CN110880555A - Coating equipment and method for mixed solution of precursor and surfactant - Google Patents

Abstract

The invention relates to a coating equipment for a mixed solution of a precursor and a surfactant, comprising a coating die head, a die head lifting platform, a post-processing device, a coating platform and a conveying device. After the head is coated, it is transported by the conveying device to the post-processing device for post-processing. Under the driving of the conveying device, the die head lift table and the coating platform move relative to each other; The syringe pump is connected, the syringe pump is connected with at least two raw material bottles, one of the raw material bottles is filled with a divalent precursor solution, the other raw material bottle is filled with a surfactant solution, and the syringe pumps are simultaneously pumping the divalent precursor. The bulk solution and the surfactant solution are injected into the mixing chamber for mixing, and the mixed solution is delivered to the coating die for use. The invention also discloses the use method and application of the coating equipment. The invention improves the coverage of the coating film and the flatness of the surface of the coating film, and obtains a perovskite film with a more uniform film thickness distribution.

Description

Coating equipment and method of mixed solution of precursor and surfactant

technical field

The invention belongs to the technical field of preparation of perovskite solar cells, and particularly relates to a coating device and a method for a mixed solution of a precursor and a surfactant.

Background technique

At present, the main methods for large-area preparation of perovskite solar cells include spray coating, blade coating, slot coating, ink printing, and inkjet printing. Slot Die Coating is one of the most convenient methods for industrial large-area preparation of perovskite solar cells. It has the advantages of short preparation process cycle, saving raw materials, and simple process operation. However, the traditional slit-coating preparation of perovskite solar cells has many defects such as more pores and serious uneven film thickness, which seriously restricts the large-area preparation and commercialization of perovskite cells by slot-coating. application.

Generally, the preparation process of perovskite solar cells includes one-step and two-step methods. Among them, in the one-step perovskite solution film formation process, the perovskite crystallization speed is fast and the morphology of the perovskite film is difficult to control. Compared with the one-step method, the two-step method for preparing perovskite thin films has more process methods and adjustment means. The two-step method is to use the bivalent precursor (also known as bivalent metal halide) solution of perovskite to prepare a bivalent precursor thin film layer on the substrate, and then use the monovalent precursor (also known as a monovalent precursor) on this basis. cationic halide) solution to prepare a monovalent precursor thin film layer. In the two-step method, the reaction degree and performance of perovskite films can be effectively regulated by regulating the film formation process of divalent metal halide and the deposition process of monovalent cation halide on the divalent metal halide film. .

In the Chinese patent with the publication number CN107437587A and the title of a method for preparing a perovskite solar cell perovskite active layer in air, it is disclosed that when a two-step method is used to prepare the perovskite layer active layer, in a lead iodide solution An appropriate amount of pyridine organic small molecules is added as an additive to reduce the influence of humidity during the preparation of the perovskite active layer, so as to realize the preparation of perovskite solar cells in the air. This small molecule additive cannot achieve the leveling effect of the precursor solution in the film formation process, and cannot really solve the defects such as holes and uneven film thickness caused by the bivalent metal halide coating film in the air environment.

As shown in Figure 1, it is a schematic diagram of the cross-section of each layer of the battery after coating with the existing perovskite solution, wherein, 11 is the substrate, and the lipophilic electron/hole transport layer 12-2 is prepared on the conductive layer 11. , the lipophilic electron/hole transport layer 12-2 adopts poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene- 2,5-diyl) (P3HT) from any of the raw materials. 16 is the coating layer of the perovskite solution. Under normal coating conditions, the perovskite solution is hydrophilic, and it is difficult to infiltrate the lipophilic electron/hole transport layer, and the surface of the electron/hole transport layer cannot be flattened. mouth. If the preparation temperature is higher, for example: 100-180 °C, many pinholes are easily generated, which not only seriously affects the quality of perovskite cells, but also reduces the conversion efficiency of perovskite cells.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a coating equipment and method for a mixed solution of a precursor and a surfactant, so as to improve the coverage of the coating film and the flatness of the surface of the coating film, and obtain a more uniform film thickness distribution. Perovskite thin films.

The present invention is achieved by providing a coating equipment for a mixed solution of a precursor and a surfactant, including a coating die, a die lift, a coating platform, a conveying device and a post-processing device. The die head is arranged on the die head lifting platform, the coating die head and the post-processing device are separated from each other and are respectively arranged above the coating platform, and the substrate to be coated placed on the coating platform is coated by the coating die head. After the cloth is transported by the conveying device to the post-processing device for post-processing, under the driving of the conveying device, the die head lift table and the coating platform move relative to each other, and the die head lift table adjusts the coating die. The height between the head and the substrate to be coated; the coating die head is connected to a syringe pump with a mixing cavity through a conduit, and the mixing cavity of the syringe pump is connected to at least two raw material bottles through pipelines. , wherein at least one raw material bottle is filled with a bivalent precursor solution of perovskite, and at least another raw material bottle is filled with a surfactant solution, and the syringe pump is simultaneously pumping the perovskite according to the set volume ratio. The bivalent precursor solution and the surfactant solution are injected into the mixing chamber for mixing, and the mixed solution obtained by mixing is transported to the coating die for use through the conduit.

The present invention is achieved by providing a method for preparing a mixed solution of a precursor and a surfactant, wherein the precursor is a bivalent precursor solution of perovskite, and the bivalent precursor solution includes A divalent metal halide BX ₂ and a divalent precursor solvent, the preparation method includes:

The divalent precursor solution is injected into one raw material bottle, and the surfactant solution is injected into the other raw material bottle. The two raw material bottles are respectively connected with the syringe pump through the pipeline, and the syringe pump simultaneously sucks two raw materials according to the set volume ratio. The valence precursor solution and the surfactant solution are injected into the mixing chamber for mixing, and after stirring, a mixed solution of the precursor and the surfactant is obtained, wherein,

B in the divalent metal halide BX ₂ is at least one of Pb ²⁺ , Sn ²⁺ , and Ze ²⁺ , X is at least one of Cl ^- , Br ^- , and I ^- , the divalent The precursor solvent is at least one of N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) and γ-butyrolactone (GBL); two The concentration of the valence precursor solution is 0.5-1.5mol/L, and the mass ratio of the surfactant to the bivalent precursor solution is 0.05-5%;

The mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution includes an active agent solute and an active agent solvent, and the active agent solute is non-ionic, cationic, anionic type, amphoteric surfactant, the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate, and acetone;

The set volume ratio of the suctioned divalent precursor solution and the surfactant solution is 1-1000; the set temperature of the environment during stirring is 10-60°C.

