Hole repairing method of perovskite solar cell and application

Abstract

The invention discloses a hole repairing method of a perovskite solar cell and application, and relates to the technical field of perovskite cells. The hole repairing method comprises the following steps: carrying out first post-treatment on a perovskite solution coated on the surface of a first transmission layer to remove a low-boiling-point solvent and form a perovskite wet film; analyzing components and proportions of a solute and a solvent in the perovskite wet film, and preparing a perovskite repair liquid; identifying holes in the perovskite wet film by adopting automatic detection equipment to form a 3D diagram, simulating and calculating the amount of the required perovskite repairing liquid according to the sizes of the holes, and dropwise adding a certain amount of the perovskite repairing liquid into the holes; and after the holes are repaired, performing secondary post-treatment on the perovskite wet film to form a perovskite dry film. By adopting the method, the perovskite layer can be effectively repaired, meanwhile, the influence on a non-repairing area is relatively small, and the performance and the stability of the cell are favorably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite cells, and in particular to a method and application of repairing holes in a perovskite solar cell. Background Art

[0002] Perovskite materials are neither calcium nor titanium, but a general term for a class of "ceramic oxides" with the same crystal structure. The molecular formula is ABX3, where A stands for "large radius cations", B stands for "metal cations", and X stands for "halogen anions". These three ions can present many magical physical properties, including but not limited to insulation, ferroelectricity, antiferromagnetism, and giant magnetic effects, through the arrangement and combination of different elements, or by adjusting the distance between each other. As the most promising new material, perovskite can be used as the active layer of solar cells. It has many excellent optoelectronic properties, such as adjustable band gap, high absorption coefficient, low exciton binding energy, high carrier mobility, and high defect tolerance. The preparation process of perovskite is simple, and it can achieve semi-transparency, ultra-lightness, ultra-thinness, and flexibility. The raw materials of perovskite are widely available and rich in content. These advantages make perovskite solar cells a new generation of technology that subverts crystalline silicon and thin-film solar cells.

[0003] At present, the perovskite light-absorbing layer of perovskite solar cells is usually prepared by a solution method, such as scraping, slit, inkjet printing, spin coating or micro-dimpling. A layer of perovskite solution is first coated on the surface of the transmission layer 1, and the perovskite solution is subjected to a first post-treatment using an air knife or VCD (vacuum concentrate drying) flash evaporation process to remove most of the low-boiling point solvents in the perovskite solution to form a perovskite wet film (a large number of crystal nuclei), in which a small part of the low-boiling point solvent and most of the high-boiling point solvent are retained; then the perovskite wet film is subjected to a second post-treatment by heating and high-temperature annealing (100-150°) to remove a small amount of low-boiling point solvent and a large amount of high-boiling point solvent, so that small crystal nuclei grow to form large grains, and finally a perovskite dry film is formed. The transmission layer 2, the buffer layer, and the electrode are sequentially prepared on the surface of the perovskite dry film layer to form a complete perovskite solar cell.

[0004] However, due to dust or film defects on the surface of the transmission layer 1, the local wettability of the surface is poor. After the perovskite solution is applied to the surface, during the first and second post-treatment processes, the solution will shrink and form holes. At this time, the transmission layer 1 is in direct contact with the transmission layer 2 (see Figure 1 ), affecting battery performance (efficiency, current density, open circuit voltage, fill factor, etc.) and battery stability.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The purpose of the present invention is to provide a method and application of repairing holes in a perovskite solar cell.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a method for repairing holes in a perovskite solar cell, comprising:

[0009] performing a first post-treatment on the perovskite solution coated on the surface of the transport layer to remove the low boiling point solvent and form a perovskite wet film;

[0010] Analyzing the composition and ratio of the solute and the solvent in the perovskite wet film, and preparing a perovskite repair solution;

[0011] An automated detection device is used to identify the holes on the perovskite wet film to form a 3D map, and the amount of perovskite repair solution required is simulated and calculated according to the size of the hole, and a certain amount of the perovskite repair solution is dripped into the hole. The perovskite repair solution erodes the surrounding area of ​​the hole to form a transition zone, and the transition zone and the hole area are used together as a repair zone;

[0012] After the holes are repaired, the perovskite wet film is subjected to a second post-treatment to form a perovskite dry film.

