CN211045478U

CN211045478U - Perovskite film coating equipment

Info

Publication number: CN211045478U
Application number: CN201922030725.6U
Authority: CN
Inventors: 毕恩兵; 陈汉; 王勐
Original assignee: Shanghai Liyuan New Energy Technology Co ltd
Current assignee: Liyuan New Energy Technology (Wuxi) Co.,Ltd.
Priority date: 2019-11-22
Filing date: 2019-11-22
Publication date: 2020-07-17
Anticipated expiration: 2029-11-22

Abstract

The utility model discloses a perovskite film coating equipment, this equipment include conveyer, material membrane roller device, guide roll device, rolling press device, air-dry device and heating device, and conveyer includes: a conveying guide rail and a conveying base; the material film roller device comprises: a material film roller and a material film roller bracket; the material membrane roll wheel includes: a first material film roller and a second material film roller; material membrane roll wheel support includes: first and second brackets; the guide roller device includes: a guide roller and a height adjusting device; the guide roller wheel includes: first and second guide rollers; the height adjusting device includes: first and second height adjusting means; the rolling press device includes: the device comprises a support frame, a vertical guide rail, a fixed frame, a roller module and a driving piece, wherein the roller module comprises at least one roller; the fixed frame is connected with the vertical guide rail, and the roller can move up and down along the vertical guide rail under the driving of the driving piece. The utility model discloses can be used to prepare the perovskite film of large tracts of land.

Description

Perovskite film coating equipment

Technical Field

The utility model relates to a solar cell technical field, in particular to perovskite film coating equipment.

Background

In recent years, perovskite solar cells have attracted much attention, and methods and apparatuses for producing perovskite thin films are now diversified. The perovskite light absorption layer is used as a core film layer of the perovskite solar cell, and the preparation process of the perovskite light absorption layer has decisive influence on the perovskite light absorption layer so as to determine the performance of the perovskite solar cell. At present, the perovskite solar cell has a plurality of problems in the process from laboratory research to large-area practical research, and specific common methods for preparing a perovskite light absorption layer comprise a one-step solution method, a two-step solution method, a gas-phase auxiliary solution method, a co-evaporation deposition method and a scraper method. Among them, the co-evaporation deposition and the gas-phase auxiliary solution method are not favorable for mass production and cost reduction because of the vacuum equipment involved and high cost.

The conventional one-step solution method process is that firstly, a perovskite solution is prepared, then a certain amount of solution is taken for spin coating, and finally, the spin-coated perovskite wet film is annealed at high temperature to form the perovskite thin film. Although the method is convenient, fast and low in cost, the thin film prepared by the method is difficult to spin coat a large-area substrate due to the process defects, so that the large-scale production is difficult.

In the two-step solution process, the first step is to deposit a preset layer of perovskite thin film from the solution. The quality of the prefabricated layer film directly determines the quality of the perovskite film obtained by the subsequent process. The film obtained by the conventional perovskite film preset layer coating process is not compact and has a plurality of defects, which are specifically represented by a plurality of pinholes on the surface of the film, large roughness, poor repeatability among batches and the like. In addition, the existing two-step solution method has the problems that the prefabricated layer cannot be dried quickly and uniformly and the film is easily influenced by environmental convection in the drying process, and the film made by the method is difficult to produce in a large scale.

The pushing out of the doctor blade method solves the problem of large-area film forming of the perovskite to a certain extent. However, the current techniques for preparing perovskite light-absorbing layers are still rare, and particularly, the techniques considering the preparation mechanization cost, the production time, the material utilization rate and the quality of the prepared perovskite light-absorbing layers need to be further developed.

Therefore, in order to realize the large-scale production of the large-area perovskite solar cell, a perovskite thin film coating device which is low in production cost, high in film forming quality, simple and easy to operate is designed.

SUMMERY OF THE UTILITY MODEL

In order to overcome the defects of the prior art, the utility model provides a perovskite film coating equipment can be used for preparing large-area perovskite film, and then overcomes the defects of the prior art.

The above object of the present invention can be achieved by the following technical solutions:

a perovskite thin film coating apparatus comprising: conveyer, material membrane roller device, guide roll device, rolling press device, air-dry device and heating device, conveyer includes: a conveying guide rail which lengthily extends along the horizontal direction and a conveying base which can move relative to the lengthways extending direction of the conveying guide rail; the conveying guide rail is provided with a first end and a second end which are opposite along the longitudinal extension direction; the material film roller device comprises: the film roller comprises a film roller wheel and a film roller wheel bracket for supporting the film roller wheel; the material membrane roll wheel includes: the first material film roller is close to the first end of the conveying guide rail, and the second material film roller is close to the second end of the conveying guide rail; the material membrane roll wheel support includes: the first bracket is used for supporting the first material film roller and the second bracket is used for supporting the second material film roller; the guide roller device includes: the device comprises a guide roller and a height adjusting device for adjusting the height of the guide roller; the guide roller wheel includes: a first guide roller and a second guide roller; the height adjusting device includes: the first height adjusting device is used for adjusting the first guide roller wheel, and the second height adjusting device is used for adjusting the second guide roller wheel; the rolling press device includes: the roller module comprises at least one roller; the fixed frame is connected with the vertical guide rail, and the roller can move up and down along the vertical guide rail under the driving of the driving piece.

In a preferred embodiment, the driving member includes a first motor for driving the fixed frame and the roller on the fixed frame to move up and down, the fixed frame is provided with a transverse guide rail, and the driving member further includes a second motor for driving the roller to move horizontally relative to the transverse guide rail.

In a preferred embodiment, the heating device is provided on the transfer base, the heating device including: heating member, temperature sensor and temperature regulator, temperature sensor is used for acquireing the temperature of heating member, temperature regulator with temperature sensor electric connection is used for with the temperature control of heating member is between 0 to 300 ℃.

