CN117320464A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 14
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 5
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H10K30/50—Photovoltaic [PV] devices
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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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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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
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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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- 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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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Abstract
The invention relates to the technical field of new energy materials, in particular to a perovskite solar cell and a preparation method thereof. The perovskite solar cell includes: a conductive substrate; an electron transport layer composited on the conductive substrate; an insulating layer composited on the electron transport layer; a hole transport layer composited on the insulating layer; and a bottom electrode composited on the hole transport layer. According to the invention, fatty acid is used as a dispersing agent, ethanol is used as a cosolvent, meanwhile, a high-shear emulsification technology is introduced to fully promote the dispersion of the fatty acid, and finally, slurry with good dispersibility and leveling property and no toxic or harmful effect is formed, and perovskite can be effectively contacted with an electron/hole transport material and a bottom electrode material, so that the transport of carriers is ensured, the carrier recombination loss is reduced, and the photoelectric conversion efficiency of a solar cell is ensured.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a perovskite solar cell and a preparation method thereof.
Background
Perovskite solar cells are emerging technologies in the solar cell field due to their advantages of high theoretical conversion efficiency, low cost, ease of preparation, etc. Perovskite solar cells are of two major types, planar and mesoporous, with mesoporous cells being favored for their efficient carrier separation. The preparation method of the mesoporous perovskite solar cell comprises the steps of firstly preparing auxiliary materials such as an electron transport material, a hole transport material and the like into nano stock solution, uniformly coating the nano stock solution on the surface of a conductive substrate, drying to form a porous structure, then pouring perovskite precursor solution into the porous structure, and inducing perovskite crystallization through means such as heating, evaporation and the like to form the mesoporous perovskite solar cell.
In order to prepare the mesoporous perovskite solar cell with good performance, the preparation of the stock solution is important. The ideal stock solution meets the requirements of high dispersibility, high leveling property, low cost, environmental protection, no pollution and the like. According to the current existing literature and patent reports, the production and preparation technologies of perovskite solar cell stock solutions are mainly divided into two types: the first is a preparation method based on an organic solvent, for example, terpineol is used as a solvent, ethyl cellulose and lauric acid are used as a thickener and a surfactant respectively, so that a stock solution with proper viscosity and good dispersibility and leveling property can be obtained (see references J. Phys. Chem. Lett. 2014, 5, 17, 2927-2934, nano Lett. 2014, 14, 2, 1000-1004, patent CN202210806436.4 and the like); the other is a preparation method based on aqueous solution, because water has large surface tension and easily causes raw liquid agglomeration, the method needs strong surface active agents such as acetylacetone, span-85 and the like to ensure the raw liquid to be fully dispersed so as to obtain raw liquid with excellent performance (see references Energy environment, mater, 2023, 0, e12582, int J Energy Res, 2022;46:22819-22831, patents CN201910966999.8, CN201310507118.9 and the like).
In the existing technology, the organic solvent route needs to adopt toxic and harmful substances such as terpineol, lauric acid and the like, and the problem that the toxic substances volatilize inevitably exists in the process of drying and roasting the device, so that serious pollution and toxicity to personnel can be caused; although the water-based solvent route does not need to adopt toxic solvents, the water-based solvent route still cannot avoid the problem of volatilization of toxic substances during drying and roasting because of adopting toxic surfactants such as acetylacetone, span-85 and the like. Therefore, it is needed to find a preparation method of green stock solution which does not need toxic solvents or toxic surfactants, and green pollution-free preparation of the battery is realized on the premise of ensuring high dispersibility and high leveling property of the stock solution.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell does not need toxic and harmful substances, and has better photoelectric conversion efficiency.
The invention provides a perovskite solar cell, comprising:
a conductive substrate;
an electron transport layer composited on the conductive substrate;
an insulating layer composited on the electron transport layer;
a hole transport layer composited on the insulating layer;
a bottom electrode composited on the hole transport layer;
the electron transport layer is prepared from an electron transport layer stock solution comprising an electron transport material, fatty acid, ethanol and deionized water;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, fatty acid, ethanol and deionized water;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, fatty acid, ethanol and deionized water;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, fatty acid, ethanol and deionized water.
Preferably, the fatty acid has the formula C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n.
