CN108057590B - Spraying liquid, perovskite layer, preparation method of perovskite layer and perovskite battery - Google Patents
Spraying liquid, perovskite layer, preparation method of perovskite layer and perovskite battery Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
- B05D2401/31—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as mixtures of monomers and polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the photovoltaic field, in particular to a spraying liquid for preparing a perovskite layer, which comprises a mixed solvent and a perovskite material; the mixed solvent is formed by mixing acetonitrile and an amine solution; the solute of the amine solution is selected from at least one of methylamine, propylamine or butylamine; the solvent of the amine solution is at least one selected from methanol, ethanol and tetrahydrofuran. The spraying liquid adopts acetonitrile and amine solution as mixed solvent to dissolve perovskite material, and after spraying and annealing, the obtained perovskite layer has good film forming property, good continuity, few holes, smoothness, uniformity and good film quality, thereby being beneficial to improving the performance of perovskite batteries. In addition, the spraying liquid has low annealing temperature and high material utilization rate, and reduces the production cost of the perovskite layer. The invention also discloses a preparation method of the perovskite layer, the perovskite layer and the perovskite battery.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to spraying liquid, a perovskite layer, a preparation method of the perovskite layer and a perovskite battery.
Background
As a new type of solar cell, the efficiency of perovskite cell has been improved from 3.8% to 22.1% in recent years, and the efficiency has reached the standard of commercial application. In addition, the perovskite battery has the advantages of wide raw material source, simple preparation process, low cost, capability of preparing large-area flexible batteries and transparent batteries and the like, so that the perovskite battery is paid more and more attention and research.
At present, a perovskite layer of the perovskite battery generally adopts a spin coating process, but the size of the perovskite layer obtained by the spin coating process is small, the amount of consumed solution is large, and the preparation of the perovskite battery with a large area is not facilitated.
In order to produce large-area perovskite layers, a spraying process then occurs. The spraying process generally comprises the following steps: dissolving the perovskite material in solvents such as DMF, DMSO, gamma-butyrolactone and the like to prepare a spraying liquid, then spraying the spraying liquid on a substrate, and annealing to obtain the perovskite layer.
However, the quality of the perovskite layer obtained by the above spraying process is poor.
Disclosure of Invention
In view of the above, it is necessary to provide a spray solution capable of improving the quality of a perovskite layer, in order to solve the problem of poor quality of a perovskite layer obtained by a spray process in the prior art.
A spray liquid for producing a perovskite layer, the spray liquid comprising a mixed solvent, and a perovskite material dissolved in the mixed solvent; the mixed solvent is formed by mixing acetonitrile and an amine solution; the solute of the amine solution is selected from at least one of methylamine, propylamine or butylamine; the solvent of the amine solution is at least one selected from methanol, ethanol, propanol and tetrahydrofuran.
The spraying liquid adopts acetonitrile and amine solution as mixed solvent to dissolve perovskite material, and after spraying and annealing, the obtained perovskite layer has good film forming property, good continuity, few holes, smoothness, uniformity and good film quality, thereby being beneficial to improving the performance of perovskite batteries. In addition, the spraying liquid has low annealing temperature and high material utilization rate, and reduces the production cost of the perovskite layer.
In one embodiment, the concentration of the amine solution is 20 wt% to 33 wt%.
In one embodiment, the volume ratio of the acetonitrile to the amine solution is 3: 1-6: 1.
In one embodiment, the amine solution is an ethanol solution of methylamine.
In one embodiment, the concentration of the perovskite material is 0.01mol/L to 0.2mol/L based on the volume of the spraying liquid.
In one embodiment, the boiling point of the spray fluid is 85 ℃ or less; the viscosity of the spraying liquid is less than or equal to 0.3 cP.
The invention also provides a preparation method of the perovskite layer.
A preparation method of a perovskite layer comprises the following steps:
the spraying liquid provided by the invention is ultrasonically sprayed on a matrix, and then is annealed to obtain a perovskite layer.
According to the preparation method of the perovskite layer, the spraying liquid provided by the invention is adopted, so that the perovskite layer is good in film forming property, good in continuity, few in film holes, smooth and uniform, and good in film quality, and the performance of the perovskite battery is favorably improved. In addition, the spraying liquid has low annealing temperature and high material utilization rate, and reduces the production cost of the perovskite layer.