In a preferred embodiment, the air drying device is provided with an air outlet, and air blown from the air outlet can evaporate and dry the perovskite precursor liquid on the surface of the substrate and form the perovskite thin film.

In a preferred embodiment, the roller module comprises a roller frame and a first roller and a second roller which are arranged on the roller frame, the roller frame is connected with the transverse guide rail through a guide rail sliding block, the roller module can move up and down along the vertical guide rail under the driving of the first motor, and the roller module can move back and forth along the transverse guide rail under the driving of the second motor.

In a preferred embodiment, the system further comprises a control system electrically connected with the conveying base, and a sensor for detecting the position of the conveying base, wherein the control system can control the motion state of the conveying base according to the detection information of the sensor.

In a preferred embodiment, the perovskite precursor solution further comprises a base, wherein the base comprises a substrate, a plurality of adhesion layers are arranged on the substrate, and the perovskite precursor solution is placed on the substrate.

In a preferred embodiment, the first material film roller and the first material film roller are used for outputting a flexible soft film, and one is used for reeling the flexible soft film, under the pressing of the rollers, the flexible soft film covers the surface of the substrate to form a compact sandwich structure with the substrate as a bottom layer and the flexible soft film as a top layer, and the perovskite precursor liquid is sandwiched between the substrate and the flexible soft film.

In a preferred embodiment, the high-pressure gas ejected from the air outlet of the air drying device is at least one of compressed air, nitrogen, argon, helium, neon, oxygen and carbon dioxide, and the flow rate of the high-pressure gas is 0 to 1000 standard milliliters per minute.

In a preferred embodiment, the flexible soft film includes any one of a polyamide film, a polyimide film, a polyester film, a polycarbonate film, a polyethylene film, a polyvinyl chloride film, a polystyrene film, a polytetrafluoroethylene film, a polypropylene film, and a graphene film.

Advantageous effects

The perovskite film coating equipment that provides in the embodiment of this application utilizes the utility model discloses the perovskite film of preparation has and forms the membrane performance good, and the perovskite crystal grain size is controllable (100nm-3 μm), advantages such as film thickness is controllable (50nm-2 μm). The utility model discloses according to the method design and the manufacturing of the continuous coating preparation perovskite film of flexible mantle, when guaranteeing low in production cost, improve the film quality, be fit for carrying out the large tracts of land large scale production of the perovskite film of basement.

Drawings

The present invention will be further described with reference to the accompanying drawings and embodiments.

FIG. 1 is a front view of a perovskite thin film coating apparatus provided in one embodiment of the present application;

FIG. 2 is a side view of a perovskite thin film coating apparatus provided in one embodiment of the present application;

fig. 3 is a flow chart of steps of a method of using a perovskite thin film coating apparatus provided in one embodiment of the present application.

Description of reference numerals:

1. a substrate;

10. an equipment platform;

11. a transfer base;

12. a transfer rail;

13. a base slider;

14. a heating device;

2. a flexible soft film;

21. a first material film roller;

22. a first bracket;

23. a second material film roller;

24. a second bracket;

31. a first guide roller;

32. a first lifting cylinder;

33. a second guide roller;

34. a second lifting cylinder;

41. a vertical guide rail;

42. a support frame;

43. a transverse guide rail;

44. a fixed mount;

45. a guide rail slider;

46. a roller frame;

47. a first roller;

48. a second roller;

5. and (7) air outlet.

Detailed Description

The technical solution of the present invention will be described in detail with reference to the accompanying drawings and specific embodiments, it should be understood that these embodiments are only used for illustrating the present invention and are not used for limiting the scope of the present invention, and after reading the present invention, the modifications of the present invention in various equivalent forms by those skilled in the art will fall within the scope defined by the claims attached to the present application.

It will be understood that when an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a unique embodiment.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The perovskite thin film coating equipment provided in the application specification can be used for preparing large-area perovskite thin films, and further overcomes the defects of the prior art. Therefore, on the premise of ensuring low production cost, the film forming quality is improved, the large-scale production process is improved, and the perovskite film forming efficiency is greatly improved.

Referring to fig. 1 to 2, a perovskite thin film coating apparatus provided in an embodiment of the present disclosure will be described in detail. The perovskite thin film coating apparatus may include: a conveying device, a material film roller device, a guide roller device, a rolling device, an air drying device and a heating device 14.

In this embodiment, the transfer device may include: a conveying guide rail 12 extending lengthwise in a first direction, and a conveying base 11 movable relative to the extending direction of the conveying guide rail 12.

Specifically, the transfer device may include: a transfer base 11, a transfer rail 12, and a base slider 13 disposed between the transfer base 11 and the transfer rail 12. Specifically, the transfer guide 12 may be elongated in a first direction, and the transfer base 11 is connected to the transfer guide 12 by a base slider 13 and is linearly movable on the transfer guide 12 in the first direction.

In the present embodiment, the heating device 14 is also provided on the transfer base 11. The heating device 14 may include: the heating element may be in the form of a heating coil, but of course, the heating element may also be in other forms and is not specifically limited herein. When the heating member is in the form of a heating coil, the heating coil may be embedded in a slot at the bottom of the stage of the transfer base 11.

Furthermore, the heating device 14 may also be provided with a temperature sensor and a temperature regulator. The temperature sensor is used for acquiring the real-time temperature of the heating coil. The temperature regulator is electrically connected with the temperature sensor and used for regulating the temperature of the heating coil. The temperature regulator and the temperature sensor are matched to control the temperature of the heating coil to be between 0 and 300 ℃.

