3D printing coating method of perovskite battery and application of 3D printing coating method

Abstract

The invention discloses a 3D printing coating method of a perovskite battery and application of the 3D printing coating method, and belongs to the field of perovskite batteries. A conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer and a metal electrode layer are sequentially prepared on a glass substrate through 3D printing and heat treatment, preparation of the perovskite cell is completed, in the 3D printing process, a P1 scribed line is reserved on the conductive substrate, a P2 scribed line and a P3 scribed line are reserved on the hole transport layer, the perovskite layer and the electron transport layer, and the P3 scribed line is reserved on the metal electrode layer. The perovskite cell prepared by the 3D printing method provided by the invention can avoid the problems of pollution and electrode corrosion in the laser etching process, ensures that the electrode and the material of the cell maintain the stability for a longer time, can also improve the photoelectric conversion efficiency, and provides powerful support for commercial application of the perovskite solar cell.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite solar cells, and particularly to a 3D printing coating method for perovskite solar cells and its application. Background Art

[0002] With the rapid development of perovskite solar cells in the past decade or so, their photoelectric conversion efficiency has approached or even rivaled that of traditional crystalline silicon solar cells, which has attracted much attention in the field of new energy. However, although the photoelectric conversion efficiency of perovskite solar cells has gradually increased and significant progress has been made, there are still a series of technical problems to be solved before commercialization.

[0003] First of all, the stability problem of perovskite solar cells remains a key bottleneck. The high-quality preparation of the perovskite layer still faces many challenges, especially how to ensure the long-term stability and moisture and ultraviolet resistance of perovskite materials during the preparation process. The structural characteristics of perovskite materials and environmental factors (such as temperature, humidity, light, etc.) have a great impact on their performance, and deterioration is likely to occur, resulting in a decline in battery performance. Therefore, how to improve the stability of the perovskite layer by improving the preparation process is still an important research direction.

[0004] Secondly, the production process of perovskite solar cells urgently needs to be further improved. In the existing manufacturing process of perovskite solar cells, laser scribing technology is often used to complete the series-parallel connection of battery components. Although this process can effectively electrically connect the batteries, there are some problems in the laser scribing process. Specifically, the laser scribing process may cause corrosion of the metal electrodes of perovskite solar cells, laser etching curling at the scribed lines, etc. In addition, when the laser beam passes through the surface of the perovskite thin film during laser scribing, a large amount of powder may be generated, and these powders will adhere to the battery surface and P2 scribed lines, thus causing pollution problems, which in turn affect the photoelectric conversion efficiency of the battery. This performance decline of battery components seriously hinders their commercialization process, especially in large-scale production.

[0005] Based on this, the application provides a 3D printing coating method for perovskite solar cells to solve the problems existing in the preparation process of the above-mentioned perovskite solar cells. Summary of the Invention

[0006] In order to solve the problems that in the existing manufacturing process of perovskite solar cells, the laser scribing process may cause corrosion of the metal electrodes of perovskite solar cells, laser etching curling at the scribed lines, and powder pollution problems, the present invention provides a 3D printing coating method for perovskite solar cells and its application.

[0007] To achieve the above object, the present invention provides the following technical solutions: The present invention provides a 3D printing coating method for perovskite solar cells, comprising: Coating a conductive substrate solution on a glass substrate by 3D printing, reserving the position of P1 scribing line during the 3D printing process, and performing heat treatment after coating to obtain a conductive substrate; Coating a hole transport solution on the conductive substrate by 3D printing, filling the P1 scribing line during the 3D printing process, reserving the positions of P2 scribing line and P3 scribing line, and performing heat treatment after coating to obtain a hole transport layer; Coating a perovskite solution on the hole transport layer by 3D printing, reserving the positions of P2 scribing line and P3 scribing line during the 3D printing process, and performing heat treatment after coating to obtain a perovskite layer; Coating an electron transport solution on the perovskite layer by 3D printing, reserving the positions of P2 scribing line and P3 scribing line during the 3D printing process, and performing heat treatment after coating to obtain an electron transport layer; Coating a metal electrode solution on the electron transport layer by 3D printing, filling the P2 scribing line during the 3D printing process, reserving the position of P3 scribing line, and performing heat treatment after coating to obtain a metal electrode layer, thus completing the preparation of the perovskite solar cell.

[0008] The width of the P1 scribing line is 45 - 55 μm, and the distance between the P2 scribing line and the P1 scribing line is less than 100 μm. The width of the P2 scribing line is 70 - 80 μm, the distance between the P3 scribing line and the P2 scribing line is less than 100 μm, and the width of the P3 scribing is 70 - 80 μm.