[0013] In an optional embodiment, the method for analyzing the composition and ratio of the solute and the solvent in the perovskite wet film includes gravimetric analysis, spectrophotometry, titration or colorimetry.

[0014] In an optional embodiment, the composition of the perovskite solution includes 40% to 60% of solute, 30% to 55% of low boiling point solvent and 5% to 10% of high boiling point solvent by mass percentage;

[0015] Preferably, the solute includes at least one of PbI2, PbBr2, MaI and CsI;

[0016] Preferably, the low boiling point solvent comprises at least one of DMF and acetonitrile;

[0017] Preferably, the high boiling point solvent includes at least one of DMSO, NMP and DMPU.

[0018] In an optional embodiment, the solute in the composition of the perovskite repair solution remains unchanged from the solute in the perovskite solution, and the volume ratio of the low boiling point solvent to the high boiling point solvent in the perovskite repair solution is 1:(15-500).

[0019] In an optional embodiment, an ionic liquid additive is further added to the perovskite repair solution, and the amount of the ionic liquid additive added accounts for 0.01 to 0.1% of the mass of the perovskite repair solution;

[0020] Preferably, the ionic liquid additive includes at least one of 1,3-bis(cyanomethyl)imidazole chloride, 2-(2-(2-aminoethoxy)ethoxy)acetic acid and 3-chlorobenzylamine.

[0021] In an optional embodiment, a self-repairing material is further added to the perovskite repair solution, and the amount of the self-repairing material added accounts for 0.01 to 0.2% of the mass of the perovskite repair solution;

[0022] Preferably, the self-healing material comprises phenylhydrazine hydrochloride.

[0023] In an optional embodiment, after the perovskite repair solution is added, the repair area is treated with gas;

[0024] Preferably, the first post-treatment comprises performing the first post-treatment for 10 to 90 seconds using an air knife or VCD flash evaporation;

[0025] Preferably, the second post-treatment comprises high temperature annealing at 100-150° C. for 10-40 min.

[0026] In a second aspect, the present invention provides an application of the hole repair method of a perovskite solar cell as described in any one of the above embodiments in the preparation of a perovskite solar cell.

[0027] In a third aspect, the present invention provides a method for preparing a perovskite solar cell, comprising: depositing a transparent conductive layer on a substrate, depositing a first transmission layer on the transparent conductive layer, coating a perovskite solution on the first transmission layer, and then repairing the perovskite layer according to the hole repair method for a perovskite solar cell described in any of the aforementioned embodiments. After the repair is completed, a second transmission layer, a buffer layer and an electrode are sequentially deposited on the surface of the perovskite dry film.

[0028] In a fourth aspect, the present invention provides a perovskite solar cell, which is prepared using the method for preparing a perovskite solar cell as described in the above embodiment.

[0029] The present invention has the following beneficial effects:

[0030] The hole repair method of the perovskite solar cell provided by the present invention is repaired on the wet film, rather than on the perovskite dry film. The present invention analyzes the composition and ratio of the solute and solvent in the wet film, and prepares a perovskite repair solution with similar composition, and uses the perovskite repair solution to repair the hole. Since the perovskite repair solution has a high concentration and relatively few solvents, it still erodes the peripheral area of ​​the hole to form a transition zone, which is conducive to connecting the repair area and the non-repair area to avoid the occurrence of a split phenomenon. In addition, the present invention is repaired on the wet film, rather than because the surface of the wet film still retains a part of the solvent, so when the perovskite repair solution is added dropwise in the hole, the diffusion of the perovskite repair solution is slow, and its influence on the perovskite wet film is small. If the perovskite repair solution is directly added dropwise to the surface of the dry film, the perovskite repair solution quickly diffuses on the surface of the dry film, and the damage caused to the dry film is large. Therefore, the hole repair method of the perovskite solar cell provided by the present invention can effectively repair the perovskite layer, while having a small influence on the non-repair area. In the process of preparing perovskite solar cells, the hole repair method of the perovskite solar cell is used to improve the performance and stability of the cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 It is a schematic diagram of the structure of the perovskite solar cell mentioned in the background technology;

[0033] Figure 2 A process flow chart of a hole repair method for a perovskite solar cell provided in Example 1 of the present invention;

