Perovskite solution coating device

Abstract

The utility model provides a perovskite solution coating device which comprises a coating module, a solution storage tank, an injection pump and a resistance detection assembly, the injection pump is respectively connected with the coating module and the solution storage tank through a liquid conveying pipeline, a reducing metal wire is arranged in the liquid conveying pipeline, and the resistance detection assembly is connected with the coating module. And the reduction metal wire is electrically connected with the resistance detection assembly. The device has the advantages of being simple, practical and economical, the perovskite solution is prevented from being oxidized, and important technical support and guarantee are provided for large-scale application of the perovskite solar cell.

Description

Technical Field

[0001] This utility model belongs to the field of solar cells, and relates to the coating of perovskite solutions, and more particularly to a perovskite solution coating device. Background Technology

[0002] Perovskite solar cells, as an emerging photovoltaic technology, have become a research hotspot in the field of renewable energy due to their advantages such as high efficiency, low cost, and simple fabrication process. Perovskite, a key material in perovskite solar cells, possesses excellent photoelectric conversion performance. However, existing perovskite materials suffer from insufficient material stability and susceptibility to environmental factors during fabrication, particularly oxidation, which leads to a decline in cell performance.

[0003] Tin-based perovskites have attracted significant attention due to their high film quality, stability, carrier mobility, and low optical bandgap, which significantly improve photoelectric conversion efficiency. The fabrication of tin-based perovskite solar cells often involves steps such as perovskite solution transport and coating. However, because the tin in tin-based perovskites is divalent, it is easily oxidized to tetravalent tin in air, posing numerous challenges to the fabrication and application of perovskite solar cells, especially during the coating and solution transfer processes, where oxidation reactions are particularly pronounced.

[0004] Currently, the oxidation problem in the fabrication process of perovskite solar cells has not been effectively solved. While traditional methods can take certain measures to reduce oxidation reactions, such as controlling the environmental atmosphere during coating or adding redox agents, these methods suffer from high costs, complex operations, and unstable results.

[0005] Therefore, avoiding oxidation problems during the fabrication process of perovskite solar cells and ensuring fabrication stability has become of paramount importance. Utility Model Content

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a perovskite solution coating device that solves the problem of oxidation of tin-based perovskite solutions during the coating and solution transfer processes, thereby effectively improving the stability and electrical performance of perovskite solar cells.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] This invention provides a perovskite solution coating device, which includes a coating module, a solution storage tank, an injection pump, and a resistance detection component. The injection pump is connected to the coating module and the solution storage tank respectively through a liquid delivery pipeline. A reducing metal wire is provided in the liquid delivery pipeline, and the reducing metal wire is electrically connected to the resistance detection component.

[0009] This invention effectively isolates the perovskite solution from external oxygen by adding a reducing metal wire inside the infusion pipeline, reducing the occurrence of oxidation reactions. At the same time, by detecting changes in the resistance value of the reducing metal wire, real-time monitoring of the oxidation status of the solution is achieved, providing a basis for parameter adjustment during the preparation process and further improving the stability and consistency of perovskite film preparation.

[0010] In a preferred embodiment of this invention, the reducing metal wire is a tin wire.

[0011] The purity of the tin wire is 99% to 99.99%, for example, it can be 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 99.99%, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0012] As a preferred technical solution of this utility model, the diameter of the reducing metal wire is 0.1 to 1 mm, for example, it can be 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1 mm, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0013] This invention uses high-purity tin wire to isolate the perovskite solution from external oxygen, ensuring that the tin wire meets the requirements and avoiding adverse effects on the properties and stability of the perovskite solution.

[0014] As a preferred embodiment of this utility model, the infusion pipeline includes a first delivery pipe and a second delivery pipe. The two ends of the first delivery pipe are respectively connected to the solution storage tank and the injection pump, and the two ends of the second delivery pipe are respectively connected to the injection pump and the coating module.

[0015] The reducing metal wire includes a first metal wire and a second metal wire. The first metal wire and the second metal wire are respectively disposed in the first delivery pipe and the second delivery pipe. The second metal wire is electrically connected to the resistance detection component.

[0016] In this invention, the reducing metal wire adopts a two-stage structure. A first metal wire is added to the pump injection stage to ensure that the perovskite solution entering the injection pump is reduced. A second reducing metal is added to the pump outlet stage, and an external resistance detection component is connected to monitor the oxidation of the perovskite solution in real time, ensuring the stability of the preparation process.