In one embodiment, the temperature of the annealing is 45 ℃ to 70 ℃.
The invention also provides a perovskite layer.
The perovskite layer is obtained by the preparation method provided by the invention.
The perovskite layer is obtained by the preparation method provided by the invention, so that the perovskite layer has the advantages of good film forming property, good continuity, few holes in the film, smoothness, uniformity and good film quality, and is beneficial to improving the performance of the perovskite battery. In addition, the annealing temperature is low, the utilization rate of the material is high, and the production cost of the perovskite layer is reduced.
The invention also provides a perovskite battery.
A perovskite battery comprises the perovskite layer provided by the invention.
The perovskite battery provided by the invention has the advantages of good film forming property, good continuity, few holes in the film, smoothness, uniformity and good film quality, and the performance of the perovskite battery is improved. In addition, the annealing temperature is low, the utilization rate of the material is high, and the production cost of the perovskite layer and the perovskite battery is reduced.
Drawings
Fig. 1 is a schematic structural view of a perovskite battery according to an embodiment of the present invention.
Fig. 2 is a plot of the current-voltage characteristics of a perovskite cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A spray coating solution for use in preparing a perovskite layer. Specifically, the spray coating liquid includes a mixed solvent, and a perovskite material dissolved in the mixed solvent; the mixed solvent is formed by mixing acetonitrile and an amine solution; the solute of the amine solution is selected from at least one of methylamine, propylamine or butylamine; the solvent of the amine solution is at least one selected from methanol, ethanol, propanol and tetrahydrofuran.
Wherein the perovskite material is a photosensitive material having a perovskite structure. Specifically, the perovskite material is preferably selected from compounds represented by the following chemical formula: MA (MA)xFA1-xPbI3-aBra、MAxFA1-xPbI3-bClb、MAxFA1-xPbBr3-cClcWherein x is 0-1, and a, b and c are all 0-3; wherein the chemical structural formula of MA is CH3NH3 +FA has the chemical formula of CH (NH)2)2 +. Of course, canIt is understood that the perovskite material of the present invention is not limited to the above-mentioned compounds, but may be other perovskite materials deemed suitable by those skilled in the art.
In the spraying liquid, the perovskite material can be directly added into the mixed solvent, and the precursor of the perovskite material can also be added into the mixed solvent. For example combining PbI2Adding the MAI and the mixed solvent. Of course, it will be appreciated that a person skilled in the art may select suitable precursors depending on the perovskite material to be formed, and will not be described in detail here.
The mixed solvent is mainly used for dissolving the perovskite material or the precursor of the perovskite material.
Preferably, the boiling point of the spraying liquid is less than or equal to 85 ℃; the viscosity of the spray liquid is less than 0.3 cP. Therefore, the perovskite film forming property is good under the conditions of lower annealing temperature and shorter time; meanwhile, the liquid drop is smaller during atomization, and the perovskite layer obtained by spraying is more compact.
Preferably, the volume ratio of the acetonitrile to the amine solution in the mixed solvent is 3: 1-6: 1. The perovskite layer obtained in the method is more compact, less in holes and smoother in film.
Preferably, the concentration of the amine solution is 20 wt% to 33 wt%. Thus, the perovskite crystal grows more compactly and has fewer surface defects.
In a preferred embodiment, the amine solution is an ethanolic solution of methylamine. The perovskite layer thus obtained is of better quality.
Preferably, the concentration of the perovskite material is 0.01mol/L to 0.2mol/L based on the volume of the spray liquid. That is, the number of moles of the perovskite material or the precursor thereof per liter of the spray solution is 0.01 to 0.2mol in terms of the number of moles of the perovskite material. The perovskite layer obtained in the method is more compact, less in holes and smoother in film.
The inventor of the invention unexpectedly finds that the spraying liquid prepared by dissolving the perovskite material by using acetonitrile and the amine solution as a mixed solvent has the advantages of good film forming property, good continuity, few film holes, smoothness, uniformity and good film quality of the perovskite layer, thereby being beneficial to improving the performance of the perovskite battery. In addition, methylamine, propylamine or butylamine and the like in the mixed solvent can also play a role in passivation when the perovskite layer is formed into a film, so that the defects are further reduced, and the performance of the perovskite layer is improved.