[0034] Figure 3 A schematic diagram of the step (1) of coating a perovskite solution in the hole repair method of a perovskite solar cell provided in Example 1 of the present invention;

[0035] Figure 4 A schematic diagram of forming a perovskite wet film in step (1) of the hole repair method for a perovskite solar cell provided in Example 1 of the present invention;

[0036] Figure 5 A schematic diagram of holes on the surface of a perovskite wet film in step (3) of the hole repairing method for a perovskite solar cell provided in Example 1 of the present invention;

[0037] Figure 6A schematic diagram of the hole on the surface of the perovskite wet film after the perovskite repair liquid is dripped in step (3) of the hole repair method of the perovskite solar cell provided in Example 1 of the present invention;

[0038] Figure 7 A schematic diagram of the structure of forming a perovskite dry film in step (4) of the hole repair method of the perovskite solar cell provided in Example 1 of the present invention, and continuing to deposit a second transmission layer, a buffer layer and an electrode;

[0039] Figure 8 This is a process flow chart of the hole repair method for perovskite solar cells provided in Example 6 of the present invention.

[0040] Icons: 100-perovskite solar cell; 110-substrate; 120-transparent conductive layer; 130-first transmission layer; 141-perovskite solution; 142-perovskite wet film; 143-hole; 144-repair area; 145-perovskite dry film; 150-second transmission layer; 160-buffer layer; 170-electrode. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0042] See also Figure 2-Figure 7 The present invention provides a method for repairing holes in a perovskite solar cell, which comprises the following steps:

[0043] (1) The perovskite solution 141 coated on the surface of the first transport layer 130 is subjected to a first post-treatment to remove the low boiling point solvent, thereby forming a perovskite wet film 142 .

[0044] In the present invention, the components of the perovskite solution 141 include 40% to 60% solute, 30% to 55% low boiling point solvent and 5 to 10% high boiling point solvent by mass percentage; wherein the solute includes but is not limited to at least one of PbI2, PbBr2, MaI and CsI; the low boiling point solvent includes but is not limited to at least one of DMF and acetonitrile; the high boiling point solvent includes but is not limited to at least one of DMSO, NMP and DMPU.

[0045] The first post-treatment includes the use of air knife or VCD flash evaporation for the first post-treatment for 10 to 90 seconds.

[0046] In the present invention, most of the low boiling point solvents in the perovskite solution 141 can be removed through the first post-treatment. At this time, there are a large number of crystal nuclei in the perovskite wet film 142, and a small amount of low boiling point solvents and most of the high boiling point solvents are retained in the wet film.

[0047] (2) Analyze the composition and ratio of the solute and solvent in the perovskite wet film 142 and prepare a perovskite repair solution.

[0048] Methods for analyzing the composition and ratio of the solute and solvent in the perovskite wet film 142 include gravimetric analysis, spectrophotometry, titration or colorimetry. Through the above analysis, the composition and ratio of the solute and solvent in the perovskite wet film 142 can be determined, and then a perovskite repair solution with similar composition and ratio can be prepared.

[0049] Specifically, the solute in the composition of the perovskite repair solution remains unchanged from the solute in the perovskite solution 141, and the volume ratio of the low boiling point solvent to the high boiling point solvent in the perovskite repair solution is 1:(15-500), preferably 1:15-30, wherein the mass percentage of the solute in the perovskite repair solution is about 75-85%, and the total mass percentage of the low boiling point solvent and the high boiling point solvent is about 15-25%.

[0050] In addition, on the basis of maintaining the above-mentioned solutes and solvents, an ionic liquid additive may be added to the perovskite repair solution, and the amount of the ionic liquid additive added accounts for 0.01 to 0.1% of the mass of the perovskite repair solution; preferably, the ionic liquid additive includes at least one of 1,3-bis(cyanomethyl)imidazole chloride, 2-(2-(2-aminoethoxy)ethoxy)acetic acid and 3-chlorobenzylamine.

[0051] In some other embodiments, a self-healing material is further added to the perovskite repair solution, and the amount of the self-healing material added accounts for 0.01 to 0.2% of the mass of the perovskite repair solution; preferably, the self-healing material includes phenylhydrazine hydrochloride.

