Perovskite cell transmission layer and preparation method and application thereof

Abstract

The invention discloses a perovskite cell transmission layer and a preparation method and application thereof, and belongs to the technical field of perovskite cells, and the method comprises the steps: firstly forming a NiOx thin film layer on a substrate through a magnetron sputtering technology, then introducing a hydroxyl group on the surface of the NiOx thin film layer through electrochemical treatment, then coating the NiOx thin film layer with a NiOx nano-particle layer, and finally preparing the perovskite cell transmission layer. The preparation method comprises the following steps: preparing a NiOx thin film layer, coating Meo-4PACZ small molecules through a spin coating process to obtain a closely arranged Meo-4PACZ small molecule layer, and inserting a NiOx nano-particle layer between the NiOx thin film layer and the Meo-4PACZ small molecule layer, so that the interface contact between a transmission layer and a perovskite layer is remarkably improved, and the photoelectric conversion efficiency and the stability of the perovskite cell are improved. Through simple electrochemical treatment and a nano intercalation technology, the distribution state of the Meo-4PACZ micromolecular layer on the surface of the substrate is effectively improved, the photoelectric conversion efficiency and the stability of the cell are improved, and a powerful guarantee is provided for efficient and stable operation of the perovskite cell.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite cells, and in particular relates to a perovskite cell transmission layer and a preparation method and application thereof. Background Art

[0002] In the context of global energy transformation and sustainable development, the efficient use of solar energy as a clean and renewable energy has become the focus of everyone's attention. Perovskite solar cells, as a representative of the new generation of solar cell technology, have rapidly emerged in recent years and become a research hotspot in the field of solar energy due to their excellent photoelectric conversion efficiency, low cost and easy preparation. As a key component of perovskite solar cells, the hole transport layer plays a vital role in the photoelectric performance of the cell. It can not only effectively transport holes, but also block the backflow of electrons, thereby increasing the open circuit voltage and fill factor of the cell, and thus improving the overall photoelectric conversion efficiency. Therefore, the development of efficient and stable hole transport layer materials and their preparation technology is of great significance to promote the commercialization of perovskite solar cells.

[0003] Among the hole transport layer materials of perovskite solar cells, nickel oxide (NiO x ) and small molecules are favored due to their unique advantages. NiO x As an inorganic semiconductor material, it has good chemical stability and high hole mobility, and is one of the ideal hole transport layer materials. At the same time, by combining with small molecule transport layer materials, the performance of the hole transport layer can be further optimized and the photoelectric conversion efficiency of the battery can be improved. At present, magnetron sputtering technology is the most widely used technology for preparing NiO x Magnetron sputtering is one of the main methods for thin films, which can accurately control the thickness and uniformity of the film and meet the high quality requirements of the hole transport layer for perovskite solar cells. However, despite its many advantages, magnetron sputtering technology still faces some challenges in practical applications.

[0004] On the one hand, NiO prepared by magnetron sputtering x The hydroxyl content on the film surface is low, which limits the small molecule transport layer material on NiO xSurface adsorption and arrangement. Hydroxyl groups, as surface active sites, are essential for the close arrangement and good contact of small molecule transport layer materials. Insufficient hydroxyl content will result in the inability of small molecule transport layer materials to form a continuous and dense film, thereby affecting the hole transport efficiency and the photoelectric performance of the battery. On the other hand, as a commonly used substrate material, indium tin oxide (ITO) has a certain degree of roughness on its surface. This roughness will further aggravate the uneven distribution of small molecule transport layer materials on the substrate surface, resulting in defects and pores in the hole transport layer, reducing the filling factor and open circuit voltage of the battery. Therefore, how to improve the arrangement state of the small molecule transport layer on the rough substrate and improve the quality and performance of the hole transport layer has become an urgent problem to be solved in the current research on perovskite solar cells. Summary of the invention

[0005] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a method for preparing a perovskite battery transport layer to solve the technical problem of how to improve the arrangement state of the small molecule transport layer on a rough substrate and improve the quality and performance of the hole transport layer.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention discloses a method for preparing a perovskite battery transmission layer, comprising the following steps: 1) Deposition of NiO on substrate x Thin film layer; 2) In NiO x Hydroxyl groups were introduced into the surface of the film layer and NiO was coated x Nanoparticle layer; 3) In NiO x A tightly arranged small molecule layer is prepared on the surface of the nanoparticle layer to obtain a perovskite battery transport layer.

[0007] Preferably, in step 1), NiO is deposited on the substrate by magnetron sputtering. x Thin film layer; the atmosphere of magnetron sputtering is argon, NiO x The thickness of the film is 10~20nm.

[0008] Preferably, in step 2), NiO is treated by hydroxylation. x Hydroxyl groups were introduced into the surface of the film layer; the conditions for hydroxylation treatment were: NiO x The film layer is used as the working electrode, Ag / AgCl is used as the reference electrode, and 0.025~1.0 M KOH aqueous solution is used as the electrolyte. After cycling at -0.6~0.2V for 10~20 times, the electrolyte is cleaned and vacuum dried. The vacuum drying temperature is 60~80 ℃, and the vacuum drying time is 1~10 h.

[0009] Preferably, in step 2), NiO x The preparation method of the nanoparticle layer includes: first preparing 3-20 mg / ml NiO x The nanoparticle aqueous solution is stirred evenly, spin-coated, and dried.