The spraying liquid has lower boiling points of all components in the mixed solvent, so the annealing can be carried out at lower annealing temperature, and the annealing time is saved; and the utilization rate of the material is high, and the production cost of the perovskite layer is reduced.
The invention also provides a preparation method of the perovskite layer.
A preparation method of a perovskite layer comprises the following steps:
the spraying liquid provided by the invention is ultrasonically sprayed on a matrix, and then is annealed to obtain a perovskite layer.
Wherein, the ultrasonic spraying is to atomize the spraying liquid flowing through the ultrasonic transducer by the ultrasonic transducer to generate micro-to nano-scale fine liquid drops; and then, the liquid drops are further crushed, smaller and homogenized by compressed gas, and the operation direction of the fog particles is guided, so that the operation power of the atomized particles is increased.
Preferably, when ultrasonic spraying is carried out, the ultrasonic frequency is 90KHz, the spraying flow is 0.5mL/min to 1mL/min, the carrier gas is nitrogen, the air pressure is 0.02MPa to 0.1MPa, and the atomization current is 0.07A. This may further improve the quality of the perovskite layer.
More preferably, the substrate is preheated at the time of ultrasonic spraying. It is further preferred that the substrate is preheated to an annealing temperature. Thus, on the one hand, the time for preparing the whole perovskite layer can be saved, and on the other hand, the quality of the perovskite layer can be further improved.
Wherein the annealing mainly has the function of volatilizing the mixed solvent and forming the perovskite film.
Preferably, the annealing temperature is 45 ℃ to 70 ℃. The perovskite layer thus obtained is more dense.
Preferably, the annealing time is 8min to 15 min. Therefore, the perovskite crystal has more moderate growth, better film quality, fewer holes and better perovskite battery effect.
According to the preparation method of the perovskite layer, the spraying liquid provided by the invention is adopted, so that the perovskite layer is good in film forming property, good in continuity, few in film holes, smooth and uniform, and good in film quality, and the performance of the perovskite battery is favorably improved. In addition, the spraying liquid has low annealing temperature and high material utilization rate, and reduces the production cost of the perovskite layer.
The invention also provides a perovskite layer.
The perovskite layer is obtained by the preparation method provided by the invention.
The perovskite layer is obtained by the preparation method provided by the invention, so that the perovskite layer has the advantages of good film forming property, good continuity, few holes in the film, smoothness, uniformity and good film quality, and is beneficial to improving the performance of the perovskite battery. In addition, the annealing temperature is low, the utilization rate of the material is high, and the production cost of the perovskite layer is reduced.
The invention also provides a perovskite battery.
A perovskite battery comprises the perovskite layer provided by the invention.
Specifically, referring to fig. 1, a perovskite battery 100 of an embodiment includes a perovskite layer 110, a hole transport layer 121, a first electrode 131, on one side of the perovskite layer 110, and an electron transport layer 122, a second electrode 132, on the other side of the perovskite layer 110.
Among them, the perovskite layer 110 is a core component layer of the perovskite cell 100, and mainly functions to absorb light energy and generate holes and electrons.
Preferably, the perovskite layer 110 has a thickness of 400nm to 600 nm. This may further improve the performance of the perovskite battery 100.
The hole transport layer 121 is located on one side (lower side in fig. 1) of the perovskite layer 110, and has a main function of separating and transporting out holes generated in the perovskite layer 110.
The hole transport layer 121 may be an organic hole transport material layer or an inorganic hole transport material layer. Specifically, when the hole transport layer 121 is an organic hole transport material layer, voidsThe hole transport layer 121 is preferably a Spiro-OMeTAD layer, a PEDOT PSS layer, a P3HT layer, PTAA layer, or PCDTBT layer. Wherein Spiro-OMeTAD represents 2,2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene. When the hole transport layer 121 is an inorganic hole transport material layer, the hole transport layer 121 is preferably a nonstoichiometric nickel oxide layer, a CuI layer, or a CuSCN layer.
Preferably, the hole transport layer 121 has a thickness of 10nm to 50 nm. Thus, the film forming quality can be ensured, and the defects of the hole transport layer 121 can be reduced; and the internal series resistance can be ensured to be lower, which is beneficial to improving the short-circuit current.