[0009] The step of coating a conductive substrate solution on a glass substrate by 3D printing, reserving the position of P1 scribing line during the 3D printing process, and performing heat treatment after coating to obtain a conductive substrate, comprises: Mixing FTO nanoparticles and polyvinylpyrrolidone evenly in a water - ethanol mixed solution to obtain a conductive substrate solution, wherein the mass fraction of FTO nanoparticles is 10 - 12 wt%, and the mass fraction of polyvinylpyrrolidone is 2 - 3 wt%; Coating the conductive substrate solution on the battery substrate by 3D printing, the needle diameter of the print head is 200 - 300 μm, the extrusion pressure is 150 - 200 kPa; the printing speed is 10 - 15 mm / s; After the conductive substrate printing is completed, pre - dry it at 80 - 100 °C for 10 - 20 min; then anneal it at 500 - 550 °C for 50 - 100 min to obtain a conductive substrate.

[0010] The step of coating a hole transport solution on the conductive substrate by 3D printing, filling the P1 scribing line during the 3D printing process, reserving the positions of P2 scribing line and P3 scribing line, and performing heat treatment after coating to obtain a hole transport layer, comprises: NiO nanoparticles and polyvinylpyrrolidone are added to the isopropanol-water mixture and mixed evenly to obtain a hole transport solution, where the mass fraction of NiO nanoparticles is 10 - 15 wt%, and the mass fraction of polyvinylpyrrolidone is 2 - 3 wt%. The hole transport solution is coated on the conductive substrate by 3D printing. The needle diameter of the print head is 200 - 300 μm, the extrusion pressure is 150 - 200 kPa, and the printing speed is 10 - 15 mm / s. After the printing of the hole transport layer is completed, it is pre-dried at 80 - 100 °C for 10 - 20 min, and then annealed at 350 - 400 °C for 50 - 100 min to obtain the hole transport layer. The perovskite solution is coated on the hole transport layer by 3D printing. During the 3D printing process, the positions of P2 and P3 lines are reserved. After the coating is completed, heat treatment is carried out to obtain the perovskite layer, including: PbI2 is added to the DMSO-DMF mixture and mixed evenly, and then FAI, CsI and additives are added in sequence and mixed evenly to obtain the perovskite solution. Among them, the molar ratio of PbI2, FAI and CsI is 1.1 : 1.0 : 0.1, and the additives include GuSCN and CsF. The mass fraction of GuSCN is 1.5 - 2 wt%, and the mass fraction of CsF is 0.3 - 0.5 wt%. The perovskite solution is coated on the hole transport layer by 3D printing. The needle diameter of the print head is 200 - 300 μm, the extrusion pressure is 100 - 150 kPa, and the printing speed is 5 - 10 mm / s. After the printing of the perovskite layer is completed, it is annealed at 150 - 200 °C for 30 - 50 min to obtain the perovskite layer.

[0011] The electron transport solution is coated on the perovskite layer by 3D printing. During the 3D printing process, the positions of P2 and P3 lines are reserved. After the coating is completed, heat treatment is carried out to obtain the electron transport layer. The electron transport layer includes C 60 layer and BCP layer. The C 60 solution and BCP solution are sequentially coated on the perovskite layer by 3D printing; The C 60 layer is coated on the perovskite layer by 3D printing. During the 3D printing process, the positions of P2 and P3 lines are reserved. After the coating is completed, heat treatment is carried out to obtain the C 60 layer, including: C 60 powder is added to ortho-dichlorobenzene and mixed evenly to obtain the C 60 solution, where the ratio of C 60 to ortho-dichlorobenzene is 20 mg / mL; The C60 A solution, the needle diameter of the print head is 100 - 200 μm, the extrusion pressure is 100 - 150 kPa; the printing speed is 5 - 10 mm / s; C 60 After the printing of layer C is completed, it is annealed at 100 - 150 °C in nitrogen for 10 - 20 min to obtain layer C 60 layer.

[0012] On layer C 60 coat the BCP solution by 3D printing. Reserve the positions of P2 and P3 lines during the 3D printing process. After coating, perform heat treatment to obtain the BCP layer, including: Add BCP powder to chloroform and mix evenly, then add polyvinylpyrrolidone and mix evenly to obtain the BCP solution; wherein, the ratio of BCP to chloroform is 2 - 3 mg / mL; the mass fraction of polyvinylpyrrolidone is 0.2 - 0.5 wt%; Use 3D printing to coat the BCP solution on layer C 60 layer. The needle diameter of the print head is 100 - 200 μm, the extrusion pressure is 100 - 150 kPa; the printing speed is 10 - 15 mm / s; After the printing of the BCP layer is completed, let it stand at room temperature for 30 - 50 min to obtain the BCP layer.

[0013] Coat the metal electrode solution on the electron transport layer by 3D printing. Fill the P2 line during the 3D printing process and reserve the position of the P3 line. After coating, perform heat treatment to obtain the metal electrode layer, including: Add copper nanoparticles to ethanol and mix evenly, then add polyvinylpyrrolidone and hydroxyethyl cellulose and mix evenly to obtain the metal electrode solution; wherein, the mass fraction of polyvinylpyrrolidone is 2 - 3 wt%, the mass fraction of hydroxyethyl cellulose is 1 - 2 wt%, and the solid content of copper nanoparticles is 30 - 40 wt%; Use 3D printing to coat the metal electrode solution on the BCP layer. The needle diameter of the print head is 150 - 200 μm, the extrusion pressure is 200 - 250 kPa; the printing speed is 15 - 20 mm / s; After the printing of the metal electrode layer is completed, anneal it at 200 - 250 °C for 30 - 50 min to obtain the metal electrode layer.

