CN114203917A - Conductive electrode and preparation method and application thereof - Google Patents

Conductive electrode and preparation method and application thereof Download PDF

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Publication number
CN114203917A
CN114203917A CN202111544191.4A CN202111544191A CN114203917A CN 114203917 A CN114203917 A CN 114203917A CN 202111544191 A CN202111544191 A CN 202111544191A CN 114203917 A CN114203917 A CN 114203917A
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conductive electrode
electrode
carbon
solution
perovskite
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CN114203917B (en
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李卫东
张赟
肖平
赵志国
丁坤
李新连
夏渊
刘入维
申建汛
梁思超
王森
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Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
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Huaneng Renewables Corp Ltd
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
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    • 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
    • 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
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
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Abstract

The invention provides a perovskite solar cell with a carbon material conductive electrode, wherein the conductive electrode is a composite conductive electrode with a carbon material as a core material; the precursor solution of the composite conductive electrode is a solution which takes a carbon material as a core and contains a plurality of components; the composite electrode may be prepared as a film by a printing process. The novel carbon electrode provided by the invention is simple and feasible to prepare, simplifies the preparation process of a battery device, and is easy to realize low-cost preparation; meanwhile, the full printing process is beneficial to preparing flexible devices, and the practical process of the perovskite solar cell is promoted; the cell adopting the carbon electrode has equivalent photoelectric conversion efficiency with the existing perovskite solar cell, and has very important significance for promoting the practical process of the cell.

Description

Conductive electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric energy sources, and particularly relates to a conductive electrode and a preparation method and application thereof.
Background
Since the first report of the 2009 perovskite solar cell, the photoelectric conversion efficiency of the cell rapidly increased from 3.8% to over 25% over ten years. Among a plurality of thin-film solar cells, a solar cell based on an organic-inorganic perovskite photoactive layer is one of the active research hotspots in the international leading research field due to its low cost, solution processability and excellent photoelectric conversion. Perovskite materials (e.g. lead methyl iodide amine, CH)3NH3PBI3) The perovskite solar cell has the advantages of high extinction coefficient, high mobility, long carrier service life, easy regulation of band gap, processing mode diversity and the like, and the high extinction coefficient and adjustable band gap indicate that the perovskite solar cell can realize photoelectric conversion of a visible light region and a part of near infrared light region, namely the cell has higher output current; the high carrier mobility and the long service life enable the photon-generated carrier recombination probability generated by the battery to be lower and the energy loss to be small. Based on the above factors, the theoretical conversion efficiency of perovskite solar cells exceeds 30%, while the theoretical conversion efficiency of silicon-based solar cells is only 27%; furthermore, given the lower material costs and the cost of solution processing for the fabrication, perovskite solar cells will beThe solar cell is expected to exceed a silicon-based solar cell in the near future, realizes industrialization and becomes a next-generation mainstream thin-film solar cell.
The basic structure of the perovskite solar cell comprises a transparent electrode, a hole transport layer, a perovskite active layer, an electron transport layer and a conductive electrode layer, and the total of five functional layers. The conductive electrode mainly plays a role in collecting charges and transferring the charges into a battery load circuit, and at present, most of conductive electrode layers used in conventional perovskite solar cells are metal electrodes such as gold, silver, copper, aluminum or composite electrodes containing metal electrodes. On one hand, the commonly used metal electrodes of gold, silver and the like of the high-efficiency perovskite battery are expensive; on the other hand, the metal electrode is usually prepared by a high vacuum thermal evaporation or low temperature sputtering process, and has the disadvantages of complex process, higher equipment cost and the like.
Disclosure of Invention
In view of the above, the present invention provides a formula and a preparation method of a carbon material conductive electrode, and also provides a preparation method of the electrode applied to a perovskite solar cell.
The present invention provides a conductive electrode comprising: a carbon material.
Preferably, the carbon material is selected from one or more of amorphous carbon, carbon black, CNT and natural graphite.
Preferably, the method further comprises the following steps:
one or more of a conjugated polymer, a dispersant and a stabilizer.
Preferably, the conjugated polymer is selected from polyvinylpyrrolidone, poly (sodium 4-styrenesulfonate), poly (9, 9-bis (3'- (N, N-dimethyl) -N-ethylaminopropyl-2, 7-fluorene) -alt-2,7- (9, 9-dioctylfluorene)) dibromide, poly (3,3' - (2-methyl-7- (p-tolyl) -9H-fluorene-9, 9-diyl) bis (N, n-dimethylpropane-1-amine)) and poly (sodium 4- (4- ((4 '-methyl- [1,1' -biphenyl ] -4-yl) (p-tolyl) amino) phenoxy) butane-1-sulfonate.
Preferably, the dispersant is an alcohol.
Preferably, the stabilizer is one or more selected from poly (4-sodium styrene sulfonate), polyethylene oxide, polymethyl methacrylate and polyvinylpyrrolidone.
Preferably, the thickness of the conductive electrode is 200-10000 nm.
The invention provides a preparation method of the conductive electrode in the technical scheme, which comprises the following steps:
preparing the precursor solution by a solution film-forming method;
the precursor solution includes: a carbon material.
