Preparation method of perovskite solar cell scraped and coated by multi-component solvent

Abstract

The invention discloses a preparation method of a perovskite solar cell scraped by a multi-component solvent. The preparation method comprises the following steps: S1, scrape-coating a hole transport layer on a conductive substrate; s2, sequentially blade-coating a perovskite active layer and an electron transport layer on the hole transport layer; s3, sequentially arranging a cathode modification layer and an electrode layer on the electron transport layer; and a solvent for forming the electron transport layer is selected from at least two of orthodichlorobenzene, chlorobenzene and chloroform. According to the invention, the PCBM electron transport layer is prepared by using the composite solvent, so that the problem of coffee ring effect caused by rapid volatilization of a single solvent is solved, the film forming uniformity of PCBM is improved, and the power conversion efficiency of the perovskite solar cell is improved; and meanwhile, the PCBM electron transport layer is prepared by adopting a blade coating process, so that the problem of PCBM agglomeration is solved, and the power conversion efficiency of the perovskite solar cell is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of perovskite solar cells, and in particular relates to a method for preparing a perovskite solar cell by scraping with multiple solvents. Background Art

[0002] Solar energy, as a renewable energy source, is a key energy source for meeting the world's growing energy needs. Solar cells, which directly convert light energy into electricity through the photoelectric effect or photochemical reaction, are the technological foundation for the widespread application of solar photovoltaic power generation. Perovskite solar cells, among others, have attracted worldwide attention as a promising new photovoltaic device.

[0003] Perovskite solar cells mainly include a substrate layer, a hole transport layer, a perovskite active layer, an electron transport layer, and an electrode layer. The preparation of the electron transport layer plays an important role in the extraction and transport of charge carriers and in suppressing carrier recombination. Therefore, the electron transport layer is a research hotspot in the field of perovskite solar cells.

[0004] PCBM is a commonly used electron transport layer material. Existing technologies often use a single solvent to dissolve PCBM, but this often results in a coffee ring effect due to rapid solvent evaporation. Furthermore, existing technologies typically use spin coating to prepare the electron transport layer. However, when using PCBM as the electron transport layer material, spin coating often causes PCBM agglomeration, which in turn affects the power conversion efficiency of perovskite solar cells. Summary of the Invention

[0005] In response to the shortcomings of the existing technology, the present invention provides a method for preparing a perovskite solar cell by scraping with multiple solvents. The present invention adopts a composite solvent to prepare the PCBM electron transport layer, thereby solving the problem of the coffee ring effect caused by the rapid volatilization of a single solvent, improving the film formation uniformity of the PCBM, and increasing the power conversion efficiency of the perovskite solar cell. At the same time, the PCBM electron transport layer is prepared by a scraping process, which solves the problem of PCBM agglomeration and effectively improves the power conversion efficiency of the perovskite solar cell.

[0006] The object of the present invention is to provide a method for preparing a perovskite solar cell by scraping with a multi-solvent coating, comprising the following steps:

[0007] S1. Coating a hole transport layer on a conductive substrate;

[0008] S2. coating the perovskite active layer and the electron transport layer on the hole transport layer in sequence;

[0009] S3. A cathode modification layer and an electrode layer are sequentially provided on the electron transport layer;

[0010] The solvent for forming the electron transport layer is selected from at least two of o-dichlorobenzene, chlorobenzene, and chloroform.

[0011] In some embodiments of the present invention, the solvent for forming the electron transport layer is selected from o-dichlorobenzene and chlorobenzene in a volume ratio of 0.8-1.2:8.8-9.2.

[0012] In some embodiments of the present invention, the solvent for forming the electron transport layer is selected from chloroform and chlorobenzene in a volume ratio of 0.8-1.2:8.8-9.2.

[0013] In some embodiments of the present invention, the solvent for forming the electron transport layer is selected from chloroform, chlorobenzene, and o-dichlorobenzene in a volume ratio of 0.4-0.6:8.8-9.2:0.4-0.6.