[0010] More preferably, the spin coating rate is 2000-8000 rpm, and the spin coating time is 5-30 s; the drying temperature is 100-150° C., and the drying time is 5-30 min.

[0011] Preferably, in step 3), the preparation method of the Meo-4PACZ small molecule layer comprises: dissolving the Meo-4PACZ small molecule in ethanol, stirring evenly, preparing a 0.3-1 mg / ml solution, and spin coating it on NiO x The nanoparticle layer, after drying, obtained the Meo-4PACZ small molecule layer.

[0012] More preferably, the spin coating rate is 2000-8000 rpm, and the spin coating time is 5-50 s; the drying temperature is 80-150° C., and the drying time is 5-30 min.

[0013] The present invention also discloses a perovskite battery transmission layer, which is prepared by the above-mentioned preparation method. The perovskite battery transmission layer includes NiO x Thin film layers, small molecule layers, and intercalated NiO x NiO between the thin film layer and the small molecule layer x Nanoparticle layer; NiO x The thin film layer is disposed on the substrate.

[0014] The present invention also discloses a perovskite solar cell, comprising: a substrate, a perovskite cell transmission layer, a perovskite layer, an electron transmission layer and an electrode layer sequentially arranged on the substrate; The perovskite battery transmission layer is prepared by using the above-mentioned preparation method of the perovskite battery transmission layer.

[0015] Preferably, the method for preparing the perovskite layer comprises: according to (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05)3, weighing FAI, MABr, CsI, PbBr2 and PbI2, and dissolving them in a mixed solvent of DMF and DMSO, and then adding 1% to 5% by mass of PbI2 and 5% to 40% by mass of MACl to obtain a perovskite precursor solution, and applying the perovskite precursor solution on the surface of the perovskite cell transport layer by a two-step spin coating method, and annealing to obtain a perovskite layer; The preparation method of the electron transport layer includes: evaporating C60 on the perovskite layer to obtain electron transport; the thickness of C60 is 20~50nm, and the evaporation rate is 0.1~0.5 Å s -1 ; The preparation method of the electrode layer includes: evaporating a gold electrode on the electron transport layer to obtain the electrode layer; the thickness of the gold electrode is 60-120 nm, and the evaporation rate is 1-5 Å s -1 .

[0016] Compared with the prior art, the present invention has the following beneficial effects: The invention discloses a method for preparing a perovskite battery transmission layer, wherein NiO x Hydroxyl groups were introduced on the surface to improve the interface contact between it and the small molecule transport layer Meo-4PACZ and increase the charge transfer efficiency. x NiO was inserted between Meo-4PACZ x The nanoparticle layer effectively fills the rough surface of the ITO substrate and the NiO x The gaps between the layers allow the Meo-4PACZ small molecules to be arranged more closely on the substrate, further improving the charge transfer efficiency. Through the improvement of the above method, the photoelectric conversion efficiency of the perovskite battery has been significantly improved. Better interface contact and tighter molecular arrangement help reduce losses during charge transfer, thereby improving the overall performance of the battery. The preparation method of the present invention is simple and easy to operate, and the steps are closely connected, which is conducive to large-scale production and application. NiO x The introduction of the nanoparticle layer and the small molecule layer not only improves the efficiency of the battery, but also enhances the stability of the battery. These layers can protect the perovskite layer from erosion by the external environment and extend the service life of the battery. The preparation method of the perovskite battery transport layer proposed in the present invention effectively improves the distribution state of the small molecule transport layer on the substrate surface through simple electrochemical treatment and nano-intercalation technology, improves the photoelectric conversion efficiency and stability of the battery, and provides a strong guarantee for the efficient and stable operation of the perovskite battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the distribution diagram of the untreated small molecule layer disclosed in Example 1 of the present invention; Figure 2This is a state diagram of the substrate after hydroxyl treatment disclosed in Example 1 of the present invention; Figure 3 This is the distribution diagram of the small molecule layer after hydroxyl treatment disclosed in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0019] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0020] The present invention is further described in detail below in conjunction with the accompanying drawings: The present invention discloses a method for preparing a perovskite battery transmission layer, which specifically comprises the following steps: 1) Magnetron sputtering NiO x Thin film layer Environmental preparation: In the magnetron sputtering equipment, ensure that the sputtering chamber is in a high vacuum state, then introduce pure argon as the working gas and adjust it to a suitable working pressure.

[0021] Sputtering parameters: Set the sputtering power and time to control the NiO x The thickness of the film layer is between 10 and 20 nm, which can ensure good conductivity while avoiding the increase of charge transfer resistance caused by excessive thickness.

[0022] Substrate treatment: Use ITO as the substrate, and clean and decontaminate it in advance to ensure that the surface is clean and free of impurities.

[0023] Sputtering process: Start the sputtering equipment, place the substrate in the magnetron sputtering chamber and evacuate the vacuum to 5×10 -4Then sputtering deposition was carried out under the condition of 90W sputtering power, and the target material was NiO x Target material, argon atmosphere, sputtering thickness of 10~20nm; NiO x The target material is sputtered onto the ITO substrate in an argon atmosphere to form a uniform NiO x Thin film layer.

[0024] 2) Hydroxylation treatment Electrochemical device: magnetron sputtered NiO x The film layer was used as the working electrode and Ag / AgCl as the reference electrode, which were inserted into an electrolytic cell containing 0.025-1.0 M KOH aqueous solution.

