perovskite solar cell, comprising the following steps:

[0042] (1) Preparation of zirconium dioxide slurry: Weigh 6 g of yttrium-stabilized cubic zirconium dioxide nanoparticles, 3 g of hydroxypropyl cellulose, 2 g of glacial acetic acid, 0.7 g of low-melting-point glass powder, and 30 g of pine alcohol, mix them with 150 g of ethanol, and then place these materials in a clean zirconium dioxide ball mill. After ball milling at a speed of 600 r / min for 48 h, take them out, and then remove the ethanol by rotary evaporation to obtain a white mesoporous titanium dioxide slurry.

[0043] (2) Preparation of perovskite solar cells: spraying a dense titanium dioxide layer on a 450°C FTO substrate, printing mesoporous titanium dioxide on the dense titanium dioxide layer and sintering at 500°C to form an electron transport layer (mesoporous titanium dioxide layer); printing the zirconium dioxide slurry prepared in step (1) on the mesoporous titanium dioxide layer and drying it at 80°C to form a mesoporous zirconium dioxide layer; printing mesoporous carbon on the mesoporous zirconium dioxide layer and sintering it at 400°C to form a carbon electrode; using a one-step drop coating method to drip the perovskite solution from the surface of the carbon electrode, annealing, and forming a perovskite solar cell.

[0044] Example 3

[0045] A method for preparing a printable mesoscopic perovskite solar cell, comprising the following steps:

[0046] (1) Preparation of zirconium dioxide slurry: Weigh 6 g of yttrium-stabilized cubic zirconium dioxide nanoparticles, 3 g of ethyl cellulose, 2 g of glacial acetic acid, 0.7 g of low-melting-point glass powder, and 30 g of pine alcohol, mix them with 150 g of ethanol, and then place these materials in a clean zirconium dioxide ball mill. After ball milling at a speed of 600 r / min for 48 h, take them out, and then remove the ethanol by rotary evaporation to obtain a white mesoporous titanium dioxide slurry.

[0047] (2) Preparation of perovskite solar cells: spraying a dense titanium dioxide layer on a 450°C FTO substrate, printing mesoporous titanium dioxide on the dense titanium dioxide layer and sintering at 500°C to form an electron transport layer (mesoporous titanium dioxide layer); printing the zirconium dioxide slurry prepared in step (1) on the mesoporous titanium dioxide layer and drying it at 80°C to form a mesoporous zirconium dioxide layer; printing mesoporous carbon on the mesoporous zirconium dioxide layer and sintering it at 400°C to form a carbon electrode; using a one-step drop coating method to drip the perovskite solution from the surface of the carbon electrode, annealing, and forming a perovskite solar cell.

[0048] Figure 1 Schematic diagram of the structure of the printable mesoscopic perovskite solar cell of Examples 1-3 of the present invention.

[0049] Comparative Example 1

[0050] The only difference from Example 1 is that the preparation method of titanium dioxide slurry is modified as follows:

[0051] Take 12g ZrO2 powder, 6g ethyl cellulose, 48g terpineol and 100mL ethanol and place them in a clean zirconia ball mill. Mill them at a speed of 350r / min for 72h, then take them out and remove the ethanol by rotary evaporation to obtain titanium dioxide slurry.

[0052] Effect verification

[0053] 1. The zirconium dioxide slurries in Example 1 and Comparative Example 1 were printed on glass surfaces, dried, and zirconium dioxide films were formed for performance comparison.

[0054] Figure 2 Macroscopic pictures of zirconium oxide films prepared using the zirconium dioxide slurries of Example 1 and Comparative Example 1.

[0055] Figure 2 In the figure, the first one on the left is comparative example 1, and the second one on the left is embodiment 1.

[0056] 2. Test the maximum short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF), and photoelectric conversion efficiency (PCE) of the perovskite solar cell in Example 1 and draw an efficiency curve. The specific test method is: under AM 1.5G lighting, the light intensity is 100mW cm -2 The JV curves of each device were recorded using a Keithley 2400 light meter. The measurement voltage range was set to 1.2 to -0.2 V, and the scan rate was 500 mV s -1 , effective area is 0.12cm 2 The test results are as follows. Figure 3 shown.

[0057] Figure 3 This is the efficiency curve of the perovskite solar cell in Example 1.

[0058] Figure 3 In the figure, FWD refers to the forward scan curve of the device, and BWD refers to the reverse scan curve of the device.

[0059] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A zirconium dioxide slurry for preparing a mesoporous zirconium dioxide spacer layer, characterized in that: Raw materials, calculated by mass, include: 8-12 parts of yttrium-stabilized cubic zirconium dioxide nanoparticles, 3-6 parts of a pore-forming agent, 0.1-4 parts of a surfactant, and 30-45 parts of a solvent.

2. The zirconium dioxide slurry according to claim 1, characterized in that The particle size of the yttrium-stabilized cubic zirconium dioxide nanoparticles is 20-60 nm.

3. The zirconium dioxide slurry according to claim 1, characterized in that The pore-forming agent is one or more of ethyl cellulose, hydroxypropyl cellulose and propyl cellulose.

4. The zirconium dioxide slurry according to claim 1, characterized in that The surfactant is one or more of glacial acetic acid, dodecanoic acid and ethyl acetate.

5. The zirconium dioxide slurry according to claim 1, characterized in that The solvent is one or more of n-butanol, terpineol, ethylene glycol and isopropyl alcohol.

6. The zirconium dioxide slurry according to claim 1, characterized in that The zirconium dioxide slurry also contains 0.5-1.5 parts by mass of a binder.

7. A method for preparing the zirconium dioxide slurry according to any one of claims 1 to 6, characterized in that: The following steps are involved: The raw materials are mixed to obtain the zirconium dioxide slurry.

8. Use of the zirconium dioxide slurry according to any one of claims 1 to 6 in the field of printable mesoscopic perovskite solar cells.

9. A method for preparing a transparent spacer layer for a printable mesoscopic perovskite solar cell, characterized in that: The following steps are involved: The zirconium dioxide slurry according to any one of claims 1 to 6 is printed on the mesoporous titanium dioxide layer of the perovskite solar cell and dried to complete the preparation of the transparent spacer layer.

10. The preparation method according to claim 9, characterized in that The drying temperature is 80°C.

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