WO2019206053A1 - 一种掺杂抗氧化剂的钙钛矿薄膜及其制备方法和应用 - Google Patents
一种掺杂抗氧化剂的钙钛矿薄膜及其制备方法和应用 Download PDFInfo
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- WO2019206053A1 WO2019206053A1 PCT/CN2019/083568 CN2019083568W WO2019206053A1 WO 2019206053 A1 WO2019206053 A1 WO 2019206053A1 CN 2019083568 W CN2019083568 W CN 2019083568W WO 2019206053 A1 WO2019206053 A1 WO 2019206053A1
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- Prior art keywords
- solvent
- perovskite
- antioxidant
- doped
- precursor
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite film doped with an antioxidant and a preparation method and application thereof.
- a solar cell is a photoelectric conversion device that converts solar energy into electrical energy using the photovoltaic effect of a semiconductor. Since its inception, solar power has become the most important renewable energy source besides hydropower and wind power.
- the semiconductors currently used for commercialization include monocrystalline silicon, polycrystalline silicon, amorphous silicon, cadmium telluride, copper indium gallium selenide, etc., but most of them are energy-intensive and costly.
- perovskite solar cell has been widely concerned, and this perovskite solar cell has an organic metal halide as a light absorbing layer.
- the perovskite molecule is a cubic octahedral structure of the ABX 3 type, as shown in FIG.
- the thin film solar cell prepared by the material has the advantages of simple process, low production cost, stability and high conversion rate. Since 2009, the photoelectric conversion efficiency has increased from 3.8% to over 22%, which is higher than the commercial crystalline silicon solar cell and has Large cost advantage.
- halogen iodide ions in perovskite solar cells The stability of halogen iodide ions in perovskite solar cells is poor, and it is easy to lose electrons into iodine, which leads to deterioration of device performance.
- additives In order to further improve the efficiency of perovskite cells, research has proposed new battery structures, or modifications at the material interface, and the exploration of new materials. It has also been suggested that the high efficiency of perovskite cells is due to the optimized morphology and quality of the materials themselves.
- the use of additives is an effective method.
- the use of additives can aid in the more uniform formation of crystal nuclei and affect the crystallization process of the material.
- the benefits of applying additives include the ability to prepare a flat film surface, increase surface coverage, control grain size, and thereby increase the parallel resistance of the perovskite cell, thereby increasing cell efficiency.
- the existing perovskite film additives mainly include polymers, fullerenes, metal halide salts, inorganic acids, solvents, organic halogen salts, nanoparticles and other kinds of additives. These methods effectively regulate the crystallization process of perovskite and obtain a dense and smooth surface film, thereby improving the performance and long-term stability of the perovskite battery.
- existing additives do not oxidize iodide ions and do not prevent aging of perovskite materials.
- the technical problem to be solved by the present invention is to provide a perovskite film doped with an antioxidant, a preparation method and application thereof, and to design a perovskite structure from a chemical point of view using an antioxidant to provide a doping resistance.
- a perovskite film and a perovskite solar cell of an active layer of an oxidizing agent are provided.
- the present invention is achieved by providing an anti-oxidant-doped perovskite film, wherein the perovskite film is doped with an antioxidant, the antioxidant being an amine, a phenol, a phosphite, At least one of thioesters, chelating agents, complexes, and the like, having a molecular weight ranging from 1,000 to 100,000.
- the antioxidant is incorporated into the perovskite film by a solution mixing method, a co-evaporation method, or an anti-solvent method or a lamination method.
- the present invention is achieved by the method of preparing a first perovskite-doped perovskite film as described above, comprising the steps of:
- Step S11 preparing a perovskite solution
- Step S12 adding an antioxidant to the perovskite solution, heating and stirring at 70 ° C for 2 h to obtain a perovskite antioxidant mixture;
- Step S13 coating the perovskite antioxidant mixture on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer containing perovskite a thin film layer of the antioxidant mixture, and annealing the film layer to obtain an anti-oxidant perovskite film layer;
- the perovskite solution contains at least one solution of a divalent metal halide precursor BX 2 , a solution of at least one monovalent reactant AX, at least one solvent additive, and a main solvent.
- B is a divalent metal cation: lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, Any one of cations and cerium
- X is at least one of iodine, bromine, chlorine and hydrazine
- A is lithium, sodium, potassium, rubidium, cesium, amine, sulfhydryl, hydrazine nitrogen-containing organic compound
- the main solvent is an amide solvent capable of dissolving a metal halide and other antioxidants, a sulfone/sulfoxide
- At least one of a solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; in the calcium Mineral solution, the concentration of BX 2 precursor solution is 0.5-2mol / L, molar reactant ratio of AX AX: BX 2 0.9-1.1, the volume ratio of the main solvent additive solvent is 0-50%; the anti- The amount of the oxidizing agent incorporated is 0.01-25% of the molar amount of the precursor BX 2 .