[0014] In some embodiments of the present invention, in S1, the material of the hole transport layer is 2MeO-PTAA doped with MeO-2Pacz.

[0015] In some embodiments of the present invention, in S1, the speed of the scraping is 3-7 mm / s.

[0016] In some embodiments of the present invention, in S1, the annealing temperature of the blade coating is 80-120° C., and the annealing time is 5-15 min.

[0017] In some embodiments of the present invention, the doping amount of MeO-2Pacz in the MeO-2Pacz-doped 2MeO-PTAA is 3-7% based on the mass percentage of the material of the hole transport layer.

[0018] In some embodiments of the present invention, the doping amount of MeO-2Pacz in the MeO-2Pacz-doped 2MeO-PTAA is 4-6% based on the mass percentage of the material of the hole transport layer.

[0019] In some embodiments of the present invention, in S1, before coating the hole transport layer on the conductive substrate, the conductive substrate is further cleaned and subjected to ultraviolet ozone treatment.

[0020] In some embodiments of the present invention, in S1, the concentration of the solution forming the hole transport layer is 1-4 mg / ml.

[0021] In some embodiments of the present invention, in S1, the thickness of the hole transport layer is 10-35 nm, including but not limited to 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, and 35 nm.

[0022] In some embodiments of the present invention, in S1, the solvent for forming the hole transport layer is selected from chlorobenzene and tetrahydrofuran in a volume ratio of 8.5-9.5:0.5-1.5.

[0023] In some embodiments of the present invention, in S1, scraping the hole transport layer on the conductive substrate specifically includes the following steps: preparing a hole transport layer solution, evenly scraping the hole transport layer solution on the conductive substrate at a scraping speed of 3-7 mm / s, and annealing at 80-120° C. for 5-15 minutes after the scraping is completed.

[0024] In some embodiments of the present invention, the preparation of the hole transport layer solution comprises the following steps: dissolving 2MeO-PTAA doped with MeO-2Pacz in chlorobenzene and shaking until completely dissolved to obtain a hole transport layer solution of 1-4 mg / ml.

[0025] In some embodiments of the present invention, in S2, the material of the perovskite active layer is selected from FA 0.98 Cs 0.02 PbI3.

[0026] In some embodiments of the present invention, in S2, the material of the electron transport layer is selected from PCBM.

[0027] In some embodiments of the present invention, in S2, the concentration of the solution for forming the electron transport layer is 15-25 mg / ml.

[0028] In some embodiments of the present invention, in S2, the thickness of the perovskite active layer is 300-500 nm, including but not limited to 300 nm, 350 nm, 400 nm, 450 nm, and 500 nm.

[0029] In some embodiments of the present invention, in S2, the thickness of the electron transport layer is 10-60 nm; including but not limited to 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm

[0030] In some embodiments of the present invention, in S2, the scraping speed of scraping the perovskite active layer on the hole transport layer is 3-7 mm / s.

[0031] In some embodiments of the present invention, in S2, the coating speed of the electron transport layer on the perovskite active layer is 15-25 mm / s.

[0032] In some embodiments of the present invention, in S2, the annealing temperature for coating the perovskite active layer on the hole transport layer is 80-120° C., and the annealing time is 50-70 min.

[0033] In some embodiments of the present invention, in S2, the step of scraping a perovskite active layer on the hole transport layer comprises the following steps: preparing a perovskite precursor solution, scraping the perovskite layer solution on the hole transport layer, and annealing at 80-120° C. for 50-70 min after scraping.

[0034] In some embodiments of the present invention, in S2, the solvent for forming the perovskite active layer is selected from N-methylpyrrolidone and 2-methoxyethanol in a volume ratio of 0.06-0.10:0.90-0.94.

[0035] In some embodiments of the present invention, in S3, the material of the cathode modification layer is BCP.

[0036] In some embodiments of the present invention, in S3, the material of the electrode layer is Ag.