[0025] Electrochemical treatment: Cyclic voltammetry scans were performed in the voltage range of -0.6~0.2V, with the number of cycles being 10~20. x Hydroxyl groups are introduced into the surface of the film layer to improve its surface properties.

[0026] Post-treatment: After the electrochemical treatment is completed, wash thoroughly with deionized water to remove residual electrolyte and impurities, and then place in a vacuum drying oven at 60~80℃ for 1~10 h to ensure that there is no moisture remaining on the surface.

[0027] 3) NiO x Nanoparticle layer preparation Solution configuration: NiO x The nanoparticles were dispersed in ultrapure water to prepare 3~20 mg / ml NiO x The nanoparticles are then uniformly dispersed by ultrasonic treatment or mechanical stirring.

[0028] Spin coating process: Use a spin coater to take 100 μL of NiO x The nanoparticle aqueous solution was added dropwise to the hydroxylated NiO x After the film layer is evenly spread, spin coat at a speed of 2000-8000 rpm for 5-30 s to ensure that NiO x The nanoparticle aqueous solution evenly covers the surface of the substrate.

[0029] Drying treatment: Spin-coated NiO x The substrate after the nanoparticle aqueous solution was placed in an oven at 100-150°C and dried for 5-30 min to make NiO x The nanoparticle layer solidifies and the solvent is removed.

[0030] 4) Preparation of Meo-4PACZ small molecule layer Solution preparation: Disperse the Meo-4PACZ small molecule in ethanol to prepare a 0.3~1 mg / ml Meo-4PACZ small molecule ethanol solution.

[0031] Spin coating process: Using the same spin coater, take 100 μL of Meo-4PACZ small molecule ethanol solution and drop it on the NiO x After the surface of the nanoparticle layer was evenly spread, spin coating was performed at a speed of 2000-8000 rpm for 5-50 s to ensure uniform coverage of the Meo-4PACZ small molecules.

[0032] Drying treatment: Place the substrate after spin coating Meo-4PACZ small molecules in an oven at 80~150 ℃ and dry for 5~30 minutes to solidify the Meo-4PACZ small molecule layer and remove the solvent to obtain the perovskite battery transport layer.

[0033] The invention discloses a perovskite battery transmission layer, comprising NiO x Thin film layers, small molecule layers, and intercalated NiO x NiO between the thin film layer and the small molecule layer x Nanoparticle layer; the NiO x The thin film layer is disposed on the substrate.

[0034] A perovskite solar cell disclosed in the present invention comprises: a substrate, a perovskite cell transmission layer, a perovskite layer, an electron transmission layer and an electrode layer which are sequentially arranged on the substrate.

[0035] Perovskite battery transport layer: prepared by the above-mentioned preparation method of the perovskite battery transport layer.

[0036] Perovskite layer: The perovskite layer is prepared on the Meo-4PACZ small molecule layer of the perovskite cell transport layer using (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, the band gap is 1.55 eV, and FAI, MABr, CsI, PbBr2 and PbI2 powders are weighed according to the stoichiometric ratio and dissolved in a mixed solvent of DMF and DMSO, with a volume ratio of DMF and DMSO of 4:1. In addition, 1%~5% of PbI2 and 5%~40% of MACl are added as anti-solvents to passivate grain boundary defects and promote crystal growth. The perovskite precursor solution is coated on the substrate surface by a two-step spin coating method. After spinning at 1000~3000 rpm for 5~15 s, it is increased to 4000~8000 rpm for 30~60 s. The anti-solvent is added at 35s, followed by annealing at 80~150℃ for 15~45 min.

[0037] Electron transport layer: C60 is evaporated on the perovskite layer to prepare an electron transport layer to improve the electron transport efficiency; the thickness of C60 is 20~50nm, and the evaporation rate is 0.1~0.5 Å s -1 .

[0038] Electrode layer: A gold electrode is deposited on the electron transport layer to obtain an electrode layer for collecting charges and transmitting current; the thickness of the gold electrode is 60-120 nm, and the evaporation rate is 1-5 Å s -1 .

[0039] The present invention proposes a method for preparing a perovskite battery transport layer, which combines electrochemical modification with nano-intercalation technology to optimize NiO x The surface properties of the thin film layer promote the close arrangement and efficient transmission of the Meo-4PACZ small molecule layer, significantly improving the photoelectric conversion efficiency and long-term stability of perovskite solar cells. x A specific voltage range is applied to the thin film layer, and the NiO x Hydroxyl groups (-OH) are introduced into the surface of the film layer. In this process, NiO x The film layer is used as the working electrode, Ag / AgCl is used as the reference electrode, and an aqueous solution containing an appropriate amount of electrolyte (such as KOH) is used as the electrolyte. x Some metal ions on the surface of the film layer combine with the hydroxide ions generated by water ionization to form stable hydroxyl functional groups. The introduction of hydroxyl groups not only increases the x The hydrophilicity of the film surface is conducive to the subsequent spreading and penetration of the Meo-4PACZ small molecule solution, and as an active site, it can enhance the interaction between the Meo-4PACZ small molecule layer and NiO x The interaction between the thin film layer and the substrate promotes the tight adsorption and orderly arrangement of the small molecule transport layer. The highly dispersed and uniformly sized NiO is synthesized by wet chemical method. x The nanoparticles were evenly coated on the NiO prepared by magnetron sputtering by spin coating technology. x By controlling the concentration of nanoparticles, spin coating speed and drying conditions, the NiO x The nanoparticle layer can effectively fill the microscopic unevenness of the ITO substrate without being too thick to affect the overall transmission performance. x The nanoparticle layer is used as an intermediate layer. Its small size and high specific surface area can effectively fill the ITO substrate and NiO xThe gaps between the film layers reduce the interface roughness and provide a smoother and continuous deposition interface for the Meo-4PACZ small molecules. This not only helps the uniform spreading of the Meo-4PACZ small molecule layer, but also reduces interface defects and improves the continuity and efficiency of hole transport.