Preferably, the electron transport material comprises TiO 2 、SnO 2 Or ZnO;
the electron transport material is nano particles with the particle size of 10-100 nm;
the mass ratio of the electron transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing an electron transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an electron transport layer stock solution.
Preferably, the insulating layer material comprises ZrO 2 、Al 2 O 3 Or SiO 2 ；
The insulating layer material is nano particles with the particle size of 10-100 nm;
the mass ratio of the insulating layer material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an insulating layer stock solution.
Preferably, the hole transport material comprises NiO x PCBM or CuSCN;
the hole transport material is nano particles with the particle size of 10-100 nm;
the mass ratio of the hole transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a hole transport layer stock solution.
Preferably, the bottom electrode material includes at least one of graphite, conductive carbon black, and carbon nanotubes;
the mass ratio of the bottom electrode material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a bottom electrode stock solution.
Preferably, the power of the high shear emulsification treatment is 1-100W/mL, and the time is 10-60 min.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
a) Sequentially coating the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry on a conductive substrate, and drying each stock solution after coating to obtain a blank device without perovskite;
the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry are respectively prepared from an electron transport layer stock solution, an insulating layer stock solution, a hole transport layer stock solution and a bottom electrode stock solution by removing ethanol;
b) Dropwise adding the perovskite precursor solution onto the bottom electrode of the blank device, and annealing after the perovskite precursor solution fully permeates into the bottom electrode, the hole transport layer, the insulating layer and the electron transport layer to obtain a perovskite-containing device;
c) And B), capping a back plate on the bottom electrode of the device obtained in the step B), connecting wires, and smearing sealant to obtain the perovskite solar cell.
Preferably, in step a), the ethanol is removed by evaporation;
the evaporating air pressure is normal pressure, the temperature is 78-99 ℃, and the time is 1-12 h;
the coating thickness of the electron transport layer slurry is 0.5-2 mu m;
the coating thickness of the insulating layer slurry is 1-3 mu m;
the coating thickness of the hole transport layer slurry is 0.5-2 mu m;
the coating thickness of the bottom electrode slurry is 5-15 mu m;
the temperature of the drying is 70-150 ℃ and the time is 5-30 min.
Preferably, in step B), the solvent in the perovskite precursor solution includes at least one of dimethylformamide and dimethyl sulfoxide; the solute is ABX 3 Wherein A is at least one of methylamine ion, formamidine ion and cesium ion, and B is Pb 2 + And Sn (Sn) 2+ At least one of X is I - 、Br - And Cl - At least one of (a) and (b);
the concentration of the perovskite precursor solution is 1.0-1.5 mol/L;
the drop-adding amount of the perovskite precursor solution on a blank device is 2-4 mu L/cm 2 ；
The annealing temperature is 60-120 ℃ and the annealing time is 4-24 hours.
The invention provides a perovskite solar cell, comprising: a conductive substrate; an electron transport layer composited on the conductive substrate; an insulating layer composited on the electron transport layer; a hole transport layer composited on the insulating layer; a bottom electrode composited on the hole transport layer; the electron transport layer is prepared from an electron transport layer stock solution comprising an electron transport material, fatty acid, ethanol and deionized water; the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, fatty acid, ethanol and deionized water; the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, fatty acid, ethanol and deionized water; the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, fatty acid, ethanol and deionized water.
According to the invention, non-toxic and harmless fatty acid with moderate viscosity is adopted as a dispersing agent, ethanol is adopted as a cosolvent (ethanol can be removed through heating evaporation), meanwhile, a high-shear emulsification technology is introduced to fully promote the dispersion of the fatty acid, and finally, a slurry with good dispersibility and leveling property and no toxic or harmful effect is formed, and perovskite can be effectively contacted with an electron/hole transport material and a bottom electrode material, so that the transport of carriers is ensured, the composite loss of carriers is reduced, and the photoelectric conversion efficiency of a solar cell is ensured.