[0014] The present invention also provides a perovskite solar cell, which is prepared according to the above 3D printing coating method of the perovskite solar cell.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: The 3D printing coating method of the perovskite solar cell provided by the present invention enables precise manufacturing of each film layer such as the conductive base layer, hole transport layer, and perovskite layer under precisely controlled conditions, and omits the step of laser scribing. Different from the traditional laser scribing process, 3D printing can avoid the problems of pollution and electrode corrosion during the laser etching process, and realizes the connection between battery components by reserving the scribing position during the printing process, ensuring the longer-term stability of the electrodes and materials of the battery. In addition, the high temperature influence that may be caused during the laser etching process can also be effectively controlled, thereby avoiding thermal damage; at the same time, the integrity and high-quality crystallization of the perovskite thin film can be ensured. Since the crystallization quality of the perovskite thin film directly affects the photoelectric conversion efficiency, by reducing the thermal damage and pollution brought by the laser etching process, the perovskite layer can grow under more ideal conditions, thereby improving the photoelectric conversion efficiency. At the same time, 3D printing reduces operations such as substrate transfer, placement, and calibration, greatly shortening the production time and improving production efficiency.

[0016] Therefore, the present invention proposes a solution for manufacturing perovskite solar cells using 3D printing technology, which can not only effectively solve problems such as pollution and corrosion in the existing manufacturing process, but also improve the photoelectric conversion efficiency, providing strong support for the commercial application of perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0018] Figure 1 It is a schematic structural diagram of the device for 3D printing of the present invention; Figure 2 It is a schematic diagram of the perovskite solar cell of the present invention; Among them, 1, cross-shaped optical rod; 2, mechanical guide rail; 3, print head; 4, hot stage; 5, glass substrate; 6, P1 scribing line; 7, P2 scribing line; 8, P3 scribing line. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0020] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, or B exists alone. Here, A and B can be singular or plural. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0021] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one of the following" or its similar expressions refer to any combination of these items, including any combination of single item(s) or plural item(s). For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0022] It should be understood that in various embodiments of this application, the magnitudes of the sequence numbers of the above processes do not imply the order of execution. Some or all of the steps can be executed in parallel or successively. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of this application.

[0023] The terms used in the embodiments of this application are only for the purpose of describing specific embodiments, and are not intended to limit this application. The singular forms of "a", "the", and "said" used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0024] The weights of the relevant components mentioned in the specification of the embodiments of this application can not only refer to the specific contents of each component, but also represent the proportional relationship of the weights between the components. Therefore, as long as the contents of the relevant components in the specification of the embodiments of this application are scaled up or down in proportion, they are within the scope disclosed in the specification of the embodiments of this application. Specifically, the mass mentioned in the specification of the embodiments of this application can be mass units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0025] Such as Figure 1 and Figure 2As shown in the figure, the 3D printing device used in this application includes a base, and mechanical guide rails 2 are arranged around the base; a cross-shaped optical rod 1 is arranged in the mechanical guide rails 2, a print head 3 is arranged on the cross-shaped optical rod 1, and a hot stage 4 is arranged on the base. The hot stage 4 is used for heat annealing treatment of each layer of the battery. Using the 3D printing device to print each layer of the perovskite battery in the middle of the hot stage 4, specifically: 3D printing is carried out on the glass substrate 5 to prepare the conductive substrate, hole transport layer, perovskite layer, electron transport layer and metal electrode layer of the perovskite solar cell. During the 3D printing process, a P1 scribing line 6 is reserved on the conductive substrate, and P2 scribing lines 7 and P3 scribing lines 8 are reserved on the hole transport layer, perovskite layer and electron transport layer, and a P3 scribing line 8 is reserved on the metal electrode layer.

[0026] In the following examples, unless otherwise specified, all materials used can be obtained through ordinary channels; the testing methods used are conventional methods in the art.