[0040] Through the dual strategy of electrochemical treatment and nano-intercalation, the present invention significantly improves the Meo-4PACZ small molecule layer on NiO x The arrangement state on the thin film layer enhances the overall quality and performance of the hole transport layer. The tightly arranged Meo-4PACZ small molecule layer effectively reduces the interface resistance and improves the hole transport efficiency, thereby improving the open circuit voltage, short circuit current and filling factor of the battery, and ultimately achieving a significant improvement in the photoelectric conversion efficiency. The introduction of hydroxyl groups and the application of nano-intercalation technology also enhance the bonding force between the hole transport layer and the substrate, improve the weather resistance and long-term stability of the battery, and lay a solid foundation for the commercial application of perovskite solar cells. The problem of the small molecule transport layer not being tightly arranged on a rough substrate has been successfully solved, providing new ideas and technical approaches for improving the photoelectric performance and stability of perovskite solar cells.

[0041] Example 1 A method for preparing a perovskite battery transmission layer comprises the following steps: 1) Magnetron sputtering NiO x Thin film layer In the magnetron sputtering equipment, ensure that the sputtering chamber is in a high vacuum state, and then introduce pure argon as the working gas; set the sputtering power and time to control the NiO x The thickness of the film layer is 10nm. The sputtering equipment is started and the cleaned ITO substrate is placed in the magnetron sputtering chamber to evacuate the vacuum to 5×10 -4 After that, sputtering deposition was carried out for 30 min at a sputtering power of 90 W, and the target material was NiO x Target material, argon atmosphere, sputtering thickness of 10nm; NiO x The target material is sputtered onto the ITO substrate in an argon atmosphere to form a uniform NiO x Thin film layer.

[0042] 2) Hydroxylation treatment The NiO after magnetron sputtering x The film layer was used as the working electrode and Ag / AgCl as the reference electrode, and was inserted into an electrolytic cell containing 0.1M KOH aqueous solution. Cyclic voltammetry was performed in the voltage range of 0.1V and the number of cycles was 15. This step was performed by electrochemical method on NiO xHydroxyl groups were introduced on the surface of the film layer to improve its surface properties. After the electrochemical treatment, it was thoroughly washed with deionized water to remove residual electrolyte and impurities, and then placed in a vacuum drying oven at 70°C for 5 hours to ensure that there was no moisture remaining on the surface.

[0043] 3) NiO x Nanoparticle layer preparation NiO x The nanoparticles were dispersed in ultrapure water to prepare 5 mg / ml NiO x Nanoparticles aqueous solution, and the particles are evenly dispersed by ultrasonic treatment or mechanical stirring. Using a spin coater, take 100 μL of NiO x The nanoparticle aqueous solution was added dropwise to the hydroxylated NiO x After the film layer is evenly spread, spin coating is performed at 4000 rpm for 20 s to ensure that NiO x The nanoparticle aqueous solution evenly covers the surface of the substrate. x The substrate after the nanoparticles aqueous solution was placed in an oven at 120 °C and dried for 10 min to make NiO x The nanoparticle layer solidifies and the solvent is removed.

[0044] 4) Preparation of Meo-4PACZ small molecule layer Disperse Meo-4PACZ small molecules in ethanol to prepare a 0.5 mg / ml Meo-4PACZ small molecule ethanol solution. Use a spin coater to take 100 μL of Meo-4PACZ small molecule ethanol solution and drop it on the NiO x After the surface of the nanoparticle layer is evenly spread, it is spin-coated at 4000 rpm for 30 s to ensure uniform coverage of Meo-4PACZ small molecules. The substrate after spin-coating Meo-4PACZ small molecules is placed in an oven at 100 °C for 10 min to solidify the Meo-4PACZ small molecule layer and remove the solvent to obtain the perovskite cell transport layer.

[0045] A method for preparing a perovskite solar cell, comprising: Step 1) to step 4) are the same as the above-mentioned method for preparing the perovskite battery transport layer.

[0046] 5) Perovskite layer preparation The perovskite layer was prepared on the Meo-4PACZ small molecule layer of the perovskite cell transport layer using (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05)3, the band gap is 1.55 eV, FAI, MABr, CsI, PbBr2 and PbI2 powders are weighed according to the stoichiometric ratio and dissolved in a mixed solvent of DMF and DMSO, and the volume ratio of DMF and DMSO is 4:1. In addition, 3% PbI2 and 30% MACl are added as anti-solvents to passivate grain boundary defects and promote crystal growth. The perovskite precursor solution is coated on the substrate surface by a two-step spin coating method. After spinning at 2000 rpm for 10 s, it is increased to 5000 rpm for 40 s. The anti-solvent is added at 35s, followed by annealing at 100°C for 30 min.

