A perovskite solar cell module and a preparation method thereof

Abstract

The present invention discloses a perovskite solar cell module and a preparation method thereof. Among them, a preparation method of a perovskite solar cell module includes: preparing a hole transport layer on the surface of a first conductive substrate; preparing an electron transport layer on the surface of a second conductive substrate; coating a perovskite layer on the surface of the hole transport layer and / or the electron transport layer; dividing the area where the hole transport layer is located into several areas to obtain a half cell A; dividing the area where the electron transport layer is located into several areas corresponding to the half cell A one by one to obtain a half cell B; overlapping the half cell A and the half cell B, and making the scratches made on the half cell A and the half cell B coincide to obtain a coincidence module; annealing the coincidence module to obtain a cell module. The present invention can efficiently prepare a perovskite solar cell module with a larger area, greatly reduce the preparation cost, and significantly improve the efficiency of module preparation.

Description

Technical Field

[0001] The present invention relates to the field of solar cells, and particularly to a perovskite solar cell module and a preparation method thereof. Background Art

[0002] There are mainly three traditional perovskite solar cell structures, namely, mesoporous structure, normal structure, and inverted structure. Among them, the mesoporous structure successively includes: FTO conductive layer, electron transport layer, mesoporous layer, perovskite layer, hole transport layer, and metal electrode; the normal structure successively includes: FTO conductive layer, electron transport layer, perovskite layer, hole transport layer, and metal electrode; the inverted structure successively includes: FTO conductive layer, hole transport layer, perovskite layer, electron transport layer, and metal electrode.

[0003] Regardless of the traditional perovskite solar cell with any structure, it is necessary to prepare a metal electrode. In most of the reported processes, the metal electrode is often prepared by a thermal evaporation process, which not only increases the cost but also increases the preparation time, which is very unfavorable for large-scale commercialization. Many documents also record various electrode preparation schemes, but it is difficult to scale them up to large-area preparation processes.

[0004] And the conventional method for expanding to a large area is as described in Chinese Patent Document CN114203919A, which requires preparing small cells and then connecting them in series to expand to a large area, which requires a very precise preparation process and has high requirements for the preparation process. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present invention is to overcome the defects of high cost and low efficiency in the preparation of large-area perovskite solar cell modules in the prior art, so as to provide a perovskite solar cell module and a preparation method thereof for solving the above problems.

[0006] A preparation method of a perovskite solar cell module includes:

[0007] Preparing a hole transport layer on the surface of a first conductive substrate;

[0008] Preparing an electron transport layer on the surface of a second conductive substrate;

[0009] Coating a perovskite layer on the surface of the hole transport layer and / or the electron transport layer;

[0010] Scoring the area where the hole transport layer is located into several areas to obtain a half cell A;

[0011] Scoring the area where the electron transport layer is located into several areas corresponding one by one to the half cell A to obtain a half cell B;

[0012] Overlap half-cell A with half-cell B and align the scratches scribed on half-cell A and half-cell B to obtain an overlapping assembly;

[0013] Anneal the overlapping assembly to obtain a battery assembly.

[0014] It should be specifically noted that when there is a perovskite layer on the surface of the electron transport layer, the perovskite layer will be scribed simultaneously during the scribing of the electron transport layer; when there is a perovskite layer on the surface of the hole transport layer, the perovskite layer will be scribed simultaneously during the scribing of the hole transport layer.

[0015] The present invention does not specifically limit the first conductive substrate and / or the second conductive substrate. For example, it can be FTO glass or ITO glass. When the first conductive substrate and / or the second conductive substrate is FTO glass or ITO glass, it is possible to avoid preparing metal electrodes in traditional solar cells, simplify the preparation process of perovskite solar cell assemblies, better reduce the preparation cost and preparation time, and improve the preparation efficiency.

[0016] The present invention does not specifically limit the material of the hole transport layer. For example, it can include NiO x , Cu2O, MoO x or one or more of them;

[0017] The present invention does not specifically limit the material of the electron transport layer. For example, it can include one or more of TiO2, SnO2, ZnO, and WO3.

[0018] One side of the first conductive substrate and the second conductive substrate includes a blank area, and after overlapping, the blank area on half-cell A and the blank area on half-cell B are located on opposite sides of the overlapping assembly;

[0019] The scribing direction is from the side away from the blank area towards the side of the blank area.