In this embodiment, the material film roll device may include: material membrane running roller and be used for supporting material membrane running roller support of material membrane running roller. The material film roller can rotate relative to the material film roller bracket. Wherein, this material membrane roll can include: a first material film roller 21 and a second material film roller 23. This material membrane roll wheel support includes: a first bracket 22 and a second bracket 24. The conveyor rail 12 has opposite first and second ends along a first direction of its longitudinal extension, wherein the first bracket 22 is disposed adjacent the first end of the conveyor rail 12 and the second bracket 24 is disposed adjacent the second end of the conveyor rail 12. The bottom of the first and

second legs

22, 24 may be connected to the equipment platform 10. The first film roller 21 is arranged on the first bracket 22, and the second film roller 23 is arranged on the second bracket 24. Of course, the film roller device may further include more film rollers and a film roller bracket, and the application is not specifically limited herein

In this embodiment, the guide roller device includes: guide roller and be used for adjusting the high adjusting device of guide roller height. Specifically, the height adjusting device may be a lifting cylinder. Wherein the guide roller may include a first guide roller 31 and a second guide roller 33. This lift cylinder can include: a first lift cylinder 32 and a second lift cylinder 34. The first guide roller 31 is disposed on the piston shaft of the first lifting cylinder 32, and can move up and down along with the piston shaft of the first lifting cylinder 32 under the action of the lifting cylinder. The second guide roller 33 can be disposed on the piston shaft of the second lifting cylinder 34, and can move up and down along with the second lifting cylinder 34 under the action of the lifting cylinder. The first lifting cylinder 32 and the second lifting cylinder 34 may be located between the film roll device and the rolling device, and disposed above the equipment platform 10, and the bottom of the first lifting cylinder is connected to the equipment platform 10.

In this embodiment, the rolling device may include: vertical guide rail 41, support frame 42, transverse guide rail 43, fixing frame 44, guide rail slide block 45, roller module and driving piece. The roller module includes at least one roller.

Wherein the bottom of the support frame 42 of the rolling device is connected with the equipment platform 10. The vertical guide rail 41 is provided on the support frame 42. The transverse guide 43 is arranged on a holder 44. The holder 44 is connected to the vertical guide 41 by a guide slider 45.

Wherein, this gyro wheel module can include: a roller frame 46, a first roller 47 and a second roller 48. The first roller 47 and the second roller 48 are both provided on the roller frame 46. The roller frame 46 is connected to the cross rail 43 by way of a rail slider 45. The roller module moves up and down along with the vertical guide rail 41. The roller module makes a reciprocating linear motion along with the transverse guide rail 43 in a plane perpendicular to the direction of the lifting motion.

Specifically, the driving member may include: the first motor is used for driving the fixed frame 44 and the roller on the fixed frame 44 to move up and down, the transverse guide rail 43 is arranged on the fixed frame 44, and the driving piece further comprises a second motor used for driving the roller to horizontally move relative to the transverse guide rail 43.

Referring to the figures, the first roller 47 and the second roller 48 are fixed to the cross member of the roller frame 46. The roller frame 46 is a frame-shaped structure, the inside of which can be used for mounting two rollers, and the outside of which is provided with a guide rail slide block 45. The roller itself does not move, but moves on the guide rail through the guide rail slider 45, and performs a lifting motion and a reciprocating linear motion. The roller is provided with a bearing, is sleeved with a cylindrical roller and can roll on the surface of the substrate 1 under the action of friction force, and the moving speed of the roller is consistent with that of the arranged guide rail.

In one embodiment, the perovskite thin film coating apparatus may be further provided with an air drying device. The air-drying device is provided with an air outlet 5, and the air outlet 5 blows air to volatilize and dry the perovskite precursor liquid on the surface of the substrate 1 and form a perovskite thin film.

In one embodiment, the perovskite thin film coating apparatus may further include: a control system electrically connected to the transfer base 11, and a sensor for detecting the position of the transfer base 11. The control system can control the movement state of the transfer base 11 according to the detection information of the sensor.

In this embodiment, the sensor may be in the form of a photoelectric sensor. The left side and the right side of the equipment platform 10 below the rolling device can be respectively provided with a photoelectric sensor, when the front end of the transmission base 11 moves to the position where the photoelectric sensor is arranged to shield the light of the sensor, the control system generates an instruction, and the transmission base 11 stops moving immediately. The predetermined position here means that the position 1/2 of the transfer base 11 is on the same horizontal straight line with the bottom 1/2 of the vertical guide rail 41 of the apparatus. In this position, the transfer base 11 is located directly below the rolling device, and the center of the rolling device is perpendicular to the center of the transfer base 11.

As shown in fig. 3, the present invention also provides a method for preparing a perovskite light-absorbing layer by using the aforementioned perovskite thin film coating apparatus, which includes the following steps:

step S11: placing the substrate 1 deposited with the perovskite precursor liquid on a conveying base 11 of a conveying device, starting the conveying device, and stopping the conveying device when the substrate is conveyed to a preset position below a rolling device through the conveying base 11;

step S12: starting a material film roller device, and conveying the unused flexible soft film 2 to the upper part of the substrate 1 by utilizing the cooperation of the first material film roller 21 and the second material film roller 23;

step S13: starting a guide roller device, adjusting the heights of the first guide roller wheel 31 and the second guide roller wheel 33, stopping after reaching the preset height of the substrate 1, and flattening the flexible film 2;

step S14: starting a first motor of the rolling device, descending a roller to a preset position above a substrate 1, and pressing the flexible soft film 2 by using the roller to enable the flexible soft film 2 to cover the surface of the substrate 1 to form a primary compact sandwich structure with the substrate 1 as a bottom layer and the flexible soft film 2 as a top layer and perovskite precursor liquid sandwiched between the substrate 1 and the flexible soft film 2;

step S15: starting a second motor on the roller device, and horizontally rolling the roller on the substrate 1 along the edge of the substrate 1 through the transverse guide rail 43 to roll the substrate 1 so as to promote the formation of a compact sandwich structure;

step S16: after the rolling is finished, the second motor on the rolling device stops running, the roller stops horizontal rolling, the first motor on the roller device runs again, the roller rises through the vertical guide rail 41 and is lifted off the surface of the substrate 1, after the preset height is reached, the vertical motor stops running, and the roller hovers;

step S17: starting the guide roller device, lifting a first guide roller wheel 31 and a second guide roller wheel 33, starting the first material film roller wheel 21 to run, gradually stripping the flexible soft film 2 from the surface of the substrate 1, and gradually exposing the perovskite precursor liquid on the substrate 1 to an environmental medium;

step S18: evaporating a solvent in the perovskite precursor liquid on the substrate 1 to form a perovskite precursor film on the substrate 1; and heating the perovskite precursor film to form a perovskite light absorption layer.