[0047] 6) Preparation of electron transport layer C60 was evaporated on the perovskite layer to prepare an electron transport layer to improve the electron transport efficiency; the thickness of C60 was 30nm and the evaporation rate was 0.3 Å s -1 .

[0048] 7) Preparation of electrode layer A gold electrode was evaporated on the electron transport layer to obtain an electrode layer for collecting charges and transmitting current; the thickness of the gold electrode was 100 nm and the evaporation rate was 2 Å s -1 ; Finally, a perovskite solar cell is obtained.

[0049] Figure 1 This is the distribution diagram of the untreated small molecule layer disclosed in Example 1 of the present invention; it can be seen from the figure that the Meo-4PACZ small molecules are distributed on the surface of the magnetron sputtered nickel oxide, and the orientation of the phosphate groups is affected by the suede structure of the substrate.

[0050] Figure 2 The state diagram of the substrate after hydroxyl treatment disclosed in Example 1 of the present invention; it can be seen from the figure that after hydroxyl treatment, NiO x The nanoparticles are evenly distributed and filled into the suede voids.

[0051] Figure 3 This is the distribution diagram of the small molecule layer after hydroxyl treatment disclosed in Example 1 of the present invention; it can be seen from the figure that the phosphate groups on the surface of the Meo-4PACZ small molecule are vertically upward, forming effective contact with the perovskite layer, thereby enhancing the charge extraction and transfer efficiency.

[0052] Example 2 A method for preparing a perovskite battery transmission layer comprises the following steps: 1) Magnetron sputtering NiO x Thin film layer In the magnetron sputtering equipment, ensure that the sputtering chamber is in a high vacuum state, and then introduce pure argon as the working gas; set the sputtering power and time to control the NiO xThe thickness of the film layer is 12nm. The sputtering equipment is started and the cleaned ITO substrate is placed in the magnetron sputtering chamber to evacuate the vacuum to 5×10 -4 After that, sputtering deposition was carried out under the condition of 90W sputtering power, and the target material was NiO x Target material, argon atmosphere, sputtering thickness of 12nm; NiO x The target material is sputtered onto the ITO substrate in an argon atmosphere to form a uniform NiO x Thin film layer.

[0053] 2) Hydroxylation treatment The NiO after magnetron sputtering x The film layer was used as the working electrode and Ag / AgCl as the reference electrode, and was inserted into an electrolytic cell containing 0.025 M KOH aqueous solution. Cyclic voltammetry scans were performed in the voltage range of -0.6 V and the number of cycles was 10. This step was performed by electrochemical method on NiO x Hydroxyl groups were introduced on the surface of the film layer to improve its surface properties. After the electrochemical treatment, it was thoroughly washed with deionized water to remove residual electrolyte and impurities, and then placed in a vacuum drying oven at 60°C for 1 h to ensure that there was no moisture remaining on the surface.

[0054] 3) NiO x Nanoparticle layer preparation NiO x The nanoparticles were dispersed in ultrapure water to prepare 3 mg / ml NiO x Nanoparticles aqueous solution, and the particles are evenly dispersed by ultrasonic treatment or mechanical stirring. Using a spin coater, take 100 μL of NiO x The nanoparticle aqueous solution was added dropwise to the hydroxylated NiO x After the film layer is evenly spread, spin coating is performed at 2000 rpm for 5 s to ensure that NiO x The nanoparticle aqueous solution evenly covers the surface of the substrate. x The substrate after the nanoparticle aqueous solution was placed in an oven at 100 °C and dried for 5 min to make NiO x The nanoparticle layer solidifies and the solvent is removed.

[0055] 4) Preparation of Meo-4PACZ small molecule layer Disperse Meo-4PACZ small molecules in ethanol to prepare a 0.3 mg / ml Meo-4PACZ small molecule ethanol solution. Use a spin coater to take 100 μL of Meo-4PACZ small molecule ethanol solution and drop it on the NiO xAfter the surface of the nanoparticle layer is evenly spread, it is spin-coated at a speed of 2000 rpm for 5 s to ensure uniform coverage of the Meo-4PACZ small molecules. The substrate after spin-coating the Meo-4PACZ small molecules is placed in an oven at 80 ° C for 5 min to solidify the Meo-4PACZ small molecule layer and remove the solvent to obtain the perovskite cell transport layer.

[0056] A method for preparing a perovskite solar cell, comprising: Step 1) to step 4) are the same as the preparation method of the above-mentioned perovskite battery transport layer.

[0057] 5) Perovskite layer preparation The perovskite layer was prepared on the Meo-4PACZ small molecule layer of the perovskite cell transport layer using (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, the band gap is 1.55 eV, FAI, MABr, CsI, PbBr2 and PbI2 powders are weighed according to the stoichiometric ratio and dissolved in a mixed solvent of DMF and DMSO, and the volume ratio of DMF and DMSO is 4:1. In addition, 1% PbI2 and 5% MACl are added as anti-solvents to passivate grain boundary defects and promote crystal growth. The perovskite precursor solution is coated on the substrate surface by a two-step spin coating method. After spinning at 1000 rpm for 5 s, it is increased to 4000 rpm for 30 s. The anti-solvent is added at 35s, followed by annealing at 80°C for 15 min.