The electron transport layer 122 is located on one side (upper side in fig. 1) of the perovskite layer 110, and has a main function of separating and transporting out electrons generated in the perovskite layer 110.
The electron transport layer 122 may be an organic electron transport layer or an inorganic electron transport layer. Specifically, when the electron transport layer 122 is an organic electron transport material layer, the electron transport layer 122 is preferably a fullerene layer (C60 layer), P3HT layer, PCBM layer. When the electron transport layer 122 is an inorganic electron transport material layer, the electron transport layer 122 is preferably a dense layer of titanium dioxide, zinc dioxide, or tin dioxide.
Preferably, the thickness of the electron transport layer 122 is 30nm to 100 nm. Thus, the film forming quality can be ensured, and the defects can be reduced; and the internal series resistance can be ensured to be lower, which is beneficial to improving the short-circuit current.
In the present invention, the electron transport layer 122 and the hole transport layer 121 may be a chemical spray coating, a spin coating, a doctor blade coating, or the like.
The first electrode 131 mainly functions to collect holes and is connected to an external circuit. The second electrode 132 mainly functions to collect electrons and is connected to an external circuit.
The perovskite battery 100 of the present invention may be of a forward structure or of a reverse structure. The forward structure means that the electron transport layer is positioned on one side of the perovskite layer close to the transparent conductive substrate, namely the hole transport layer is positioned on one side of the perovskite layer far away from the transparent conductive substrate. The inverted structure means that the electron transport layer is positioned on one side of the perovskite layer far away from the transparent conductive substrate, namely the hole transport layer is positioned on one side of the perovskite layer close to the transparent conductive substrate.
When the perovskite battery 100 is of a forward structure, the first electrode 131 is a metal electrode; the second electrode 132 is a transparent conductive substrate. More preferably, when the perovskite battery 100 is of a forward structure, the hole transport layer 121 is selected to be an organic hole transport material layer.
When the perovskite cell 100 is of an inverted structure, the first electrode 131 is a transparent conductive substrate; the second electrode 132 is a metal electrode. The perovskite battery with the inverted structure has the advantages of simple device structure, convenient preparation, unobvious hysteresis effect and capability of manufacturing flexible devices. More preferably, when the perovskite battery 100 is of an inverted structure, the hole transport layer 121 is selected from inorganic hole transport material layers. Therefore, the perovskite battery is an all-inorganic perovskite battery, and the stability and the service life of the perovskite battery can be further improved.
Wherein the transparent conductive substrate provides support for the other layers of the perovskite cell 100. The transparent conductive substrate side is the light facing side of the perovskite cell 100.
Specifically, the transparent conductive substrate includes a transparent substrate layer and a transparent conductive thin film layer attached on the transparent substrate layer. The thickness of the transparent conductive thin film layer is preferably 300nm to 500 nm. This may further improve the performance of the perovskite battery. The transparent conductive thin film layer is preferably an ITO layer, an FTO layer, a ZTO layer, an AZO layer, an IWO layer, or the like.
The thickness of the transparent substrate layer is preferably 1.1mm to 2.5 mm. This ensures sufficient mechanical load bearing and reduces the absorption of light by the transparent substrate layer, allowing more light to enter the perovskite layer 110, thereby increasing the absorption of light.
The transparent conductive thin film layer may be formed on the transparent base layer by a physical vapor deposition method, evaporation, or sputtering.
Specifically, the transparent conductive substrate is preferably transparent conductive glass or transparent conductive plastic. That is, the transparent base layer in forming the transparent base layer is a glass layer or a plastic layer. Such as FTO conductive glass, FTO conductive plastic, ITO conductive glass, ITO conductive plastic. When the transparent conductive substrate is ITO conductive glass or ITO conductive plastic, the thickness of the ITO layer is preferably 300nm to 400 nm. When the transparent conductive substrate is FTO conductive glass or FTO conductive plastic, the thickness of the FTO layer is 500 nm.
Wherein the metal electrode side is the backlight side of the perovskite battery 100.
Preferably, the metal electrode is a silver electrode, an aluminum electrode, or a gold electrode.
Preferably, the thickness of the metal electrode is 100nm to 200 nm.
Preferably, the metal electrode is formed by vacuum evaporation or vacuum sputtering.
