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

Abstract

The invention discloses a preparation method of a transparent spacer layer in a printable mesoscopic perovskite solar cell, and belongs to the field of photovoltaic devices. The zirconium dioxide slurry for preparing the mesoporous zirconium dioxide spacing layer comprises the following raw materials: 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, which is prepared from the zirconium dioxide slurry designed by the invention, is higher in transparency degree, and the light transmittance of a device is greatly increased, so that the photoelectric conversion efficiency of the device can be obviously improved. The invention aims to solve the problem of transparency of the mesoporous zirconium dioxide spacer layer, and the method successfully realizes the remarkable improvement of the light transmittance of the spacer layer, effectively promotes the enhancement of the photoelectric conversion efficiency of a device, and provides powerful support for optimizing the performance of a printable mesoscopic perovskite solar cell.

Description

Technical Field

[0001] The 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 ten years, 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, the mesoporous zirconium dioxide spacer layer under the current preparation technology generally has the problems of insufficient transparency and high light shielding rate. This defect seriously hinders the effective use of incident light by perovskite solar cells, which in turn affects the improvement of their photoelectric conversion efficiency, and becomes one of the key factors restricting the large-scale commercial application of printable mesoscopic perovskite solar cells. In view of the urgency of the transparency problem of mesoporous zirconium dioxide spacer layers, 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 pore-forming agent, 0.1-4 parts of surfactant and 30-45 parts of solvent.

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

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

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

[0011] In addition to the pore-forming effect, the pore former of the present invention can also act 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 zirconia slurry further contains 0.5 - 1.5 parts by mass of a binder.

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

[0016] The second technical solution of the present invention: provides a method for preparing the above-mentioned zirconia slurry, including the following steps:

[0017] Mix the raw materials to obtain the zirconia slurry.

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

[0019] The fourth technical solution of the present invention: provides a method for preparing a transparent spacer layer of a printable mesoscopic perovskite solar cell, including the following steps:

[0020] Print the above-mentioned zirconia slurry on the mesoporous titanium dioxide layer of the perovskite solar cell, and dry it 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 prepared with the zirconia slurry designed by the present invention has a higher degree of transparency, greatly increasing the light transmittance of the device, and thus significantly improving the photoelectric conversion efficiency of the device.

[0024] The present invention aims to solve the transparency problem of the mesoporous zirconia spacer layer. This method has successfully achieved a significant improvement in the light transmittance of the spacer layer, effectively promoting the enhancement of the device's photoelectric conversion efficiency, and providing strong support for optimizing the performance of printable mesoscopic perovskite solar cells. Description of the Drawings

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0026] Figure 1 It is a schematic structural diagram of the printable mesoscopic perovskite solar cell of Embodiments 1-3 of the present invention.

[0027] Figure 2 It is a macroscopic physical diagram of the zirconia thin film prepared from the zirconia slurry of Embodiment 1 and Comparative Example 1.

[0028] Figure 3 It is the efficiency curve of the perovskite solar cell in Embodiment 1. Detailed Embodiments

[0029] Now, various exemplary embodiments of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention. It should be understood that the terms used in the present invention are only for describing specific implementation modes and are not used to limit the present invention.

[0030] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

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

[0032] Regarding the use of "comprising", "including", "having", "containing", etc. in the present invention, they are all open-ended terms, meaning including but not limited to.

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

[0034] The present invention does not particularly limit the preparation methods used in the processes of spraying a dense titanium dioxide layer, printing mesoporous titanium dioxide, printing mesoporous carbon, and the one-step drop coating method, and the methods well-known to those skilled in the art can be adopted.

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

[0036] Example 1

[0037] A preparation method of a printable mesoscopic perovskite solar cell is as follows:

[0038] (1) Preparation of zirconia slurry: Weigh 12 g of yttrium-stabilized cubic zirconia 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 terpineol, mix them with 150 g of ethanol, then place these materials in a washed zirconia ball mill jar, ball mill at a rotation speed of 600 r / min for 48 h and then take out, and then rotary evaporate to remove ethanol to obtain a white mesoporous titanium dioxide slurry.

[0039] (2) Preparation of perovskite solar cell: Spray a dense titanium dioxide layer (c-TiO2) on an FTO substrate at 450 °C, print mesoporous titanium dioxide on the dense titanium dioxide layer and sinter at 500 °C to form an electron transport layer (mesoporous titanium dioxide layer, m-TiO2); print the zirconia slurry prepared in step (1) on the mesoporous titanium dioxide layer and dry at 80 °C to form a mesoporous zirconia layer (m-ZrO2); print mesoporous carbon on the mesoporous zirconia layer and sinter at 400 °C to form a carbon electrode (m-C); use the one-step drop coating method to drop the perovskite solution from the surface of the carbon electrode, and anneal to form a perovskite solar cell.