Preferably, the solution film forming method is one or more selected from spin coating, wire bar coating, blade coating, screen printing, gravure printing and letterpress printing.
The invention provides a perovskite solar cell of a carbon material conductive electrode, which comprises:
a substrate material;
a hole transport layer;
a perovskite active layer;
an electron transport layer;
the conductive electrode of the technical scheme.
The carbon electrode with the carbon material as the core is prepared by mixing two or more materials in different proportions to obtain a series of solutions (or named as slurry) with different viscosities as precursor solutions of the electrode and then performing a printing or coating process. The carbon electrode provided by the invention has the advantages that: on one hand, the material source is wide, and the cost is low; on the other hand, the electrode preparation process is simple and easy to implement, and the requirement on high-precision equipment is low. The novel conductive electrode taking the carbon material as the core provided by the invention has the advantages of simple preparation process and huge cost potential, simplifies the preparation process of the battery, and provides related technical reserve for the industrialization process of the perovskite solar battery.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite solar cell of a carbon material conductive electrode according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides a conductive electrode comprising: a carbon material.
In the present invention, the carbon material preferably includes: one or more of amorphous carbon, carbon black, CNT and natural graphite, and more preferably includes amorphous carbon, carbon black, CNT (carbon nanotube) and natural graphite.
In the present invention, the mass ratio of the amorphous carbon, the carbon black, the CNT and the natural graphite is a: b: c: d, a is preferably 0-0.2, more preferably 0.1; b is preferably 0 to 0.5, more preferably 0.1 to 0.4, and most preferably 0.2 to 0.3; c is preferably 0 to 1, more preferably 0.3 to 0.7, and most preferably 0.5; d is preferably 0 to 1, more preferably 0.3 to 0.7, and most preferably 0.5.
In the present invention, the conductive electrode preferably further comprises: one or more of a conjugated polymer, a dispersant and a stabilizer, and more preferably comprises the conjugated polymer, the dispersant and the stabilizer.
In the present invention, the conjugated polymer is preferably an alcohol-soluble conjugated polymer, more preferably a material having a conjugated backbone and side chains of strongly polar groups (e.g., amine groups, diethanolamine groups, phosphate groups, carboxyl groups, quaternary ammonium salts, carboxylate groups, sulfonate groups, zwitterionic groups, etc.), more preferably a material selected from PVP (polyvinylpyrrolidone), PFNBr (poly (9, 9-bis (3' - (N, N-dimethyl) -N-ethylaminopropyl-2, 7-fluorene) -alt-2,7- (9, 9-dioctylfluorene)) dibromide), PFN (poly (3,3' - (7,7' -dimethyl-9 ', 9' -dioctyl-9H, 9' H- [2,2' -bifluoro ] -9, 9-diyl) bis (N, n-dimethylpropane-1-amine))), poly (3,3' - (2-methyl-7- (p-tolyl) -9H-fluorene-9, 9-diyl) bis (N, N-dimethylpropane-1-amine)) and poly (4- (4- ((4' -methyl- [1,1' -biphenyl ] -4-yl) (p-tolyl) amino) phenoxy) butane-1-sulfonic acid sodium salt; most preferably one selected from PVP, PFN and PFNBr.
In the invention, the molecular weight of PVP is preferably 3,000-1,500,000, more preferably 5000-1000000, more preferably 10000-800000, more preferably 50000-600000, more preferably 100000-500000, more preferably 200000-40000, and most preferably 300000; the molecular weight of the PFN and the PFNBr is preferably 5,000-100,000 independently, more preferably 10000-80000, more preferably 30000-60000 and most preferably 40000-50000.
In the invention, the dispersing agent is preferably selected from green volatile substances, more preferably alcohols, more preferably low-boiling point alcohols, and most preferably one or more selected from methanol, ethanol, ethylene glycol and isopropanol.
In the present invention, the stabilizer also generally functions as a thickener in order to make the resulting solution (or slurry) more suitable for use in printing or coating processes.
In the present invention, the stabilizer is preferably selected from one or more of poly (sodium 4-styrenesulfonate) (PSSA), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), and polyvinylpyrrolidone (PVP), and more preferably from one or more of alcohol-soluble PSSA and PVP.
In the invention, the molecular weights of the PSSA and the PVP are preferably independently 3,000-50,000, more preferably 5000-40000, more preferably 10000-30000 and most preferably 20000; the molecular weight of the PEO and the molecular weight of the PMMA are preferably 3000-100,000 independently, more preferably 5000-80000, more preferably 10000-60000, more preferably 20000-50000 and most preferably 30000-40000.
In the present invention, the mass ratio of the carbon material to the other material is 1: (0.1 to 10), more preferably 1: (0.5 to 5), more preferably 1: (1-4), most preferably 1: (2-3), wherein the other materials are one or more of a conjugated polymer, a dispersing agent and a stabilizing agent; the mass ratio of the conjugated polymer to the dispersing agent to the stabilizing agent is preferably (0-1): (0-1): (0 to 1), more preferably (0.3 to 0.7): (0.3-0.7): (0.3 to 0.7), most preferably 0.5: 0.5: 0.5.
in the invention, the thickness of the conductive electrode is preferably 200nm to 10,000nm, more preferably 500nm to 8000nm, more preferably 1000nm to 6000nm, more preferably 2000 nm to 5000nm, and most preferably 3000nm to 4000 nm.