The present invention is achieved in this way, and provides a method for using a coating device for a mixed solution of a precursor and a surfactant as described above, which is characterized in that it includes the following steps:

In the first step, the bivalent perovskite precursor solution and the surfactant solution prepared according to the preparation method of a mixed solution of a precursor and a surfactant as described above are injected into different raw material bottles. The bottles are respectively connected with the syringe pump through the pipeline. The syringe pump simultaneously sucks the bivalent precursor solution and the surfactant solution according to the set volume ratio and injects them into the mixing chamber for mixing. After stirring, the precursor and the surfactant are obtained. mixed solution;

In the second step, the substrate to be coated is placed on the coating platform, the syringe pump and the conveying device are turned on, and the mixed solution is transported to the coating die head through the conduit, and driven by the conveying device, the die head There is relative movement between the lifting platform and the coating platform, and the height between the coating die and the substrate to be coated is adjusted through the die lifting platform, and the coating die head is placed on the coating platform. The surface is coated, and the wet film containing the mixed solution is obtained after the substrate surface is coated;

In the third step, the post-processing device is turned on, and the coated substrate is transported by the conveying device to the post-processing device for post-processing, thereby preparing a thin film layer containing a divalent precursor on the surface of the substrate.

The present invention is achieved in this way, and provides a method for preparing a perovskite solar cell, characterized in that, in the process of preparing the perovskite solar cell, a mixed solution of the aforementioned precursor and a surfactant is used to prepare the perovskite solar cell. Coating equipment, including the following steps:

S1. Pour the perovskite bivalent precursor solution and the surfactant solution prepared according to the preparation method of a mixed solution of a precursor and a surfactant as described above into different raw material bottles, and the two raw material bottles They are respectively connected with the syringe pump through the pipeline. The syringe pump simultaneously sucks the calcium divalent precursor solution and the surfactant solution respectively according to the set volume ratio and injects it into the mixing chamber for mixing. After stirring, the precursor and the surfactant are obtained. mixed solution;

S2. Place the substrate on which the conductive layer and the electron/hole transport layer have been prepared on the coating platform, turn on the syringe pump and the transfer device, and the mixed solution is transported to the coating die through the conduit, where the transfer Driven by the device, the die head lift table and the coating platform move relative to each other, and the height between the coating die head and the substrate to be coated is adjusted through the die head lift table. The substrate surface to be coated on the cloth platform is coated, and the wet film containing the mixed solution is obtained after the substrate surface is coated;

S3. Turn on the post-processing device, and the coated substrate is transported by the conveying device to the post-processing device for post-processing, so that a thin film layer containing a divalent precursor is prepared on the electron/hole transport layer on the surface of the substrate. ;

S4, continue to prepare the monovalent precursor thin film layer of perovskite, the hole/electron transport layer and the back electrode layer on the surface of the thin film layer containing the divalent precursor of the substrate, until the preparation of the perovskite solar cell is completed.

The present invention is achieved by providing a perovskite solar cell, comprising a perovskite thin film layer, and the perovskite thin film layer is formed by the coating equipment of the mixed solution of the precursor and the surfactant as described above. prepared, or prepared by using the method for using the coating equipment of the mixed solution of the precursor and the surfactant as mentioned above, or prepared by using the method for preparing the perovskite solar cell as mentioned above.

Compared with the prior art, the coating equipment and method of the mixed solution of the precursor and the surfactant of the present invention, after adding the surfactant to the bivalent metal halide precursor solution, improves the divalent metal halide film. Film thickness uniformity and reduced void defects. The mixed cavity method is used to effectively adjust the content of surfactants in the perovskite precursor according to the difference in the hydrophilicity of the substrate, adjust the film-forming morphology of the bivalent metal halide precursor, and reduce the introduction of surfactants. Efficiency reduction of perovskite solar cells, etc. Adding a surfactant solution to the bivalent precursor solution of slit-coated perovskite is beneficial to reduce shrinkage cavities caused by poor infiltration between the bivalent precursor solution and the surface of the transport layer of the substrate, and excessive volatilization of the solution. Pinholes and uneven distribution of the coating solution cause serious uneven film thickness defects; improve the coverage of the coating film and the flatness of the coating surface, and obtain a perovskite film layer with a more uniform film thickness distribution, thereby improving the perovskite film. Efficiency of solar cells. The coating equipment and the method of the present invention are not only applied to the technical field of perovskite solar cells, but also widely used in the technical fields of organic solar cells, dye-sensitized solar cells and quantum dot solar cells.

Description of drawings

1 is a schematic cross-sectional view of a perovskite thin film layer in the prior art after coating;

Figure 2 is a schematic diagram of the cross-sectional structure of a commonly used perovskite solar cell;

3 is a schematic perspective view of a preferred embodiment of the coating equipment for the mixed solution of the precursor and the surfactant of the present invention;

Fig. 4 is a three-dimensional schematic diagram of the mixing chamber in Fig. 3;

5 is a schematic diagram of the morphology of the perovskite thin film layer prepared by the prior art method;

6 is a schematic cross-sectional view of a perovskite thin film layer made from a mixed solution of a precursor and a surfactant after coating;

7 is a schematic diagram of the morphology of the first embodiment of preparing the perovskite thin film layer by using the coating equipment of the mixed solution of the precursor and the surfactant of the present invention;

FIG. 8 is a schematic diagram illustrating the comparison of the efficiencies of the perovskite solar cells produced in the first embodiment and the second embodiment of the present invention.

Detailed ways

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

Please refer to FIG. 2 , which is a schematic diagram of a cross-sectional structure of a commonly used perovskite solar cell. A conductive layer 11 , an electron/hole transport layer 12 , a perovskite thin film layer 13 , a hole/electron transport layer 14 , and a back electrode layer 15 are prepared in sequence on the substrate, of which the most critical is the perovskite thin film layer 13 preparation.

The present invention first discloses a coating device for preparing the perovskite thin film layer 13, the coating device is used for coating the bivalent precursor solution containing surfactant on the electron/hole transport layer 12 to prepare perovskite Mineral film layer 13 .

Please refer to FIG. 3 and FIG. 4 at the same time, the preferred embodiment of the coating equipment for the mixed solution of the precursor and the surfactant of the present invention includes a coating die 101 , a die lifting platform 102 , and a coating platform 106 , a transfer device 107 and a post-processing device 105 .

The coating die head 101 is arranged on the die head lifting platform 102 , and the substrate 108 to be coated is placed on the coating platform 106 . The coating die 101 and the post-processing device 105 are separated from each other and are respectively disposed above the coating platform 106 . The die lifting platform 102 is disposed on both sides of the coating platform 106 . The substrate 108 to be coated is coated by the coating die 101 and then transported by the conveying device 107 to the post-processing device 105 for post-processing.