[0020] There are two ways to form the blank area. One is that during the battery preparation process, one side of the first conductive substrate and the second conductive substrate is not covered with other film layers, and the area on this side without covering other film layers constitutes the blank area; the other is that during the battery preparation process, other film layers are covered, but during the preparation process, the other film layers covered on one side of the first conductive substrate and the second conductive substrate are removed, and the area on this side where the other film layers are removed constitutes the blank area.

[0021] The specifications of the conductive substrates of half-cell A and half-cell B are the same, and the widths of the blank areas are also the same; the width of the blank area is 0.3 - 1 cm.

[0022] The total thickness of the perovskite layer is 400 - 1000 nm, the thickness of the hole transport layer is 10 - 50 nm, and the thickness of the electron transport layer is 10 - 50 nm.

[0023] The areas of several regions formed by scribing on the half - cell A and the half - cell B are the same;

[0024] The scribing method is laser etching, and the film layers etched by laser on the overlapping component include: a conductive substrate, a perovskite layer, a hole transport layer, and an electron transport layer.

[0025] The annealing method includes at least one of hot pressing and heating in a gas atmosphere containing the solvent used in the perovskite precursor solution.

[0026] The conditions for hot pressing include: a pressure of 15 - 25 MPa, a temperature of 90 - 120 °C, and a time of 20 - 120 min;

[0027] The type of the solvent used in the perovskite precursor solution is not specifically limited. For example, it may include one or more of DMF and DMSO; the conditions for heating in a gas atmosphere containing the solvent used in the perovskite precursor solution include: the concentration of the solvent used in the perovskite precursor solution in the container is 1 - 15 mL / m 3 , a temperature of 90 - 120 °C, and a time of 20 - 120 min.

[0028] A passivation layer is provided between the electron transport layer and the perovskite layer, and / or between the hole transport layer and the perovskite layer.

[0029] The material of the passivation layer may include one or several of CsBr, CsI, and PbBr2, or may also include other materials that meet the passivation requirements. The present invention does not make specific limitations.

[0030] A perovskite solar cell module is prepared by using the preparation method of a perovskite solar cell module described above.

[0031] The technical solution of the present invention has the following advantages:

[0032] 1. A preparation method of a perovskite solar cell module provided by the present invention, wherein the perovskite layer is prepared by coating, and the region where the hole transport layer is located is divided into several regions to form a half cell A by scribing, and the region where the electron transport layer is located is divided into several regions to form a half cell B, and then the half cell A and the half cell B are overlapped and annealed to form a battery module. Since the perovskite layer is divided into several regions by scribing in the present invention, compared with the preparation of traditional large-area battery modules, the perovskite solar cell module prepared by the method of the present invention has a higher error tolerance. Even if the large-area coating method is directly adopted, the preparation of the perovskite layer can be effectively realized. Therefore, the preparation efficiency is significantly improved, the cost is reduced, and a larger-area perovskite solar cell module can be efficiently prepared. At the same time, since the perovskite solar cell module prepared by the method of the present invention does not require fine adjustment during scribing, the module prepared by it can be easily expanded to a larger area, greatly simplifying the preparation process and having stronger industrialization potential. Moreover, the method of the present invention only needs to perform one-time laser scribing on the perovskite layer. Compared with the method that requires three times of scribing in the preparation of traditional battery modules, it is not only simpler in operation, but also less damaging to the battery. At the same time, a double-sided module can be prepared by the present invention, which can better utilize solar light and has a higher overall power generation efficiency. In summary, the method of the present invention can effectively maintain the performance of the battery module while increasing the preparation area and efficiency, obtaining a better photoelectric conversion efficiency, and the effect is remarkable.

[0033] 2. In the preparation method provided by the present invention, the conductive substrates used for the half cell A and the half cell B have the same specifications, and the widths of the blank regions therein are the same; the areas of the several regions formed by the laser scribing are also the same; since the half cells are prepared on the same specifications and the specifications of the regions constituting the sub-cells are the same, it is possible to quickly overlap each region in the half cell one by one without worrying about misalignment problems, and the preparation process is faster and simpler. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0035] Figure 1 It is the process flow chart prepared by the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The following embodiments are provided to better understand the present invention further. It is not limited to the described optimal embodiment, and does not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other existing technologies falls within the protection scope of the present invention.