[0052] The addition of ionic liquid additives and self-healing materials is beneficial to delaying crystallization and passivating interfaces and grain boundaries, thereby achieving self-healing, further reducing the occurrence of holes 143, and improving battery performance and stability.

[0053] (3) An automated detection device is used to identify the holes 143 on the perovskite wet film 142 to form a 3D image. The required amount of perovskite repair liquid is simulated and calculated according to the size of the holes 143, and a certain amount of perovskite repair liquid is added to the holes 143. The perovskite repair liquid erodes the surrounding area of ​​the holes 143 to form a transition zone. The transition zone and the area of ​​the holes 143 together serve as the repair zone 144.

[0054] The automatic hole 143 identification device can identify the hole 143 on the perovskite wet film 142, and then use the software algorithm to simulate the shape of the hole 143, calculate the volume of the hole 143, and set the required volume of the repair liquid on the dripping device to drip the repair liquid on the hole 143. Please refer to Figure 8 After the perovskite repair liquid is added, the repair area 144 is treated with gas; by treating the repair area 144 with gas, the local low-boiling point solvent in the repair area 144 can be volatilized, keeping the repair area 144 consistent with the process in other areas, reducing differences, forming a uniform film, and further improving the performance and stability of the battery.

[0055] In addition, in the present invention, the perovskite repair liquid corrodes the surrounding area of ​​the hole 143 to form a transition zone, which is conducive to connecting the repair area 144 with the non-repair area 144 to avoid the occurrence of splitting. At the same time, the area of ​​the repair area 144 in the present invention is larger than the area of ​​the hole 143 area.

[0056] (4) After the hole 143 is repaired, the perovskite wet film 142 is subjected to a second post-treatment to form a perovskite dry film 145 .

[0057] The second post-treatment includes high temperature annealing at 100-150° C. for 10-40 min.

[0058] The present invention adopts the above-mentioned hole repair method of the perovskite solar cell to effectively repair the perovskite layer, and the present invention performs the repair on the wet film instead of the perovskite dry film 145. Since a part of the solvent is still retained on the surface of the wet film, when the perovskite repair liquid is dripped into the hole 143, the diffusion of the perovskite repair liquid is slow, and the impact on the perovskite wet film 142 is small. If the perovskite repair liquid is directly dripped onto the surface of the dry film, the perovskite repair liquid quickly diffuses on the surface of the dry film, causing greater damage to the dry film.

[0059] The hole repair method of the perovskite solar cell provided by the present invention can be widely used in the preparation of the perovskite solar cell 100.

[0060] For example, the present invention provides a method for preparing a perovskite solar cell 100, which includes: depositing a transparent conductive layer 120 on a substrate 110, depositing a first transmission layer 130 on the transparent conductive layer 120, coating a perovskite solution 141 on the first transmission layer 130, and then repairing the perovskite layer according to the above-mentioned hole repair method of the perovskite solar cell. After the repair is completed, a second transmission layer 150, a buffer layer 160 and an electrode 170 are sequentially deposited on the surface of the perovskite dry film 145.

[0061] In addition, the present invention provides a perovskite solar cell 100, which is prepared by the above-mentioned preparation method of the perovskite solar cell 100. The perovskite solar cell 100 of the present invention can repair the perovskite layer holes 143, avoid direct contact between the first transmission layer 130 and the second transmission layer 150, and greatly improve the performance and stability of the battery.

[0062] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0063] Example 1

[0064] This embodiment provides a method for repairing holes in a perovskite solar cell, which includes:

[0065] (1) A layer of perovskite solution 141 (such as Figure 3 As shown), the coating amount of the perovskite solution 141 is 50ul, and the components of the perovskite solution 141 include 50% solute, 44% low boiling point solvent and 6% high boiling point solvent by mass percentage, wherein the solute is CsI, PbI2, FAI, PbBr2 and MACl with a mass ratio of 1:1:1:1, the low boiling point solvent is DMF, and the high boiling point solvent is DMSO and NMP with a mass ratio of 1:1; after the coating is completed, the first post-treatment is performed with an air knife for 40s. The first post-treatment can remove most of the low boiling point solvent to form a perovskite wet film 142 (as shown Figure 4 shown).

