Annealing preparation method for large-area perovskite solar cell modules

Abstract

This invention proposes an annealing preparation method for large-area perovskite solar cell modules, comprising the following steps: S1: preparation of modification layer one; S2: preparation of the perovskite layer; S3: annealing of the perovskite layer: placing the perovskite layer from S2 on a laminator, covering the perovskite layer with a clean PET film, allowing the solvent that has not completely evaporated to remain on the lower surface of the PET film and form solvent annealing with the perovskite layer to improve the upper surface of the perovskite layer; S4: after lamination, removing the PET film, and blowing dry gas onto the perovskite surface to completely evaporate the solvent; S5: preparation of modification layer two; S6: preparation of the back electrode. This method solves the problem of uneven annealing caused by easy deformation of the hot plate annealing glass in large-area modules, improves product reliability, and improves interface transport, extending the lifespan of the module, resulting in a high-efficiency, high-reliability product, and overall enhancing the product's market competitiveness.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic technology, and in particular to an annealing preparation method for large-area perovskite solar cell modules. Background Technology

[0002] This invention relates to a novel annealing and crystallization process for large-area perovskite solar cell modules. Traditional energy sources such as coal and oil will eventually be depleted, while clean and renewable energy sources such as solar, wind, and tidal power will gradually replace traditional energy sources to meet people's ever-increasing energy demands. Perovskite solar cells, as a new type of solar cell, have advantages such as simple fabrication, low cost, high conversion efficiency, and the ability to fabricate flexible modules, and are expected to gradually replace currently commercialized silicon solar cells. Currently, the efficiency of small-area perovskite solar cell devices in the laboratory has exceeded 25%, but the fabrication of large-size perovskite solar cell modules still faces some difficulties, and the annealing process is one of the challenges in fabricating large-area perovskite solar cell modules. The mainstream annealing process for small-area perovskite devices generally uses hot-plate annealing, while some literature uses microwave, ultraviolet, and infrared annealing methods. For large-area batteries, hot plates face the problem of uneven heating due to glass deformation. Microwave, ultraviolet, and infrared heating also have the effects of uneven heating and reduced stability. Existing large-area annealing processes all use tunnel furnaces and layered furnaces. Tunnel furnace and layered furnace annealing heats the perovskite surface, which can easily leave solvent residues in the perovskite layer, resulting in suboptimal results. To address these issues, we have developed a new annealing process that achieves uniform annealing and better crystallinity in large-area perovskite layers. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention proposes an annealing preparation method for large-area perovskite solar cell modules, comprising the following steps:

[0004] S1: Preparation of modification layer one;

[0005] S2: Preparation of the perovskite layer: The perovskite precursor solution is uniformly coated onto the first modification layer, and the surface of the perovskite layer is initially dried;

[0006] S3: Annealing of the perovskite layer: Place the perovskite layer from S2 on a laminator, cover the perovskite layer with a clean PET film, so that the solvent that has not completely evaporated remains on the lower surface of the PET and forms solvent annealing with the perovskite layer to improve the upper surface of the perovskite layer.

[0007] S4: After lamination, remove the PET film and blow dry gas onto the perovskite surface to completely evaporate the solvent;

[0008] S5: Preparation of modified layer two;

[0009] S6: Preparation of back electrode: It is prepared on the modification layer 2 by one or more of the following deposition methods, including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, and atomic layer deposition.

[0010] Preferably, in S2, the surface of the perovskite layer is initially dried by one or more of the following methods: vacuum flash evaporation and air knife method.

[0011] Preferably, the lamination temperature in S3 is 120-150℃ and the lamination time is 15-30min.

[0012] Preferably, the modification layer is prepared on transparent conductive glass by one of the following deposition methods: magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, atomic layer deposition, slot coating, or spraying.

[0013] Preferably, the first modification layer is an electron transport layer or a hole transport layer, and the second modification layer is a hole transport layer or an electron transport layer.

[0014] Preferably, the first modification layer is an electron transport layer or a hole transport layer, and the second modification layer is a hole transport layer or an electron transport layer. When the first modification layer is an electron transport layer, the second modification layer is a hole transport layer, and when the first modification layer is a hole transport layer, the second modification layer is an electron transport layer.

[0015] Preferably, the electron transport layer comprises one of PCBM, TiO2, SnO2, ZnO, and Nb2O5.