[0027] Example 1 A 3D printing coating method for perovskite batteries includes: S1, preparing a conductive substrate Add FTO nanoparticles and the dispersant polyvinylpyrrolidone (PVP) to the water-ethanol mixed solution, ultrasonicate for 2 hours, then centrifuge at 3000 rpm for 10 min to remove undispersed particles, and adjust the viscosity of the conductive substrate solution to 20 mPa·s to obtain the conductive substrate solution; among them, the mass fraction of FTO nanoparticles is 10 wt%, the volume ratio of water and ethanol is 1:1, and the mass fraction of PVP is 2 wt%; Coat the conductive substrate solution on the glass substrate by 3D printing, reserve the position of the P1 scribing line during printing, the needle diameter of the print head is 200 μm, the extrusion pressure is 150 kPa; the printing speed is 10 mm / s; After the conductive substrate printing is completed, heat treatment is carried out. First, pre-dry on a hot stage at 80 °C for 10 min to remove residual solvents; then anneal at 500 °C for 60 min to obtain the conductive substrate; S2, preparing a hole transport layer, Add NiO nanoparticles and the dispersant PVP to the isopropanol-water mixed solution; ultrasonicate for 1 hour, then centrifuge at 4000 rpm for 15 min to remove undispersed particles, and adjust the viscosity of the hole transport solution to 50 mPa·s to obtain the hole transport solution; among them, the particle size of NiO nanoparticles is 20 nm, the volume ratio of isopropanol and water is 3:1; the mass fraction of NiO nanoparticles is 10 wt%; the mass fraction of PVP is 2 wt%; Coat the hole transport solution on the conductive substrate by 3D printing. When printing, fill the P1 scribed line and reserve the positions of the P2 scribed line and the P3 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 150 kPa; the printing speed is 10 mm / s; After the hole transport layer printing is completed, perform heat treatment. First, pre-dry on a hot stage at 100 °C for 10 min to remove residual solvents, and then anneal at 350 °C for 1 hour to obtain the hole transport layer; S3 Prepare the perovskite layer Add PbI2 to the DMSO-DMF mixed solution, stir at 60 °C until completely dissolved, add FAI, CsI and additives in sequence, and continue to stir for 4 hours to form a homogeneous solution; filter the homogeneous solution through a 0.45 μm PTFE filter membrane to remove undissolved particles, and adjust the viscosity to 10 mPa·s to obtain the perovskite solution; among them, the molar ratio of PbI2, FAI and CsI is 1.1 : 1.0 : 0.1; the volume ratio of DMSO:DMF is 4:1; the additives include guanidine thiocyanate (GuSCN) and cesium fluoride (CsF), the mass fraction of GuSCN is 1.5 wt%, and the mass fraction of the additive CsF is 0.3 wt%; Coat the perovskite solution on the hole transport layer by 3D printing. When printing, reserve the positions of the P2 scribed line and the P3 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 100 kPa; the printing speed is 5 mm / s; After the perovskite layer printing is completed, perform heat treatment, and anneal at 150 °C for 30 min to obtain the perovskite layer; S4 Prepare the electron transport layer, and the electron transport layer includes C 60 layer and BCP layer, Add C 60 powder (purity > 99.9%) to ortho-dichlorobenzene (ODCB), stir magnetically at 60 °C for 6 hours, perform ultrasonic treatment for 30 min, and then filter through a 0.22 μm PTFE filter membrane to adjust the viscosity to 100 mPa·s to obtain C 60 solution; among them, the ratio of C 60 to ODCB is 20 mg / mL; Coat the C 60 solution on the perovskite layer by 3D printing. When printing, reserve the positions of the P2 scribed line and the P3 scribed line. The needle diameter of the print head is 100 μm, the extrusion pressure is 100 kPa; the printing speed is 5 mm / s; C 60 layer After the printing is completed, perform heat treatment, and anneal at 100 °C in nitrogen for 10 min to obtain the C 60 layer; Add BCP powder into chloroform, stir at room temperature for 2 hours, then add PVP and mix evenly. Subsequently, filter with a 0.22 μm PTFE membrane, adjust the viscosity to 15 mPa·s to obtain a BCP solution; wherein, the ratio of BCP to chloroform is 2 mg / mL; the mass fraction of PVP is 0.2 wt%. Coat the BCP solution on layer C by 3D printing, leaving positions for P2 and P3 scribed lines during printing. The needle diameter of the print head is 100 μm, the extrusion pressure is 100 kPa; the printing speed is 10 mm / s; 60 After the BCP layer is printed, let it stand at room temperature for 30 min to obtain the BCP layer; S5 Prepare the metal electrode layer Add copper (Cu) nanoparticles into ethanol, ultrasonically treat for 1 hour, add the dispersant PVP and hydroxyethyl cellulose (HEC), magnetically stir for 4 hours, then centrifuge at 3000 rpm for 15 min to remove undispersed particles, adjust the viscosity to 300 mPa·s to obtain a metal electrode solution; wherein, the mass fraction of PVP is 2 wt%, the mass fraction of HEC is 1 wt%, the mass fraction of copper (Cu) nanoparticles is 30 wt%, and the particle size of the copper nanoparticles is 20 nm; Coat the metal electrode solution on the BCP layer by 3D printing, fill the P2 scribed line during printing, leaving the position for the P3 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 200 kPa; the printing speed is 15 mm / s; After the metal electrode layer is printed, perform heat treatment, anneal at 200 °C for 30 min to obtain the metal electrode layer, and obtain a perovskite solar cell.

[0028] The width of the P1 scribed line is 45 μm, the distance between the P2 scribed line and the P1 scribed line P1P2 < 100 μm, the width of the P2 scribed line is 70 μm, the distance between the P3 scribed line and the P2 scribed line P2P3 < 100 μm, and the width of the P3 scribed line is 70 μm.

[0029] Perform conventional performance tests on the perovskite solar cell prepared in Example 1, and the test results are as follows: the short-circuit current density of the perovskite solar cell in this example is 26.44 mA / cm2, the open-circuit voltage is 1.234 V, the fill factor is 79.94%, and the photoelectric conversion efficiency is 24.78%.