[0037] In some embodiments of the present invention, in S3, the thickness of the cathode modification layer is 1-10 nm, including but not limited to 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, and 10 nm.

[0038] In some embodiments of the present invention, in S3, the thickness of the electrode layer is 70-120 nm, including but not limited to 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, 115 nm, and 120 nm.

[0039] Another object of the present invention is to provide a perovskite solar cell, which is prepared by the preparation method of the perovskite solar cell by multi-solvent blade coating.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) The present invention adopts a composite solvent to prepare the PCBM electron transport layer, thereby solving the problem of the coffee ring effect caused by the rapid volatilization of a single solvent, improving the film formation uniformity of PCBM, and improving the power conversion efficiency of perovskite solar cells.

[0042] (2) The present invention adopts a scraping process to prepare the PCBM electron transport layer, which solves the problem of PCBM agglomeration and effectively improves the power conversion efficiency of perovskite solar cells.

[0043] (3) The present invention adopts a scraping process when preparing the hole transport layer and the perovskite active layer, which effectively improves the power conversion efficiency of the perovskite solar cell.

[0044] (4) The hole transport layer material of the present invention adopts 2MeO-PTAA doped with MeO-2Pacz, which effectively improves the power conversion efficiency of the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Schematic diagram of the structure of the perovskite solar cell of the present invention. DETAILED DESCRIPTION

[0046] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0047] MeO-2Pacz is 2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl phosphate;

[0048] The structure of 2MeO-PTAA is shown below:

[0049] ;

[0050] Among them, the number average molecular weight is 11317 g / mol and the PDI is 1.9.

[0051] Example 1

[0052] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0053] S1. Ultrasonic cleaning of a rigid glass substrate. A flexible PET substrate coated with an anode material, ITO, is then bonded to the rigid glass substrate using UV-curable adhesive and cured to obtain a pretreated substrate. P1 laser scribing is performed on the pretreated substrate to form multiple small subunits.

[0054] S2. 5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz. The 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was then scraped onto the substrate after etching P1 at a scraping speed of 5 mm / s. The solution was annealed at 100°C for 10 min and then cooled to room temperature to obtain a 20 nm hole transport layer.

[0055] S3. 280 mg PbI2, 84.1 mg FAI, 5.2 mg MACl, and 2.6 mg CsI were dissolved in 600 μl N-methylpyrrolidone (NMP) and 2-methoxyethanol (2-Me) solution, where the volume ratio of NMP to 2-Me was 0.08:0.92. The mixture was stirred at room temperature for 2.5 hours to prepare a perovskite precursor solution (FA 0.98 Cs 0.02 PbI3). The substrate with the hole transport layer was moved into a low-temperature vacuum glove box, and the perovskite precursor solution was coated on the hole transport layer by blade coating at a rate of 5 mm / s. The solution was then heated at 100°C for 60 min for annealing to obtain a 400 nm perovskite layer, i.e., the perovskite active layer.

[0056] S4. 20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and stirred for 24 hours to form a 20 mg / ml PCBM solution. The PCBM solution was then applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer.

[0057] S5. BCP was evaporated onto the electron transport layer by thermal evaporation under vacuum to obtain a 5 nm cathode modification layer;

[0058] S6. Under vacuum, laser scribe the P2 and P3 lines on the device after the cathode modification layer is evaporated, and cathode material Ag is evaporated onto the device after the P2 and P3 lines are scribed by thermal evaporation. The thickness of the Ag electrode is 100 nm.

[0059] Example 2

[0060] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0061] S1. Ultrasonic cleaning of a rigid glass substrate. A flexible PET substrate coated with an FTO anode material is then bonded to the rigid glass substrate using UV-curable adhesive and cured to obtain a pretreated substrate. P1 laser scribing is performed on the pretreated substrate to form multiple small subunits.