Driven by the conveying device 107 , the die head lift table 102 and the coating platform 106 move relative to each other, so that the coating die head 101 can apply the coating die 101 to the surface of the substrate to be coated 108 placed on the coating platform 106 . Coating is performed. The die lift table 102 adjusts the height between the coating die 101 and the substrate 108 to be coated. The coating die 101 is connected to the syringe pump 104 with the mixing chamber 111 through the conduit 103, and the mixing chamber 111 of the syringe pump 104 is respectively connected to at least two raw material bottles through the pipelines 112 and 115, wherein at least One raw material bottle 109 contains a bivalent precursor solution of perovskite, and at least another raw material bottle 110 contains a surfactant solution. The syringe pump 104 simultaneously sucks the perovskite bivalent precursor solution and the surfactant solution according to the set volume ratio of 1 to 1000 and injects them into the mixing chamber 111 of the syringe pump 104 for mixing, and the mixed mixed solution passes through The conduit 103 is fed to the coating die 101 for use.

There are two kinds of assembling and connecting relationships between the die head lifting platform 102 , the coating platform 106 and the conveying device 107 . The first assembly connection relationship is: the conveying device 107 drives the coating platform 106 to move, the coating die 101 and the die lifting platform 102 remain stationary, and the die lifting platform 102 and the coating platform 106 remain stationary. produce relative movement. The second assembly connection relationship is: the conveying device 107 drives the movement of the coating die head 101 and the die head lifting platform 102 , the coating platform 106 remains stationary, and the die lifting platform 102 and the coating platform 106 are connected. relative movement between them.

The die head lift table 102 is also provided with a film forming device that performs film forming treatment on the wet film just coated on the surface of the substrate 108 within 0-60 s after the coating of the coating die 101 is completed (Fig. not shown). The film-forming device includes a heater and a blower or a blower, or a heater and a vacuum pump.

Specifically, the post-processing device includes a heater, a vacuum pump, and a closed chamber that is convenient to open and close.

Specifically, a stirring device or an ultrasonic vibration device is further provided in the mixing chamber 111 . Please refer to FIG. 4 , the mixing chamber 111 is connected with the raw material bottle 109 containing the perovskite solution and the raw material bottle 110 containing the surfactant solution through pipelines 112 and 115 respectively, and the syringe pump 104 is in a volume ratio of 1 ∼1000 pumped the perovskite solution and the surfactant solution and injected them into the mixing chamber 111, respectively. The solution 114 in the mixing chamber 111 is uniformly mixed by the stirring device 113 . The mixed solution 114 is quickly delivered to the die 101 through the conduit 103 for coating.

After the divalent precursor solution is mixed with a certain amount of surfactant solution, the hydrophilicity of the surface of the electron/hole transport layer during coating is improved, and the flatness and adjustment of the surface in contact with the air after the film formation of the perovskite solution is adjusted. The volatilization speed of the solvent in the bivalent precursor solution, thereby reducing defects such as shrinkage craters, pinholes, and uneven film thickness during coating. After the complete solar cell is prepared, the interface defects between the perovskite layer and the transport layer and the internal defects of the perovskite layer can also be passivated, which can effectively improve the carrier transport performance of the perovskite solar cell and suppress the electron-hole carrier. The recombination of charge pairs, thereby increasing the efficiency of perovskite solar cells.

On the other hand, after the bivalent precursor solution is mixed with a certain amount of surfactant solution, it is quickly coated and used. The characteristic of this process is that most of the surfactant cannot be completely dissolved in the bivalent precursor solution. , which can ensure that most of the surfactants can be quickly dispersed into the bivalent precursor solution, and avoid the occurrence of inconsistency between the surfactant and the bivalent precursor solution due to the long-term placement of the surfactant directly into the bivalent precursor solution. Compatible and layered phenomenon. In addition, this process method also has the advantages of wide variety of surfactants suitable for perovskite film formation, greatly improved uniformity after perovskite film formation, fewer defects in perovskite films, and divalent perovskite films. Precursor solutions can be stored for longer periods of time.

In the mixed solution obtained by adding the surfactant solution to the bivalent precursor solution, during the slit coating process using the coating equipment of the present invention, the surfactant plays a leveling effect on the bivalent precursor solution, The non-uniform film thickness and hole defects of the formed perovskite thin film are reduced, and the efficiency of the formed perovskite solar cell is improved. Compared with the prior art, the present invention also relates to the functions of surfactants in emulsifying, solubilizing and suspending in perovskite solutions.

The invention also discloses a preparation method of a mixed solution of a precursor and a surfactant, the precursor is a bivalent precursor solution of perovskite, and the bivalent precursor solution includes a bivalent metal halide BX ₂ and Divalent precursor solvent, the preparation method is:

Pour the bivalent precursor solution of perovskite with a concentration of 0.5-1.5mol/L into a raw material bottle 109, and pour the surfactant solution with a mass ratio of 0.05-5% to the bivalent precursor solution into another. In the raw material bottle 110, the two raw material bottles are respectively connected with the syringe pump 104 through the pipelines 112 and 115. The syringe pump 104 simultaneously sucks the divalent precursor solution and the surfactant solution according to the set volume ratio of 1 to 1000 and injects it into the syringe pump 104. Mixing is carried out in the mixing chamber 111, and after stirring, a mixed solution of the precursor and the surfactant is obtained, wherein,

B in the divalent metal halide BX ₂ is at least one of Pb ²⁺ , Sn ²⁺ , and Ze ²⁺ , X is at least one of Cl ^- , Br ^- , and I ^- , the divalent The precursor solvent is at least one of N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) and γ-butyrolactone (GBL); the The mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution includes an active agent solute and an active agent solvent, and the active agent solute is non-ionic, cationic, and anionic. , amphoteric surfactant, the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate, acetone; The fixed temperature is 10-60℃.