Drawings
Fig. 1 is a J-V test curve of perovskite solar cells obtained in examples 1 to 3 and comparative examples 1 to 3.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a perovskite solar cell, comprising:
a conductive substrate;
an electron transport layer composited on the conductive substrate;
an insulating layer composited on the electron transport layer;
a hole transport layer composited on the insulating layer;
a bottom electrode composited on the hole transport layer;
the electron transport layer is prepared from an electron transport layer stock solution comprising an electron transport material, fatty acid, ethanol and deionized water;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, fatty acid, ethanol and deionized water;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, fatty acid, ethanol and deionized water;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, fatty acid, ethanol and deionized water.
Regarding the conductive substrate:
the conductive substrate comprises FTO glass, ITO glass, or any other transparent conductive substrate, preferably FTO glass. The film thickness of the conductive substrate is 200-500 nm, preferably 350 nm.
Regarding the electron transport layer:
the electron transport material comprises TiO 2 、SnO 2 ZnO or any other n-type semiconductor material.
The electron transport material is nano particles with the particle size of 10-100 nm; preferably, the particle size is 30 to 50 nm.
The chemical formula of the fatty acid is C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n; preferably, the fatty acid is oleic acid (C 18 H 34 COOH) or linoleic acid (C 18 H 32 COOH). The fatty acid is a dispersant.
The mass ratio of the electron transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100; preferably 10:5:50:100.
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing an electron transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an electron transport layer stock solution.
The power of the high-shear emulsification treatment is 1-100W/mL, preferably 10W/mL; the time is 10-60 min, preferably 30min.
Regarding the insulating layer:
the insulating layer material comprises ZrO 2 、Al 2 O 3 、SiO 2 Or any other insulating material.
The insulating layer material is nano particles with the particle size of 10-100 nm; preferably, the particle size is 30 to 50 nm.
The chemical formula of the fatty acid is C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n; preferably, the fatty acid is oleic acid (C 18 H 34 COOH) or linoleic acid (C 18 H 32 COOH）。
The mass ratio of the insulating layer material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100; preferably 10:5:50:100.
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an insulating layer stock solution.
The power of the high-shear emulsification treatment is 1-100W/mL, preferably 10W/mL; the time is 10-60 min, preferably 30min.
Regarding the hole transport layer:
the hole transport material comprises NiO x PCBM, cuSCN, or any other p-type semiconductor material.
The hole transport material is nano particles with the particle size of 10-100 nm; preferably, the particle size is 30 to 50 nm.
The chemical formula of the fatty acid is C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n; preferably, the fatty acid is oleic acid (C 18 H 34 COOH) or linoleic acid (C 18 H 32 COOH）。
The mass ratio of the hole transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100; preferably 10:5:50:100.
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a hole transport layer stock solution.
The power of the high-shear emulsification treatment is 1-100W/mL, preferably 10W/mL; the time is 10-60 min, preferably 30min.
Regarding the bottom electrode:
the bottom electrode material comprises graphite, conductive carbon black, carbon nanotubes or any other conductive carbon material or mixture thereof; preferably, graphite with the particle size of 5-10 mu m and conductive carbon black with the particle size of 30-50 nm are adopted, and the mass ratio is 3:1, a step of; or graphite with the particle size of 5-10 mu m is adopted.
The chemical formula of the fatty acid is C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n; preferably, the fatty acid is oleic acid (C 18 H 34 COOH) or linoleic acid (C 18 H 32 COOH）。
The mass ratio of the bottom electrode material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100; preferably 10:5:50:100. 20:10:50:100.
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a bottom electrode stock solution.
The power of the high-shear emulsification treatment is 1-100W/mL, preferably 10W/mL; the time is 10-60 min, preferably 30min.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
a) Sequentially coating the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry on a conductive substrate, and drying each stock solution after coating to obtain a blank device without perovskite;
the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry are respectively prepared from an electron transport layer stock solution, an insulating layer stock solution, a hole transport layer stock solution and a bottom electrode stock solution by removing ethanol;
b) Dropwise adding the perovskite precursor solution onto the bottom electrode of the blank device, and annealing after the perovskite precursor solution fully permeates into the bottom electrode, the hole transport layer, the insulating layer and the electron transport layer to obtain a perovskite-containing device;
c) And B), capping a back plate on the bottom electrode of the device obtained in the step B), connecting wires, and smearing sealant to obtain the perovskite solar cell.