[0017] As a preferred embodiment of this utility model, the length of the first metal wire is 1 / 3 to 1 / 2 of the length of the first conveying tube, for example, it can be 1 / 3, 2 / 5 or 1 / 2, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] As a preferred embodiment of this utility model, the length of the second metal wire is 1 / 4 to 1 / 3 of the length of the second conveying tube, for example, it can be 1 / 4, 3 / 10 or 1 / 3, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] This invention features a rational layout inside the infusion pipeline, which ensures the uniform distribution of reducing metal wires and guarantees their effective coverage area, thereby improving the oxygen isolation effect and the accuracy of oxidation monitoring.

[0020] As a preferred embodiment of this utility model, the coating module includes a platform base, a lifting assembly, and a coating assembly; an adsorption plate is provided on the surface of the platform base, the coating assembly is located above the adsorption plate, the coating assembly is connected to the second conveying pipe, the lifting assembly is fixed on the platform base, and the lifting assembly is connected to the coating assembly for driving the coating assembly to rise and fall.

[0021] In the application process, this invention uses an injection pump to pump the perovskite solution into the coating assembly through a second delivery pipe, and then uniformly coats the perovskite solution onto the surface of the adsorption plate to form a perovskite wet film. At the same time, a lifting assembly is used to adjust the distance between the coating assembly and the adsorption plate to control the coating process parameters.

[0022] As a preferred embodiment of this utility model, the coating assembly includes a support beam connected to the lifting assembly, and a coating blade is provided on the side of the support beam near the adsorption plate, the coating blade being connected to the second conveying pipe.

[0023] As a preferred technical solution of this utility model, the lifting assembly includes a guide rail and a support driving part that are slidably connected. The guide rail is fixed on the platform base, and the support driving part is connected to the support beam and is used to drive the support beam to lift and lower, thereby driving the coating blade head to move away from or towards the adsorption plate.

[0024] As a preferred embodiment of the present invention, the perovskite solution coating device further includes a frame, and the platform base and the injection pump are both fixed on the frame.

[0025] Compared with the prior art, the beneficial effects of this utility model are as follows:

[0026] This invention provides a perovskite solution coating device that not only solves the oxidation problem in the preparation process of perovskite solar cells, but is also simple to operate, low in cost, and stable in effect. It can effectively improve the stability and electrical performance of perovskite solar cells, providing important technical support and guarantee for the large-scale application of perovskite solar cells. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the perovskite solution coating device provided by this utility model.

[0028] The components are as follows: 1-frame; 2-platform base; 3-guide rail; 4-adsorption plate; 5-support beam; 6-support drive unit; 7-injection pump; 8-first delivery pipe; 9-second delivery pipe; 10-coating blade; 11-solution storage tank; 12-resistance detection assembly. Detailed Implementation

[0029] It should be understood that in the description of this utility model, the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used solely for the convenience of describing this utility model and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this utility model, unless otherwise stated, "a plurality of" means two or more.

[0030] It should be noted that, in the description of this utility model, unless otherwise explicitly specified and limited, the terms "set," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0031] Those skilled in the art should understand that this utility model necessarily includes the necessary pipelines, conventional valves and general pump equipment for achieving complete process, but the above content is not the main improvement of this utility model. Those skilled in the art can add layouts based on the process flow and equipment structure selection. This utility model does not make any special requirements or specific limitations in this regard.

[0032] The technical solution of this utility model will be further described below with reference to the accompanying drawings and specific embodiments.

[0033] In one specific embodiment, this utility model provides a perovskite solution coating device, including a coating module, a solution storage tank, an injection pump, and a resistance detection component. The injection pump is connected to the coating module and the solution storage tank via a delivery pipeline. The solution storage tank stores the perovskite solution. The injection pump pumps the perovskite solution from the solution storage tank through the delivery pipeline and pumps it into the coating module. The coating module performs a coating operation on the perovskite solution to prepare a perovskite thin film. A reducing metal wire is installed inside the delivery pipeline to isolate the perovskite solution from external oxygen. The reducing metal wire is electrically connected to the resistance detection component via an external circuit. By detecting changes in the resistance value of the reducing metal wire, the oxidation state of the perovskite solution is determined.