[0030] Example 2 A 3D printing coating method for a perovskite solar cell, comprising: S1, prepare a conductive substrate Add FTO nanoparticles and dispersant PVP into the water-ethanol mixture, ultrasonicate for 2 hours, and then centrifuge at 3000 rpm for 10 min to remove undispersed particles. Adjust the viscosity of the conductive substrate solution to 22 mPa·s to obtain the conductive substrate solution. Among them, the mass fraction of FTO nanoparticles is 12 wt%, the volume ratio of water to ethanol is 1:1, and the mass fraction of PVP is 2.5 wt%. Coat the conductive substrate solution on the glass substrate by 3D printing. Reserve the position of P1 scribed line during printing. The needle diameter of the print head is 200 μm, the extrusion pressure is 200 kPa, and the printing speed is 15 mm / s. After the conductive substrate printing is completed, perform heat treatment. First, pre-dry on a hot plate at 90 °C for 15 min to remove residual solvents. Then, anneal at 550 °C for 50 min to obtain the conductive substrate. S2. Prepare the hole transport layer Add NiO nanoparticles and dispersant PVP into the isopropanol-water mixture; ultrasonicate for 1 hour, and then centrifuge at 4000 rpm for 15 min to remove undispersed particles. Adjust the viscosity of the hole transport solution to 55 mPa·s to obtain the hole transport solution. Among them, the particle size of NiO nanoparticles is 20 nm, the volume ratio of isopropanol to water is 3:1; the mass fraction of NiO nanoparticles is 15 wt%; the mass fraction of PVP is 2.5 wt%. Coat the hole transport solution on the conductive substrate by 3D printing. Fill the P1 scribed line during printing and reserve the positions of P2 and P3 scribed lines. The needle diameter of the print head is 200 μm, the extrusion pressure is 200 kPa, and the printing speed is 15 mm / s. After the hole transport layer printing is completed, perform heat treatment. First, pre-dry on a hot plate at 90 °C for 15 min to remove residual solvents, and then anneal at 400 °C for 50 min to obtain the hole transport layer. S3. Prepare the perovskite layer Add PbI2 into the DMSO-DMF mixture, stir at 60 °C until completely dissolved, sequentially add FAI, CsI and additives, and continue stirring for 4 hours to form a homogeneous solution; filter the homogeneous solution through a 0.45 μm PTFE membrane to remove undissolved particles, and adjust the viscosity to 15 mPa·s to obtain the perovskite solution. Among them, the molar ratio of PbI2, FAI and CsI is 1.1:1.0:0.1; the volume ratio of DMSO:DMF is 4:1; the additives include GuSCN and CsF, the mass fraction of GuSCN is 1.8 wt%, and the mass fraction of additive CsF is 0.4 wt%. Coat the perovskite solution on the hole transport layer by 3D printing. Leave the positions of P2 and P3 lines unprinted during printing. The needle diameter of the print head is 200 μm, and the extrusion pressure is 150 kPa; the printing speed is 8 mm / s; After the perovskite layer printing is completed, perform heat treatment. Anneal it at 200 °C for 40 min to obtain the perovskite layer; S4 Prepare the electron transport layer. The electron transport layer includes C 60 layer and BCP layer. Add C 60 powder (purity > 99.9%) into ortho-dichlorobenzene (ODCB), stir magnetically at 60 °C for 6 hours, perform ultrasonic treatment for 30 min, then filter with a 0.22 μm PTFE filter membrane, and adjust the viscosity to 120 mPa·s to obtain C 60 solution; among them, the ratio of C 60 to ODCB is 25 mg / mL; Coat the C 60 solution on the perovskite layer by 3D printing. Leave the positions of P2 and P3 lines unprinted during printing. The needle diameter of the print head is 100 μm, and the extrusion pressure is 150 kPa; the printing speed is 10 mm / s; C 60 layer After the printing is completed, perform heat treatment. Anneal it in nitrogen at 150 °C for 15 min to obtain the C 60 layer; Add BCP powder into chloroform, stir at room temperature for 2 hours, then add PVP and mix evenly. Subsequently, filter with a 0.22 μm PTFE filter membrane, and adjust the viscosity to 20 mPa·s to obtain the BCP solution; among them, the ratio of BCP to chloroform is 2.5 mg / mL; the mass fraction of PVP is 0.4 wt%; Coat the BCP solution on the C 60 layer by 3D printing. Leave the positions of P2 and P3 lines unprinted during printing. The needle diameter of the print head is 100 μm, and the extrusion pressure is 150 kPa; the printing speed is 15 mm / s; After the BCP layer printing is completed, let it stand at room temperature for 40 min to obtain the BCP layer; S5 Prepare the metal electrode layer Add copper (Cu) nanoparticles into ethanol, perform ultrasonic treatment for 1 hour, add the dispersant PVP and hydroxyethyl cellulose (HEC), stir magnetically for 4 hours, then centrifuge at 3000 rpm for 15 min to remove the undispersed particles, and adjust the viscosity to 350 mPa·s to obtain the metal electrode solution; among them, the mass fraction of PVP is 3 wt%, the mass fraction of HEC is 1.5 wt%, the mass fraction of copper (Cu) nanoparticles is 35 wt%, and the particle size of the copper nanoparticles is 20 nm; Coat the metal electrode solution on the BCP layer by 3D printing. When printing, fill the P2 scribed line and reserve the position of the P3 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 250 kPa, and the printing speed is 20 mm / s. After the printing of the metal electrode layer is completed, perform heat treatment. Anneal it at 250 °C for 40 min to obtain the metal electrode layer, and thus obtain the perovskite solar cell.