[0062] S2. 5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 8.5:1.5 to obtain a 1 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz. The 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was then applied to the substrate after etching P1 by scraping at a speed of 3 mm / s. The solution was annealed at 120°C for 5 min and then cooled to room temperature to obtain a 10 nm hole transport layer.

[0063] S3. 280 mg PbI2, 84.1 mg FAI, 5.2 mg MACl, and 2.6 mg CsI were dissolved in 600 μl N-methylpyrrolidone (NMP) and 2-methoxyethanol (2-Me) solution, where the volume ratio of NMP to 2-Me was 0.06:0.94. The mixture was stirred at room temperature for 2.5 hours to prepare a perovskite precursor solution (FA 0.98 Cs 0.02 PbI3). The substrate with the hole transport layer was moved into a low-temperature vacuum glove box, and the perovskite precursor solution was coated on the hole transport layer by a doctor blade method at a rate of 7 mm / s. The solution was then heated at 80°C for 70 min for annealing to obtain a 500 nm thick perovskite layer, i.e., the perovskite active layer.

[0064] S4. 15 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 0.8:9.2, and stirred for 24 hours to form a 15 mg / ml PCBM solution. The PCBM solution was applied by a doctor blade at a rate of 25 mm / s to obtain a 10 nm electron transport layer.

[0065] S5. BCP was deposited onto the electron transport layer by thermal evaporation under vacuum to obtain a 10 nm cathode modification layer;

[0066] S6. Under vacuum, laser scribe the P2 and P3 lines on the device after the cathode modification layer is evaporated, and cathode material Ag is evaporated onto the device after the P2 and P3 lines are scribed by thermal evaporation. The thickness of the Ag electrode is 70nm.

[0067] Example 3

[0068] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0069] S1. Ultrasonic cleaning of a rigid glass substrate. A flexible PET substrate coated with an anode material, ITO, is then bonded to the rigid glass substrate using UV-curable adhesive and cured to obtain a pretreated substrate. P1 laser scribing is performed on the pretreated substrate to form multiple small subunits.

[0070] S2. 5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9.5:0.5 to obtain a 4 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz. The 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was then applied to the substrate after etching P1 at a scraping speed of 7 mm / s. The solution was annealed at 80°C for 15 min and then cooled to room temperature to obtain a 35 nm hole transport layer.

[0071] S3. 280 mg PbI2, 84.1 mg FAI, 5.2 mg MACl, and 2.6 mg CsI were dissolved in 600 μl N-methylpyrrolidone (NMP) and 2-methoxyethanol (2-Me) solution, where the volume ratio of NMP to 2-Me was 0.10:0.90. The mixture was stirred at room temperature for 2.5 hours to prepare a perovskite precursor solution (FA 0.98 Cs 0.02 PbI3). The substrate with the hole transport layer was moved into a low-temperature vacuum glove box, and the perovskite precursor solution was coated on the hole transport layer by a doctor blade method at a rate of 3 mm / s. The solution was then heated at 120°C for 50 min for annealing to obtain a 500 nm thick perovskite layer, i.e., the perovskite active layer.

[0072] S4. Dissolve 25 mg of PCBM in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene (volume ratio of o-dichlorobenzene to chlorobenzene:1.2:8.8). Stir for 24 hours to form a 25 mg / ml PCBM solution. Apply the PCBM solution using a doctor blade at a rate of 15 mm / s to obtain a 60 nm electron transport layer.

[0073] S5. BCP was evaporated onto the electron transport layer by thermal evaporation under vacuum to obtain a 1 nm cathode modification layer;

[0074] S6. Under vacuum, laser scribe the P2 and P3 lines on the device after the cathode modification layer is evaporated, and cathode material Ag is evaporated onto the device after the P2 and P3 lines are scribed by thermal evaporation. The thickness of the Ag electrode is 120 nm.

[0075] Example 4

[0076] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0077] In S2 of Example 1, "5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a scraping speed of 5 mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer" was replaced with "3 parts by mass of 2MeO-Pacz and 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a speed of 5 mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer" was replaced with "3 parts by mass of 2MeO-Pacz and 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz 97 parts by mass were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 3 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 3 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a scraping speed of 5 mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer. The other steps remained unchanged to obtain a perovskite solar cell.