Wherein, the active agent solute is polyethylene glycol monooleate, dicoconut dimethyl ammonium chloride, dimethyl dihydrogenated tallow ammonium chloride, dimethyl dihydrogenated tallow ammonium methosulfate, double tallow Quaternary ammonium salt, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, cetyldimethylbenzyl Ammonium chloride, cetylpyridinium bromide, cetylpyridinium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, polyglycerol fatty acid ester, polyglycerol Polyricinoleate, Trimethyl Soybean Oil Ammonium Chloride, Dialkyl Dimethyl Ammonium Chloride, Dimethyl Dihydrogenated Tallow Ammonium Chloride, Dimethyl Dicocoammonium Chloride, Trimethyl Ammonium Chloride Methyl tallow ammonium chloride, N-tallow pentamethyl propane diammonium dichloride, L-α-phosphatidyl choline, sodium lauryl sulfate, diddecyl dimethyl ammonium bromide, Alkyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, linear alcohol polyoxyethylene ether, dioctyl sulfosuccinate sodium salt, N-octadecyl sulfosuccinamide bis Sodium Salt, Cocamidopropyl Betaine, Ethoxylated Sulfosuccinate Disodium Salt, Alkylethanolamide Sulfosuccinate Disodium Salt, Alkyl Sulfosuccinate Disodium Salt, Fatty Alcohol Sulfuric Acid Ester ammonium salt, alkylphenol polyoxyethylene ether sulfate sodium and ammonium salt, nonylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene sorbitan monooleate, polyoxyethylene ether phosphoric acid Esters, isooctylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene fatty amide, fatty alcohol phosphate, sorbitan monostearate, sorbitan Alcohol monooleate, tetradecyl dimethyl ammonium oxide, hexadecyl dimethyl ammonium oxide, octadecyl dimethyl ammonium oxide, C8-18 alkyl dimethyl ammonium oxide, hexadecane trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, dicocoyl dimethyl ammonium chloride, polyethylene glycol sorbitol lauric acid Esters, Polyoxyethylene Sorbitan Oleate, Polyoxyethylene Sorbitan Tetraester, Polyoxyethylene Castor Oil, Polyoxyethylene Propylene Glycol Monostearate, Polyoxyethylene Sorbitol, Polyoxyethylene Sorbitol Tetraoleate, polyoxyethylene sorbitan hexaoleate, polyoxyethylene stearate, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene fatty amine, coconut oil ethylene oxide Adducts, polyoxyethylene castor oil, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylaryl polyoxyethylene ether, alkyl polyoxyethylene ether, alkyl Phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, stearyl alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene fatty amine, polyoxyethylene fatty amine, 2-bromo-2-nitropropane-1 ,3-Diol, alkyldimethylethylbenzylammonium chloride, N-alkyldimethylbenzylammonium chloride, N-tetradecyldimethylbenzylammonium chloride, N-alkyl Dimethyl-1-naphthylmethylammonium chloride, coconut fatty acid diethanolamide, sodium alkylarylsulfonate, sodium linear alkylbenzenesulfonate, propylene glycol monofatty acid ester, carboxypolymethylene compound, linear alcohol Polyoxyethylene ether, lauryl alcohol polyoxyethylene ether sulfur Ammonium acid ester, sodium lauryl polyoxyethylene ether sulfate, nonylphenol polyoxyethylene ether, dodecanol polyoxyethylene ether, N,N-dimethylhydroxyethyl octadecamido quaternary ammonium nitrate Salt, N,N-Dimethylhydroxyethyl octadecamidophosphoric acid quaternary ammonium salt, polyether, glucosylaminopropyldimethyl-2-hydroxyethylammonium chloride, 2-hydroxyethylammonium chloride , cetyl trimethyl ammonium bromide, cetyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium bromide, fatty alcohol polyoxyethylene ether, propylene glycol and fatty acid, polyethylene glycol Alcohol stearate, polyoxyethylene castor oil, nonylphenol polyoxyethylene ether, polyoxyethylene stearate, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sodium alkylnaphthalene sulfonate, Potassium alkyl naphthalene sulfonate, monocalcium alkaryl sulfonic acid, tridecamethylsiloxysilicate, nonylphenol polyoxyethylene ether, C10-13 fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene Vinyl ether, fatty alcohol polyoxyethylene ether, sodium alkylbenzene sulfonate, polyoxyethylene alkylamine, coconut fatty acid polyoxyethylene ester, propylene glycol polyoxypropylene polyoxyethylene ether, alkyl phenolic resin polyether, sucrose fatty acid Ester, nonylphenol polyoxyethylene ether, sodium dodecyl diphenyl ether disulfonate, sodium n-decyl diphenyl ether disulfonate, 4-dodecyl-2,3-oxo-bisbenzenesulfonic acid disodium acid, propylene oxide ethylene oxide block copolymer, sodium alkyl benzene sulfonate, coco-1,3-propanediamine diacetate, N-tallow-1,3-propanediamine Diacetate, N-coco-1,3-propanediamine, N-tallow-1,3-propanediamine, diethanolamine lauryl sulfate, alkyl polyglycol ether, fatty acid alkylamide sulfonate Sodium sulfosuccinic acid monoester, fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester sodium, polyoxyethylene fatty acid alkanolamide sulfosuccinic acid monoester sodium, fatty alcohol phosphate, alkyl polyoxyethylene ether phosphate sodium salt, alkylaryl polyoxyethylene ether, alkyl phosphate sodium salt, disodium sulfosuccinate, sulfosuccinate dialkyl alcohol amide, alkyl aryl sulfonate, alkyl dimethyl betaine, Alkyl tertiary amine oxide, oleic acid polyoxyethylene ester, fatty acid polyethylene glycol ester, alkyl polyethylene glycol ether, polyoxyethylene fatty amine, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkane Phenol polyoxyethylene ether, tridecyloxypolyoxyethylene ethanol, fatty alcohol polyoxyethylene ether, oleic acid polyoxyethylene ether, fatty alcohol polyoxyethylene ether, stearic acid polyoxyethylene ether, polyoxyethylene Ethylene castor oil, alpha-alkenyl sulfonate, polyoxyethylene coconut amide, polyoxyethylene oleamide, nonylphenol polyoxyethylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, polyoxyethylene fatty amine, modified Alkylphenol polyoxyethylene ether, nonylphenol polyethylene glycol ether, fatty alcohol polyethylene glycol ether, octadecyl pyridine chloride, hexadecyl pyridinium bromide, tetradecyl pyridinium bromide, Cetyltrimethylammonium bromide, propylene glycol monoricinoleate, glycerol monoricinoleate, ethylene glycol monoricinoleate, ammonium perfluoroalkanesulfonate, perfluoroalkanesulfonic acid Potassium, potassium fluoroalkyl carboxylates, fluoroalkyl quaternary ammonium sulfonates, ammonium perfluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl alkoxylates, perfluoroalkyl poly Oxyethylene polyoxypropylene ether, polyoxyethylene sorbitan hexaoleate, polyoxyethylene glycerin fat Acid ester, polyoxyethylene polyoxypropylene monostearate, polyoxyethylene coconut fatty amine, alkyl dimethyl ammonium chloride, alkyl polyglycol ether sulfate sodium salt, propylene glycol polyoxyethylene polyoxypropylene Ether, imidazolidinyl urea, polyoxyethylene methyl glucoside sesquistearate, fatty alcohol phosphate, mixed organic phosphate, sodium α-olefin sulfonate, sodium secondary alkane sulfonate, fatty alcohol polyoxyethylene Ether, polyoxyethylene diisobutylphenoxyethyldimethylbenzyl ammonium chloride, linear fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, nonyl Phenol polyoxyethylene ether, dinonylphenol polyoxyethylene ether, dodecylphenol polyoxyethylene ether, sodium oleoyloxyethanesulfonate, sodium N-palmitoyl-N-cyclohexyl taurate, N-methyl Sodium-N-oleoyl sulfonate, fatty alcohol polyoxyethylene ether, 3-trifluoromethyl-4,4'-dichloro-N,N-diphenylurea, polypropylene glycol, polyethylene glycol, N- Alkyl trimethyl ammonium chloride, polyethylene glycol fatty acid ester, silicone, polyoxyethylene fatty amine, fatty acid polyethylene glycol ester, alkylphenol polyethylene glycol ether, cocoyl alkyl betaine, Cocoyl hydrolyzed animal protein potassium salt, propylene glycol fatty acid ester and its potassium salt, polyoxyethylene castor oil, nonylphenol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, polyoxyethylene stearate, polyoxyethylene Er oil, sodium oleamidobenzene sulfonate, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dodecanol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, saponin, alkyl benzene sulfonate Acid alkanolamine salt, sodium alkyl phenol polyoxyethylene ether sulfate, cationic modified polyoxyethylene fatty acid ester, carboxymethyl cellulose, polyethylene glycol stearate, nonylphenol polyoxyethylene Vinyl ether, alkyl alcohol polyoxyethylene ether, polyquaternary vinyl alcohol, monocarboxylated coconut imidazoline derivatives, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, alkane Alkyl phenol polyoxyethylene ether, mixture of sodium alkyl benzene sulfonate and fatty acid polyethylene glycol ester, alkyl phenolic resin polyether, alkylphenolic resin polyether, sodium alkyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate , Secondary alcohol polyoxyethylene ether, C13~15 secondary alcohol polyoxyethylene ether, secondary alcohol polyoxyethylene ether sulfate, sorbitan stearate, polyoxyethylene sorbitan stearate, nonyl Base phenol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, C8 fatty alcohol polyoxyethylene ether sulfate sodium salt, propylene oxide ethylene oxide block copolymer, propylene oxide ethylene oxide block copolymer Cetyl alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether diphosphate, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether , sucrose monolaurate, sucrose monooleate, sucrose monopalmitate, sucrose distearate, sucrose mono, distearate, polyethylene glycol distearate, nonylphenol polyoxygen Vinyl ether, fatty alcohol polyoxyethylene ether, oleyl alcohol/cetyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, oleic acid polyoxyethylene ester, oleyl alcohol polyoxyethylene ether, Polyoxyethylene eicosanoate, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-ethylhexyl-p-methoxylaurate, fatty alcohol polyoxyethylene ether, alkyl methyl polyoxygen Vinyl ether quaternary ammonium salt, dimethyl polysiloxane polyether, methylparaben, propylparaben and ethanol monophenyl ether alkyl phosphate potassium, alkyl phosphate potassium, propylene glycol polyoxyethylene polyoxy Propylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, ethylenediamine polyoxypropylene polyoxyethylene ether, compound of stearyl alcohol polyoxyethylene ether and stearyl alcohol, glycerin Polyoxypropylene oxyethylene ether, quaternary amino ether of ethoxylated cellulose, polyoxyethylene sorbitan fatty acid ester, C16-20 fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene Vinyl ether, ethylenediamine polyoxyethylene polyoxypropylene ether, petroleum sulfonate, quaternized strychmidazoline, sodium stearoyl lactylate, nonylphenol polyvinyl ether, lauryl polyoxyethylene ether sulfate sodium salt, Derivatives of lanolin sterols, sodium dodecylbenzene sulfonate, diisopropyl dimer acid, alkyl amine oxides, alkyl diethanolamides, polyoxyethylene type nonionic surfactants, propylene glycol propylene oxide Ethylene oxide block copolymer, alkyl phenolic resin polyether, dimethylsiloxane, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, hard lauryl alcohol Acid triethanolamine, lauryl alcohol polyoxyethylene ether sulfate sodium salt, polyoxyethylene synthetic fatty acid monoethanolamide, primary alcohol polyoxyethylene ether, alkyl polyoxyethylene ether, fatty alcohol polyvinyl ether mixture, quaternary ammonium salt, diethyl ether Methyldistearylamine chloride, polyoxyethylene fatty amide, polyoxyethylene stearate, neutral lecithin, sorbitan monolaurate, sorbitan monopalmitate, sorbitan Monostearate, Sorbitan Tristearate, Sorbitan Monooleate, Sorbitan Trioleate, Cocoic Acid Diethanolamide, Lauric Acid Diethanolamide, Imidazole Derivatives, Fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, alkylbenzene sulfonate, secondary alkyl sodium sulfate, nonylphenol polyoxyethylene ether, ethylenediamine polyoxypropylene Polyoxyethylene ether, tridecanol polyoxyethylene ether sulfate sodium salt, lauryl alcohol diethanolamide, alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene polyoxyethylene ether, fatty alcohol polyoxypropylene polyoxyethylene At least one of ether succinate.