[0031] The width of the P1 scribed line is 50 μm, the distance P1P2 between the P2 scribed line and the P1 scribed line is less than 100 μm, the width of the P2 scribed line is 75 μm, the distance P2P3 between the P3 scribed line and the P2 scribed line is less than 100 μm, and the width of the P3 scribed line is 75 μm.

[0032] Example 3 A 3D printing coating method for a perovskite solar cell, comprising: S1, prepare a conductive substrate Add FTO nanoparticles and dispersant PVP to the water-ethanol mixture, ultrasonicate for 2 hours, then centrifuge at 3000 rpm for 10 min to remove undispersed particles, and adjust the viscosity of the conductive substrate solution to 25 mPa·s to obtain the conductive substrate solution; wherein, the mass fraction of FTO nanoparticles is 11 wt%, the volume ratio of water to ethanol is 1:1, and the mass fraction of PVP is 3 wt%. Coat the conductive substrate solution on the glass substrate by 3D printing. When printing, reserve the position of the P1 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 150 kPa, and the printing speed is 10 mm / s. After the printing of the conductive substrate is completed, perform heat treatment. First, pre-dry it on a hot plate at 100 °C for 10 min to remove residual solvents; then anneal it at 500 °C for 100 min to obtain the conductive substrate. S2, prepare a hole transport layer Add NiO nanoparticles and dispersant PVP to the isopropanol-water mixture; ultrasonicate for 1 hour, then centrifuge at 4000 rpm for 15 min to remove undispersed particles, and adjust the viscosity of the hole transport solution to 60 mPa·s to obtain the hole transport solution; wherein, the particle size of NiO nanoparticles is 20 nm, the volume ratio of isopropanol to water is 3:1; the mass fraction of NiO nanoparticles is 12 wt%; the mass fraction of PVP is 3 wt%. Coat the hole transport solution on the conductive substrate by 3D printing. When printing, fill the P1 scribed line and reserve the positions of the P2 scribed line and the P3 scribed line. The needle diameter of the print head is 200 μm, the extrusion pressure is 150 kPa, and the printing speed is 10 mm / s. After the hole transport layer is printed, heat treatment is carried out. First, it is pre-dried on a hot plate at 100 °C for 10 min to remove residual solvents, and then annealed at 350 °C for 1 hour to obtain the hole transport layer; S3 Prepare the perovskite layer Add PbI2 to the DMSO-DMF mixture, stir at 60 °C until completely dissolved, add FAI, CsI and additives in sequence, and continue stirring for 4 hours to form a homogeneous solution; filter the homogeneous solution through a 0.45 μm PTFE filter membrane to remove undissolved particles, and adjust the viscosity to 12 mPa·s to obtain the perovskite solution; among them, the molar ratio of PbI2, FAI and CsI is 1.1:1.0:0.1; the volume ratio of DMSO:DMF is 4:1; the additives include GuSCN and CsF, the mass fraction of GuSCN is 2 wt%, and the mass fraction of the additive CsF is 0.5 wt%; Coat the perovskite solution on the hole transport layer by 3D printing, leaving positions for P2 and P3 scribed lines during printing. The needle diameter of the print head is 200 μm, the extrusion pressure is 150 kPa; the printing speed is 10 mm / s; After the perovskite layer is printed, heat treatment is carried out, and it is annealed at 150 °C for 50 min to obtain the perovskite layer; S4 Prepare the electron transport layer, and the electron transport layer includes C 60 layer and BCP layer, Add C 60 powder (purity > 99.9%) to ortho-dichlorobenzene (ODCB), stir magnetically at 60 °C for 6 hours, ultrasonically treat for 30 min, and then filter through a 0.45 μm PTFE filter membrane, and adjust the viscosity to 110 mPa·s to obtain C 60 solution; among them, the ratio of C 60 to ODCB is 20 mg / mL; Coat the C 60 solution on the perovskite layer by 3D printing, leaving positions for P2 and P3 scribed lines during printing. The needle diameter of the print head is 100 μm, the extrusion pressure is 100 kPa; the printing speed is 8 mm / s; C 60 After the layer is printed, heat treatment is carried out, and it is annealed at 100 °C in nitrogen for 20 min to obtain the C 60 layer; Add BCP powder to chloroform, stir at room temperature for 2 hours, then add PVP and mix evenly, and then filter through a 0.22 μm PTFE filter membrane, and adjust the viscosity to 15 mPa·s to obtain the BCP solution; among them, the ratio of BCP to chloroform is 3 mg / mL; the mass fraction of PVP is 0.5 wt%; Coat the C 60Coat the BCP solution on the layer. Reserve the positions of P2 and P3 scribelines during printing. The needle diameter of the print head is 100 μm, the extrusion pressure is 100 kPa, the printing speed is 12 mm / s; After the printing of the BCP layer is completed, let it stand at room temperature for 50 min to obtain the BCP layer; S5 Prepare the metal electrode layer Add copper (Cu) nanoparticles into ethanol, ultrasonically treat for 1 hour, add the dispersant PVP and hydroxyethyl cellulose (HEC), magnetically stir for 4 hours, then centrifuge at 3000 rpm for 15 min to remove the undispersed particles, and adjust the viscosity to 350 mPa·s to obtain the metal electrode solution; among them, the mass fraction of PVP is 2 wt%, the mass fraction of HEC is 2 wt%, the mass fraction of copper (Cu) nanoparticles is 40 wt%, and the particle size of the copper nanoparticles is 20 nm; Use 3D printing to coat the metal electrode solution on the BCP layer. Fill the P2 scribeline during printing and reserve the position of the P3 scribeline. The needle diameter of the print head is 200 μm, the extrusion pressure is 200 kPa, the printing speed is 15 mm / s; After the printing of the metal electrode layer is completed, perform heat treatment, anneal at 200 °C for 50 min to obtain the metal electrode layer, and obtain the perovskite solar cell.