Hereinafter, each step will be described in detail.

First, step S11: the substrate 1 deposited with the perovskite precursor liquid is firstly placed on a conveying base 11 of a conveying device, and when the substrate is conveyed to a preset position below the rolling device through the conveying base 11, the conveying device is stopped.

In this embodiment, the substrate 1 is a substrate or a substrate with one or more adhesion layers. The substrate 1 is generally rectangular in shape, but may be processed into other shapes as required, and the surface of the substrate 1 on which the perovskite precursor solution is deposited is a plane.

The substrate is structurally made of glass, metal, ceramic or high-temperature-resistant organic polymer with a smooth and flat surface. The surface of the substrate can be provided with an adhesion layer according to production requirements, and the adhesion layer comprises a conductive layer, a barrier layer, a porous layer, a hole transport layer or an electron transport layer.

Step S12: then, the film roller device is started, and the second film roller 23 is matched with the first film roller 21, so that the unused flexible film 2 can be output above the substrate 1. For example, the second web roll 23 may transport the unused pliable membrane 2 and the first web roll 21 takes up the used pliable membrane 2 until a new unused membrane is transported over the substrate 1. Of course, the second web roll 23 may be used for winding and the first web roll 21 may be used for feeding.

Step S13: and then, the guide roller device is started, the first guide roller 31 and the second guide roller 33 descend in the first lifting cylinder 32 and the second lifting cylinder 34, and stop after reaching a preset height, the flexible soft film 2 is supported, and the liquid level of the flexible soft film 2 is prevented from being damaged by sagging or skewing.

In the present embodiment, the predetermined height is set in relation to three factors, namely the thickness of the substrate 1, the thickness of the perovskite layer to be coated, and the thickness of the flexible soft film 2. The thickness of the substrate 1 commonly used in the apparatus is generally between 0.5mm and 2mm, and the predetermined height is set to be 0.01mm to 2mm higher than the thickness of the substrate 1 according to the specific coating requirements.

Step S14: the rolling device starts, and the first motor on the roller device operates, and through vertical guide rail 41, the last gyro wheel of rolling device descends, and when the gyro wheel arrived basement 1 top predetermined position, rolling device's first motor stop operation under the suppression of gyro wheel, flexible mantle 2 covers on basement 1 surface, forms one kind and uses basement 1 as the bottom, and flexible mantle 2 is the top layer, presss from both sides the inseparable sandwich structure of preliminary of perovskite precursor liquid between the two.

Step S15: then, the transverse motor on the roller device operates, and the rollers horizontally roll on the substrate 1 along the edge of the substrate 1 through the transverse guide rail 43 to roll the substrate 1, so as to promote the formation of a compact sandwich structure.

In the embodiment, the compact sandwich structure is formed, so that the thickness of the perovskite precursor liquid film layer has higher consistency, and the good uniformity of the prepared perovskite thin film is ensured. Secondly, the perovskite precursor liquid is gradually expanded by virtue of the capillary attraction between the flexible soft film 2 and the substrate, so that bubbles are not generated on a tight interlayer between the substrate 1 and the flexible soft film 2 basically, and a uniform perovskite precursor liquid film layer is formed more easily.

In the present embodiment, the movement along the edge means that the roller rolls from the head end of the surface of the substrate 1 to the tail end of the substrate 1. a pad of 1 × 10cm is provided on the stage of the transferring base 11 to fix the substrate 1 against sliding, wherein, the end of the substrate 1 near the pad is the front end, and the roller rolls from the pad to the tail end of the substrate 1, thereby rolling the entire substrate 1.

Step S16: and the transverse motor on the rolling device stops running, the roller stops horizontal rolling, the vertical motor on the roller device runs again, the roller rises through the vertical guide rail 41 and is lifted off the surface of the substrate 1, after the preset height is reached, the vertical motor stops running, and the roller hovers.

Step S17: the guide roller device is started, the first guide roller 31 and the second guide roller 33 are lifted, the first material film roller 21 starts to run, the flexible soft film 2 is gradually stripped from the surface of the substrate 1, and the perovskite precursor liquid on the substrate 1 is gradually exposed in the environment medium.

In order to ensure that the flexible soft film 2 can be smoothly peeled off from the surface of the substrate 1, firstly, the coated substrate 1 is subjected to a UV surface treatment before use to enhance the curing capability of the perovskite solution on the surface of the substrate 1, so that the perovskite precursor solution is left on the substrate 1. Secondly, the flexible soft film 2 is pretreated, and the wettability of the surface of the flexible soft film 2 material is changed, so that adhesion of perovskite precursor liquid on the surface of the soft film is reduced. Thirdly, the flexible soft film 2 is gradually stripped, the perovskite precursor liquid film layer is gradually exposed in an environment medium, the perovskite precursor liquid can be remained on the surface of the substrate 1 by controlling the stripping speed and the stripping temperature, and the solvent in the solution can be uniformly and orderly removed, so that a compact and uniform perovskite layer is formed.

Step S18: and after the solvent in the perovskite precursor liquid on the substrate 1 is evaporated by wind at an air outlet 5 of the air drying device, a perovskite precursor film is formed on the substrate 1. The heating coil heat-treats the substrate 1 from below the substrate 1 to form a perovskite thin film (i.e., a perovskite light-absorbing layer).