[0037] For those embodiments where specific experimental steps or conditions are not indicated, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0038] In the description of the present invention, it should be noted that the orientation or positional relationships indicated by the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0039] In the description of the present invention, it should be noted that unless otherwise clearly specified and limited, the terms "installation", "connection", and "coupling" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0040] In addition, the technical features involved in different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0041] Example 1

[0042] A preparation method of a perovskite solar cell module, comprising:

[0043] Preparing a scribed half-cell A and a scribed half-cell B on FTO glass with a size of 5 cm × 5 cm respectively. Overlapping the scribed half-cell A and the scribed half-cell B with the perovskite surfaces facing each other and superposing them so that the scribed sub-cell parts completely coincide to form a complete cell structure, and then annealing it at 100 °C for 30 min under a pressure of 25 MPa to obtain the perovskite solar cell module.

[0044] Among them, the structure of the half-cell A is: FTO / NiO x / Perovskite. The specific preparation process is as follows: Use FTO glass with a specification of 5 cm × 5 cm, and prepare NiO on the FTO glass by a conventional preparation method x hole transport layer, NiO x The thickness of the hole transport layer is 20 nm; then, a perovskite layer with a thickness of 300 nm is prepared on the NiO x hole transport layer by slot coating. Remove the hole transport layer and the perovskite layer on one side. The width of the removed hole transport layer and perovskite layer on this side is 0.7 cm. The area of the removed hole transport layer and perovskite layer is the blank area; then use a laser to scribe the area where the hole transport layer and the perovskite layer are located into several areas. The scribing direction is set from the side away from the blank area towards the side of the blank area. Each area after scribing forms a sub-cell. The number of sub-cells is 7, and the size of each sub-cell is 4.3 cm × 0.5 cm.

[0045] The structure of sub-cell B is: FTO / SnO2 / Perovskite. The specific preparation process is as follows: Use FTO glass with a specification of 5 cm × 5 cm, and prepare an SnO2 electron transport layer on the FTO glass by a conventional preparation method. The thickness of the SnO2 electron transport layer is 20 nm; then, a perovskite layer with a thickness of 300 nm is prepared on the SnO2 electron transport layer by slot coating. Remove the electron transport layer and the perovskite layer on one side. The width of the removed electron transport layer and perovskite layer on this side is 0.7 cm. The area of the removed electron transport layer and perovskite layer is the blank area; then use a laser to scribe the area where the electron transport layer and the perovskite layer are located into several areas. The scribing direction is set from the side away from the blank area towards the side of the blank area. Each area after scribing forms a sub-cell. The number of sub-cells is 7, and the size of each sub-cell is 4.3 cm × 0.5 cm.

[0046] Example 2

[0047] A preparation method of a perovskite solar cell module, comprising:

[0048] Prepare the scribed sub-cell A and sub-cell B on FTO glass with a size of 10 cm × 10 cm respectively. Overlap the scribed sub-cell A and sub-cell B with the perovskite surfaces facing each other and stack them so that the scribed sub-cell parts completely overlap to form a complete cell structure. Then, anneal it at 100 °C for 30 min under a pressure of 25 MPa to obtain a perovskite solar cell module.

[0049] Among them, the structure of sub-cell A is: FTO / NiO x / Perovskite. The specific preparation process is as follows: Use FTO glass with a specification of 10 cm × 10 cm, and prepare NiO on the FTO glass by a conventional preparation method x hole transport layer, NiO x The thickness of the hole transport layer is 20 nm; then, a perovskite layer with a thickness of 300 nm is prepared on the NiO x hole transport layer by slit coating. Remove the hole transport layer and the perovskite layer on one side. The width of the removed hole transport layer and perovskite layer on this side is 0.7 cm. The area where the hole transport layer and the perovskite layer are removed is the blank area; then use a laser to scribe the area where the hole transport layer and the perovskite layer are located into several areas. The scribing direction is set from the side far away from the blank area towards the side of the blank area. Each area after scribing forms a sub-cell. The number of sub-cells is 18, and the size of each sub-cell is 9.3 cm × 0.5 cm.

[0050] The structure of the half-cell B is: FTO / SnO2 / Perovskite. The specific preparation process is as follows: Use FTO glass with a specification of 10 cm × 10 cm, and prepare an SnO2 electron transport layer on the FTO glass by a conventional preparation method. The thickness of the SnO2 electron transport layer is 20 nm; then, a perovskite layer with a thickness of 300 nm is prepared on the SnO2 electron transport layer by slit coating. Remove the electron transport layer and the perovskite layer on one side. The width of the removed electron transport layer and perovskite layer on this side is 0.7 cm. The area where the electron transport layer and the perovskite layer are removed is the blank area; then use a laser to scribe the area where the electron transport layer and the perovskite layer are located into several areas. The scribing direction is set from the side far away from the blank area towards the side of the blank area. Each area after scribing forms a sub-cell. The number of sub-cells is 18, and the size of each sub-cell is 9.3 cm × 0.5 cm.