[0033] The width of the P1 scribeline is 55 μm, the distance P1P2 between the P2 scribeline and the P1 scribeline is less than 100 μm, the width of the P2 scribeline is 80 μm, the distance P2P3 between the P3 scribeline and the P2 scribeline is less than 100 μm, and the width of the P3 scribeline is 80 μm.

[0034] In the ranges and any values disclosed in the present invention, the endpoints and any values of the ranges are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein. In the following text, the various technical solutions can be combined with each other in principle to obtain new technical solutions, which should also be regarded as specifically disclosed herein.

[0035] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art can still modify the specific embodiments of the present invention or make equivalent replacements. Any modifications or equivalent replacements that do not depart from the spirit and scope of the present invention are within the scope of the claims of the present invention awaiting approval.

Claims

1. A 3D printing coating method for perovskite solar cells, characterized in that, Including: Coating a conductive substrate solution on a glass substrate by 3D printing, reserving the position of the P1 scribeline during the 3D printing process, and performing heat treatment after coating to obtain a conductive substrate; Coating a hole transport solution on the conductive substrate by 3D printing, filling the P1 scribeline during the 3D printing process, reserving the positions of the P2 scribeline and the P3 scribeline, and performing heat treatment after coating to obtain a hole transport layer; Coating a perovskite solution on the hole transport layer by 3D printing, reserving the positions of the P2 scribeline and the P3 scribeline during the 3D printing process, and performing heat treatment after coating to obtain a perovskite layer; Coating an electron transport solution on the perovskite layer by 3D printing, reserving the positions of the P2 scribeline and the P3 scribeline during the 3D printing process, and performing heat treatment after coating to obtain an electron transport layer; Coating a metal electrode solution on the electron transport layer by 3D printing, filling the P2 scribeline during the 3D printing process, reserving the position of the P3 scribeline, and performing heat treatment after coating to obtain a metal electrode layer, thus completing the preparation of the perovskite solar cell.

2. The 3D printing coating method of a perovskite battery according to claim 1, wherein The width of the P1 scribeline is 45 - 55 μm, and the distance between the P2 scribeline and the P1 scribeline is less than 100 μm.

3. The 3D printing coating method of a perovskite battery according to claim 1, characterized in that The width of the P2 scribeline is 70 - 80 μm, the distance between the P3 scribeline and the P2 scribeline is less than 100 μm, and the width of the P3 scribeline is 70 - 80 μm.

4. The 3D printing coating method of a perovskite battery according to claim 1, characterized in that, The step of coating a conductive substrate solution on a glass substrate by 3D printing, reserving the position of the P1 scribeline during the 3D printing process, and performing heat treatment after coating to obtain a conductive substrate includes: Adding FTO nanoparticles and polyvinylpyrrolidone to a water - ethanol mixed solution and mixing evenly to obtain a conductive substrate solution, wherein the mass fraction of the FTO nanoparticles is 10 - 12 wt%, and the mass fraction of the polyvinylpyrrolidone is 2 - 3 wt%; Coating the conductive substrate solution on the battery substrate by 3D printing, with the needle diameter of the print head being 200 - 300 μm, the extrusion pressure being 150 - 200 kPa, and the printing speed being 10 - 15 mm / s; After the conductive substrate printing is completed, pre - dry it at 80 - 100 °C for 10 - 20 min; then anneal it at 500 - 550 °C for 50 - 100 min to obtain the conductive substrate.