[0016] Preferably, the hole transport layer comprises one of NiO, Spiro-OMeTAD, CuGaO2, CuSCN, P3HT, and PEDOT:PSS.

[0017] Preferably, the perovskite layer comprises one of MAPbI3, FAPbI3, FAMAPbI3, FACsPbI3, and FAMACsPbI3.

[0018] Preferably, the solvent is one or a combination of DMF, DMSO, NMP, and γ-GBL.

[0019] The back electrode includes, but is not limited to, one or a combination of gold, silver, copper, metal oxides such as ITO and IWO, silver nanowires, and transparent conductive polymer materials.

[0020] The annealing preparation method for large-area perovskite solar cell modules proposed in this invention has the following beneficial effects: it solves the problem of uneven annealing caused by easy deformation of the glass during hot plate annealing of large-area modules, improves the reliability of the product, and solvent annealing improves the interface transport, extends the service life of the module, forms a high-efficiency and high-reliability product, and enhances the overall market competitiveness of the product. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below.

[0022] Figure 1 The figures show experimental data of MPPT for embodiments and comparative examples of the present invention. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0024] The fabrication processes of the electron transport layer, hole transport layer, and perovskite layer involved in this case are methods disclosed by the applicant in prior applications. For details, please refer to the following listed patents: CN112054123A, CN114220921A, CN113611804A, CN112259629A, CN112038492A, and other patent documents disclosed by the applicant. Therefore, the specific steps will not be repeated in this embodiment, and only the method names will be used for description. Example

[0025] This invention proposes an annealing preparation method for large-area perovskite solar cell modules, comprising the following steps:

[0026] S1: Preparation of Modification Layer 1: This layer was prepared on conductive glass using magnetron sputtering. The conductive glass selected was FTO glass, forming a hole transport layer. The hole transport layer was NIO. X .

[0027] S2: Preparation of the perovskite layer: The perovskite precursor solution FAMACsPbI3 was uniformly coated onto the first modification layer by a blade coating method, and then the perovskite layer was initially dried by vacuum flash evaporation to form an active layer of intermediate phase.

[0028] S3: Annealing of the perovskite layer: The conductive glass with the perovskite layer from S2 and the first modification layer is placed on a laminator. A clean PET film is then placed over the pre-dried perovskite layer, allowing any remaining solvent to remain on the lower surface of the PET film, forming a solvent annealing process that improves the upper surface of the perovskite layer. Lamination is then performed at 120°C for 15 minutes. The clean PET film is used to prevent contamination of the perovskite layer from contact with the upper surface of the laminator and to block solvent evaporation, allowing any remaining solvent to remain on the lower surface of the PET film, forming a solvent annealing process that improves the upper surface of the perovskite layer. This process allows for hot-plate annealing of large-area perovskite layers without glass deformation. Covering with the PET film allows the solvent to remain on the perovskite surface (the lower surface of the PET film) after evaporation, achieving the purpose of solvent annealing. The perovskite surface is then evaporated completely using methods including, but not limited to, a blower, dry compressed air, or inert gas.

[0029] S4: After lamination, remove the PET film and blow the perovskite surface with a blower, dry compressed air, inert gas, or other means to completely evaporate the solvent.

[0030] S5: Preparation of the second modification layer; the second modification layer is an electron transport layer, which is formed by coating PCBM onto the perovskite layer using a blade coating method.

[0031] S6: Preparation of back electrode: The back electrode is prepared on the modified layer 2 by one or more of the following deposition methods, including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, and atomic layer deposition. The back electrode is included, but is not limited to one or more of the following materials: gold, silver, copper, metal oxides such as ITO and IWO, silver nanowires, and transparent conductive polymer materials. In this embodiment, ITO is selected.

[0032] Example 2

[0033] This invention proposes an annealing preparation method for large-area perovskite solar cell modules, comprising the following steps:

[0034] S1: Preparation of the first modification layer: It is prepared on conductive glass by thermal evaporation. The conductive glass selected is FTO glass, which forms an electron transport layer. The electron transport layer is SNO2.

[0035] S2: Preparation of the perovskite layer: The perovskite precursor solution FAMAPbI3 is uniformly coated onto the first modification layer by a blade coating method, and then the perovskite layer is initially dried by vacuum flash evaporation to form an active layer of intermediate phase.