The invention provides a preparation method of the conductive electrode in the technical scheme, which comprises the following steps:
the precursor solution is prepared by a solution film-forming method.
In the present invention, the precursor solution includes: a carbon material.
In the present invention, the precursor solution preferably further includes:
conjugated polymers, dispersants and stabilizers.
In the present invention, the components and the dosage ratios of the carbon material, the conjugated polymer, the dispersant and the stabilizer are consistent with the above technical scheme, and are not described herein again.
In the present invention, the precursor solution preferably further includes a solvent.
In the invention, the solvent is preferably a green volatile solvent, more preferably an alcohol solvent, more preferably a low-boiling-point alcohol solvent, and most preferably one or more selected from methanol, ethanol, ethylene glycol and isopropanol.
In the present invention, it is particularly pointed out that the PVP material, which can be used as a stabilizer and a conjugated polymer in a carbon electrode precursor solution, can be directly used as an electron transport layer material in an organic solar cell; in addition, PFN and PFNBr in the conjugated polymer can also be used as electron transport layer materials in organic solar cells.
In the present invention, the method for preparing the conductive electrode preferably includes:
mixing a stabilizer and a solvent to obtain a stabilizer solution;
mixing the conjugated polymer and the stabilizer solution to obtain a mixed solution
Mixing a carbon material with the mixed solution to obtain a precursor solution;
and forming a film on the surface of the electron transport layer by using the precursor solution to obtain the carbon electrode (conductive electrode).
In the present invention, the solvent is preferably an alcohol solvent, and more preferably one or more selected from methanol, ethanol, isopropanol, and ethylene glycol.
In the invention, the concentration of the stabilizer in the stabilizer solution is 0.2-5 mg/ml, more preferably 0.5-4 mg/ml, more preferably 1-3 mg/ml, and most preferably 2 mg/ml.
In the invention, the concentration of the conjugated polymer in the mixed solution is preferably 0.2-10 mg/ml, more preferably 0.5-8 mg/ml, more preferably 1-6 mg/ml, more preferably 2-5 mg/ml, and most preferably 3-4 mg/ml.
In the present invention, the carbon material is preferably treated, and the method of treatment preferably includes:
mixing and soaking the carbon material and hydrochloric acid, and drying.
In the invention, the concentration of the hydrochloric acid is preferably 8-12 mol/L, more preferably 9-11 mol/L, and most preferably 10 mol/L; the soaking time is preferably 20-30 hours, more preferably 22-28 hours, and most preferably 24-26 hours; the purpose of the hydrochloric acid soaking is to remove impurities such as residual metals, catalysts and the like in the carbon material.
In the present invention, the mixing of the carbon material and the mixed solution is preferably dispersed with the aid of ultrasound.
In the present invention, the ultrasonic assistance preferably employs an ultrasonic cell disruptor as an ultrasonic supply source; the ultrasonic power range in the ultrasonic auxiliary process is preferably 1-50W, more preferably 5-40W, more preferably 10-30W, and most preferably 20W; the ultrasonic time is preferably 5 to 60 minutes, more preferably 10 to 50 molecules, more preferably 20 to 40 minutes, and most preferably 30 minutes.
In the present invention, it is preferable that the carbon material and the mixed solution further include, after mixing:
the carbon material not dispersed in the obtained mixed solution was removed.
In the present invention, the removal method is preferably removal by high-speed centrifugation; the high-speed centrifugation speed is preferably 2000-20,000 revolutions per minute, more preferably 5000-15000 revolutions per minute, more preferably 8000-12000 revolutions per minute, and most preferably 10000 revolutions per minute.
In the present invention, the carbon material precursor solution preferably further includes: one or more of PEO, PMMA and PSSA for adjusting the viscosity of the solution.
In the present invention, the film forming method includes, but is not limited to, one or more of spin coating, wire bar coating, blade coating, screen printing, gravure printing and letterpress printing.
In the present invention, after film formation, it is preferable to further include:
and (5) airing the film-formed product to obtain the carbon electrode.
In the present invention, the drying is preferably carried out in a low vacuum dryer; the degree of vacuum of the low vacuum is preferably 10-3～10-2Pa; the airing temperature is preferably room temperature; the airing time is preferably 2-24 hours, more preferably 5-20 hours, and most preferably 10-15 hours.
The invention provides a perovskite solar cell of a carbon material conductive electrode, which comprises:
a substrate material;
a hole transport layer;
a perovskite active layer;
an electron transport layer;
the conductive electrode is the conductive electrode in the technical scheme.
FIG. 1 is a schematic structural diagram of a perovskite solar cell with a carbon material conductive electrode provided by an embodiment of the invention, wherein 1 is a transparent electrode layer; 2-a hole transport layer; a 3-perovskite active layer; 4-an electron transport layer; 5-metal electrode layer.