5. The 3D printing coating method of a perovskite battery according to claim 1, characterized in that, The step of coating a hole transport solution on the conductive substrate by 3D printing, filling the P1 scribeline during the 3D printing process, reserving the positions of the P2 scribeline and the P3 scribeline, and performing heat treatment after coating to obtain a hole transport layer includes: Adding NiO nanoparticles and polyvinylpyrrolidone to an isopropanol - water mixed solution and mixing evenly to obtain a hole transport solution, wherein the mass fraction of the NiO nanoparticles is 10 - 15 wt%, and the mass fraction of the polyvinylpyrrolidone is 2 - 3 wt%; Coating the hole transport solution on the conductive substrate by 3D printing, with the needle diameter of the print head being 200 - 300 μm, the extrusion pressure being 150 - 200 kPa, and the printing speed being 10 - 15 mm / s; After the hole transport layer printing is completed, pre - dry it at 80 - 100 °C for 10 - 20 min; then anneal it at 350 - 400 °C for 50 - 100 min to obtain the hole transport layer.

6. A 3D printing coating method for a perovskite battery according to claim 1, characterized in that Coating a perovskite solution on the hole transport layer by 3D printing, reserving the positions of P2 and P3 lines during the 3D printing process, and performing heat treatment after coating to obtain a perovskite layer, including: Adding PbI2 into a DMSO-DMF mixture and mixing evenly, then successively adding FAI, CsI and additives and mixing evenly to obtain a perovskite solution; wherein, the molar ratio of PbI2, FAI and CsI is 1.1:1.0:0.1, and the additives include GuSCN and CsF, the mass fraction of GuSCN is 1.5-2wt%, and the mass fraction of CsF is 0.3-0.5wt%; Coating the perovskite solution on the hole transport layer by 3D printing, the needle diameter of the print head is 200-300μm, and the extrusion pressure is 100-150kPa; the printing speed is 5-10mm / s; After the perovskite layer printing is completed, it is annealed at 150-200°C for 30-50 minutes to obtain a perovskite layer.

7. A 3D printing coating method for a perovskite solar cell according to claim 1, wherein The electron transport solution is coated on the perovskite layer by 3D printing. During the 3D printing process, the positions of P2 and P3 lines are reserved. After coating, heat treatment is carried out to obtain the electron transport layer, and the electron transport layer includes a C 60 layer and a BCP layer. The C 60 solution and the BCP solution are sequentially coated on the perovskite layer by 3D printing; Coating C on the perovskite layer by 3D printing 60 layer, reserving the positions of P2 and P3 scribelines during the 3D printing process, and performing heat treatment after coating to obtain C 60 layer, including: Add C 60 powder to o-dichlorobenzene and mix evenly to obtain C 60 solution, where the ratio of C 60 to o-dichlorobenzene is 20 mg / mL; Coat C on the perovskite layer by 3D printing 60 The solution, the needle diameter of the print head is 100 - 200 μm, the extrusion pressure is 100 - 150 kPa; the printing speed is 5 - 10 mm / s; C 60 The printing of layer C is ended and it is annealed in nitrogen at 100 - 150 °C for 10 - 20 min to obtain layer C 60 layer.

8. The 3D printing coating method of a perovskite battery according to claim 7, characterized in that, On layer C 60 Coat the BCP solution by 3D printing, leaving positions for P2 and P3 lines during the 3D printing process. After coating, perform heat treatment to obtain the BCP layer, including: Adding BCP powder into chloroform and mixing evenly, then adding polyvinylpyrrolidone and mixing evenly to obtain a BCP solution; wherein, the ratio of BCP to chloroform is 2-3mg / mL; the mass fraction of polyvinylpyrrolidone is 0.2-0.5wt%; Coating the BCP solution on layer C by 3D printing 60 The needle diameter of the print head is 100 - 200 μm, the extrusion pressure is 100 - 150 kPa, and the printing speed is 10 - 15 mm / s. After the BCP layer printing is completed, it is left standing at room temperature for 30-50 minutes to obtain a BCP layer.

9. A 3D printing coating method for a perovskite battery according to claim 1, characterized in that, Coating a metal electrode solution on the electron transport layer by 3D printing, filling the P2 line during the 3D printing process, reserving the position of the P3 line, and performing heat treatment after coating to obtain a metal electrode layer, including: Adding copper nanoparticles into ethanol and mixing evenly, then adding polyvinylpyrrolidone and hydroxyethyl cellulose and mixing evenly to obtain a metal electrode solution; wherein, the mass fraction of polyvinylpyrrolidone is 2-3wt%, the mass fraction of hydroxyethyl cellulose is 1-2wt%, and the solid content of copper nanoparticles is 30-40wt%; Coating the metal electrode solution on the BCP layer by 3D printing, the needle diameter of the print head is 150-200μm, and the extrusion pressure is 200-250kPa; the printing speed is 15-20mm / s; After the metal electrode layer printing is completed, it is annealed at 200-250°C for 30-50 minutes to obtain a metal electrode layer.

10. A perovskite solar cell, characterized in that, Prepared by the 3D printing coating method of the perovskite battery according to any one of claims 1-9.

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