In step A):
the method of removing ethanol is removing ethanol by evaporation. The evaporating air pressure is normal pressure, the temperature is 78-99 ℃ (reaching the boiling point of ethanol and lower than the boiling point of water, preferably 85 ℃), and the time is 1-12 h (preferably 6 h).
The thickness of the electron transport layer paste is 0.5-2 μm, preferably 1 μm.
The thickness of the insulating layer paste is 1 to 3 μm, preferably 1.5 μm.
The thickness of the hole transport layer slurry is 0.5-2 μm, preferably 1 μm.
The coating thickness of the bottom electrode slurry is 5-15 mu m, preferably 10 mu m; such as 5 μm.
The coating method is a slit coating method.
The temperature of the drying is 70-150 ℃, preferably 120 ℃; the time is 5-30 min, preferably 15min.
In step B):
in the perovskite precursor solution, the solvent comprises at least one of Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and the solute is ABX 3 (wherein A is at least one of methylamine ion, formamidine ion and cesium ion, and B is Pb 2+ And Sn (Sn) 2+ At least one of X is I - 、Br - And Cl - At least one of). In certain embodiments, the solvent comprises DMF and DMSO in a volume ratio of 4:1.
the concentration of the perovskite precursor solution is 1.0-1.5 mol/L, preferably 1.2 mol/L.
The perovskite precursor solution is emptyThe drop adding amount on the white device is 2-4 mu L/cm 2 Preferably 3. Mu.L/cm 2 。
The annealing temperature is 60-120 ℃ and the annealing time is 4-24 hours; preferably, when the annealing temperatures are 60 ℃/80 ℃/100 ℃/120 ℃ respectively, the corresponding times are 24h/16h/8h/4h respectively. The annealing serves to remove the solvent from the perovskite precursor solution and precipitate the perovskite.
In step C):
the backboard is made of glass, organic glass or other airtight plates.
The method of connecting the wires is not particularly limited in the present invention, and a method of connecting the wires, which is well known to those skilled in the art, may be employed.
The sealant is prepared from commercial sealant, and the common components are epoxy resin or ethylene-vinyl acetate copolymer.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The beneficial effects are that:
1) Environmental protection and no pollution: deionized water is used as a solvent in all the slurries prepared by the invention, and no toxic or harmful solvent is added; in all the slurries prepared by the invention, fatty acid is used as a dispersing agent, and no toxic or harmful dispersing agent is added. Because no toxic raw materials are introduced in the preparation process of the slurry, no toxic or harmful products are produced, and the problem of volatilization of toxic or harmful substances in the conventional slurry preparation process is solved.
2) The process is simple: the high-shear emulsification and coating are common industrial production processes, the equipment cost is low, extreme conditions such as vacuum, high temperature and high pressure are not needed, and the production process is mild and easy to operate.
3) In order to fully disperse the fatty acid surfactant in the water-based slurry, the present invention introduces ethanol as a co-solvent, and then removes the ethanol by evaporation.
4) The process compatibility is high: the method is applicable to various electron transport materials, hole transport materials, insulating materials and bottom electrode materials.
5) The device performance is high: because the slurry obtained by the method has high dispersibility, the perovskite can be effectively contacted with the electron/hole transport material and the bottom electrode material, thereby ensuring the transport of carriers and reducing the recombination loss of the carriers, and further ensuring the photoelectric conversion efficiency of the solar cell.
In order to further illustrate the present invention, the following examples are provided to describe a perovskite solar cell and a method for manufacturing the same in detail, but the present invention is not to be construed as being limited to the scope of the present invention.