[0034] The perovskite solution coating apparatus provided by this invention has a wide range of applications and can be used for coating processes of various types of perovskite solutions, especially tin-based perovskite solutions, and particularly suitable for coating tin-lead mixed perovskite solutions. Furthermore, those skilled in the art can adjust the coating module to use either spin coating or slot coating methods according to actual process requirements; this invention does not specifically limit this. In some embodiments, the reducing metal wire is a tin wire with a purity of 99-99.99% and a diameter of 0.1-1 mm. The perovskite solution in this invention is a tin-lead perovskite precursor solution well-known to those skilled in the art. The tin element it contains is prone to oxidation in oxygen-containing environments, leading to damage to the active materials in the solution and reducing the performance and stability of the solar cell. The oxidation reaction is particularly prominent during the coating and solution transfer processes, posing numerous challenges to the fabrication and application of perovskite solar cells. This invention solves the problem of perovskite oxidation by adding high-purity tin material into the infusion pipeline for transporting perovskite solution. This not only reduces the perovskite solution but also does not adversely affect its properties and stability.

[0035] In some embodiments, the infusion pipeline includes a first delivery pipe and a second delivery pipe, and the reducing metal wire includes a first metal wire and a second metal wire. The first delivery pipe is connected at both ends to the solution storage tank and the injection pump, respectively. The first metal wire is disposed within the first delivery pipe to ensure that the perovskite solution entering the injection pump from the solution storage tank is reduced. The second delivery pipe is connected at both ends to the injection pump and the coating module, respectively. The second metal wire is disposed within the second delivery pipe and is electrically connected to the resistance detection component to monitor the oxidation status of the perovskite solution pumped into the coating module by the injection pump in real time. This invention determines the current oxidation status of the perovskite solution by detecting changes in the resistance value of the second metal wire. If the resistance value continuously increases, it indicates that the second metal wire is being continuously worn down, i.e., the perovskite solution is being oxidized, thus determining whether the coating of the perovskite solution needs to be terminated.

[0036] Specifically, the length of the first metal wire is 1 / 3 to 1 / 2 of the length of the first conveying tube, and the length of the second metal wire is 1 / 4 to 1 / 3 of the length of the second conveying tube. This invention, by rationally arranging the added length of the metal wires, ensures their effective coverage area, maximizing the oxygen isolation effect and improving the accuracy of oxidation monitoring.

[0037] The perovskite solution coating device of this invention has a wide range of applications. It can be used not only for the fabrication of single-cell perovskite solar cells, but also for the fabrication of tandem perovskite solar cells, such as all-perovskite tandem cells or perovskite-crystalline silicon tandem cells, which are well known to those skilled in the art.

[0038] The solution storage tank and the injection pump are also provided with necessary connecting pipelines and switch control valves. This utility model does not impose any special limitations on these. Those skilled in the art should reasonably adjust, add, or delete them according to actual production needs. It should be noted that new technical solutions generated by deleting some unnecessary connecting pipelines and switch control valves, or replacing single-function switch control valves with multi-function integrated control valves, or using external automatic control systems electrically connected to the switch control valves to control the opening of the corresponding valves, etc., which are common and well-known technical means by those skilled in the art, also fall within the scope of disclosure and protection of this utility model.

[0039] This invention does not specifically limit the type and structure of the resistance detection component. It can use the voltmeter-ammeter method resistance detection component commonly used by those skilled in the art, and perform resistance detection by connecting an external ammeter or an external voltmeter.

[0040] In some embodiments, the coating module includes a platform base, a lifting assembly, and a coating assembly. An adsorption plate is disposed on the surface of the platform base, which supports the substrate for fabricating perovskite solar cells. The coating assembly is located above the adsorption plate and is connected to a second delivery pipe for feeding the perovskite solution into the coating assembly. The coating assembly then uniformly coats the perovskite solution onto the substrate surface on the adsorption plate. The lifting assembly is fixed to the platform base and connected to the coating assembly, driving the coating assembly to move up and down, thereby adjusting the distance between the coating assembly and the adsorption plate. Specifically, the substrate can be a conductive substrate with a deposited transport layer, as is well known to those skilled in the art, to coat the perovskite solution onto the surface of the transport layer to form a perovskite thin film.