In the invention, the substrate material preferably contains a transparent electrode, a commercial high-transmittance FTO glass or ITO glass and other hard substrates can be adopted, and ITO-covered flexible substrate materials can also be adopted; the flexible substrate material may be PET, PEN, PI, PC film, etc.
In the present invention, the thickness of the substrate material is preferably 0.2mm to 5mm, more preferably 0.5 mm to 4mm, more preferably 1 mm to 3mm, and most preferably 2 mm.
In the present invention, the hole transport layer preferably includes: NiOx, PEDOT PSS or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA).
In the present invention, the hole transport layer is preferably prepared by a magnetron sputtering method.
In the present invention, the thickness of the hole transport layer is preferably 20 to 30nm, more preferably 23 to 27nm, and most preferably 25 nm.
In the present invention, the perovskite active layer preferably includes:
ABX3a compound of the formula (I), wherein A is selected from K+、Rb+、Cs+、CH3NH3 +Or CH (NH)2)2 +B is selected from Pb2+X is Cl-、Br-、I-Or SCN-。
In the invention, the thickness of the perovskite active layer is preferably 100-1000 nm, more preferably 200-800 mm, more preferably 300-600 nm, and most preferably 400-500 nm.
In the present invention, the electron transport layer preferably includes:
TiO2、SnO2PCBM (fullerene derivative), C60And BCP (hole blocking material); more preferably PCBM and BCP combined film or C60 and BCP combined film, i.e. the electron transport layer comprises a two-layer structure of PCBM layer and BCP layer, or C60A two-layer structure of a layer and a BCP layer.
In the present invention, the PCBM layer or the C60 layer is preferably disposed on the surface of the perovskite active layer; the BCP layer is preferably arranged on the surface of the PCBM layer or the C60 layer.
In the invention, the PCBM layer is preferably prepared by a solution film-forming method, more preferably by a spin-coating method, wherein the spin-coating speed is preferably 3000-5000 rpm/min, more preferably 3500-4500 rpm/min, and most preferably 4000 rpm/min; the thickness of the PCBM layer is preferably 10-50 nm, more preferably 20-40 nm, and most preferably 30 nm.
In the invention, the BCP layer is preferably prepared by deposition by a vacuum thermal evaporation method, and the speed in the thermal evaporation process is preferably 0.01-0.2 angstroms per second, more preferably 0.05-0.15 angstroms per second, and most preferably 0.1 angstroms per second; the thickness of the BCP layer is preferably 5-10 nm, and more preferably 6-8 nm.
In the invention, the C60 layer is preferably prepared by deposition through a vacuum thermal evaporation method, and the speed in the thermal evaporation process is preferably 0.01-0.2 angstroms per second, more preferably 0.05-0.15 angstroms per second, and most preferably 0.1 angstroms per second; said C is60The thickness of the layer is preferably 5 to 25nm, more preferably 10 to 20nm, and most preferably 25 nm.
In the present invention, the conductive electrode preferably further comprises: and a metal electrode.
In the present invention, the metal electrode is preferably one or more selected from a gold electrode, a copper electrode, a silver electrode and an aluminum electrode.
In the present invention, the conductive electrode is preferably a composite electrode of a metal electrode and a carbon material electrode (the conductive electrode described in the above-mentioned embodiment).
In the present invention, the method for manufacturing a perovskite solar cell of the carbon material conductive electrode preferably includes:
cleaning the substrate material;
preparing a hole transport layer on the surface of the cleaned substrate;
preparing a perovskite active layer on the surface of the hole transport layer;
preparing an electron transport layer on the surface of the perovskite active layer;
and preparing a conductive electrode on the surface of the electron transport layer.
In the present invention, the method of cleaning preferably includes:
the substrate material is cleaned by sequentially adopting a surfactant, water, acetone and isopropanol, then dried and then subjected to ultraviolet ozone treatment.
In the present invention, the water is preferably deionized water; the cleaning is preferably ultrasonic cleaning; the cleaning is preferably performed twice by each reagent, and the time for each cleaning is preferably 10-15 minutes, more preferably 11-14 minutes, and most preferably 12-13 minutes; the drying method is preferably drying or nitrogen blow drying; the time of the ultraviolet ozone (UVO) treatment is preferably 10-20 minutes, more preferably 12-18 minutes, and most preferably 14-16 minutes.
In the present invention, the method for producing the perovskite active layer preferably includes:
and performing thin film deposition after preparing the precursor solution.
In the present invention, the precursor solution preferably includes:
methyl Ammonium Iodide (MAI), lead iodide (PbI2), N-dimethylformamide, and dimethyl sulfoxide (DMSO).
In the present invention, the method for preparing the precursor solution preferably includes:
mixing Methyl Ammonium Iodide (MAI) and lead iodide (PbI)2) Dissolving in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).