Alternatively, after the heat treatment is completed, the substrate 1 is conveyed out from below the air outlet 5 by a conveying device.

In the above-mentioned perovskite thin film coating apparatus preparation method, the said basement 1 is the base plate or base plate with one or more adhesion layer; the substrate may be selected from glass, metal, ceramic or high temperature resistant organic polymers (e.g., PET sheets); the adhesion layer includes a conductive layer, a barrier layer, a porous layer, a hole transport layer, or an electron transport layer.

The perovskite thin film coating device provided in the embodiment of the application has the function of preparing a perovskite light absorption layer. Wherein the purpose of adding the adhesion layer is to make the perovskite solar cell through subsequent processing. And these adhesion layers are not required on the substrate 1 and are chosen according to the type of perovskite cell to be produced.

The perovskite solar cell comprises a planar heterojunction forward perovskite solar cell or a planar heterojunction reverse perovskite solar cell.

In the perovskite solar cell with the forward plane heterojunction, the following components are sequentially arranged from the bottom layer to the top layer: transparent electrode, electron transport layer, perovskite light absorption layer, hole transport layer and metal electrode. In the perovskite solar cell with the reverse plane heterojunction, the following steps are sequentially performed from the bottom layer to the top layer: substrate 1 layer, dense layer, porous layer, perovskite light-absorbing layer, hole transport layer and back electrode.

The function of the conductive layer is to provide a conductive path; the function of the barrier layer and the porous layer is to inhibit electron recombination and provide an electron transmission channel; the hole transport layer and the electron transport layer are respectively used for transporting positive and negative charges generated by the perovskite thin film

In the above method for preparing a perovskite thin film coating apparatus, the solute in the perovskite precursor solution may be a mixture of PbI2, PbBr2, CH3NH3I and CH3NH3Br, a mixture of PbCl2 and CH3NH3I, or a mixture of PbI2 and CH3NH 3I.

In addition, the solution and solute of the perovskite precursor solution may be selected according to the conventional materials in the art. The flexible film 2 used may be selected from conventional materials existing in the art.

In the above method for preparing a perovskite light absorption layer, the solvent in the perovskite precursor solution comprises one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Dimethylacetamide (DMCA), N-methylpyrrolidone (NMP), gamma-butyrolactone (GB L) and ethylpyrrolidone (NEP).

In the above method for producing a perovskite light absorbing layer, the flexible soft film 2 used includes: polyamide film, polyimide film, polyester film, polycarbonate film, polyethylene film, polyvinyl chloride film, polystyrene film, polytetrafluoroethylene film, polypropylene film, graphene film. The composite material can also be a composite material (for example, the composite material is obtained by coating a film on a substrate, so that the composite material has the characteristics of no reaction with the perovskite precursor liquid, smooth and flat surface, high temperature resistance and the like on the whole).

The utility model discloses a realize like this, provide a perovskite film coating equipment's application, be arranged in the perovskite light-absorbing layer of preparation among the perovskite solar cell to this perovskite film mantle continuous coating equipment.

The invention will be further illustrated with reference to specific examples of a method for producing a perovskite light-absorbing layer of a perovskite solar cell.

Example 1

(1) Carrying out ultrasonic cleaning on the substrate for 20 minutes by sequentially passing through an active agent, deionized water, ethanol and acetone, and then drying; the substrate is covered with an adhesive layer as a base 1 for coating.

The substrate 1 is composed of a substrate and an adhesion layer adhered to the substrate, the substrate is made of glass (the roughness is 10nm), a conductive layer and a hole transport layer are sequentially adhered to the glass, and the conductive layer is SnO doped with fluorine₂And the hole transport layer is a nickel oxide layer (with the thickness of 20 nm).

(2) A compact sandwich structure is formed by taking a substrate 1 as a bottom layer and a flexible soft film 2 as a top layer, and perovskite precursor liquid is clamped between the substrate 1 and the flexible soft film 2, and the compact sandwich structure specifically comprises the following components:

a. preparation of perovskite precursor liquid

Will PbI₂And CH₃NH₃Dissolving I powder in 1 ml of N, N-Dimethylformamide (DMF) according to a molar ratio of 1:1 to prepare 0-2 mol/L perovskite solution, stirring the prepared solution at room temperature for 1 hour, and filtering by using a filter screen with the aperture of 200nm to obtain CH₃NH₃PbI₃A perovskite precursor liquid.

b. Fixing the substrate 1 in the step (1) on a conveying base 11, dropwise adding newly-configured perovskite precursor liquid on the surface of the substrate 1, starting coating equipment, conveying a new flexible soft film 2 by a film roller device, pressing down by a guide roller device and a rolling device to enable the substrate 1 to cover the flexible soft film 2, standing for 5-10s, enabling a roller to horizontally roll on the substrate 1 in a reciprocating manner along the edge of the substrate 1, rolling the substrate 1, and enabling the perovskite precursor liquid to form a continuous perovskite precursor liquid film between the substrate 1 and the flexible soft film 2.

The flexible soft film 2 is a polyimide film, the thickness of the flexible soft film is 0.025mm, and the width of the flexible soft film is 1 time of the width of the substrate. The selection of the material of the flexible soft film 2 needs to meet the following requirements: (1) the selected material does not react with the species in the perovskite precursor liquid; (2) the selected material can be used in certain high temperature environment (according to the requirement in the process, the material with certain temperature resistance is selected). Preferably, the dragged film is a conductive film, preferably a transparent conductive film, so as to observe the state of the perovskite precursor liquid film layer. The thickness of the flexible soft film 2 is required to have light, thin and flexible properties while being not easily deformed. Too thick a soft film will extrude the perovskite precursor solution, while too thin a film is not sufficient to form a tight interlayer. The thickness of the flexible soft film 2 is 0.01-0.75mm, preferably 0.0125 mm. The width of the flexible film 2 is required to be able to cover the entire surface of the substrate 1, and is generally 1 to 2 times, preferably 1 time, the width of the substrate 1.