[0078] Example 5

[0079] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0080] In S2 of Example 1, "5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a scraping speed of 5 mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer" was replaced with "7 parts by mass of 2MeO-Pacz and 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a ... 93 parts by mass were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 7 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 7 wt% 2MeO-Pacz was scraped on the substrate after etching P1 at a scraping speed of 5 mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer. The other steps remained unchanged to obtain a perovskite solar cell.

[0081] Example 6

[0082] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0083] In S2 of Example 1, the steps of “mixing 5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA, adding chlorobenzene and tetrahydrofuran in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; applying the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz on the substrate after etching P1 at a scraping speed of 5 mm / s, heating at 100°C for 10 min for annealing, and then naturally cooling to room temperature to obtain a 20 nm hole transport layer” are replaced with “adding chlorobenzene and tetrahydrofuran in a volume ratio of 9:1 to 100 parts by mass of 2MeO-Pacz to obtain a 2.5 mg / ml 2MeO-Pacz solution; applying the 2MeO-Pacz solution on the substrate after etching P1 at a scraping speed of 5 mm / s. mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer". Other steps remain unchanged to obtain a perovskite solar cell.

[0084] Example 7

[0085] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0086] In S2 of Example 1, the steps of "mixing 5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA, adding chlorobenzene and tetrahydrofuran in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; applying the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz on the substrate after etching P1 at a scraping speed of 5 mm / s, heating at 100°C for 10 min for annealing, and then naturally cooling to room temperature to obtain a 20 nm hole transport layer" are replaced with "adding chlorobenzene and tetrahydrofuran in a volume ratio of 9:1 to 100 parts by mass of 2MeO-PTAA to obtain a 2.5 mg / ml 2MeO-PTAA solution; applying the 2MeO-PTAA solution on the substrate after etching P1 at a scraping speed of 5 mm / s. mm / s, heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer". Other steps remain unchanged to obtain a perovskite solar cell.

[0087] Example 8

[0088] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0089] In S4 of Example 1, the following steps were replaced with “20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer”: “20 mg of PCBM was dissolved in 1 ml of a mixed solvent of chloroform and chlorobenzene, wherein the volume ratio of chloroform to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer”. The other steps remained unchanged to obtain a perovskite solar cell.

[0090] Example 9

[0091] This embodiment provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0092] In S4 of Example 1, the step “20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer” was replaced with “20 mg of PCBM was dissolved in 1 ml of a mixed solvent of chloroform, chlorobenzene, and o-dichlorobenzene, wherein the volume ratio of chloroform, chlorobenzene, and o-dichlorobenzene was 0.5:9:05, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer”. The other steps remained unchanged to obtain a perovskite solar cell.

[0093] Comparative Example 1

[0094] This comparative example provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0095] In S4 of Example 1, the following steps were replaced with “20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution. The PCBM solution was then applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer”: “20 mg of PCBM was dissolved in 1 ml of chlorobenzene, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution. The PCBM solution was then applied using a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer.” The other steps remained unchanged to obtain a perovskite solar cell.

[0096] Comparative Example 2

[0097] This comparative example provides a method for preparing a perovskite solar cell by scraping with a multi-solvent coating. The only difference from Example 1 is that "scraping the hole transport layer on the conductive substrate" is changed to "spin coating the hole transport layer on the conductive substrate". The details are as follows:

[0098] In S2 of Example 1, the phrase "5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped onto the substrate after etching P1 at a scraping speed of 5 mm / s, and the mixture was heated at 100°C for 10 min for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer" was replaced with "5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped onto the substrate after etching P1 at a speed of 5 mm / s, and the mixture was annealed at 100°C for 10 min, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer" was replaced with "5 parts by mass of 2MeO-Pacz and 95 parts by mass of 2MeO-PTAA were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was scraped onto the substrate after etching P1 at a speed of 5 mm / s, and the mixture was annealed at 1 95 parts by mass of the above-mentioned raw materials were mixed, and chlorobenzene and tetrahydrofuran were added in a volume ratio of 9:1 to obtain a 2.5 mg / ml 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz; the 2MeO-PTAA solution doped with 5 wt% 2MeO-Pacz was spin-coated on the substrate after etching P1, and the spin coating process was 500 r / min for 3 seconds, then 5000 r / min for 30 seconds, and then heated at 100°C for 10 minutes for annealing, and then naturally cooled to room temperature to obtain a 20 nm hole transport layer; the other steps remained unchanged to obtain a perovskite solar cell.

[0099] Comparative Example 3

[0100] This comparative example provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0101] The perovskite precursor solution (FA) was prepared by dissolving 280 mg PbI2, 84.1 mg FAI, 5.2 mg MACl, and 2.6 mg CsI in 600 μl N-methylpyrrolidone (NMP) and 2-methoxyethanol (2-Me) solution, wherein the volume ratio of NMP to 2-Me was 0.08:0.92, and stirring at room temperature for 2.5 hours. 0.98 Cs 0.02 PbI3). The substrate with the hole transport layer was moved into a low-temperature vacuum glove box, and the perovskite precursor solution was coated on the hole transport layer by a scraping method at a rate of 5 mm / s. The solution was heated at 100°C for 60 min for annealing to obtain a 400 nm perovskite layer, i.e., the perovskite active layer. 280 mg PbI2, 84.1 mg FAI, 5.2 mg MACl, and 2.6 mg CsI were dissolved in 600 ul N-methylpyrrolidone (NMP) and 2-methoxyethanol (2-Me) solution, wherein the volume ratio of NMP to 2-Me was 0.08:0.92, and stirred at room temperature for 2.5 hours to obtain a perovskite precursor solution (FA 0.98 Cs 0.02The substrate with the hole transport layer was moved into a low-temperature vacuum glove box. A perovskite precursor solution was spin-coated on the hole transport layer at 500 rpm for 3 seconds, followed by 5000 rpm for 30 seconds. The solution was then annealed at 100°C for 60 minutes to obtain a 400nm thick perovskite layer, the so-called "perovskite active layer." The other steps remained unchanged to obtain a perovskite solar cell.

[0102] Comparative Example 4

[0103] This comparative example provides a method for preparing a perovskite solar cell by scraping with multiple solvents, comprising the following steps:

[0104] The steps in S4 of Example 1, "20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was applied by a doctor blade at a rate of 20 mm / s to obtain a 30 nm electron transport layer" were replaced with "20 mg of PCBM was dissolved in 1 ml of a mixed solvent of o-dichlorobenzene and chlorobenzene, wherein the volume ratio of o-dichlorobenzene to chlorobenzene was 1:9, and the mixture was stirred for 24 hours to form a 20 mg / ml PCBM solution, and the PCBM solution was spin-coated by a spin coating method, wherein the spin coating process was 500 r / min for 3 s, and then 5000 r / min for 30 s to obtain a 30 nm electron transport layer" and the other steps remained unchanged to obtain a perovskite solar cell.

[0105] Performance testing:

[0106] The perovskite solar cells of Examples 1-9 and Comparative Examples 1-4 were tested for performance. The JV characteristic curves of the devices were measured using a Keithley 2440 light source under a simulated AM1.5G spectrum. A solar simulator (Newport, 91160) was used to calibrate the light intensity using a standard silicon solar cell device from NREL. The effective measurement area was 0.07 cm 2 , under reverse and forward bias sweeps with a sweep rate of 100 mV / s and a bias range of −0.2 V to 1.2 V.

[0107] Table 1. Performance tests of perovskite solar cells of Examples 1-9 and Comparative Examples 1-4.