[0040] Example 2

[0041] A preparation method of a printable mesoscopic perovskite solar cell is as follows:

[0042] (1) Preparation of zirconia slurry: Weigh 6 g of yttrium-stabilized cubic zirconia 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 terpineol, mix them with 150 g of ethanol, then place these materials in a washed zirconia ball mill jar, ball mill at a rotation speed of 600 r / min for 48 h and then take out, and then rotary evaporate to remove ethanol to obtain a white mesoporous titanium dioxide slurry.

[0043] (2) Preparation of perovskite solar cells: Spray a dense titanium dioxide layer on the FTO substrate at 450 °C, print mesoporous titanium dioxide on the dense titanium dioxide layer and sinter at 500 °C to form an electron transport layer (mesoporous titanium dioxide layer); Print the zirconia slurry prepared in step (1) on the mesoporous titanium dioxide layer and dry it at 80 °C to form a mesoporous zirconia layer; Print mesoporous carbon on the mesoporous zirconia layer and sinter at 400 °C to form a carbon electrode; Use the one-step drop-coating method to drop the perovskite solution from the surface of the carbon electrode, and anneal to form a perovskite solar cell.

[0044] Example 3

[0045] A preparation method of a printable mesoscopic perovskite solar cell is as follows:

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

[0047] (2) Preparation of perovskite solar cells: Spray a dense titanium dioxide layer on the FTO substrate at 450 °C, print mesoporous titanium dioxide on the dense titanium dioxide layer and sinter at 500 °C to form an electron transport layer (mesoporous titanium dioxide layer); Print the zirconia slurry prepared in step (1) on the mesoporous titanium dioxide layer and dry it at 80 °C to form a mesoporous zirconia layer; Print mesoporous carbon on the mesoporous zirconia layer and sinter at 400 °C to form a carbon electrode; Use the one-step drop-coating method to drop the perovskite solution from the surface of the carbon electrode, and anneal to form a perovskite solar cell.

[0048] Figure 1 It is a schematic structural diagram of the printable mesoscopic perovskite solar cell of Examples 1-3 of the present invention.

[0049] Comparative Example 1

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

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

[0052] Effect verification

[0053] 1. The zirconia slurries in Example 1 and Comparative Example 1 were respectively printed on the glass surface, dried, and a zirconia film was formed for performance comparison.

[0054] Figure 2 is the macroscopic physical diagram of the zirconia films prepared from the zirconia slurries of Example 1 and Comparative Example 1.

[0055] Figure 2 Among them, the first one on the left is Comparative Example 1, and the second one on the left is Example 1.

[0056] 2. Test the short-circuit maximum current density (Jsc), open-circuit voltage (Voc), fill factor (FF), and photoelectric conversion efficiency (PCE) of the perovskite solar cell in Example 1, and plot the efficiency curve. The specific test method is as follows: Under AM 1.5G illumination with a light intensity of 100 mW cm -2 , use a Keithley 2400 light source meter to record the J-V curves of each device. Set the measurement voltage range to 1.2 to -0.2 V, the scanning rate to 500 mV s -1 , and the effective area to 0.12 cm 2 . The test results are as Figure 3 shown.

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

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

[0059] The above-described embodiments are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

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

2. The zirconia slurry according to claim 1, wherein The particle size of the yttrium - stabilized cubic zirconia nanoparticles is 20 - 60 nm.

3. The zirconia slurry according to claim 1, wherein, The pore - forming agent is one or more of ethyl cellulose, hydroxypropyl cellulose, and propyl cellulose.

4. The zirconia slurry according to claim 1, wherein, The surfactant is one or more of glacial acetic acid, dodecanoic acid, and ethyl acetate.

5. The zirconia slurry according to claim 1, wherein, The solvent is one or more of n - butanol, terpineol, ethylene glycol, and isopropyl alcohol.

6. The zirconia slurry according to claim 1, wherein The zirconia slurry further contains 0.5 - 1.5 mass parts of binder.

7. A method for preparing the zirconia slurry according to any one of claims 1-6, characterized in that, It includes the following steps: Mix the raw materials to obtain the zirconia slurry.

8. Application of the zirconia slurry according to any one of claims 1 - 6 in the field of printable mesoscopic perovskite solar cells.

9. A method for preparing a transparent spacer layer of a printable mesoscopic perovskite solar cell, characterized in that, It includes the following steps: Print the zirconia slurry according to any one of claims 1 - 6 on the mesoporous titanium dioxide layer of the perovskite solar cell, and dry it 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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