(3) Gradually stripping the flexible soft film 2 to gradually expose the perovskite precursor liquid on the substrate 1 to the environment, specifically:

keeping the fixed state of the substrate 1, lifting the guide roller device and the rolling device away from the flexible soft film 2, and operating the material film roller device to drive the flexible soft film 2 to peel off the flexible soft film 2. Wherein, the stripping process is as follows: the first material film roller 21 is started to lift one end of the polyimide film, and the first material film roller 21 winds the polyimide film to uniformly roll the polyimide film from the substrate 1. Wherein the rate of tearing off may be 55 mm/s.

It has been found through experiments that the rate of tearing away the flexible soft film 2 affects the thickness of the perovskite thin film: the speed is too slow, the prepared perovskite thin film is too thick, and the defects of the thin film are increased; the speed is too high, the flexible soft film 2 can take away part of perovskite precursor liquid, so that the thickness is reduced, and the efficiency of the prepared perovskite battery is low; therefore, the flexible film 2 is preferably peeled off at a constant speed of 1 to 150mm/s, preferably 55 mm/s.

(4) After the solvent in the perovskite precursor liquid on the substrate 1 is evaporated, a perovskite thin film is formed on the substrate 1, and the method specifically comprises the following steps:

starting the conveying device, conveying the substrate to the lower part of the air drying device by the conveying base 11, starting the air drying device, enabling the wind direction to be vertical to the substrate 1, and quickly volatilizing the solvent by the air drying device; then, the heating device 14 is turned on to perform a heat treatment, and as the solvent evaporates, the solute is crystallized into a perovskite layer on the substrate 1, i.e., a light-absorbing layer of the perovskite solar cell.

Example 2

(1) Carrying out ultrasonic cleaning on the substrate for 20 minutes by sequentially passing through an active agent, deionized water, ethanol and acetone, and then drying; covering an adhesion layer on a substrate as a base 1 for coating;

the base 1 is composed of a substrate and an adhesion layer adhered to the substrate,the substrate is made of glass (the roughness is 30nm), a conductive layer and a hole transport layer are sequentially attached to the glass, and the conductive layer is SnO doped with fluorine₂A layer, the hole transport layer being a titanium oxide layer (thickness 100 nm);

a. preparation of perovskite precursor liquid

Will PbI₂And CH₃NH₃Dissolving the I powder in 1 ml of N, N-Dimethylformamide (DMF) according to a molar ratio of 1:1 to prepare 0-2 mol/L perovskite solution, stirring the prepared solution at room temperature for 1 hour, and filtering by using a filter screen with the aperture of 200nm to obtain CH3NH3PbI3 perovskite precursor solution.

b. Fixing the substrate 1 in the step (1) on a conveying base 11, starting coating equipment, conveying a new flexible soft film 2 by a material film roller device, pressing down a guide roller device and a rolling device to cover the flexible soft film 2 on the substrate 1, covering the flexible soft film 2 on the substrate 1, starting a material film roller on one side, pulling up one end of the flexible soft film 2 to expose the substrate 1 with the length of 2mm, injecting newly-configured perovskite precursor liquid into the substrate 1 through a slit between the exposed substrate 1 and the flexible soft film 2, standing for 5-10s after the injection is finished, horizontally and reciprocally rolling the roller on the substrate 1 along the edge of the substrate 1 to roll the substrate 1, and enabling the perovskite precursor liquid film to form continuous perovskite precursor liquid between the substrate 1 and the flexible soft film 2.

The flexible soft film 2 is a polyimide film, the thickness of the flexible soft film is 0.025mm, and the width of the flexible soft film is 1 time of the width of the substrate.

keep basement 1's fixed state, lift off flexible mantle 2 with guide roll device and rolling press device, material membrane roller device operation drives flexible mantle 2, peels off flexible mantle 2, and the process of peeling off is: starting the first material film roller 21, lifting one end of the polyimide film, coiling the polyimide film by the first material film roller 21, and uniformly winding the polyimide film on the substrate 1; the rate of tearing off was 80 mm/s.

Example 3

(1) And (3) carrying out ultrasonic cleaning on the substrate for 20 minutes by sequentially passing through an active agent, deionized water, ethanol and acetone, and then drying.

The substrate 1 is a substrate layer, and the substrate is made of alumina ceramics (with the roughness of 600 nm).

a. preparation of perovskite precursor liquid

Adding solute PbCl₂And CH₃NH₃Mixing the I and a solvent (a mixed solvent consisting of DMSO and NEP, the volume ratio of DMSO to NEP is 3:2), stirring the mixed solution for 3-5 hours, and filtering the solution by using a filter screen with the aperture of 200nm to obtain the perovskite precursor solution.

The flexible soft film 2 is a polyimide film, the thickness of the flexible soft film is 0.05mm, and the width of the flexible soft film is 1 time of the width of the substrate.

keep basement 1's fixed state, lift off flexible mantle 2 with guide roll device and rolling press device, material membrane roller device operation drives flexible mantle 2, peels off flexible mantle 2, and the process of peeling off is: starting the first material film roller 21, lifting one end of the polyimide film, coiling the polyimide film by the first material film roller 21, and uniformly winding the polyimide film on the substrate 1; the rate of tearing off was 100 mm/s.

starting the conveying device, conveying the substrate to the lower part of the air drying device by the conveying base 11, starting the air drying device, enabling the wind direction to be vertical to the substrate 1, and quickly volatilizing the solvent in the perovskite precursor liquid by the air drying device; then, the heating device 14 is turned on to perform a heat treatment, and as the solvent evaporates, the solute is crystallized into a perovskite layer on the substrate 1, i.e., a light-absorbing layer of the perovskite solar cell.