In the present invention, the Methyl Ammonium Iodide (MAI) and lead iodide (PbI)2) The molar ratio of (a) to (b) is preferably (0.5 to 1.5): 1, more preferably (0.8 to 1.2): 1, most preferably 1: 1.
in the invention, the volume ratio of the N, N-Dimethylformamide (DMF) to the dimethyl sulfoxide (DMSO) is preferably (0.2-5): 1, more preferably (0.5 to 4): 1, more preferably (1 to 3): 1, most preferably 2: 1.
in the invention, the total concentration of the Methyl Ammonium Iodide (MAI) and the lead iodide (PbI2) in the precursor solution is preferably 0.5-5 mol/ml, more preferably 1-4 mol/ml, and most preferably 2-3 mol/ml.
In the present invention, the method of depositing the thin film is preferably one or more selected from spin coating, wire bar coating, doctor blade coating, slot extrusion coating, screen printing, gravure printing, and letterpress printing.
In the invention, the perovskite active layer is preferably a high-efficiency perovskite light absorption layer, and the high-efficiency perovskite light absorption layer is preferably prepared by an anti-solvent method, which specifically comprises the following steps:
and dropwise adding the precursor solution to the surface of the hole transport layer, then carrying out spin coating to prepare a film, dropwise adding an anti-solvent in the spin coating process, and annealing after obtaining a coating.
In the present invention, the spin coating preferably includes:
the slow spin coating is performed first and then the fast spin coating is performed.
In the invention, the speed of the slow spin coating is preferably 1000-4000 rpm/min, more preferably 2000-3000 rpm/min, and most preferably 2500 rpm/min; the time of the slow spin coating is preferably 1-3 seconds, and more preferably 2 seconds.
In the invention, the speed of the rapid spin coating is preferably 4000-5000 rpm/min, more preferably 4300-4700 rpm/min, and most preferably 4500 rpm/min; the time for the rapid spin coating is preferably 30 to 50 seconds, more preferably 35 to 45 seconds, and most preferably 40 seconds.
In the present invention, the antisolvent is preferably chlorobenzene; the dosage of the anti-solvent is preferably 100-200 mu l, more preferably 130-170 mu l, and most preferably 150 mu l; the anti-solvent is preferably added dropwise starting 20 seconds before the spin-coating is stopped, preferably within 2 seconds.
In the invention, the preparation method of the conductive electrode is consistent with the technical scheme.
In the present invention, the structural formula of the compound employed is as follows:
Figure BDA0003415353990000101
the carbon electrode with the carbon material as the core is prepared by mixing two or more materials in different proportions to obtain a series of solutions (or named as slurry) with different viscosities as precursor solutions of the electrode and then performing a printing or coating process. The carbon electrode provided by the invention has the advantages that: on one hand, the material source is wide, and the cost is low; on the other hand, the electrode preparation process is simple and easy to implement, and the requirement on high-precision equipment is low. The novel conductive electrode taking the carbon material as the core provided by the invention has the advantages of simple preparation process and huge cost potential, simplifies the preparation process of the battery, and provides related technical reserve for the industrialization process of the perovskite solar battery.
Example 1 perovskite Battery preparation with Metal electrode as conductive electrode
Dissolving 2mg of PTAA in 1ml of toluene solvent under nitrogen atmosphere, stirring overnight at room temperature until the PTAA is completely dissolved to prepare a hole transport layer precursor solution with the concentration of 2 mg/ml;
cleaning the patterned ITO glass, carrying out UVO treatment for 15 minutes, and then moving the patterned ITO glass into a nitrogen-protected glove box for later use;
the precursor solution of the PTAA hole transport layer is spin-coated on ITO glass, the spin-coating speed is 6000rpm/min, the spin-coating time is 30 seconds, then annealing is carried out at 100 ℃ for 30 minutes, and the thickness of a thin film is about 30nm (the hole transport layer).
1290.8mg of PbI are taken2And 445.2mg of MAI in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO is 4:1), stirring at normal temperature overnight to obtain a perovskite precursor solution, wherein the total concentration of solute in the solution is 1.4 mol/ml.
Taking 12.5mg of PC61BM is dissolved in 1ml of toluene solvent, and stirred overnight at normal temperature to obtain the precursor solution of the electron transport layer, wherein the concentration of the solution is 12.5 mg/ml.
Spin coating a perovskite precursor solution on the hole transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 3 seconds at 4000 rpm/min; then spin-coating at 5000rpm/min for 30 seconds; and finally, spin-coating at a high speed of 5000rpm/min for 11 seconds, and dripping 200 μ l of chlorobenzene (anti-solvent) in a dropwise manner, wherein the dripping of all the anti-solvent is required to be completed within 2 seconds, and the thickness of the perovskite light absorption layer is controlled to be about 500 nm.
Annealing the perovskite light absorption layer obtained in the step (A) at 75 ℃ for 2 minutes under the nitrogen protection environment, and then heating to 90 ℃ for annealing for 4 minutes.
Spin coating the PC on the perovskite light absorption layer61And (3) spin coating the BM solution at 4000rpm/min for 3 seconds and 5000rpm/min for 30 seconds, wherein the film thickness is about 20 nm.