[0041] Furthermore, the coating assembly includes a support beam connected to the lifting assembly. A coating blade is disposed on the side of the support beam near the adsorption plate, and the coating blade is connected to the second delivery pipe. The lifting assembly includes a guide rail and a support drive unit slidably connected. The guide rail is fixed on the platform base, and the support drive unit is connected to the support beam for driving the support beam to rise and fall, thereby causing the coating blade to move away from or towards the adsorption plate.

[0042] For example, the support drive unit includes a movable bracket and a servo motor connected by a transmission connection. The servo motor drives the movable bracket to slide up and down along the guide rail surface. The support beam is fixed on the movable bracket and thus rises and falls as the movable bracket slides. Further, the guide rail includes a first slide rail and a second slide rail respectively disposed on both sides of the platform base. The support drive unit includes two sets of the movable brackets and servo motors. The two movable brackets are respectively connected to both ends of the support beam. During application, the two servo motors drive the two movable brackets to slide synchronously along the first slide rail and the second slide rail respectively, thereby moving the support beam.

[0043] In some embodiments, the perovskite solution coating apparatus further includes a frame, on which both the platform base and the injection pump are fixed. Specifically, the frame includes a main body, with several support columns at its bottom to ensure stability. The platform base is fixed to the main body, and a top bracket is also provided on the main body to support the injection pump, bringing it closer to the coating assembly to shorten the length of the infusion pipeline and reduce production costs.

[0044] The method of using the perovskite solution coating device provided by this utility model includes: placing a conductive substrate with a deposited transport layer on the surface of an adsorption plate; placing a first metal wire and a second metal wire in a first delivery pipe and a second delivery pipe respectively, and connecting the second metal wire to a resistance detection component through an external circuit; preparing a tin-lead perovskite precursor solution in a glove box, removing air bubbles from the precursor solution in a transition chamber within the glove box, sealing it, and then transferring it to a solution storage tank; pumping the tin-lead perovskite precursor solution from the solution storage tank into a coating blade using an injection pump, adjusting the distance between the coating blade and the adsorption plate using a lifting component, and starting the coating component to coat the solution, thereby forming a perovskite wet film on the surface of the transport layer; using a resistance detection component to detect the change in resistance value of the second metal wire in real time. If the resistance value continuously increases, it indicates that the current tin-lead perovskite precursor solution is oxidized, and thus it is determined whether the coating operation of the coating component needs to be terminated.

[0045] Example 1

[0046] This embodiment provides a perovskite solution coating device, such as... Figure 1 As shown, the system includes a frame 1, a coating module, a solution storage tank 11, an injection pump 7, and a resistance detection assembly 12. Both the solution storage tank 11 and the injection pump 7 are fixed to the frame 1. The solution storage tank 11 stores the tin-lead perovskite precursor solution. The inlet of the injection pump 7 is connected to the solution storage tank 11 via a first delivery pipe 8. A first metal wire, made of 99.5% pure tin wire with a diameter of 0.1 mm and a length one-third the length of the first delivery pipe 8, is installed inside the first delivery pipe 8.

[0047] The coating module includes a platform base 2, a lifting assembly, and a coating assembly. The platform base 2 is fixed to the frame 1, and an adsorption plate 4 is provided on the surface of the platform base 2. The coating assembly includes a support beam 5, which is located above the adsorption plate 4. A coating blade 10 is provided on the side of the support beam 5 closest to the adsorption plate 4. The coating blade 10 is connected to the outlet end of the injection pump 7 through a second delivery pipe 9. A second metal wire, which is 99.5% pure tin wire with a diameter of 0.1 mm and a length that is 1 / 4 of the length of the first delivery pipe 8, is provided inside the second delivery pipe 9. The lifting assembly includes a slidingly connected guide rail 3 and a support drive unit 6. The guide rail 3 is fixed to the platform base 2, and the support drive unit 6 is connected to the support beam 5 and is used to drive the support beam 5 to rise and fall, thereby moving the coating blade 10 away from or closer to the adsorption plate 4.