[0066] (2) Scrape a small amount of wet film, weigh the wet film, put it into a thermogravimetric device, and after heating, the volatilization degree of the material is different at different time periods and temperatures. Weigh the wet film at different times to determine the weight of the low boiling point solvent and the high boiling point solvent. The remainder is the weight of the solute. The composition and ratio of the solute and solvent in the perovskite wet film 142 are analyzed by the above analysis method, and a perovskite repair solution is prepared, wherein the perovskite repair solution includes 80% solute, 1% low boiling point solvent, and 19% high boiling point solvent by mass percentage.

[0067] (3) Using automated detection equipment to identify holes 143 (such as Figure 5 As shown in FIG. 1 ), a 3D graph is formed, and the amount of perovskite repair solution required is calculated according to the size of the hole 143. A certain amount of perovskite repair solution is added to the hole 143. The perovskite repair solution erodes the surrounding area of ​​the hole 143 to form a transition zone. The transition zone and the area of ​​the hole 143 are used together as the repair zone 144 (as shown in FIG. 1 ). Figure 6 shown).

[0068] (4) After the hole 143 is repaired, the perovskite wet film 142 is subjected to a second post-treatment at 120° C. for 20 min to form a perovskite dry film 145 (e.g. Figure 7 shown).

[0069] Example 2

[0070] This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the components of the perovskite solution 141 include, by mass percentage, 50% solute, 42% low boiling point solvent and 8% high boiling point solvent, wherein the solute is CsI, PbI2, FAI, PbBr2 and MACl in a mass ratio of 1:1:1:1, the low boiling point solvent is DMF, and the high boiling point solvent is DMSO and NMP in a mass ratio of 1:1.

[0071] The perovskite repair solution includes 80% of solute, 0.9% of low boiling point solvent and 19.1% of high boiling point solvent by mass percentage.

[0072] Example 3

[0073] This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the components of the perovskite solution 141 include, by mass percentage, 50% solute, 40% low boiling point solvent and 10% high boiling point solvent, wherein the solute is CsI, PbI2, FAI, PbBr2 and MACl in a mass ratio of 1:1:1:1, the low boiling point solvent is DMF, and the high boiling point solvent is DMSO and NMP in a mass ratio of 1:1.

[0074] The perovskite repair solution comprises 80% of solute, 0.7% of low boiling point solvent and 19.3% of high boiling point solvent by mass percentage.

[0075] Example 4

[0076] This embodiment is basically the same as the embodiment 1, except that 0.05% of the ionic liquid additive 1,3-bis(cyanomethyl)imidazole chloride is further added to the perovskite repair solution.

[0077] Example 5

[0078] This embodiment is basically the same as the embodiment 1, except that 0.05% of the self-healing material phenylhydrazine hydrochloride is also added to the perovskite repair solution.

[0079] Example 6

[0080] This embodiment is basically the same as the embodiment 1, except that an automated detection device is used to identify the holes 143 on the perovskite wet film 142 to form a 3D map, and the amount of perovskite repair liquid required is simulated and calculated according to the size of the holes 143. A certain amount of perovskite repair liquid is added to the holes 143, and the perovskite repair liquid corrodes the surrounding area of ​​the holes 143 to form a transition zone. The transition zone and the area of ​​the holes 143 are used together as the repair zone 144. Figure 8As shown, the repair area 144 is treated with an air gun so that the low-boiling point solvent in the repair area 144 evaporates, keeping the repair area 144 consistent with the process of other areas, reducing the difference, and forming a uniform film.

[0081] Comparative Example 1

[0082] In this comparative example, the perovskite wet film 142 is not repaired, and steps (2) and (3) of Example 1 are omitted. The perovskite wet film 142 is directly subjected to a second post-treatment to obtain a perovskite dry film 145 .

[0083] Comparative Example 2

[0084] This comparative example is basically the same as Example 1, except that the composition of the perovskite repair solution used in step (2) of this comparative example is exactly the same as the composition of the perovskite solution 141.

[0085] Comparative Example 3

[0086] This comparative example is basically the same as Example 1, except that the components of the perovskite repair solution used in step (2) of this comparative example include: tetramethylene sulfoxide as a ligand solvent, anisole as a non-ligand solvent, and the volume ratio of the ligand solvent to the non-ligand solvent is 0.2:1.