Example 1
1) TiO is adopted 2 Is an electron transport material, and has a particle size of 30-50 nm; an electron transport material (TiO 2 ) The mass ratio of the dispersant (oleic acid), the ethanol and the deionized water is 2:1:5:10, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 85 ℃ for 6h to remove ethanol, and obtaining an electron transport layer stock solution;
2) By ZrO 2 Is an insulating layer material, and has the grain diameter of 30-50 nm; insulating layer material (ZrO 2 ) The mass ratio of the dispersant (oleic acid), the ethanol and the deionized water is 2:1:5:10, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 85 ℃ for 6h to remove ethanol, and obtaining insulating layer slurry;
3) NiO is adopted x The particle size of the material is 30-50 nm; hole transport material (NiO) x ) The mass ratio of the dispersant (oleic acid), the ethanol and the deionized water is 2:1:5:10, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 85 ℃ for 6h to remove ethanol, and obtaining hole transport layer slurry;
4) Graphite is adopted as a bottom electrode material, and the grain diameter is 5-10 mu m; the bottom electrode material, dispersant (oleic acid), ethanol and deionized water are mixed according to the mass ratio of 2:1:5:10, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 85 ℃ for 6h to remove ethanol, and obtaining a bottom electrode;
5) Sequentially coating the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry on the surface of FTO glass (the glass thickness is 2mm, and the FTO film thickness is 350 nm) by a slit coating method, wherein the coating thickness is sequentially 1 mu m, 1.5 mu m, 1 mu m and 10 mu m, and drying at 120 ℃ for 15min after each slurry coating is carried out to obtain a blank device without perovskite;
6) The solute is MAPbI 2.8 Cl 0.2 The perovskite precursor solution (concentration 1.2mol/L, solvent comprises DMF and DMSO, volume ratio is 4:1) is dripped on the bottom electrode of the blank device obtained in step 5), and the dripping amount is 3 mu L/cm 2 Annealing at 80 ℃ for 16 hours to obtain a perovskite-containing device;
7) And (3) covering a glass back plate on the bottom electrode of the device obtained in the step (6), connecting wires, and coating commercial sealant (epoxy resin) to obtain the perovskite solar cell.
Example 2
The difference from example 1 is that:
the electron transport material is SnO 2 The grain diameter is 30-50 nm;
the coating thickness of the electron transport layer slurry is 500nm;
1) -4) in: the dispersant is replaced by a mixed solution of oleic acid and linoleic acid (volume ratio is 1:1);
the solute in the perovskite precursor solution is MA 0.5 FA 0.5 PbI 2.8 Cl 0.2 ；
The rest of the procedure was the same as in example 1 to obtain a perovskite solar cell.
Example 3
The difference from example 1 is that:
the bottom electrode material is replaced by carbon nano tubes;
4) The mass ratio of the bottom electrode material to the dispersing agent to the ethanol to the deionized water is 2:1:5:10;
1) -4) in: oleic acid is replaced by mixed liquid of oleic acid and linoleic acid (volume ratio is 1:1);
5) The thickness of the coating of the bottom electrode slurry is 5 mu m;
the rest of the procedure was the same as in example 1 to obtain a perovskite solar cell.
Comparative example 1
The difference from example 1 is that:
1) -4) in: the oleic acid is replaced by Span-85, the deionized water is replaced by terpineol, and the evaporation is replaced by rotary evaporation at 50 ℃ under the atmospheric pressure of 0.05;
the rest of the procedure was the same as in example 1 to obtain a perovskite solar cell.
Comparative example 2
The difference from example 2 is that:
1) -4) in: the oleic acid is replaced by Span-85, the deionized water is replaced by terpineol, and the evaporation is replaced by rotary evaporation at 50 ℃ under the atmospheric pressure of 0.05;
the rest of the procedure was the same as in example 2 to obtain a perovskite solar cell.
Comparative example 3
The difference from example 1 is that:
1) -4) in: the oleic acid is replaced by acetylacetone, the deionized water is replaced by terpineol, and the evaporation is replaced by rotary evaporation at 50 ℃ under the atmospheric pressure of 0.05;
the rest of the procedure was the same as in example 1 to obtain a perovskite solar cell.
Fig. 1 is a J-V test curve of perovskite solar cells obtained in examples 1 to 3 and comparative examples 1 to 3. The relevant electrical performance parameters are shown in table 1. The test was performed at 25.+ -. 2 ℃ with a scan rate of 10mV/s and the scan direction was reverse scan (scan from maximum voltage to zero voltage).