Example 4

(1) Carrying out ultrasonic cleaning on the substrate for 20 minutes by sequentially passing through an active agent, deionized water, ethanol and acetone, and then drying;

the substrate 1 is a substrate layer, and the substrate is made of PET (polyethylene terephthalate substrate with the roughness of 30 nm);

a. preparation of perovskite precursor liquid

Mixing solute PbI2 and CH3NH3I powder with solvent (NMP), stirring the mixed solution for 2-3 hours, and filtering with a filter screen with the aperture of 200nm to obtain the perovskite precursor solution.

keep basement 1's fixed state, lift off flexible mantle 2 with guide roll device and rolling press device, material membrane roller device operation drives flexible mantle 2, peels off flexible mantle 2, and the process of peeling off is: starting the first material film roller 21, lifting one end of the polyimide film, coiling the polyimide film by the first material film roller 21, and uniformly winding the polyimide film on the substrate 1; the rate of tearing off was 120 mm/s.

Example 5

(1) Carrying out ultrasonic cleaning on the substrate for 20 minutes by sequentially passing through an active agent, deionized water, ethanol and acetone, and then drying; the substrate 1 is a substrate layer, and the substrate is made of alumina ceramics (with the roughness of 600 nm).

a. preparation of perovskite precursor liquid

Solutes PbCl2 and CH3NH3I were mixed with a solvent (a mixed solvent composed of DMSO and NEP, volume ratio DMSO: NEP ═ 3:2), and the mixed solution was stirred for 3-5 hours, and then filtered using a filter screen with a pore size of 200nm to obtain a perovskite precursor solution.

Example 6

the substrate 1 is a substrate layer, and the substrate is made of metal Al (the roughness is 50 nm);

a. preparation of perovskite precursor liquid

Solute PbI₂、CH(NH₂)₂I、CH₃NH₃Br was mixed with a solvent (a mixed solvent of DMF and NMP in a volume ratio of DMF: NMP of 1:2), and the mixed solution was stirred for 15 to 17 hours, and then filtered using a filter screen having a pore diameter of 200nm to obtain a perovskite precursor solution.

The flexible soft film 2 is a polyimide film, the thickness of the flexible soft film is 0.025mm, and the width of the flexible soft film is 1.2 times of the width of the substrate.

keep basement 1's fixed state, lift off flexible mantle 2 with guide roll device and rolling press device, material membrane roller device operation drives flexible mantle 2, peels off flexible mantle 2, and the process of peeling off is: starting the first material film roller 21, lifting one end of the polyimide film, coiling the polyimide film by the first material film roller 21, and uniformly winding the polyimide film on the substrate 1; the rate of tear-off was 75 mm/s.

Example 7

the substrate 1 consists of a substrate and an adhesion layer adhered to the substrate, the substrate is made of glass (the roughness is 20nm), a conductive layer and a hole transport layer are sequentially adhered to the glass, the conductive layer is a fluorine-doped SnO2 layer, and the hole transport layer is a nickel oxide layer (the thickness is 100 nm);

a. preparation of perovskite precursor liquid

Mixing solutes PbI2 and CH (NH2)2I, CH3NH3Br with a solvent (a mixed solvent consisting of DMF and NMP, wherein the volume ratio of DMF to NMP is 1:2), stirring the mixed solution for 15-17 hours, and filtering by using a filter screen with the aperture of 200nm to obtain a perovskite precursor solution;

b. fixing the substrate 1 in the step (1) on a conveying base 11, dropwise adding newly-configured perovskite precursor liquid on the surface of the substrate 1, starting coating equipment, conveying a new flexible soft film 2 by a film roller device, pressing down by a guide roller device and a rolling device to enable the substrate 1 to cover the flexible soft film 2, standing for 5-10s, enabling a roller to horizontally roll on the substrate 1 in a reciprocating manner along the edge of the substrate 1, rolling the substrate 1, and enabling the perovskite precursor liquid to form a continuous perovskite precursor liquid film between the substrate 1 and the flexible soft film 2;

the flexible soft film 2 is a polytetrafluoroethylene film, the thickness is 0.01mm, and the width is 1.2 times of the width of the substrate;

keep basement 1's fixed state, lift off flexible mantle 2 with guide roll device and rolling press device, material membrane roller device operation drives flexible mantle 2, peels off flexible mantle 2, and the process of peeling off is: starting the first material film roller 21, lifting one end of the polyimide film, coiling the polyimide film by the first material film roller 21, and uniformly winding the polyimide film on the substrate 1; the rate of tearing off was 85 mm/s;

Each of the examples provided in the application uses different perovskite precursor liquids, substrates 1, flexible soft films 2 and process parameters. Different perovskite precursor liquid combinations are selected in each embodiment, which shows that the device can be coated with a plurality of perovskite precursor liquids, is not limited to one or more perovskite formulas, and has wider application. In examples 1, 2 and 7, a conventional substrate 1 made of glass is used, which illustrates that the present apparatus can be used to fabricate perovskite cells as is conventional in the art. Examples 3, 4, 5, 6 use the substrate 1 made of metal, ceramic or high temperature resistant organic polymer, which illustrates that the device can coat the perovskite light absorbing layer on special materials, which proves that the device has a wide application range.

The perovskite thin film coating equipment provided by the application provides two liquid adding modes, namely 'first liquid adding and then film covering' in the embodiment 1 and 'first film covering and then liquid adding' in the embodiments 2-7, and can be flexibly selected according to the property of the perovskite precursor liquid. Specifically, the perovskite precursor liquid can be selected to be 'covered with a film first and then filled with liquid' if the perovskite precursor liquid cannot be exposed in the environment for a long time, and the perovskite precursor liquid can be selected to be 'filled with liquid first and then covered with a film' if the perovskite precursor liquid needs to be exposed in the environment for a period of time and then coated.