The perovskite battery adopts the perovskite layer provided by the invention, and the perovskite layer provided by the invention has the advantages of good film forming property, good continuity, few film holes, smoothness, uniformity and good film quality, and improves the performance of the perovskite battery. In addition, the annealing temperature is low, the utilization rate of the material is high, and the production cost of the perovskite layer and the perovskite battery is reduced.
The present invention is further illustrated by the following specific examples.
Example 1
1. Cleaning transparent conductive substrates
And ultrasonically cleaning the FTO conductive glass in ethanol and deionized water for 15min respectively, and then drying by using nitrogen.
2. Preparation of n-type conductive layer
Preparing 25mg/mL SnCl2〃5H2O, and adding 5mg/mL of lithium bistrifluoromethanesulfonylimide (Li-TFSI) ethanol solution, and carrying out ultrasonic dissolution.
Filtering the ultrasonic solution by using a filter head with the diameter of 0.45 mu m, coating the filtered solution on FTO conductive glass in a spin coating mode, wherein the rotating speed is 3000rpm/s, and heating the FTO conductive glass on a heating plate at the temperature of 200 ℃ for 1h after spin coating for 20 s.
3. Preparation of perovskite layer
In a beaker, 0.794g of methylamine iodide (MAI), 2.454g of PbI were added2Then 80mL of B was addedNitrile (CAN) and 20mL of 33 wt% methylamine ethanol solution are dissolved by ultrasonic to prepare 0.05M perovskite precursor solution, and the color of the solution is light yellow; thus obtaining the spraying liquid.
And (3) heating the heating substrate to 70 ℃, placing the matrix obtained in the step (2) on the heating substrate for heating, and ultrasonically spraying the spraying liquid on the matrix at 70 ℃, wherein the carrier gas is nitrogen, the air pressure is 0.02MPa, the atomization current is 0.07A, the ultrasonic frequency of ultrasonic spraying equipment is 90KHz, the spraying flow is 0.5mL/min, the spraying time is 3min, and the color of the matrix is completely changed from yellow to black after the spraying is finished for 1 min. Heating the matrix on the heating substrate for 10min to obtain a perovskite layer.
4. preparation of p-type conductive layer
80mg of Spiro-MeOTAD was dissolved in 1mL of Chlorobenzene (CB), and 17.5. mu.L of a 520mg/mL solution of Li-TFSI acetonitrile and 28.5. mu.L of a 39.54mg/mL solution of BPO in Chlorobenzene (CB) were added and dissolved by sonication.
And (3) spin-coating the dissolved solution on the perovskite layer at the spin-coating parameter of 2500rpm/s for 30 s.
5. Ag electrode preparation
And performing vapor deposition on the p-type conducting layer to evaporate a 120nm thick Ag electrode.
The resulting perovskite cell was designated as a 1.
Example 2
Essentially the same as in example 1, except that a perovskite layer was prepared. The method comprises the following specific steps:
in a beaker, 0.794g of methylamine iodide (MAI), 2.454g of PbI were added2Then adding 80mL of acetonitrile (CAN) and 20mL of 33 wt% methylamine ethanol solution, and ultrasonically dissolving to prepare 0.05M perovskite precursor solution, wherein the color of the solution is light yellow; thus obtaining the spraying liquid.
And (3) heating the heating substrate to 45 ℃, placing the matrix obtained in the step (2) on the heating substrate for heating, and ultrasonically spraying the spraying liquid on the 45 ℃ matrix, wherein the carrier gas is nitrogen, the air pressure is 0.02MPa, the atomization current is 0.07A, the ultrasonic frequency of ultrasonic spraying equipment is 90KHz, the spraying flow is 0.5mL/min, the spraying time is 3min, and the color of the matrix is completely changed from yellow to black after the spraying is finished for 1 min. And heating the matrix on a heating substrate for 15min to obtain a perovskite layer.
A perovskite cell was obtained and was designated a 2.
Comparative example 1
Essentially the same as in example 1, except that a perovskite layer was prepared. The method comprises the following specific steps:
in a beaker, 0.794g of MAI, 2.454g of PbI were added2And adding 50mL of DMF solution, and performing ultrasonic dissolution to prepare 0.1M perovskite precursor solution, wherein the color of the solution is yellow.