Table 1 electrical properties of perovskite solar cells obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from the performance data of the examples and the comparative examples, the battery device prepared by the invention has obviously better performance than the device prepared by using acetylacetone and Span-85 as dispersing agents, and the green and environment-friendly preparation method adopted by the invention can replace the preparation method which adopts acetylacetone with high pollution and high cost.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A perovskite solar cell comprising:
a conductive substrate;
an electron transport layer composited on the conductive substrate;
an insulating layer composited on the electron transport layer;
a hole transport layer composited on the insulating layer;
a bottom electrode composited on the hole transport layer;
the electron transport layer is prepared from an electron transport layer stock solution comprising an electron transport material, fatty acid, ethanol and deionized water;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, fatty acid, ethanol and deionized water;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, fatty acid, ethanol and deionized water;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, fatty acid, ethanol and deionized water.
2. The perovskite solar cell of claim 1, wherein the fatty acid has a chemical formula of C n H m COOH, wherein n is more than or equal to 4 and less than or equal to 18, and n+1 is more than or equal to m and less than or equal to 2n.
3. The perovskite solar cell of claim 1, wherein the electron transport material comprises TiO 2 、SnO 2 Or ZnO;
the electron transport material is nano particles with the particle size of 10-100 nm;
the mass ratio of the electron transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing an electron transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an electron transport layer stock solution.
4. The perovskite solar cell of claim 1, wherein the insulating layer material comprises ZrO 2 、Al 2 O 3 Or SiO 2 ；
The insulating layer material is nano particles with the particle size of 10-100 nm;
the mass ratio of the insulating layer material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain an insulating layer stock solution.
5. The perovskite solar cell of claim 1, wherein the hole transport material comprises NiO x PCBM or CuSCN;
the hole transport material is nano particles with the particle size of 10-100 nm;
the mass ratio of the hole transport material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a hole transport layer stock solution.
6. The perovskite solar cell of claim 1, wherein the bottom electrode material comprises at least one of graphite, conductive carbon black, and carbon nanotubes;
the mass ratio of the bottom electrode material to the fatty acid to the ethanol to the deionized water is 5-25: 1-10: 25-75: 100;
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, fatty acid, ethanol and deionized water, and performing high-shear emulsification treatment to obtain a bottom electrode stock solution.
7. The perovskite solar cell according to any one of claims 3 to 6, wherein the power of the high shear emulsification treatment is 1 to 100W/mL for 10 to 60 minutes.
8. A method for manufacturing a perovskite solar cell according to any one of claims 1 to 7, comprising the steps of:
a) Sequentially coating the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry on a conductive substrate, and drying each stock solution after coating to obtain a blank device without perovskite;
the electron transport layer slurry, the insulating layer slurry, the hole transport layer slurry and the bottom electrode slurry are respectively prepared from an electron transport layer stock solution, an insulating layer stock solution, a hole transport layer stock solution and a bottom electrode stock solution by removing ethanol;
b) Dropwise adding the perovskite precursor solution onto the bottom electrode of the blank device, and annealing after the perovskite precursor solution fully permeates into the bottom electrode, the hole transport layer, the insulating layer and the electron transport layer to obtain a perovskite-containing device;
c) And B), capping a back plate on the bottom electrode of the device obtained in the step B), connecting wires, and smearing sealant to obtain the perovskite solar cell.
9. The process according to claim 8, wherein in step a), the ethanol is removed by evaporation;
the evaporating air pressure is normal pressure, the temperature is 78-99 ℃, and the time is 1-12 h;
the coating thickness of the electron transport layer slurry is 0.5-2 mu m;
the coating thickness of the insulating layer slurry is 1-3 mu m;
the coating thickness of the hole transport layer slurry is 0.5-2 mu m;
the coating thickness of the bottom electrode slurry is 5-15 mu m;
the temperature of the drying is 70-150 ℃ and the time is 5-30 min.
10. The method of producing according to claim 8, wherein in step B), the solvent in the perovskite precursor solution includes at least one of dimethylformamide and dimethylsulfoxide; the solute is ABX 3 Wherein A is at least one of methylamine ion, formamidine ion and cesium ion, and B is Pb 2+ And Sn (Sn) 2+ At least one of X is I - 、Br - And Cl - At least one of (a) and (b);
the concentration of the perovskite precursor solution is 1.0-1.5 mol/L;
the drop-adding amount of the perovskite precursor solution on a blank device is 2-4 mu L/cm 2 ；
The annealing temperature is 60-120 ℃ and the annealing time is 4-24 hours.
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