[0048] Application Example 1

[0049] This application example uses the perovskite solution coating apparatus provided in Example 1 to fabricate a tin-lead perovskite solar cell, specifically including the following steps: A layer of NiO is prepared on the surface of an FTO (Fluorine-doped Tin Oxide) glass substrate by magnetron sputtering. x As a hole transport layer, it is placed on the adsorption plate 4. Two solder wires are placed in the first delivery tube 8 and the second delivery tube 9 respectively, and the solder wire in the second delivery tube 9 is connected to the resistance detection component 12 through an external circuit. 60 mL of FA is prepared in a glove box. 0.7 MA 0.3 Pb 0.5 Sn 0.5 The I3 tin-lead perovskite precursor solution is first purified by removing air bubbles in a transition chamber within a glove box, then sealed and transferred to solution storage tank 11. The tin-lead perovskite precursor solution in solution storage tank 11 is pumped into coating head 10 using injection pump 7. The distance between coating head 10 and adsorption plate 4 is adjusted using a lifting assembly, and coating head 10 is activated to form a perovskite wet film on the surface of the hole transport layer. A resistance detection assembly 12 monitors the resistance change of the second metal wire in real time. If the resistance continuously increases, it indicates that the tin-lead perovskite precursor solution is being oxidized, thus determining whether the coating operation needs to be terminated. After coating, the perovskite wet film is purged with nitrogen using a purge air knife to remove solvent. Benzaldehyde gas at a partial pressure of 5% is added to the purge air knife, and the speed of the purge air knife is controlled to assist crystallization, forming a perovskite light-absorbing layer. Subsequently, the perovskite light-absorbing layer was removed, and an electron transport layer and a SnO layer were sequentially fabricated on the surface of the perovskite light-absorbing layer. x A tin-lead perovskite solar cell was obtained by self-assembling the layer and the top electrode. This cell consists of a hole transport layer, an electron transport layer, and a SnO layer. x The materials and fabrication processes for the self-assembly layer and the top electrode are all known to those skilled in the art.

[0050] The applicant declares that the above description is only a specific embodiment of the present utility model, but the protection scope of the present utility model is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present utility model fall within the protection and disclosure scope of the present utility model.

Claims

1. A perovskite solution coating apparatus characterized by comprising: The perovskite solution coating device comprises a coating module, a solution storage tank, an injection pump and a resistance detection assembly, the injection pump is connected with the coating module and the solution storage tank through infusion pipelines, a reducing metal wire is arranged in the infusion pipeline, and the reducing metal wire is electrically connected with the resistance detection assembly.

2. The perovskite solution coating apparatus according to claim 1, characterized by The reducing metal wire is a tin wire. The purity of the tin wire is 99% to 99.99%.

3. The perovskite solution coating apparatus according to claim 1 or 2, characterized by The diameter of the reducing metal wire is 0.1 to 1 mm.

4. The perovskite solution coating apparatus according to claim 1, wherein The infusion pipeline comprises a first conveying pipe and a second conveying pipe, two ends of the first conveying pipe are connected with the solution storage tank and the injection pump respectively, and two ends of the second conveying pipe are connected with the injection pump and the coating module respectively. The reducing metal wire comprises a first metal wire and a second metal wire, the first metal wire and the second metal wire are arranged in the first conveying pipe and the second conveying pipe respectively, and the second metal wire is electrically connected with the resistance detection assembly.

5. The perovskite solution coating apparatus according to claim 4, wherein The length of the first metal wire is 1 / 3 to 1 / 2 of the length of the first conveying pipe.

6. The perovskite solution coating apparatus according to claim 4, wherein The length of the second metal wire is 1 / 4 to 1 / 3 of the length of the second conveying pipe.

7. The perovskite solution coating apparatus according to claim 4, wherein The coating module comprises a platform base, a lifting assembly and a coating assembly. A suction plate is arranged on the surface of the platform base, the coating assembly is located above the suction plate, the coating assembly is connected with the second conveying pipe, the lifting assembly is fixed on the platform base, the lifting assembly is connected with the coating assembly and is used for driving the coating assembly to lift and fall.

8. The perovskite solution coating apparatus according to claim 7, wherein The coating assembly comprises a support beam, the support beam is connected with the lifting assembly, a coating cutter head is arranged on the side of the support beam close to the suction plate, and the coating cutter head is connected with the second conveying pipe.

9. The perovskite solution coating apparatus according to claim 8, wherein The lifting assembly comprises a guide rail and a supporting driving part in sliding connection, the guide rail is fixed on the platform base, the supporting driving part is connected with the support beam and is used for driving the support beam to lift and fall, so as to drive the coating cutter head to move away from or close to the suction plate. 10.The perovskite solution coating apparatus according to claim 7, wherein The perovskite solution coating device further comprises a rack, and the platform base and the injection pump are fixed on the rack.

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