[0108] sample Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Example 1 1.34 25.15 76.32 25.72 Example 2 1.32 24.98 76.67 25.28 Example 3 1.31 25.09 75.96 24.97 Example 4 1.01 25.11 75.90 19.25 Example 5 1.03 25.05 75.87 19.58 Example 6 1.29 22.32 77.01 22.17 Example 7 1.32 22.44 76.93 22.79 Example 8 1.24 24.93 76.08 23.52 Example 9 1.33 25.01 76.19 25.34 Comparative Example 1 1.29 22.37 60.42 17.44 Comparative Example 2 0.95 21.86 67.24 13.96 Comparative Example 3 0.98 22.03 64.55 13.94 Comparative Example 4 0.93 22.10 62.72 12.89

[0109] As can be seen from Table 1, the energy conversion efficiency of the perovskite solar cells prepared in Examples 1 to 9 of the present invention is high, while in Comparative Example 1, a single solvent is used to prepare the electron transport layer, and the energy conversion efficiency of the perovskite solar cell prepared is reduced; in Comparative Example 2, a spin coating method is used to prepare the hole transport layer, and the energy conversion efficiency of the perovskite solar cell prepared is reduced; in Comparative Example 3, a spin coating method is used to prepare the perovskite active layer, and the energy conversion efficiency of the perovskite solar cell prepared is reduced; in Comparative Example 4, a spin coating method is used to prepare the electron transport layer, and the energy conversion efficiency of the perovskite solar cell prepared is reduced.

[0110] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, technicians can still modify or replace the specific implementation methods of the present invention with equivalents, but these modifications or changes do not depart from the scope of protection of the pending claims of the present application.

Claims

1. A method for preparing a perovskite solar cell by multi-solvent blade coating, characterized in that: The steps include: S1. Coating a hole transport layer on a conductive substrate; S2. coating the perovskite active layer and the electron transport layer on the hole transport layer in sequence; S3. A cathode modification layer and an electrode layer are sequentially provided on the electron transport layer; The solvent for forming the electron transport layer is selected from at least two of o-dichlorobenzene, chlorobenzene, and chloroform.

2. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S1, the material of the hole transport layer is 2MeO-PTAA doped with MeO-2Pacz; And / or, the speed of the scraping is 3-7 mm / s; And / or, the annealing temperature of the blade coating is 80-120° C., and the annealing time is 5-15 minutes.

3. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 2, characterized in that: Calculated by the mass percentage of the material of the hole transport layer, the doping amount of MeO-2Pacz in the 2MeO-PTAA doped with MeO-2Pacz is 3-7%.

4. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S1, the concentration of the solution forming the hole transport layer is 1-4 mg / ml; And / or, the thickness of the hole transport layer is 10-35 nm.

5. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S2, the material of the perovskite active layer is selected from FA 0.98 Cs 0.02 PbI3; And / or, the material of the electron transport layer is selected from PCBM.

6. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S2, the concentration of the solution forming the electron transport layer is 15-25 mg / ml; And / or, the thickness of the perovskite active layer is 300-500 nm; And / or, the thickness of the electron transport layer is 10-60 nm.

7. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S2, the scraping speed of scraping the perovskite active layer on the hole transport layer is 3-7 mm / s; And / or, the coating speed of the electron transport layer on the perovskite active layer is 15-25 mm / s.

8. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S2, the annealing temperature for coating the perovskite active layer on the hole transport layer is 80-120° C., and the annealing time is 50-70 min.

9. The method for preparing a perovskite solar cell by multi-solvent blade coating according to claim 1, characterized in that: In S3, the material of the cathode modification layer is BCP; And / or, the material of the electrode layer is Ag; And / or, the thickness of the cathode modification layer is 1-10 nm; And / or, the thickness of the electrode layer is 70-120 nm.

10. A perovskite solar cell, characterized in that: The solar cell is prepared by the method for preparing a perovskite solar cell by multi-solvent coating according to any one of claims 1 to 9.

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