[0087] Comparative Example 4

[0088] This comparative example is basically the same as Example 1, except that in this comparative example, the perovskite repairing liquid in step (2) of Example 1 is used as the repairing liquid to repair the surface of the perovskite dry film 145. Specifically, it includes:

[0089] (1) A layer of perovskite solution 141 (such as Figure 3 As shown), the coating amount of the perovskite solution 141 is 50ul, and the components of the perovskite solution 141 include 50% solute, 44% low boiling point solvent and 6% high boiling point solvent by mass percentage, wherein the solute is CsI, PbI2, FAI, PbBr2 and MACl in a mass ratio of 1:1:1:1, the low boiling point solvent is DMF, and the high boiling point solvent is DMSO and NMP in a mass ratio of 1:1; after the coating is completed, the first post-treatment is carried out with an air knife for 40s, and the first post-treatment can remove most of the low boiling point solvent to form a perovskite wet film 142.

[0090] (2) The perovskite wet film 142 is subjected to a second post-treatment at 100-150° C. for 20 min to form a perovskite dry film 145 .

[0091] (3) An automated detection device is used to identify the hole 143 on the perovskite dry film 145 to form a 3D image. The required amount of perovskite repair liquid is simulated and calculated according to the size of the hole 143, and a certain amount of the perovskite repair liquid in Example 1 is dripped into the hole 143. The perovskite repair liquid corrodes the surrounding area of ​​the hole 143 to form a transition zone. The transition zone and the area of ​​the hole 143 together serve as the repair area 144.

[0092] Experimental Example 1

[0093] The photoelectric performance of the solar cells prepared in the above embodiments and comparative examples was tested, wherein the preparation method of the solar cell includes: depositing a transparent conductive layer 120 with a thickness of 150 nm on a substrate 110, depositing a first transmission layer 130 with a thickness of 130 nm on the transparent conductive layer 120, coating a perovskite solution 141 with a thickness of 150 μm on the first transmission layer 130, and then repairing the perovskite layer according to the above-mentioned hole repair method of the perovskite solar cell. After the repair is completed, a second transmission layer 150 with a thickness of 30 nm, a buffer layer 160 with a thickness of 20 nm, and an electrode 170 with a thickness of 100 nm are sequentially deposited on the surface of the perovskite dry film 145.

[0094]

[0095] Among them, the evaluation method of battery stability is: after continuous irradiation for 100 hours, the efficiency decay is less than 1%, which is evaluated as good; after continuous irradiation for 100 hours, the efficiency decay is between 1% and 2%, which is evaluated as fair; after continuous irradiation for 100 hours, the efficiency decay is greater than 2%, which is evaluated as poor.

[0096] As can be seen from the above table, the battery parameters and stability are the best when the holes are repaired on the wet film after the perovskite coating and the first air knife or VCD treatment. In Comparative Example 1, no repair was performed, and the battery parameters and stability at this time were the worst. In Comparative Example 2, the perovskite solution 141 was directly used for repair. At this time, the composition of the perovskite solution 141 changed compared to the wet film, and its repair effect was poor, but slightly better than Comparative Example 1. In Comparative Example 3, other ingredients were used as the repair liquid, and its repair effect was similar to that of Comparative Example 2, but still significantly worse than Example 1. In Comparative Example 4, repair was performed on the dry film. At this time, the perovskite repair liquid diffused rapidly on the surface of the dry film, causing greater damage to the dry film, resulting in poor battery parameters and stability.

[0097] In summary, the hole repair method of the perovskite solar cell provided by the present invention is repaired on the wet film instead of on the perovskite dry film 145. The present invention analyzes the composition and ratio of the solute and solvent in the wet film, and prepares a perovskite repair solution with similar composition, and uses the perovskite repair solution to repair the hole 143. Since the concentration of the perovskite repair solution is high and the solvent is relatively small, it will still erode the surrounding area of ​​the hole 143 to form a transition zone, which is conducive to connecting the repair area 144 with the non-repair area 144 to avoid the occurrence of splitting. In addition, the present invention is repaired on the wet film. Since the surface of the wet film still retains a part of the solvent, when the perovskite repair solution is dripped into the hole 143, the diffusion of the perovskite repair solution is slow, and its effect on the perovskite wet film 142 is small. If the perovskite repair solution is directly dripped onto the surface of the dry film, the perovskite repair solution quickly diffuses on the surface of the dry film at this time, causing greater damage to the dry film. Therefore, the hole repair method of the perovskite solar cell provided by the present invention can effectively repair the perovskite layer, while having little impact on the non-repaired area 144. In the process of preparing the perovskite solar cell 100, the hole repair method of the perovskite solar cell described above can improve the performance and stability of the cell.