[0051] Example 3

[0052] The difference between this example and Example 2 is that ITO glass is used to replace FTO glass, and the specification of the ITO glass is 15 cm × 15 cm; under this specification, the width of the blank area on the ITO glass is 0.8 cm; the number of sub-cells is set to 17, and the size of each sub-cell is 14.2 cm × 0.8 cm.

[0053] Example 4

[0054] The difference between this embodiment and Embodiment 2 is that the material of the hole transport layer is Cu2O, and the material of the electron transport layer is TiO2. A passivation layer made of CsBr with a thickness of 10 nm prepared by a conventional method is also provided between the hole transport layer and the perovskite layer, and between the electron transport layer and the perovskite layer.

[0055] Embodiment 5

[0056] The difference between this embodiment and Embodiment 2 is that in this embodiment, annealing treatment is carried out in a DMF solvent atmosphere instead of heating at 100 °C for 30 min under a pressure of 25 MPa to achieve annealing. The specific process of annealing treatment in a DMF solvent atmosphere is as follows: After overlapping the scribed half-cell A and half-cell B, the whole is placed in a gas atmosphere containing DMF (dimethylformamide) solvent with a concentration of 15 mL / m 3 The gas atmosphere can be air or preferably an inert gas; in this embodiment, an air atmosphere containing 15 mL / m 3 of DMF is used, and annealing is carried out at 100 °C for 30 min to obtain a complete perovskite solar cell module.

[0057] Embodiment 6

[0058] The difference between this embodiment and Embodiment 2 is that in this embodiment, annealing treatment is carried out in a DMF solvent atmosphere instead of heating at 100 °C for 30 min under a pressure of 25 MPa to achieve annealing. Specifically, the specific process of annealing treatment in a DMF solvent atmosphere is as follows: After overlapping the scribed half-cell A and half-cell B, the whole is placed in a gas atmosphere containing DMF (dimethylformamide) solvent with a concentration of 1 mL / m 3 The gas atmosphere can be air or preferably an inert gas; in this embodiment, an air atmosphere containing 1 mL / m 3 of DMF is used, and annealing is carried out at 120 °C for 120 min to obtain a complete perovskite solar cell module.

[0059] Embodiment 7

[0060] The difference between this embodiment and Embodiment 2 is that the coating method is different in this embodiment. In this embodiment, the doctor blade coating method is used instead of the slot die coating method. The thickness of the perovskite layer after doctor blade coating is the same as that in Embodiment 2, and other steps are also the same as those in Embodiment 2.

[0061] Embodiment 8

[0062] The difference between this embodiment and Embodiment 2 is that the thicknesses of each layer in this embodiment are different. In this embodiment, the total thickness of the perovskite layer is 400 nm, that is, the thickness of the perovskite layer in half-cell A is 200 nm, and the thickness of the perovskite layer in half-cell B is 200 nm; the thickness of the hole transport layer is 10 nm, and the thickness of the electron transport layer is 10 nm. Others are the same as those in Embodiment 2.

[0063] Example 9

[0064] The difference between this embodiment and Embodiment 2 is that the thicknesses of each layer in this embodiment are different. In this embodiment, the total thickness of the perovskite layer is 1000 nm, that is, the thickness of the perovskite layer in half-cell A is 500 nm, and the thickness of the perovskite layer in half-cell B is 500 nm; the thickness of the hole transport layer is 50 nm, and the thickness of the electron transport layer is 50 nm. Others are the same as those in Embodiment 2.

[0065] Example 10

[0066] The difference between this embodiment and Embodiment 2 is that the annealing parameters in this embodiment are different. In this embodiment, the hot pressing treatment conditions are: pressure 15 MPa, temperature 120 °C, time 100 min, and others are the same as those in Embodiment 2.

[0067] Example 11

[0068] The difference between this embodiment and Embodiment 2 is that in this embodiment, only the perovskite layer is coated in half-cell A, and the coating thickness is 600 nm, and the perovskite layer is not coated in half-cell B; other process steps and parameters are exactly the same as those in Embodiment 2.

[0069] Comparative Example 1

[0070] The difference between this comparative example and Embodiment 2 is that in the preparation process of half-cell A and half-cell B, the perovskite layer is prepared by vacuum evaporation, and laser scribing is not performed in this comparative example, and others are exactly the same as the preparation steps in Embodiment 2.