Transferring the obtained film into a vacuum evaporation chamber, and vacuumizing until the vacuum degree is lower than 4 x 10-4Heat is started after PaPreparing an electron transport layer by an evaporation deposition method; c60The evaporation rate is less than 0.05 angstrom/second, and the film thickness is 20 nm; the evaporation rate of BCP is less than 0.1 angstrom/second, and the film thickness is 9 nm.
Preparing silver electrode from the obtained film by thermal evaporation deposition method, and controlling vacuum degree to be lower than 4 x 10-4Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the silver electrode is 100nm, so that the perovskite battery is prepared.
Example 2 perovskite cell preparation with carbon electrodes of different thicknesses as conductive electrodes
A perovskite cell hole transport layer, a perovskite light absorption layer and an electron transport layer were prepared according to the method of example 1.
Preparing a carbon electrode precursor solution: weighing 50mg of PVP, dissolving in 100ml of methanol, stirring at normal temperature until the PVP is completely dissolved (clear and transparent solution), wherein the concentration of the PVP is 0.5 mg/ml; weighing 200mg of amorphous carbon, carbon black, CNT and natural graphite respectively, adding into 200ml of 10mol/L hydrochloric acid solution respectively, soaking for 24 hours to remove metal impurities in the hydrochloric acid solution, performing suction filtration, washing with deionized water to remove residual hydrochloric acid, performing ultrasonic cleaning for 2 times with deionized water, acetone and isopropanol sequentially, performing 15 minutes each time, and drying the solid product obtained after suction filtration again in a vacuum oven chamber under negative pressure; weighing 45mg of dried amorphous carbon, adding the dried amorphous carbon into the PVP solution, and dispersing the amorphous carbon by using a supersonic wave crusher (VCX 130) of the company Sonics in America, wherein the supersonic power is 5W, and the supersonic time is 30 minutes; transferring the dispersed solution into a centrifuge tube, centrifuging at a high speed to remove undispersed amorphous carbon, wherein the centrifugation speed is 3000 r/min, the centrifugation time is 15 min, and the concentration of the amorphous carbon in the centrifuged solution is 0.5 mg/ml; adding carbon black according to the steps, adjusting the ultrasonic power to 10W, and finally obtaining a solution with the carbon black concentration of 0.8 mg/ml; adding CNT and natural graphite according to the steps, adjusting the ultrasonic power to 20W, wherein the concentration of the CNT and the concentration of the graphite in the finally obtained solution are respectively 1.5mg/ml and 1mg/ml, and the mass ratio of the four carbon materials in the solution is 0.5:0.8:1.5: 1.2; and adding 1.55g of PVP into the obtained mixed solution, and stirring at room temperature until the PVP is completely dissolved, so as to adjust the viscosity of the precursor solution, wherein the total solid content of the obtained precursor solution is 20 mg/ml.
Preparing a carbon electrode: in the prepared electron transport layer, i.e. C60Preparing carbon electrode with scraper coating process on the surface of the layer, coating width of 1.5 cm, coating speed of 2.5 m/min, controlling film thickness at 200nm, placing the coated carbon electrode into a vacuum drier, and maintaining vacuum degree at 2 x 10-3Pa, standing for 12 hours, and taking out to obtain the perovskite battery.
Example 3
A perovskite battery was prepared according to the method of example 2, differing from example 2 in that the blade coating speed was 1.5 m/min and the carbon electrode thickness was controlled at 500 nm.
Example 4
A perovskite battery was prepared according to the method of example 2, differing from example 2 in that the blade coating speed was 1.0 m/min and the carbon electrode thickness was controlled at 1000 nm.
Example 5
A perovskite battery was prepared according to the method of example 2, differing from example 2 in that the blade coating speed was 0.5 m/min and the carbon electrode thickness was controlled at 3000 nm.
Example 6
A perovskite battery was manufactured according to the method of example 2, differing from example 2 in that the blade coating speed was 0.2 m/min and the carbon electrode thickness was controlled at 8000 nm.
Example 7 perovskite Battery preparation with different component carbon materials as conductive electrodes
A perovskite cell hole transport layer, a perovskite light absorption layer and an electron transport layer were prepared according to the method of example 1.
Preparing a carbon electrode precursor solution: weighing 100mg of PVP, dissolving in 100ml of methanol, stirring at normal temperature until the PVP is completely dissolved (clear and transparent solution), wherein the concentration of the PVP is 1 mg/ml; weighing 200mg of carbon black, CNT and natural graphite respectively in turn, adding into 200ml of 10mol/L hydrochloric acid solution respectively, soaking for 24 hours to remove metal impurities in the hydrochloric acid solution, washing with deionized water after suction filtration to remove residual hydrochloric acid, then ultrasonically cleaning with deionized water, acetone and isopropanol for 2 times in turn for 15 minutes each time, and drying the solid product obtained after suction filtration again in a vacuum oven chamber under negative pressure; weighing dried 85mg of carbon black, adding the carbon black into the PVP solution, and dispersing amorphous carbon by using a ultrasonic crusher (VCX 130) of the American sonics company, wherein the ultrasonic power is 5W, and the ultrasonic time is 30 minutes; transferring the dispersed solution into a centrifuge tube, centrifuging at a high speed to remove undispersed carbon black, wherein the centrifugation speed is 3000 r/min, the centrifugation time is 15 min, and the concentration of the carbon black in the centrifuged solution is 0.8 mg/ml; adding CNT and natural graphite according to the method, adjusting the ultrasonic power to 20W, wherein the concentration of CNT and graphite in the finally obtained solution is 1.8mg/ml and 1.4mg/ml respectively, and the mass ratio of the four carbon materials in the solution is 0:0.8:1.8: 1.4; and adding 1.5g of PVP into the mixed solution, and stirring at room temperature until the PVP is completely dissolved, so as to adjust the viscosity of the precursor solution, wherein the total solid content of the obtained precursor solution is 20 mg/ml.