Specifically, a certain proportion of hydrophobic substances are pre-added in the raw material bottle 110 of the surfactant solution to increase the surface leveling effect of the mixed bivalent precursor solution. The hydrophobic substance is at least one of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, and polyether polysiloxane copolymer. The added hydrophobic substance accounts for 0-50% of the mass ratio of the surfactant.

The present invention also discloses a method for using the coating equipment for the mixed solution of the precursor and the surfactant, which comprises the following steps:

In the first step, the bivalent perovskite precursor solution and the surfactant solution prepared according to the preparation method of a mixed solution of a precursor and a surfactant as described above are poured into different raw material bottles. The raw material bottle is connected with the syringe pump 104 through the pipelines 112 and 115 respectively. The syringe pump 104 simultaneously sucks the bivalent precursor solution and the surfactant solution according to the set volume ratio of 1 to 1000 and injects them into the mixing chamber 111 for mixing. After stirring, a mixed solution of the precursor and the surfactant is obtained.

In the second step, the surface of the substrate 108 to be coated is placed on the coating platform 106, the syringe pump 104 and the conveying device 107 are turned on, and the mixed solution is conveyed to the coating die 101 through the conduit 103. Driven by the device 107, a relative movement occurs between the die head lift table 102 and the coating platform 106, and the die head lift table 102 is used to adjust the height between the coating die head 101 and the substrate 108 to be coated, and the coating The die 101 coats the surface of the substrate 108 to be coated placed on the coating platform 106, and after the surface of the substrate 108 is coated, a wet film containing the mixed solution is obtained.

In the third step, the post-processing device is turned on, and the coated substrate 108 is transported by the conveying device 107 to the post-processing device 105 for post-processing, so as to promote the solvent in the wet film to further volatilize, thereby preparing a layer on the surface of the substrate 108 containing two Thin film layers of valence precursors.