Examples 1 to 6 examples selected the flexible film 2 which is a polyimide film having strong hydrophilicity. The flexible soft membrane 2 selected in example 7 is a polytetrafluoroethylene film, and has strong hydrophobicity. The different flexible soft films 2 are chosen to meet the requirements for different perovskite thin film thicknesses. When the thickness of the perovskite film is required to be thin, a polyimide film can be selected, and partial solution can be taken away due to strong hydrophilicity, so that the thickness of the perovskite film is reduced; when the thickness of the perovskite film is required to be thick, a polytetrafluoroethylene film can be selected, and the perovskite precursor liquid can be more remained on the surface of the substrate 1 due to strong hydrophobicity, so that the thickness of the perovskite film is increased.

The perovskite thin film prepared by the utility model has the advantages of good film forming performance, controllable size (100nm-3 mu m) of perovskite crystal grains, controllable thickness (50nm-2 mu m) of the thin film and the like. The utility model discloses according to the method design and the manufacturing of the continuous coating preparation perovskite film of flexible mantle, when guaranteeing low in production cost, improve the film quality, be fit for carrying out the large tracts of land large scale production of the perovskite film of basement 1.

It should be noted that, in the description of the present application, the terms "first", "second", and the like are used for descriptive purposes only and for distinguishing similar objects, and no precedence between the two is intended or should be construed to indicate or imply relative importance. In addition, in the description of the present application, "a plurality" means two or more unless otherwise specified.

The above embodiments in the present specification are all described in a progressive manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment is described with emphasis on being different from other embodiments.

The above description is only a few embodiments of the present invention, and although the embodiments of the present invention are disclosed as above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A perovskite thin film coating apparatus, characterized by comprising: the device comprises a conveying device, a material film roller device, a guide roller device, a rolling device, an air drying device and a heating device;

the transfer device includes: a conveying guide rail which lengthily extends along the horizontal direction and a conveying base which can move relative to the lengthways extending direction of the conveying guide rail; the conveying guide rail is provided with a first end and a second end which are opposite along the longitudinal extension direction;

the material film roller device comprises: the film roller comprises a film roller wheel and a film roller wheel bracket for supporting the film roller wheel; the material membrane roll wheel includes: the first material film roller is close to the first end of the conveying guide rail, and the second material film roller is close to the second end of the conveying guide rail; the material membrane roll wheel support includes: the first bracket is used for supporting the first material film roller and the second bracket is used for supporting the second material film roller;

the guide roller device includes: the device comprises a guide roller and a height adjusting device for adjusting the height of the guide roller; the guide roller wheel includes: a first guide roller and a second guide roller; the height adjusting device includes: the first height adjusting device is used for adjusting the first guide roller wheel, and the second height adjusting device is used for adjusting the second guide roller wheel;

the rolling press device includes: the roller module comprises at least one roller; the fixed frame is connected with the vertical guide rail, and the roller can move up and down along the vertical guide rail under the driving of the driving piece.

2. The perovskite thin film coating apparatus as claimed in claim 1, wherein the driving member comprises a first motor for moving the fixing frame and the roller on the fixing frame up and down, a transverse rail is provided on the fixing frame, and the driving member further comprises a second motor for moving the roller horizontally relative to the transverse rail.

3. The perovskite thin film coating apparatus as claimed in claim 2, wherein the heating device is provided on the transfer base, the heating device comprising: heating member, temperature sensor and temperature regulator, temperature sensor is used for acquireing the temperature of heating member, temperature regulator with temperature sensor electric connection is used for with the temperature control of heating member is between 0 to 300 ℃.

4. The perovskite thin film coating apparatus as claimed in claim 2, wherein the air drying device is provided with an air outlet, and the perovskite precursor liquid on the surface of the substrate is evaporated and dried by air blown from the air outlet and forms the perovskite thin film.

5. The perovskite thin film coating apparatus as claimed in claim 2, wherein the roller module comprises a roller frame and a first roller and a second roller which are arranged on the roller frame, the roller frame is connected with the transverse rail through a rail slider, the roller module is capable of moving up and down along the vertical rail under the driving of the first motor, and the roller module is capable of moving back and forth along the transverse rail under the driving of the second motor.

6. The perovskite thin film coating apparatus as claimed in claim 2, further comprising a control system electrically connected to the transport base, and a sensor for detecting a position of the transport base, the control system being capable of controlling a motion state of the transport base based on detection information of the sensor.

7. The perovskite thin film coating apparatus of claim 1 or 6, further comprising a substrate having a plurality of adhesion layers disposed thereon, the substrate being configured to receive a perovskite precursor liquid thereon.

8. The perovskite thin film coating apparatus as claimed in claim 7, wherein the first film roll and the first film roll are one for feeding out the flexible soft film and one for winding up the flexible soft film,

under the pressing of the roller, the flexible soft film covers the surface of the substrate to form a compact sandwich structure which takes the substrate as a bottom layer and the flexible soft film as a top layer and clamps the perovskite precursor liquid between the substrate and the flexible soft film.

9. The perovskite thin film coating apparatus as claimed in claim 1, wherein the high pressure gas ejected from the air outlet of the air drying device is at least one of compressed air, nitrogen, argon, helium, neon, oxygen and carbon dioxide, and the flow rate of the high pressure gas is 0 to 1000 standard ml/min.

10. The perovskite thin film coating apparatus as claimed in claim 8, wherein the flexible soft film comprises any one of a polyamide thin film, a polyimide thin film, a polyester thin film, a polycarbonate thin film, a polyethylene thin film, a polyvinyl chloride thin film, a polystyrene thin film, a polytetrafluoroethylene thin film, a polypropylene thin film, and a graphene thin film.