CN117320465A - Mesoporous perovskite solar cell and preparation method thereof - Google Patents

Mesoporous perovskite solar cell and preparation method thereof Download PDF

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CN117320465A
CN117320465A CN202311600420.9A CN202311600420A CN117320465A CN 117320465 A CN117320465 A CN 117320465A CN 202311600420 A CN202311600420 A CN 202311600420A CN 117320465 A CN117320465 A CN 117320465A
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transport layer
bottom electrode
hole transport
stock solution
insulating layer
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唐梓彭
李啸宇
魏超
上官炫烁
曹席华
邹文珍
马奎超
申宇
周宇昊
周璐
何梓瑜
俞泂晶
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Huadian Electric Power Research Institute Co Ltd
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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
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    • 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 mesoporous perovskite solar cell and a preparation method thereof. The mesoporous 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. Ethanol and glycerol are used as solvents, the ethanol promotes the dispersion of nano particles in the slurry, and then the ethanol is removed by rotary evaporation so as to improve the viscosity of the slurry and facilitate coating; the glycerol can also play a role of a surfactant to a certain extent, and toxic and harmful surfactants are not required to be added; meanwhile, a high-shear emulsification technology is introduced, so that slurry with good performance and no toxic effect is finally formed, and perovskite can be effectively contacted with an electron/hole transport material and a bottom electrode material, so that the carrier transport is ensured, the carrier recombination loss is reduced, and the photoelectric conversion efficiency of the solar cell is ensured.