The present invention also discloses a preparation method of a perovskite solar cell. In the process of preparing the perovskite solar cell, the coating equipment of the mixed solution of the precursor and the surfactant as described above is used, which includes the following steps:

S1. The divalent precursor and the surfactant solution prepared according to the preparation method of a mixed solution of a precursor and a surfactant as described above are injected into different raw material bottles, and the two raw material bottles are respectively injected through pipelines and injected The pump is connected, and the syringe pump simultaneously sucks the bivalent precursor solution and the surfactant solution into the mixing chamber for mixing according to the set volume ratio of 1 to 1000. After stirring, the mixed solution of the precursor and the surfactant is obtained.

S2 , placing the substrate 108 on which the conductive layer and the electron/hole transport layer have been prepared on the coating platform 106 . Turn on the syringe pump 104 and the conveying device 107, and the mixed solution is conveyed to the coating die head 101 through the conduit 103. Driven by the conveying device 107, the die head lift table 102 and the coating platform 106 are opposed to each other. Move, adjust the height between the coating die 101 and the substrate 108 to be coated by the die lifting platform 102 , and the coating die 101 coats the surface of the substrate 108 to be coated placed on the coating platform 106 , a wet film containing the mixed solution is obtained after the surface of the substrate 108 is coated.

S3. The post-processing device is turned on, and the coated substrate 108 is transported by the conveying device 107 to the post-processing device 105 for post-processing, so as to promote the solvent in the wet film to further volatilize, so that the coated substrate 108 can be deposited on the electron/hole transport layer on the surface of the substrate. A thin film layer containing a divalent precursor is prepared.

S4, continue to prepare the monovalent precursor thin film layer of perovskite, the hole/electron transport layer and the back electrode layer on the surface of the thin film layer containing the divalent precursor of the substrate, until the preparation of the perovskite solar cell is completed.

Specifically, in S2, when the coating die 101 is coating, the working parameter conditions of the coating die 101 are: the amount of coating liquid is 0.2-2ul/cm ² , and the coating speed is 0.5 -50cm/s, the liquid outlet temperature of the coating die is 60-180°C, and the coating temperature is 60-180°C; the coating die also meets the following environmental conditions during coating: the ambient temperature is 15-30°C, Ambient humidity 0-50%RH, in general atmospheric environment or inert protective atmosphere.

Specifically, a film forming device is also provided on the die head lifting platform to perform film forming treatment on the wet film that has just been coated on the surface of the substrate within 0-60 s after the coating of the coating die head (Fig. not shown). The film forming apparatus includes a heater and a blower or an exhaust fan, or a heater and a vacuum pump.

Specifically, the film formation treatment is heat treatment or drying treatment. The heat treatment refers to placing the substrate coated with the bivalent precursor wet film under a low vacuum pressure of 10 ^-5 -10 ⁵ Pa and an air temperature of 25-150°C for 10-600s for annealing treatment. The drying treatment refers to the rapid drying of the bivalent precursor wet film by air convection caused by blowing or exhausting, and the wind speed of the air flow caused by the blowing or exhausting is 0.5-10m/s, and the temperature of the flowing air is 25. -150℃.

In S4, the post-processing process performed by the post-processing device includes: placing the substrate coated with the wet film of the bivalent precursor mixed solution in a vacuum, dry air, nitrogen, H ₂ O (water), DMF (N , N-dimethylformamide), DMSO (dimethyl sulfoxide), GBL (γ-butyrolactone), NMP (N-methylpyrrolidone) in the environment where at least one gas acts, the ambient pressure is 10 ^-5 -10 ⁶ Pa, the ambient temperature is 100-150°C, and the standing time is 5-120min to dry the wet film into a semi-dry film.

The present invention also discloses a perovskite solar cell, comprising a perovskite thin film layer, wherein the perovskite thin film layer is prepared by using the aforementioned coating equipment of a mixed solution of a precursor and a surfactant, or It is prepared by using the method of using the coating equipment of the mixed solution of the precursor and the surfactant as described above, or by the method of preparing the perovskite solar cell as described above.

The technical solutions of the present invention are further described below in conjunction with specific implementations.

Example 1

The perovskite thin film layer was prepared using the existing two-step method. First, the bivalent precursor solution of 1 mol/L PbI ₂ perovskite was coated on the substrate prepared with the PTAA electron/hole transport layer by slit coating, wherein the bivalent precursor solution of perovskite was The medium divalent precursor solvents were DMF and DMSO, and the volume ratio of DMF and DMSO was 9:1. Then, the coated substrate was post-treated to obtain a PbI ₂ -containing thin film layer. Then a MAI monovalent precursor thin film layer is prepared on the surface of the PbI ₂ thin film layer to obtain a perovskite thin film layer.

Among them, the slit coating conditions of the PbI ₂ divalent precursor solution: under the temperature of 25 ° C and the humidity of 30% RH, the coating liquid amount is 1 ul/cm ² , the slit width is 100 um, and the coating speed is 5cm/s. Drying conditions after coating: hot air drying, the wind speed near the substrate surface is 2m/s, the temperature near the substrate surface is 60°C, and the substrate containing the _PbI2 thin film layer is annealed at 100°C for 2min after coating.

Please refer to Figure 5, there are many white holes in the perovskite thin film layer, this is because the hydrophilic PbI ₂ solution is difficult to infiltrate the surface of the lipophilic PTAA electron/hole transport layer when the PbI ₂ solution is coated. The cohesive force of the PbI ₂ solution is greater than the adhesion force of the surface in contact with the PTAA electron/hole transport layer, which causes the PbI ₂ solution to have a tendency to "shrink", resulting in many holes.

Embodiment 2

Using a two-step process, adding a surfactant to the bivalent precursor solution of the perovskite coating, and then coating the monovalent precursor solution after the coating is completed, the perovskite thin film layer as shown in Figure 6 is obtained. Schematic diagram of the cross section after coating.

The conductive layer 11 and the electron/hole transport layer 12-2 are prepared in sequence on the substrate, and the perovskite thin film layer 16 prepared on the electron/hole transport layer 12-2, because the electron/hole transport layer 12- 2 is coated with a bivalent precursor solution of perovskite containing a surfactant, and there is a surfactant 17 on the lower surface of the perovskite thin film layer 16 . In the figure, the small dots of the surfactant 17 are hydrophilic groups, and the curves are lipophilic groups. The hydrophilic groups are distributed on the side close to the perovskite thin film layer 16 , and the lipophilic groups are distributed on the air side of the lipophilic electron/hole transport layer 12 - 2 and the perovskite thin film layer 16 . The addition of the surfactant 17 effectively improves the wettability of the perovskite thin film layer 16 to the lipophilic electron/hole transport layer 12-2, and improves the flatness of the surface of the perovskite solution in contact with the air. The coverage of the electron/hole transport layer 12-2 by the thin film and the uniformity of the film thickness.

The embodiment of preparing the perovskite thin film layer by using the coating equipment of the mixed solution of the precursor and the surfactant of the present invention includes the following steps:

First, a surfactant was prepared with a mixed solvent of chlorobenzene and dimethylformamide in a volume ratio of 1:2, and 5% dimethicone added with a mass fraction of 10% N-dodecylethanolamine.