Adjusting the temperature of a heating substrate to 100 ℃, placing the substrate on the heating substrate for heating, spraying the solution dissolved by ultrasound on the substrate at 100 ℃, wherein the carrier gas is nitrogen, the air pressure is 0.02MPa, the atomization current is 0.07A, the ultrasound frequency of an ultrasonic spraying device is 90KHz, the spraying flow is 2mL/min, the spraying time is 3min, and the substrate is heated on the heating substrate for 40min to obtain the perovskite layer.
A perovskite cell was obtained and was designated D1.
And (3) performance testing:
keithley2400SMU at AM1.5,100mW/cm was used for perovskite cells A1-A2, and D12The device test is performed under the irradiation of standard light intensity, and the test results are shown in table 1 and fig. 2.
TABLE 1
As can be seen from table 1 and fig. 2, compared with the perovskite cell D1, the open-circuit voltage, the short-circuit current density, the fill factor, and the photoelectric conversion efficiency of the perovskite cells a1-a2 are greatly improved, which indicates that the spraying liquid provided by the present invention can effectively improve the quality of the perovskite layer.
In addition, as can be seen from table 1 and fig. 2, the perovskite batteries a1 and a2 have small performance difference, which indicates that the annealing temperature has little influence on the quality of the perovskite layer by using the spraying liquid of the present invention, so the spraying liquid of the present invention can greatly reduce the requirement of the spraying process time, improve the production efficiency, and further reduce the cost.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A spray liquid for producing a perovskite layer, characterized by comprising a mixed solvent, and a perovskite material dissolved in the mixed solvent; the mixed solvent is formed by mixing acetonitrile and an amine solution; the solute of the amine solution is selected from at least one of methylamine, propylamine or butylamine; the solvent of the amine solution is at least one selected from methanol, ethanol and tetrahydrofuran;
the boiling point of the spraying liquid is less than or equal to 85 ℃; the viscosity of the spraying liquid is less than or equal to 0.3 cP.
2. The spray solution for producing a perovskite layer as claimed in claim 1, wherein the concentration of the amine solution is 20 to 33 wt%.
3. The spray solution for producing a perovskite layer as claimed in claim 1, wherein the volume ratio of the acetonitrile to the amine solution is 3:1 to 6: 1.
4. The spray solution for producing a perovskite layer as claimed in claim 1, wherein the amine solution is an ethanol solution of methylamine.
5. The spray liquid for producing a perovskite layer as claimed in claim 1, wherein the concentration of the perovskite material is 0.01 to 0.2mol/L based on the volume of the spray liquid.
6. The spray liquid for producing a perovskite layer as claimed in claim 1, wherein the perovskite material is a photosensitive material having a perovskite structure.
7. A preparation method of a perovskite layer is characterized by comprising the following steps:
ultrasonically spraying the spraying liquid of any one of claims 1 to 6 on a substrate, and then annealing to obtain a perovskite layer.
8. The method of producing a perovskite layer as claimed in claim 7, wherein the annealing temperature is 45 ℃ to 70 ℃.
9. A perovskite layer obtained by the production method according to any one of claims 7 to 8.
10. A perovskite battery comprising the perovskite layer as set forth in claim 9.
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| CN108832029A (en) * | 2018-06-11 | 2018-11-16 | 浙江理工大学 | A kind of in-situ method growing method of perovskite thin film and application |
| GB201817167D0 (en) * | 2018-10-22 | 2018-12-05 | Univ Oxford Innovation Ltd | Process for producing a layer with mixed solvent system |
| CN109638161B (en) * | 2018-12-04 | 2022-11-29 | 储天新能源科技（长春）有限公司 | Preparation method of efficient perovskite solar cell and perovskite solar cell |
| CN109599490B (en) * | 2019-01-11 | 2023-05-19 | 昆山协鑫光电材料有限公司 | Binary mixed solvent system and application thereof in preparing perovskite material |
| CN109742246B (en) * | 2019-01-11 | 2023-09-05 | 昆山协鑫光电材料有限公司 | Controllable mixed solvent system and application thereof in preparing perovskite material |
| CN109888113A (en) * | 2019-03-25 | 2019-06-14 | 苏州协鑫纳米科技有限公司 | Calcium titanium ore bed and preparation method thereof, perovskite solar battery |
| CN111463350A (en) * | 2020-04-20 | 2020-07-28 | 浙江大学 | X-ray detector based on perovskite quantum dots and preparation method thereof |
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