[0058] 6) Preparation of electron transport layer C60 was evaporated on the perovskite layer to prepare an electron transport layer to improve the electron transport efficiency; the thickness of C60 was 20 nm and the evaporation rate was 0.1 Å s -1 .

[0059] 7) Preparation of electrode layer A gold electrode was evaporated on the electron transport layer to obtain an electrode layer for collecting charges and transmitting current; the thickness of the gold electrode was 60 nm and the evaporation rate was 1 Å s -1 ; Finally, a perovskite solar cell is obtained.

[0060] Example 3 A method for preparing a perovskite battery transmission layer comprises the following steps: 1) Magnetron sputtering NiO x Thin film layer In the magnetron sputtering equipment, ensure that the sputtering chamber is in a high vacuum state, and then introduce pure argon as the working gas; set the sputtering power and time to control the NiOx The thickness of the film layer is 15nm. The sputtering equipment is started and the cleaned ITO substrate is placed in the magnetron sputtering chamber to evacuate the vacuum to 5×10 -4 After that, sputtering deposition was carried out under the condition of 90W sputtering power, and the target material was NiO x Target material, argon atmosphere, sputtering thickness of 15nm; NiO x The target material is sputtered onto the ITO substrate in an argon atmosphere to form a uniform NiO x Thin film layer.

[0061] 2) Hydroxylation treatment The NiO after magnetron sputtering x The film layer was used as the working electrode and Ag / AgCl as the reference electrode, and was inserted into an electrolytic cell containing 0.05M KOH aqueous solution. Cyclic voltammetry was performed in the voltage range of -0.1V and the number of cycles was 12. This step was performed by electrochemical method on NiO x Hydroxyl groups were introduced on the surface of the film layer to improve its surface properties. After the electrochemical treatment, it was thoroughly washed with deionized water to remove residual electrolyte and impurities, and then placed in a vacuum drying oven at 75°C for 6 hours to ensure that there was no moisture remaining on the surface.

[0062] 3) NiO x Nanoparticle layer preparation NiO x The nanoparticles were dispersed in ultrapure water to prepare 10 mg / ml NiO x Nanoparticles aqueous solution, and the particles are evenly dispersed by ultrasonic treatment or mechanical stirring. Using a spin coater, take 100 μL of NiO x The nanoparticle aqueous solution was added dropwise to the hydroxylated NiO x After the film layer is evenly spread, spin coating is performed at 6000 rpm for 10 s to ensure that NiO x The nanoparticle aqueous solution evenly covers the surface of the substrate. x The substrate after the nanoparticles aqueous solution was placed in an oven at 110 °C and dried for 20 min to make NiO x The nanoparticle layer solidifies and the solvent is removed.

[0063] 4) Preparation of Meo-4PACZ small molecule layer Disperse Meo-4PACZ small molecules in ethanol to prepare a 0.6 mg / ml Meo-4PACZ small molecule ethanol solution. Use a spin coater to take 100 μL of Meo-4PACZ small molecule ethanol solution and drop it on the NiO xAfter the surface of the nanoparticle layer is evenly spread, it is spin-coated at 6000 rpm for 20 s to ensure uniform coverage of Meo-4PACZ small molecules. The substrate after spin-coating Meo-4PACZ small molecules is placed in an oven at 120 ° C for 20 min to solidify the Meo-4PACZ small molecule layer and remove the solvent to obtain the perovskite cell transport layer.

[0064] A method for preparing a perovskite solar cell, comprising: Step 1) to step 4) are the same as the preparation method of the above-mentioned perovskite battery transport layer.

[0065] 5) Perovskite layer preparation The perovskite layer was prepared on the Meo-4PACZ small molecule layer of the perovskite cell transport layer using (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, the band gap is 1.55 eV, FAI, MABr, CsI, PbBr2 and PbI2 powders are weighed according to the stoichiometric ratio and dissolved in a mixed solvent of DMF and DMSO, and the volume ratio of DMF and DMSO is 4:1. In addition, 4% PbI2 and 20% MACl are added as anti-solvents to passivate grain boundary defects and promote crystal growth. The perovskite precursor solution is coated on the substrate surface by a two-step spin coating method. After spinning at 1500 rpm for 12 s, it is increased to 6000 rpm for 50 s. The anti-solvent is added at 35s, followed by annealing at 120°C for 35 min.

[0066] 6) Preparation of electron transport layer C60 was evaporated on the perovskite layer to prepare an electron transport layer to improve the electron transport efficiency; the thickness of C60 was 40nm and the evaporation rate was 0.2 Å s -1 .

[0067] 7) Preparation of electrode layer A gold electrode was evaporated on the electron transport layer to obtain an electrode layer for collecting charges and transmitting current; the thickness of the gold electrode was 80 nm and the evaporation rate was 3 Å s -1 ; Finally, a perovskite solar cell is obtained.

[0068] Example 4 A method for preparing a perovskite battery transmission layer comprises the following steps: 1) Magnetron sputtering NiO x Thin film layer In the magnetron sputtering equipment, ensure that the sputtering chamber is in a high vacuum state, and then introduce pure argon as the working gas; set the sputtering power and time to control the NiO x The thickness of the film layer is 20 nm. The sputtering equipment is started, and the cleaned ITO substrate is placed in the magnetron sputtering chamber and the vacuum is reduced to 5×10 -4 After that, sputtering deposition was carried out under the condition of 90W sputtering power, and the target material was NiO x Target material, argon atmosphere, sputtering thickness of 20nm; NiO x The target material is sputtered onto the ITO substrate in an argon atmosphere to form a uniform NiO x Thin film layer.