Next, a PbI ₂ perovskite divalent precursor solution with a molar concentration of 1.2 M was prepared with a mixed solvent of dimethyl sulfoxide and dimethyl formamide in a volume ratio of 1:9.

Again, the surfactant solution and the _PbI2 divalent precursor solution were charged into two raw material bottles, respectively. According to the volume ratio of the surfactant solution and the perovskite solution being 1:20, the mixture is stirred and mixed uniformly in the mixing chamber 211 . The volume ratio can be controlled by the pumped solution injection flow rate.

Next, using the coating equipment for the mixed solution of the precursor and the surfactant as described above, the prepared mixed solution was slit-coated on the PTAA electron/hole transport layer substrate. Among them, the conditions of slit coating: the temperature is 25°C and the humidity is 30%RH, the coating liquid amount is 0.7ul/cm ² , the slit width is 100um, and the coating speed is 5cm/s.

Next, the wet film on the substrate after coating is heated to make the semi-dry film of the thin film layer containing the divalent precursor obtained by volatilizing the solvent. Among them, the film forming treatment conditions: hot air drying, the wind speed of the hot air near the coated substrate surface is 2m/s, the temperature near the substrate surface is 60°C, and the duration is 60 seconds. Dry film treatment conditions: The substrate coated with the PbI ₂ divalent precursor thin film was placed at a temperature of 100° C., a pressure of 10 ³ Pa, and annealed for 10 minutes in a dry air environment.

Please refer to FIG. 7 , it can be clearly seen from the figure that, compared with Example 1, in addition to a small amount of shrinkage cavities, the perovskite thin film layer of this example has no effect on the lipophilic PTAA electrons/holes. The coverage of the transmission layer substrate is greatly improved, and its outer surface is more flat and smooth.

Please refer to FIG. 8 , which is an efficiency diagram after the perovskite thin film layers of Example 1 and Example 2 are completely prepared into a perovskite solar cell in the same manner. The structure of the fabricated perovskite solar cell is: ITO/hole transport layer/perovskite layer/C ₆₀ /BCP/Cu, and the tested effective cell area is 1 cm ² . The test results show that the cell efficiencies of Example 1 and Example 2 are 6.3% and 16.5%, respectively.

It can be seen from Figure 8 that due to the large number of shrinkage pores in the perovskite film in Example 1, the coverage of the perovskite layer on the electron/hole transport layer substrate is low, resulting in the short-circuit current density JSC of the battery. and fill factor FF is poor. Due to the existence of holes, the leakage of the battery may also be caused, resulting in a poor open circuit voltage VOC.

In the bivalent precursor mixed solution obtained by adding surfactant to the bivalent precursor solution of perovskite, in the process of slit coating using the coating equipment of the present invention, the surfactant plays a role in reducing the perovskite The leveling effect of the bivalent precursor solution of the ore reduces the uneven film thickness and hole defects of the formed perovskite thin film, and improves the efficiency of the fabricated perovskite solar cell. Compared with the prior art, the present invention also relates to the functions of surfactants in emulsifying, solubilizing and suspending in perovskite solutions.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (20)

1. The coating equipment of the mixed solution of the precursor and the surfactant is characterized by comprising a coating die head, a die head lifting platform, a coating platform, a conveying device and a post-treatment device, wherein the coating die head is arranged on the die head lifting platform, the coating die head and the post-treatment device are separated from each other and are respectively arranged above the coating platform, a substrate to be coated placed on the coating platform is conveyed to the post-treatment device for post-treatment by the conveying device after being coated by the coating die head, the die head lifting platform and the coating platform are driven by the conveying device to generate relative movement, and the die head lifting platform adjusts the height between the coating die head and the substrate to be coated; the coating die head is communicated with an injection pump with a mixing cavity through a conduit, the mixing cavity of the injection pump is respectively communicated with at least two raw material bottles through pipelines, at least one raw material bottle contains a divalent precursor solution of perovskite, at least one other raw material bottle contains a surfactant solution, the injection pump respectively and simultaneously pumps the divalent precursor solution of perovskite and the surfactant solution according to a set volume ratio, the two raw material bottles and the surfactant solution are injected into the mixing cavity to be mixed, and the mixed solution obtained through mixing is conveyed to the coating die head through the conduit for use.

2. The apparatus and method for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein the conveyor moves a coating platform, the coating die and a die lifting platform are kept stationary, and the die lifting platform and the coating platform move relatively.

3. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein the conveyor moves a coating die and a die lift, the coating platform is kept stationary, and the die lift and the coating platform are moved relatively to each other.

4. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 2 or 3, wherein a film-forming device for forming a film on a wet film on the surface of the substrate immediately after the coating of the coating die is completed within 0 to 60 seconds is further provided on the die lift, and the film-forming device comprises a heater, and a blower or an exhaust fan, or a heater and a vacuum pump.

5. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 2 or 3, wherein the post-treatment means comprises a heater, a vacuum pump, and a closed chamber which is easy to open and close.

6. The apparatus for coating a mixed solution of a precursor and a surfactant according to claim 1, wherein a stirring device or an ultrasonic oscillation device is further provided in the mixing chamber.

7. The preparation method of the mixed solution of the precursor and the surfactant is characterized in that the precursor is a divalent precursor solution of perovskite, and the divalent precursor solution comprises a divalent metal halide BX₂And a divalent precursor solvent, the formulation method comprising:

injecting a divalent precursor solution into one raw material bottle, injecting a surfactant solution into the other raw material bottle, respectively communicating the two raw material bottles with an injection pump through pipelines, simultaneously and respectively pumping the divalent precursor solution and the surfactant solution into a mixing cavity by the injection pump according to a set volume ratio for mixing, and stirring to obtain a mixed solution of a precursor and the surfactant, wherein,

the divalent metal halide BX₂B in (A) is Pb²⁺、Sn²⁺、Ze²⁺At least one of (1), X is Cl^-、Br^-、I^-The divalent precursor solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and gamma-butyrolactone; the concentration of the divalent precursor solution is 0.5-1.5mol/L, and the mass ratio of the surfactant to the divalent precursor solution is 0.05-5%;

the mass ratio of the surfactant solution to the divalent precursor solution is 5-100%, the surfactant solution comprises an active agent solute and an active agent solvent, the active agent solute is a nonionic, cationic, anionic or amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone;

pumping a divalent precursor solution and a surfactant solution at a set volume ratio of 1-1000; the ambient set temperature during stirring was 10-60 ℃.

8. Polyoxyethylene sorbitan, polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene sorbitan polyoxyethylene sorbitan polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene ether, polyoxyethylene.