[0098] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for repairing holes in a perovskite solar cell, characterized in that: It includes: performing a first post-treatment on the perovskite solution coated on the surface of the first transport layer to remove the low boiling point solvent and form a perovskite wet film; Analyzing the composition and ratio of the solute and the solvent in the perovskite wet film, and preparing a perovskite repair solution; An automated detection device is used to identify the holes on the perovskite wet film to form a 3D map, and the amount of perovskite repair solution required is simulated and calculated according to the size of the hole, and a certain amount of the perovskite repair solution is dripped into the hole. The perovskite repair solution erodes the surrounding area of ​​the hole to form a transition zone, and the transition zone and the hole area are used together as a repair zone; After the holes are repaired, the perovskite wet film is subjected to a second post-treatment to form a perovskite dry film.

2. The method for repairing holes in a perovskite solar cell according to claim 1, characterized in that: Methods for analyzing the composition and ratio of the solute and the solvent in the perovskite wet film include gravimetric analysis, spectrophotometry, titration or colorimetry.

3. The method for repairing holes in a perovskite solar cell according to claim 1, characterized in that: The composition of the perovskite solution includes 40% to 60% of solute, 30% to 55% of low boiling point solvent and 5% to 10% of high boiling point solvent by mass percentage; Preferably, the solute includes at least one of PbI2, PbBr2, MaI and CsI; Preferably, the low boiling point solvent comprises at least one of DMF and acetonitrile; Preferably, the high boiling point solvent includes at least one of DMSO, NMP and DMPU.

4. The method for repairing holes in a perovskite solar cell according to claim 3, characterized in that: The solute in the composition of the perovskite repair solution remains unchanged with the solute in the perovskite solution, and the volume ratio of the low boiling point solvent to the high boiling point solvent in the perovskite repair solution is 1:(15-500).

5. The method for repairing holes in a perovskite solar cell according to claim 1, characterized in that: An ionic liquid additive is also added to the perovskite repair solution, and the amount of the ionic liquid additive added accounts for 0.01 to 0.1% of the mass of the perovskite repair solution; Preferably, the ionic liquid additive includes at least one of 1,3-bis(cyanomethyl)imidazole chloride, 2-(2-(2-aminoethoxy)ethoxy)acetic acid and 3-chlorobenzylamine.

6. The method for repairing holes in a perovskite solar cell according to claim 1, characterized in that: A self-repairing material is also added to the perovskite repair solution, and the amount of the self-repairing material added accounts for 0.01 to 0.2% of the mass of the perovskite repair solution; Preferably, the self-healing material comprises phenylhydrazine hydrochloride.

7. The method for repairing holes in a perovskite solar cell according to claim 1, characterized in that: After the perovskite repair solution is added dropwise, the repair area is treated with gas; Preferably, the first post-treatment comprises performing the first post-treatment for 10 to 90 seconds using an air knife or VCD flash evaporation; Preferably, the second post-treatment comprises high temperature annealing at 100-150° C. for 10-40 min.

8. Use of the hole repair method of a perovskite solar cell according to any one of claims 1 to 7 in the preparation of a perovskite solar cell.

9. A method for preparing a perovskite solar cell, characterized in that: It includes: A transparent conductive layer is deposited on a substrate, a first transmission layer is deposited on the transparent conductive layer, a perovskite solution is coated on the first transmission layer, and then the perovskite layer is repaired according to the hole repair method of a perovskite solar cell according to any one of claims 1 to 8. After the repair is completed, a second transmission layer, a buffer layer and an electrode are sequentially deposited on the surface of the perovskite dry film.

10. A perovskite solar cell, characterized in that: It is prepared by the method for preparing a perovskite solar cell according to claim 9.

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