[0069] 2) Hydroxylation treatment The NiO after magnetron sputtering x The film layer was used as the working electrode and Ag / AgCl as the reference electrode, and was inserted into an electrolytic cell containing 1.0M KOH aqueous solution. Cyclic voltammetry was performed over a voltage range of 0.2 V and the number of cycles was 20. This step was performed by electrochemical method on NiO x Hydroxyl groups were introduced on the surface of the film layer to improve its surface properties. After the electrochemical treatment, it was thoroughly washed with deionized water to remove residual electrolyte and impurities, and then placed in a vacuum drying oven at 80°C for 10 hours to ensure that there was no moisture remaining on the surface.

[0070] 3) NiO x Nanoparticle layer preparation NiO x The nanoparticles were dispersed in ultrapure water to prepare 20 mg / ml NiO x Nanoparticles aqueous solution, and the particles are evenly dispersed by ultrasonic treatment or mechanical stirring. Using a spin coater, take 100 μL of NiO x The nanoparticle aqueous solution was added dropwise to the hydroxylated NiO x After the film layer is evenly spread, spin coating is performed at 8000 rpm for 30 s to ensure that NiO x The nanoparticle aqueous solution evenly covers the surface of the substrate. x The substrate after the nanoparticles aqueous solution was placed in an oven at 150°C and dried for 30 min to make NiO x The nanoparticle layer solidifies and the solvent is removed.

[0071] 4) Preparation of Meo-4PACZ small molecule layer Disperse Meo-4PACZ small molecules in ethanol to prepare a 1 mg / ml Meo-4PACZ small molecule ethanol solution. Use a spin coater to take 100 μL of Meo-4PACZ small molecule ethanol solution and drop it on the NiO x After the surface of the nanoparticle layer is evenly spread, it is spin-coated at 8000 rpm for 50 s to ensure uniform coverage of Meo-4PACZ small molecules. The substrate after spin-coating Meo-4PACZ small molecules is placed in an oven at 150 ° C for 30 min to solidify the Meo-4PACZ small molecule layer and remove the solvent to obtain the perovskite cell transport layer.

[0072] A method for preparing a perovskite solar cell, comprising: Step 1) to step 4) are the same as the preparation method of the above-mentioned perovskite battery transport layer.

[0073] 5) Perovskite layer preparation The perovskite layer was prepared on the Meo-4PACZ small molecule layer of the perovskite cell transport layer using (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, the band gap is 1.55 eV, FAI, MABr, CsI, PbBr2 and PbI2 powders are weighed according to the stoichiometric ratio and dissolved in a mixed solvent of DMF and DMSO, and the volume ratio of DMF and DMSO is 4:1. In addition, 5% PbI2 and 40% MACl are added as anti-solvents to passivate grain boundary defects and promote crystal growth. The perovskite precursor solution is coated on the substrate surface by a two-step spin coating method. After spinning at 3000 rpm for 15 s, it is increased to 8000 rpm for 60 s. The anti-solvent is added at 35s, followed by annealing at 150°C for 45 min.

[0074] 6) Preparation of electron transport layer C60 was evaporated on the perovskite layer to prepare an electron transport layer to improve the electron transport efficiency; the thickness of C60 was 50 nm and the evaporation rate was 0.5 Å s -1 .

[0075] 7) Preparation of electrode layer A gold electrode was evaporated on the electron transport layer to obtain an electrode layer for collecting charges and transmitting current; the thickness of the gold electrode was 120 nm and the evaporation rate was 5 Å s -1 ; Finally, a perovskite solar cell is obtained.

[0076] Comparative Example 1 A method for preparing a perovskite battery transmission layer comprises the following steps: The difference between this embodiment and Example 1 is that no hydroxylation treatment is performed.

[0077] Table 1 Comparison of electrical properties of the perovskite battery transport layer obtained in Example 1 of the present invention and Comparative Example 1

[0078] See Table 1 for a comparison of the electrical properties of the perovskite battery transport layer obtained in Example 1 of the present invention and in Comparative Example 1. It can be seen from the table that the open circuit voltage of Example 1 is 0.04V higher than that of Comparative Example 1, indicating that the battery of Example 1 can generate a higher voltage in the open circuit state, which is a positive indicator of improved battery performance. The fill factor of Example 1 is slightly higher than that of Comparative Example 1. Although the increase is not large (only 0.004), the increase in fill factor means that the battery can be closer to its theoretical maximum efficiency under actual working conditions. The short circuit current of Example 1 is 0.2mAcm higher than that of Comparative Example 1. - ², which shows that under short-circuit conditions, the battery of Example 1 can transmit more current. The efficiency of Example 1 is 1.1 percentage points higher than that of Comparative Example 1, which is the most direct manifestation of the improved battery performance. The improvement in efficiency means that the battery can more effectively utilize light energy in the process of converting light energy into electrical energy. By comparing the electrical performance data of Example 1 with that of Comparative Example 1, we can clearly see that Example 1 is superior to Comparative Example 1 in open circuit voltage, fill factor, short-circuit current and efficiency. This shows that the preparation method or material selection adopted in Example 1 of the present invention has a significant effect on improving the electrical properties of the perovskite battery transmission layer, and the battery performance of Example 1 is better and has higher application value.