Description

Mesoporous perovskite solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of new energy materials, in particular to a mesoporous perovskite solar cell and a preparation method thereof.
Background
Perovskite solar cells are an emerging technology in the field of solar cells, with higher conversion efficiency and low cost. The mesoporous perovskite solar cell is a perovskite solar cell with at least one charge transmission layer interface in a mesoporous structure, and has the advantages of high-efficiency carrier separation, low current and voltage loss, easiness in large-area preparation and the like. The mesoporous perovskite solar cell is prepared by preparing nano slurry from electron transport materials, hole transport materials, insulating layers and the like, uniformly coating the nano slurry on the surface of a conductive substrate (such as FTO glass), drying to remove a solvent to form a porous film, pouring a perovskite precursor solution into holes, heating for evaporation, and inducing perovskite crystallization.
The performance of mesoporous perovskite solar cells is greatly affected by the slurry. The good slurry has the advantages of high dispersibility, high leveling property, low cost, environmental protection, no pollution and the like. According to the previous literature and patent report, perovskite solar cell slurry production technologies are mainly divided into two technical routes: the first is a preparation method based on an organic solvent, for example, using terpineol as a solvent, ethyl cellulose as a thickener and a pore-forming agent, and lauric acid as a surfactant, so as to obtain a slurry with proper viscosity, high dispersibility and high leveling property (see literature J. Phys. Chem. Lett. 2014, 5, 17, 2927-2934, nano Lett. 2014, 14, 2, 1000-1004, patent CN202210806436.4, etc.); the other is a preparation method based on aqueous solution, because of high water surface tension and easy slurry agglomeration, powerful surfactants such as acetylacetone, span-85 and the like are needed to promote the slurry to be fully dispersed (see documents Energy environment, mater, 2023, 0, e12582, int J Energy Res, 2022;46:22819-22831, patents CN201910966999.8, CN201310507118.9 and the like).
In the two technical routes, the organic solvent needs to adopt toxic and harmful raw materials such as terpineol, lauric acid and the like, and the volatilization of the toxic substances can cause serious environmental pollution and the hazard of personnel being poisoned; although the water-based solvent route does not need toxic solvents, the water-based solvent route still cannot cause the problem of environmental pollution caused by volatilization of toxic substances because of the need of toxic surfactants such as acetylacetone, span-85 and the like. Based on the above, there is a need to develop a green and environment-friendly slurry preparation method which does not need toxic solvents or toxic surfactants, and solves the problem of volatilization of toxic substances on the premise of ensuring that the slurry has good properties.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a mesoporous perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell does not need to use toxic and harmful substances, and has better photoelectric conversion efficiency.
The invention provides a mesoporous perovskite solar cell, which comprises:
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, glycerol and ethanol;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, glycerol and ethanol;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, glycerol and ethanol;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, glycerol and ethanol.
Preferably, the mass ratio of the glycerol to the ethanol is 1-2: 1.
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 glycerol is 5-25: 100;
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing the electron transport material, glycerol and ethanol, 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 glycerol is 5-25: 100;
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, glycerol and ethanol, 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 glycerol is 5-25: 100;
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, glycerol and ethanol, 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 glycerol is 5-25: 100;
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, glycerol and ethanol, 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 mesoporous 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 mesoporous perovskite solar cell.
Preferably, in step a), the ethanol is removed by evaporation;
the evaporating air pressure is normal pressure, the temperature is 78-289 ℃, 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 290-350 ℃ 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 mesoporous perovskite solar cell, which comprises: 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, glycerol and ethanol; the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, glycerol and ethanol; the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, glycerol and ethanol; the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, glycerol and ethanol.
Ethanol and glycerol are used as solvents, are environment-friendly and pollution-free organic solvents, are used for increasing the fluidity of slurry in the preparation process and promoting the dispersion of nano particles in the slurry, and are removed by rotary evaporation to improve the viscosity of the slurry and facilitate coating; glycerol is a solvent with moderate viscosity, and can also play a role of a surfactant to a certain extent, so that the addition of toxic and harmful surfactants such as acetylacetone is not needed. In order to promote the uniform dispersion of the nano material in the slurry, the invention adopts a high shear emulsification technology to fully promote the dispersion of the nano particles, and finally the slurry with good dispersibility and leveling property and no toxic or harmful effect is formed, and the perovskite can be effectively contacted with the electron/hole transport material and the bottom electrode material, thereby ensuring the transport of carriers, reducing the carrier recombination loss and further ensuring the photoelectric conversion efficiency of the solar cell.
Drawings
Fig. 1 is a J-V test curve of the mesoporous perovskite solar cell obtained in examples 1 to 2 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 mesoporous perovskite solar cell, which comprises:
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, glycerol and ethanol;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, glycerol and ethanol;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, glycerol and ethanol;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, glycerol and ethanol.
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.
With respect to electron transport layers
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 mass ratio of the glycerol to the ethanol is 1-2: 1, preferably 1.5:1.
the mass ratio of the electron transport material to the glycerol is 5-25: 100, preferably 10:100.
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing the electron transport material, glycerol and ethanol, 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.
With respect to insulating layers
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 mass ratio of the glycerol to the ethanol is 1-2: 1, preferably 1.5:1.
the mass ratio of the insulating layer material to the glycerol is 5-25: 100, preferably 10:100.
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, glycerol and ethanol, 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.
With respect to 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 mass ratio of the glycerol to the ethanol is 1-2: 1, preferably 1.5:1.
the mass ratio of the hole transport material to the glycerol is 5-25: 100, preferably 10:100.
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, glycerol and ethanol, 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 mass ratio of the glycerol to the ethanol is 1-2: 1, preferably 1.5:1.
the mass ratio of the bottom electrode material to the glycerol is 5-25: 100, preferably 10:100.