[0036] S3: Annealing of the perovskite layer: The conductive glass with the perovskite layer and decorative layer from S2 is placed on a laminator. A clean PET film is placed over the perovskite layer, allowing any remaining solvent to remain on the lower surface of the PET film, forming a solvent annealing process with the perovskite layer to improve the upper surface of the perovskite layer. Lamination is then performed at 150°C for 20 minutes. A clean PET film is used to prevent the perovskite layer from contacting the upper surface of the laminator and to block solvent evaporation, allowing any remaining solvent to remain on the lower surface of the PET film, thus forming a solvent annealing process with the perovskite layer to improve the upper surface of the perovskite layer. This process allows for hot-plate annealing of large-area perovskite layers without glass deformation. Covering with a PET film allows the solvent to remain on the perovskite surface (the lower surface of the PET film) after evaporation, achieving the purpose of solvent annealing. The perovskite surface is then evaporated completely using methods including, but not limited to, a blower, dry compressed air, or inert gas.

[0037] S4: After lamination, remove the PET film and blow the perovskite surface with a blower, dry compressed air, inert gas, or other means to completely evaporate the solvent.

[0038] S5: Preparation of the second modification layer; the second modification layer is a hole transport layer, and Spiro-OMeTAD is coated onto the perovskite layer by a slit coating method.

[0039] S6: Preparation of back electrode: The back electrode is prepared on the modified layer 2 by one or more of the following deposition methods, including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, atomic layer deposition, etc. The back electrode is included in, but is not limited to, one or more of the following materials, including gold, silver, copper, metal oxides such as ITO and IWO, silver nanowires, transparent conductive polymer materials, etc. In this embodiment, silver is selected.

[0040] Comparative Example

[0041] In this embodiment, the materials and processes for preparing the perovskite component are the same as in Example 1. The difference is that the methods in S3 and S4 are replaced by layer furnace annealing at a temperature of 120°C for 15 minutes.

[0042] The perovskite solar cell modules prepared through the above embodiments were subjected to MPPT (Power Performance Tracking) tests. It can be seen that, under the same conditions, the initial efficiency and stability of the embodiments are better than those of the comparative examples. The annealing method described herein improves the stability and efficiency of the perovskite modules, as detailed in the attached figures.

Claims

1. An annealing preparation method for a large-area perovskite solar cell module, characterized in that, Includes the following steps: S1: Preparation of modification layer one; S2: Preparation of the perovskite layer: The perovskite precursor solution is uniformly coated onto the first modification layer, and the surface of the perovskite layer is initially dried; S3: Annealing of the perovskite layer: Place the perovskite layer from S2 on a laminator and cover it with a clean PET film to prevent solvent evaporation. This allows the remaining solvent to remain on the lower surface of the PET film and form solvent annealing with the perovskite layer to improve the upper surface of the perovskite layer. S4: After lamination, remove the PET film and blow dry gas onto the perovskite surface to completely evaporate the solvent; S5: Preparation of modified layer two; S6: Preparation of back electrode: It is prepared on modification layer two by one or a combination of deposition methods including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, and atomic layer deposition.

2. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, In S2, the surface of the perovskite layer is initially dried by one or more of the following methods: vacuum flash evaporation and air knife method.

3. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, The lamination temperature in S3 is 120-150℃, and the lamination time is 15-30min.

4. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, The modification layer is prepared on transparent conductive glass by one of the following deposition methods: magnetron sputtering, thermal evaporation, reactive ion deposition, vapor deposition, atomic layer deposition, slot coating, or spraying.

5. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, The first modification layer is an electron transport layer or a hole transport layer, and the second modification layer is a hole transport layer or an electron transport layer. When the first modification layer is an electron transport layer, the second modification layer is a hole transport layer, and when the first modification layer is a hole transport layer, the second modification layer is an electron transport layer.

6. The annealing preparation method for a large-area perovskite solar cell module according to claim 5, characterized in that, The electron transport layer includes one of PCBM, TiO2, SnO2, ZnO, and Nb2O5.

7. The annealing preparation method for a large-area perovskite solar cell module according to claim 5, characterized in that, The hole transport layer includes one of NiO, Spiro-OMeTAD, CuGaO2, CuSCN, P3HT, and PEDOT:PSS.

8. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, The perovskite layer includes one of MAPbI3, FAPbI3, FAMAPbI3, FACsPbI3, and FAMACsPbI3.

9. The annealing preparation method for a large-area perovskite solar cell module according to claim 1, characterized in that, The solvent is one or a combination of DMF, DMSO, NMP, and γ-GBL.

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