Preparing a carbon electrode: in the prepared electron transport layer, i.e. C60Preparing carbon electrode with scraper coating process on the surface of the layer, coating width of 1.5 cm, coating speed of 0.5 m/min, controlling film thickness at 3000nm, placing the coated carbon electrode into a vacuum drier, and maintaining vacuum degree at 2 x 10-3And Pa, standing for 12 hours, and taking out to obtain the perovskite battery.
Example 8
A perovskite cell hole transport layer, a perovskite light absorption layer and an electron transport layer were prepared according to the method of example 1.
Preparing a carbon electrode precursor solution: weighing 150mg of PVP, dissolving in 100ml of methanol, stirring at normal temperature until the PVP is completely dissolved (clear and transparent solution), wherein the concentration of the PVP is 1.5 mg/ml; weighing 250mg of CNT and natural graphite respectively in turn, adding the weighed CNT and natural graphite into 250ml of 10mol/L hydrochloric acid solution respectively, soaking for 24 hours to remove metal impurities in the solution, washing with deionized water after suction filtration to remove residual hydrochloric acid, then ultrasonically cleaning with deionized water, acetone and isopropanol for 2 times in turn for 15 minutes each time, and putting a solid product obtained after suction filtration again into a vacuum oven chamber for negative pressure drying; weighing 210mg of dried CNT, adding the CNT into the PVP solution, and dispersing the CNT by using an ultrasonic crusher (VCX 130) of the company Sonics in America, wherein the ultrasonic power is 25W, and the ultrasonic time is 30 minutes; transferring the dispersed solution into a centrifuge tube, centrifuging at a high speed to remove undispersed CNT, wherein the centrifugation speed is 3000 r/min, the centrifugation time is 15 min, and the concentration of the CNT in the centrifuged solution is 2 mg/ml; adding natural graphite according to the method, wherein the concentration of graphite in the finally obtained solution is 2mg/ml, and the ratio of the four carbon materials in the solution is 0:0:2: 2; and adding 1.45g of PVP into the obtained mixed solution, and stirring at room temperature until the PVP is completely dissolved, so as to adjust the viscosity of the precursor solution, wherein the total solid content of the obtained precursor solution is 20 mg/ml.
Preparing a carbon electrode: in the prepared electron transport layer, i.e. C60Preparing carbon electrode with scraper coating process on the surface of the layer, coating width of 1.5 cm, coating speed of 0.5 m/min, controlling film thickness at 3000nm, placing the coated carbon electrode into a vacuum drier, and maintaining vacuum degree at 2 x 10-3And Pa, standing for 12 hours, and taking out to obtain the perovskite battery.
Example 9 perovskite Battery preparation with different component carbon materials as conductive electrodes
A perovskite cell hole transport layer, a perovskite light absorption layer and an electron transport layer were prepared according to the method of example 1.
Preparing a carbon electrode precursor solution: weighing 200mg of PVP, dissolving in 100ml of methanol, stirring at normal temperature until the PVP is completely dissolved (clear and transparent solution), wherein the concentration of the PVP is 2 mg/ml; weighing 450mg of natural graphite, adding the natural graphite into 450ml of 10mol/L hydrochloric acid solution, soaking for 24 hours to remove metal impurities in the natural graphite, washing with deionized water after suction filtration to remove residual hydrochloric acid, then ultrasonically cleaning with deionized water, acetone and isopropanol for 2 times, 15 minutes each time, and placing a solid product obtained after suction filtration again into a vacuum oven chamber for negative pressure drying; weighing dried 410mg of natural graphite, adding the natural graphite into the PVP solution, and dispersing the natural graphite by using an ultrasonic crusher (VCX 130) of the American sonic company with ultrasonic power of 45W and ultrasonic time of 30 minutes; transferring the dispersed solution into a centrifuge tube, centrifuging at a high speed to remove undispersed graphite, wherein the centrifugation speed is 3000 r/min, the centrifugation time is 15 min, the concentration of graphite in the centrifuged solution is 4mg/ml, and the ratio of four carbon materials in the solution is 0:0:0: 4; and adding 1.4g of PVP into the obtained mixed solution, and stirring at room temperature until the PVP is completely dissolved, so as to adjust the viscosity of the precursor solution, wherein the total solid content of the obtained precursor solution is 20 mg/ml.