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, glycerol and ethanol, 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 mesoporous 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 mesoporous 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 78-289 ℃ (the boiling point of ethanol is reached and is lower than the boiling point of water, preferably 120 ℃), 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 290-350 ℃, preferably 300 ℃; 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 drop-adding amount of the perovskite precursor solution on a blank 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.
Advantageous effects
1) Environmental protection and no pollution: in all the slurries prepared by the invention, ethanol and glycerol are used as solvents, and no toxic or harmful solvents are added; no additional surfactant is required other than glycerol. 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) The cost is low: the main raw materials are ethanol, glycerol and the like, which are all common and cheap chemical raw materials, and the adopted high-shear emulsifying machine, coating machine and heating evaporation equipment are low-cost equipment, and have no high-cost raw materials or equipment.
4) The dispersibility of the slurry is good: the invention adopts a high shear emulsification method, utilizes the synergistic effect of ethanol and glycerol, and utilizes the glycerol as a solvent and a surfactant simultaneously to effectively inhibit the aggregation and sedimentation of the slurry, thereby being beneficial to obtaining the slurry with high dispersibility.
5) The process compatibility is high: since glycerol is a widely applicable solvent and surfactant, the method adopted by the invention is applicable to various electron transport materials, hole transport materials, insulating materials and bottom electrode materials.
6) The device performance is high: the slurry obtained by the method has high dispersibility, and the perovskite can be effectively contacted with an electron/hole transmission material and a bottom electrode material, so that the transmission of carriers is ensured, the carrier recombination loss is reduced, and the photoelectric conversion efficiency of the solar cell is ensured.
In order to further illustrate the present invention, the following examples are provided to describe a mesoporous perovskite solar cell and a preparation method thereof in detail, but the scope of the present invention is not limited thereto.
Example 1
1) TiO is adopted 2 Is an electron transport material, and has a particle size of 30-50 nm; transmitting electronsMaterial for Transfusion (TiO) 2 ) Glycerol and ethanol in a mass ratio of 0.15:1.5:1, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 120 ℃ 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 ) Glycerol and ethanol in a mass ratio of 0.15:1.5:1, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 120 ℃ 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 glycerol and the ethanol is 0.15:1.5:1, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 120 ℃ 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 (graphite), glycerin and ethanol are mixed according to the mass ratio of 0.15:1.5:1, mixing, adopting 10W/mL power high shear emulsification for 30min, evaporating at normal pressure and 120 ℃ 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 (glass thickness is 2mm, 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 300 ℃ 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 by 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 mesoporous perovskite solar cell.
Example 2
The difference from example 1 is that:
1) In which the electron transport material is replaced by SnO 2 The grain diameter is 30-50 nm;
6) In the perovskite precursor solution, the solute is replaced by MA 0.5 FA 0.5 PbI 2.8 Cl 0.2 The method comprises the steps of carrying out a first treatment on the surface of the Annealing at 60℃for 24h.
The rest steps are the same as in example 1, and a mesoporous perovskite solar cell is obtained.
Comparative example 1
The difference from example 1 is that:
1) -4) in: the glycerol is replaced by terpineol, and the evaporation is replaced by rotary evaporation at 50 ℃ under the atmospheric pressure of 0.05;
the rest steps are the same as in example 1, and a mesoporous perovskite solar cell is obtained.
Comparative example 2
The difference from example 2 is that:
1) -4) in: the glycerol is replaced by terpineol, and the evaporation is replaced by rotary evaporation at 50 ℃ under the atmospheric pressure of 0.05;
the rest steps are the same as in example 2, and a mesoporous perovskite solar cell is obtained.
Comparative example 3
The difference from example 1 is that:
1) -4) in: glycerol was replaced with lauric acid and evaporation was replaced with rotary evaporation at 50 ℃ at 0.05 atm;
the rest steps are the same as in example 1, and a mesoporous perovskite solar cell is obtained.
Fig. 1 is a J-V test curve of the mesoporous perovskite solar cell obtained in examples 1 to 2 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 reversed (from maximum voltage scan to zero voltage).
Table 1 electrical properties of perovskite solar cells obtained in examples 1 to 2 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 method is obviously better than the device prepared by adopting terpineol and lauric acid as solvents in performance, and the green and environment-friendly preparation method adopted by the method has the capability of replacing the preparation method 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 mesoporous 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, glycerol and ethanol;
the insulating layer is prepared from insulating layer stock solution comprising insulating layer materials, glycerol and ethanol;
the hole transport layer is prepared from a hole transport layer stock solution comprising a hole transport material, glycerol and ethanol;
the bottom electrode is prepared from a bottom electrode stock solution comprising a bottom electrode material, glycerol and ethanol.
2. The mesoporous perovskite solar cell according to claim 1, wherein the mass ratio of glycerin to ethanol is 1-2: 1.
3. the mesoporous 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 glycerol is 5-25: 100;
the preparation method of the electron transport layer stock solution comprises the following steps:
mixing the electron transport material, glycerol and ethanol, and performing high-shear emulsification treatment to obtain an electron transport layer stock solution.
4. The mesoporous 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 glycerol is 5-25: 100;
the preparation method of the insulating layer stock solution comprises the following steps:
mixing the insulating layer material, glycerol and ethanol, and performing high-shear emulsification treatment to obtain an insulating layer stock solution.
5. The mesoporous 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 glycerol is 5-25: 100;
the preparation method of the hole transport layer stock solution comprises the following steps:
and mixing the hole transport material, glycerol and ethanol, and performing high-shear emulsification treatment to obtain a hole transport layer stock solution.
6. The mesoporous 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 glycerol is 5-25: 100;
the preparation method of the bottom electrode stock solution comprises the following steps:
mixing the bottom electrode material, glycerol and ethanol, and performing high-shear emulsification treatment to obtain a bottom electrode stock solution.
7. The mesoporous perovskite solar cell according to any one of claims 3 to 6, wherein the high shear emulsification treatment is performed at a power of 1 to 100W/mL for 10 to 60 minutes.
8. A method for preparing the mesoporous perovskite solar cell according to any one of claims 1 to 7, comprising 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 mesoporous 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 78-289 ℃, 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 290-350 ℃ 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.
CN202311600420.9A 2023-11-27 2023-11-27 Mesoporous perovskite solar cell and preparation method thereof Pending CN117320465A (en)

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