[0079] The present invention provides a method for preparing a perovskite battery transmission layer. The method uses an electrochemical method to prepare a perovskite battery transmission layer on the NiO x Hydroxyl groups are formed on the surface of the film layer. On the other hand, in magnetron sputtering NiO x NiO is inserted between the thin film layer and the Meo-4PACZ small molecule layer x The nanoparticle layer fills the gaps. Through the above method, the Meo-4PACZ small molecule layer is closely arranged on the substrate, which improves the photoelectric conversion efficiency of the perovskite cell. This method uses a simple electrochemical treatment method and nano-intercalation technology to increase the NiO x The hydroxyl content on the surface of the film layer improves the distribution of the small molecule transport layer on the substrate surface and improves the quality and performance of the hole transport layer. x Rich hydroxyl groups are formed on the surface of the film layer, providing more adsorption sites for small molecule transport layer materials; at the same time, by inserting NiO xThe nanoparticle layer fills the rough surface of the substrate and provides a smoother and continuous interface for the small molecule transport layer. The present invention effectively solves the problem that the small molecule transport layer cannot be closely arranged on the rough substrate, and improves the photoelectric conversion efficiency and stability of the perovskite solar cell.

[0080] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a perovskite battery transport layer, characterized in that: The following steps are involved: 1) Deposition of NiO on substrate x Thin film layer; 2) In NiO x Hydroxyl groups were introduced into the surface of the film layer and NiO was coated x Nanoparticle layer; 3) In NiO x A tightly arranged small molecule layer is prepared on the surface of the nanoparticle layer to obtain a perovskite battery transport layer.

2. The method for preparing the perovskite battery transport layer according to claim 1, characterized in that: In step 1), NiO is deposited on the substrate by magnetron sputtering. x The magnetron sputtering atmosphere is argon, NiO x The thickness of the film is 10~20nm.

3. The method for preparing the perovskite battery transport layer according to claim 1, characterized in that: In step 2), hydroxylation is used to treat NiO x Hydroxyl groups are introduced into the surface of the film layer; The conditions of the hydroxylation treatment are: NiO x The film layer is used as the working electrode, Ag / AgCl is used as the reference electrode, and a 0.025-1.0 M KOH aqueous solution is used as the electrolyte. After cycling at -0.6-0.2 V for 10-20 times, the electrolyte is cleaned and vacuum dried. The vacuum drying temperature is 60-80°C, and the vacuum drying time is 1-10 h.

4. The method for preparing the perovskite battery transport layer according to claim 1, characterized in that: In step 2), the NiO x The preparation method of the nanoparticle layer includes: first preparing 3-20 mg / ml NiO x The nanoparticle aqueous solution is stirred evenly, spin-coated, and dried.

5. The method for preparing the perovskite battery transport layer according to claim 4, characterized in that: The spin coating speed is 2000-8000 rpm, and the spin coating time is 5-30 s; the drying temperature is 100-150° C., and the drying time is 5-30 min.

6. The method for preparing the perovskite battery transport layer according to claim 1, characterized in that: In step 3), the preparation method of the Meo-4PACZ small molecule layer includes: dissolving the Meo-4PACZ small molecule in ethanol, stirring evenly, preparing a 0.3-1 mg / ml solution, and spin coating it on NiO x The nanoparticle layer, after drying, obtained the Meo-4PACZ small molecule layer.

7. The method for preparing the perovskite battery transport layer according to claim 6, characterized in that: The spin coating speed is 2000-8000 rpm, and the spin coating time is 5-50 s; the drying temperature is 80-150° C., and the drying time is 5-30 min.

8. A perovskite battery transport layer, characterized in that: The perovskite battery transmission layer is prepared by the preparation method according to any one of claims 1 to 7, and comprises NiO x Thin film layers, small molecule layers, and intercalated NiO x NiO between the thin film layer and the small molecule layer x Nanoparticle layer; the NiO x The thin film layer is disposed on the substrate.

9. A perovskite solar cell, characterized in that: include: A substrate, a perovskite cell transport layer, a perovskite layer, an electron transport layer and an electrode layer sequentially arranged on the substrate; The perovskite battery transmission layer is prepared by the preparation method described in any one of claims 1 to 7.

10. The perovskite solar cell according to claim 9, characterized in that: The preparation method of the perovskite layer comprises: according to (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, weighing FAI, MABr, CsI, PbBr2 and PbI2, and dissolving them in a mixed solvent of DMF and DMSO, and then adding 1% to 5% by mass of PbI2 and 5% to 40% by mass of MACl to obtain a perovskite precursor solution, and applying the perovskite precursor solution on the surface of the perovskite cell transport layer by a two-step spin coating method, and annealing to obtain a perovskite layer; The preparation method of the electron transport layer comprises: evaporating C60 on the perovskite layer to obtain electron transport; the thickness of the C60 is 20-50 nm, and the evaporation rate is 0.1-0.5 Å s -1 ; The preparation method of the electrode layer comprises: evaporating a gold electrode on the electron transport layer to obtain the electrode layer; the thickness of the gold electrode is 60-120 nm, and the evaporation rate is 1-5 Å s -1 .

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