[0071] Experimental Example

[0072] Perform performance tests on the solar cell modules prepared in the above embodiments and comparative examples, including open-circuit voltage (Voc), power conversion efficiency (PCE), fill factor (FF), short-circuit current (Jsc), area (Area), series internal resistance (Rs), parallel internal resistance (Rsh), etc. The test results are shown in Table 1 below.

[0073] Table 1

[0074]

[0075]

[0076] It can be seen from the results in Table 1 above that: in Examples 1 to 3, even though the area increased significantly, the photoelectric conversion efficiency of the perovskite solar cell modules prepared by the method of the present invention did not decrease significantly, and it had good performance in terms of open circuit voltage (Voc), fill factor (FF), short circuit current (Jsc), series internal resistance (Rs), parallel internal resistance (Rsh), etc. By comparing Example 2 with Comparative Example 1, even though the perovskite layer was prepared by vacuum evaporation with fewer defects in Comparative Example 1, the performance of the prepared battery was significantly worse than that of Example 2, which proved that the method of the present invention could effectively improve the performance of the prepared perovskite solar cell modules, with remarkable effects; and compared with the preparation process of the existing battery modules, the method of the present invention was simpler and more time-saving in the preparation process, greatly improving the preparation effect of the perovskite solar cell modules. In Examples 4 to 11, at the same area, different process parameters, thicknesses, structures and materials had an impact on the performance, but compared with Comparative Example 2, the performance was also significantly improved, which proved that the method of the present invention was applicable to the performance improvement of perovskite solar cell modules under various process parameters, materials, thicknesses and materials.

[0077] Obviously, the above examples are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or alterations can be made on the basis of the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or alterations derived therefrom are still within the protection scope of the present invention.

Claims

1. A preparation method of a perovskite solar cell module, characterized in that, Including: Preparing a hole transport layer on the surface of a first conductive substrate; Preparing an electron transport layer on the surface of a second conductive substrate; Coating a perovskite layer on the surface of the hole transport layer and / or the electron transport layer; Scoring the area where the hole transport layer is located into several regions to obtain a half cell A; Scoring the area where the electron transport layer is located into several regions corresponding one by one to the half cell A to obtain a half cell B; Overlapping the half cell A and the half cell B, and making the scratches scored on the half cell A and the half cell B coincide to obtain a coincidence assembly; Annealing the coincidence assembly to obtain a battery assembly.

2. The preparation method according to claim 1, characterized in that, One side of the first conductive substrate and the second conductive substrate includes a blank area, and after overlapping, the blank area on the half cell A and the blank area on the half cell B are located on opposite sides of the coincidence assembly; The scoring direction is from the side away from the blank area towards the side of the blank area.

3. The preparation method according to claim 2, wherein The conductive substrates of the half cell A and the half cell B have the same specifications, and the widths of the blank areas are also the same; the width of the blank area is 0.3 - 1 cm.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The total thickness of the perovskite layer is 400 - 1000 nm, the thickness of the hole transport layer is 10 - 50 nm, and the thickness of the electron transport layer is 10 - 50 nm.

5. The preparation method according to any one of claims 1 - 4, wherein The areas of the several regions formed by scoring on the half cell A and the half cell B are the same; The scoring method is laser etching, and the film layers laser-etched on the coincidence assembly include: a conductive substrate, a perovskite layer, a hole transport layer, and an electron transport layer.

6. The preparation method according to any one of claims 1 to 5, characterized in that, The annealing method includes at least one of hot pressing and heating in a gas atmosphere containing the solvent of the perovskite precursor solution.

7. The preparation method according to claim 6, characterized in that, The conditions of the hot pressing include: a pressure of 15 - 25 MPa, a temperature of 90 - 120 °C, and a time of 20 - 120 min.

8. The preparation method according to claim 6, characterized in that, The solvent of the perovskite precursor solution includes at least one of DMF and DMSO; The conditions for heating in the gas atmosphere containing the solvent used in the perovskite precursor solution include: the concentration of the solvent used in the perovskite precursor solution in the container is 1 to 15 mL / m 3 , the temperature is 90 to 120 °C, and the time is 20 to 120 min.

9. The preparation method according to any one of claims 1 to 8, characterized in that, A passivation layer is provided between the electron transport layer and the perovskite layer, and / or between the hole transport layer and the perovskite layer.

10. A perovskite solar cell module, characterized in that, Prepared by using the preparation method of a perovskite solar cell assembly according to any one of claims 1 - 9.

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