Preparing a carbon electrode: in the prepared electron transport layer, i.e. C60Preparing carbon electrode with scraper coating process on the surface of the layer, coating width of 1.5 cm, coating speed of 0.5 m/min, controlling film thickness at 3000nm, placing the coated carbon electrode into a vacuum drier, and maintaining vacuum degree at 2 x 10-3And Pa, standing for 12 hours, and taking out to obtain the perovskite battery.
Example 10 perovskite Battery preparation with different component carbon materials as conductive electrodes
A perovskite cell was prepared according to the method of example 9, differing from example 9 in that natural graphite was replaced with amorphous carbon.
Example 11 perovskite Battery preparation with different component carbon materials as conductive electrodes
A perovskite cell was prepared according to the method of example 9, except that natural graphite was replaced with carbon black from example 9.
Example 12 perovskite Battery preparation with different component carbon materials as conductive electrodes
A perovskite battery was prepared according to the method of example 9, differing from example 9 in that natural graphite was replaced with CNT.
Battery performance detection
The perovskite solar cell prepared in example was irradiated with sunlight at a standard solar intensity (AM1.5G, 100 mW/cm) using a solar simulator (xenon lamp as a light source)2) The following tests were performed, in which the solar simulator was calibrated with a silicon solar cell (certified by the american national renewable energy laboratory), and the corresponding test results were as follows:
Figure BDA0003415353990000151
as can be seen from the cell performance test data, the perovskite solar cell based on the carbon material-based conductive electrode of the invention all showed comparable photoelectric conversion efficiency to that of the perovskite solar cell based on the conventional copper electrode; furthermore, the perovskite solar cell with higher efficiency can be obtained by regulating and controlling the proportion of each solvent in the novel blending solvent.
From the above embodiments, the carbon electrode with the carbon material as the core provided by the invention is prepared by mixing two or more materials in different proportions to obtain a series of solutions (or called as slurries) with different viscosities as precursor solutions of the electrode, and then performing a printing or coating process. The carbon electrode provided by the invention has the advantages that: on one hand, the material source is wide, and the cost is low; on the other hand, the electrode preparation process is simple and easy to implement, and the requirement on high-precision equipment is low. The novel conductive electrode taking the carbon material as the core provided by the invention has the advantages of simple preparation process and huge cost potential, simplifies the preparation process of the battery, and provides related technical reserve for the industrialization process of the perovskite solar battery.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A conductive electrode, comprising: a carbon material.
2. The conductive electrode of claim 1, wherein the carbon material is selected from one or more of amorphous carbon, carbon black, CNT, and natural graphite.
3. The conductive electrode of claim 1, further comprising:
one or more of a conjugated polymer, a dispersant and a stabilizer.
4. The conductive electrode of claim 3, wherein the conjugated polymer is selected from the group consisting of polyvinylpyrrolidone, poly (sodium 4-styrenesulfonate), poly (9, 9-bis (3'- (N, N-dimethyl) -N-ethylaminopropyl-2, 7-fluorene) -alt-2,7- (9, 9-dioctylfluorene)) dibromide, poly (3,3' - (2-methyl-7- (p-tolyl) -9H-fluorene-9, 9-diyl) bis (N, n-dimethylpropane-1-amine)) and poly (sodium 4- (4- ((4 '-methyl- [1,1' -biphenyl ] -4-yl) (p-tolyl) amino) phenoxy) butane-1-sulfonate.
5. The conductive material of claim 3, wherein the dispersant is an alcohol.
6. The conductive electrode of claim 3, wherein the stabilizer is selected from one or more of poly (4-sodium styrene sulfonate), polyethylene oxide, polymethyl methacrylate, and polyvinylpyrrolidone.
7. The conductive electrode according to claim 1, wherein the conductive electrode has a thickness of 200 to 10000 nm.
8. A method of making the conductive electrode of claim 1, comprising:
preparing the precursor solution by a solution film-forming method;
the precursor solution includes: a carbon material.
9. The method according to claim 8, wherein the solution film forming method is selected from one or more of spin coating, wire bar coating, doctor blade coating, screen printing, gravure printing and letterpress printing.
10. A perovskite solar cell of a carbon material conductive electrode, comprising:
a substrate material;
a hole transport layer;
a perovskite active layer;
an electron transport layer;
the conductive electrode of claim 1.
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CN113285034A (en) * 2021-05-19 2021-08-20 华能新能源股份有限公司 PVP (polyvinyl pyrrolidone) -doped zinc oxide film as well as preparation method and application thereof
CN113517406A (en) * 2021-06-16 2021-10-19 中国科学院物理研究所 Preparation method of carbon electrode, carbon electrode and perovskite solar cell

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Publication number Priority date Publication date Assignee Title
CN108269918A (en) * 2016-12-31 2018-07-10 中国科学院上海硅酸盐研究所 Porous perovskite thin film, carbon pastes and the solar cell based on carbon electrode
CN107275494A (en) * 2017-06-28 2017-10-20 南方科技大学 Blade coating preparation method of flexible perovskite solar cell
CN113285034A (en) * 2021-05-19 2021-08-20 华能新能源股份有限公司 PVP (polyvinyl pyrrolidone) -doped zinc oxide film as well as preparation method and application thereof
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