9. The method according to claim 7, wherein a hydrophobic substance is added to the raw material bottle of the surfactant in advance in a predetermined proportion, and the hydrophobic substance is at least one of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, and polyether polysiloxane copolymer.

10. Use of a device for coating a mixed solution of a precursor and a surfactant according to any one of claims 1 to 6, characterized in that it comprises the following steps:

firstly, injecting a divalent precursor solution and a surfactant solution of perovskite prepared according to the preparation method of the mixed solution of the precursor and the surfactant as claimed in claim 7, 8 or 9 into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pump simultaneously and respectively pumps the divalent precursor solution and the surfactant solution according to a set volume ratio, the divalent precursor solution and the surfactant solution are injected into a mixing cavity for mixing, and the mixed solution of the precursor and the surfactant is obtained after stirring;

secondly, placing the substrate to be coated on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, driving the die head lifting platform and the coating platform to move relatively, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;

and thirdly, starting the post-treatment device, conveying the coated substrate to the post-treatment device by the conveying device for post-treatment, and preparing a film layer containing a divalent precursor on the surface of the substrate.

11. The method of using a coating apparatus of a mixed solution of a precursor and a surfactant according to claim 10, wherein in the second step, when the coating die is coated, the operating setting parameter conditions of the coating die are as follows: the amount of the coating liquid is 0.2-2ul/cm²The coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 60-180 ℃, and the coating temperature is 60-180 ℃; the coating die head also meets the following environmental conditions when coating: the environment temperature is 15-30 ℃, the environment humidity is 0-50% RH, and the device is in the common atmospheric environment or the environment of inert protective atmosphere.

12. The method of using a coating apparatus for a mixed solution of a precursor and a surfactant according to claim 10, wherein a film-forming device for forming a film on a wet film on a substrate surface immediately after coating of the coating die is completed within 0 to 60 seconds is further provided on the die lift, and the film-forming device includes a heater and a blower or an exhaust fan, or a heater and a vacuum pump.

13. The method of using the apparatus for coating a mixed solution of a precursor and a surfactant according to claim 12, wherein the film forming process comprises a heat treatment of placing the substrate coated with the wet film of the divalent precursor at a low vacuum pressure of 10 or a drying process^-5-10⁵Pa, airPlacing at 25-150 deg.C for 10-600s for annealing; the drying treatment refers to rapidly drying the divalent precursor wet film by air convection caused by blowing or air draft, wherein the air speed caused by blowing or air draft is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.

14. The method for using a coating apparatus of a mixed solution of a precursor and a surfactant according to claim 10, wherein in the fourth step, the post-treatment process performed by the post-treatment device includes: placing the substrate coated with the wet film of the mixed solution in an environment under the action of at least one gas selected from vacuum, dry air, nitrogen, water, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone and N-methylpyrrolidone, wherein the environmental pressure is 10^-5-10⁶Pa, the ambient temperature is 100-150 ℃, and the standing time is 5-120min, so that the wet film is dried into a semi-dry film.

15. A method for manufacturing a perovskite solar cell, characterized in that a coating apparatus of a mixed solution of a precursor according to any one of claims 1 to 6 and a surfactant is used in the process of manufacturing the perovskite solar cell, comprising the steps of:

s1, pouring a divalent precursor solution of perovskite and a surfactant solution prepared according to the preparation method of the mixed solution of the precursor and the surfactant as claimed in claim 7, 8 or 9 into different raw material bottles, wherein the two raw material bottles are respectively communicated with an injection pump through pipelines, the injection pumps simultaneously and respectively pump the divalent precursor solution of calcium and the surfactant solution according to a set volume ratio and inject the divalent precursor solution of calcium and the surfactant solution into a mixing cavity for mixing, and stirring to obtain a mixed solution of the precursor and the surfactant;

s2, placing the substrate with the conductive layer and the electron/hole transport layer prepared on the surface on a coating platform, starting an injection pump and a conveying device, conveying the mixed solution to a coating die head through a conduit, generating relative movement between the die head lifting platform and the coating platform under the driving of the conveying device, adjusting the height between the coating die head and the substrate to be coated through the die head lifting platform, coating the surface of the substrate to be coated placed on the coating platform by the coating die head, and obtaining a wet film containing the mixed solution after coating the surface of the substrate;

s3, starting the post-processing device, conveying the coated substrate to the post-processing device by the conveying device for post-processing, and preparing a film layer containing a divalent precursor on the electron/hole transport layer on the surface of the substrate;

s4, continuously preparing a monovalent precursor thin film layer, a hole/electron transport layer and a back electrode layer of the perovskite on the surface of the thin film layer containing the divalent precursor of the substrate until the perovskite solar cell is prepared.

16. The method for producing a perovskite solar cell as claimed in claim 15, wherein in S2, the coating die is coated under the conditions of the operating parameters of the coating die: the amount of the coating liquid is 0.2-2ul/cm²The coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 60-180 ℃, and the coating temperature is 60-180 ℃; the coating die head also meets the following environmental conditions when coating: the environment temperature is 15-30 ℃, the environment humidity is 0-50% RH, and the device is in the common atmospheric environment or the environment of inert protective atmosphere.

17. The method for producing a perovskite solar cell as claimed in claim 15, wherein a film forming device for performing a film forming process on a wet film on the surface of the substrate just before coating within a time of 0 to 60 seconds after the coating of the coating die is completed is further provided on the die lift, and the film forming device comprises a heater and a blower or a suction fan, or a heater and a vacuum pump.

18. The method for producing the perovskite solar cell as claimed in claim 17, wherein the film forming process comprises a heat treatment of placing the substrate coated with the wet film of the divalent precursor at a low vacuum pressure of 10 a or a drying process^-5-10⁵Pa, air temperature 25-150 deg.CThen, the mixture is placed for 10 to 600 seconds to carry out annealing treatment; the drying treatment refers to rapidly drying the divalent precursor wet film by air convection caused by blowing or air draft, wherein the air speed caused by blowing or air draft is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.

19. The method for producing a perovskite solar cell as claimed in claim 15, wherein in S4, the post-treatment process performed by the post-treatment apparatus comprises: placing the substrate coated with the wet film of the mixed solution in an environment under the action of at least one gas selected from vacuum, dry air, nitrogen, water, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone and N-methylpyrrolidone, wherein the environmental pressure is 10^-5-10⁶Pa, the ambient temperature is 100-150 ℃, and the standing time is 5-120min, so that the wet film is dried into a semi-dry film.

20. A perovskite solar cell comprising a perovskite thin film layer, characterized in that the perovskite thin film layer is produced using the coating apparatus of the mixed solution of the precursor and the surfactant according to any one of claims 1 to 6, or the use method of the coating apparatus of the mixed solution of the precursor and the surfactant according to any one of claims 10 to 14, or the production method of the perovskite solar cell according to any one of claims 15 to 19.

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