- the present invention is achieved by the method of preparing a second anti-oxidant-doped perovskite film as described above, comprising the steps of:
- Step S21 preparing an antioxidant-containing precursor BX 2 mixture: adding an antioxidant to the precursor BX 2 solution, heating and stirring at 70 ° C for 2 h;
- Step S22 coating the mixed solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a precursor BX 2 film containing an antioxidant. a layer, and annealing the film layer to obtain an antioxidant-doped precursor BX 2 film layer;
- Step S23 the anti-oxidant-preventing precursor BX 2 film layer substrate prepared in step S22 is placed in the film forming cavity, and the vacuum degree in the film forming cavity is controlled between 10 -5 Pa - 10 5 Pa;
- Step S24 heating the reactant AX powder previously placed in the film forming cavity at a heating temperature range of 100-200 ° C, so that the precursor BX 2 film layer containing the antioxidant is placed in the vapor environment of the reactant AX while giving The substrate is heated, the heating temperature of the substrate is controlled at 30 ° C ⁇ 150 ° C, the reaction time is controlled from 10 min to 120 min, and the reactant AX gas molecules react with the precursor BX 2 molecules to form an anti-oxidant perovskite film to form calcium. Titanium ore active layer;
- the precursor BX 2 solution contains at least one divalent metal halide precursor BX 2 , at least one solvent additive and a main solvent
- B is a divalent metal cation: lead, tin, tungsten , copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine And at least any one of bromine, chlorine and hydrazine
- the main solvent is an amide solvent capable of dissolving a metal halide and other antioxidants, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogen Any one of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sul
- a of the reactant AX is at least any one of a nitrogen-containing organic compound such as lithium, sodium, potassium, rubidium, cesium, an amine group, a fluorenyl group or a hydrazine, and the antioxidant-doped calcium
- a nitrogen-containing organic compound such as lithium, sodium, potassium, rubidium, cesium, an amine group, a fluorenyl group or a hydrazine
- the present invention is achieved by the method of preparing a third anti-oxidant-doped perovskite film as described above, comprising the steps of:
- Step S31 placing the substrate on which the transport layer is deposited in the film forming cavity, and controlling the vacuum degree in the film forming cavity to be between 10 -8 Pa and 10 5 Pa, and simultaneously heating the substrate, the heating temperature of the substrate Control at 30 ° C ⁇ 150 ° C;
- Step S32 placing the precursor BX 2 , the reactant AX, and the antioxidant in different evaporation sources, the evaporation rate of the reactant AX is 0.1-10 ⁇ /s, and the evaporation rate of the precursor BX 2 is 0.1-10 ⁇ /s.
- the evaporation rate of the antioxidant is 0.05-5 ⁇ /s, so that the precursor BX 2 , the reactant AX and the antioxidant react with each other to form an anti-oxidant perovskite film to form a perovskite active layer;
- the present invention is achieved by providing a fourth method for preparing an anti-oxidant-doped perovskite film as described above, comprising the steps of:
- Step S41 dissolving the antioxidant in the anti-solvent, heating and stirring at 60 ° C for 2 h, to prepare an anti-solvent solution;
- Step S42 preparing a perovskite solution
- Step S43 coating the perovskite solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer of perovskite film;
- Step S44 applying the anti-solvent solution to the substrate on which the perovskite film layer is deposited by any one of spin coating, blade coating, slit continuous coating or spraying, and annealing to obtain doping a perovskite film layer of an antioxidant;
- the anti-solvent is benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3- At least one of dichlorobenzene, 1,4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, pentanol, the concentration of the antioxidant in the anti-solvent solution is 0.01-3 mol / L;
- the perovskite solution contains at least one divalent metal halide precursor BX 2 , at least one solution of the monovalent reactant AX, at least one solvent additive and a main solvent, and B is divalent.
- Metal cations lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony Any one of the cations, X is at least one of iodine, bromine, chlorine, and hydrazine, and A is at least any one of lithium, sodium, potassium, rubidium, cesium, amine, sulfhydryl, and hydrazine nitrogen-containing organic compounds.
- the main solvent is an amide solvent capable of dissolving metal halides and other antioxidants, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, Any one of an ether solvent and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, or a ketone solvent.
- At least one of an ether solvent and an aromatic hydrocarbon; in the perovskite solution, the former BX concentration was 2 solution is 0.5-2mol / L, the molar ratio of the reactants AX AX: BX 2 0.9-1.1, with the main solvent additive solvent volume ratio of 0-50%;
- Step S51 depositing a buffer layer on the substrate
- Step S52 using a method for preparing a doped antioxidant-containing perovskite film according to any one of the foregoing first to fourth embodiments, preparing an antioxidant-containing perovskite film to be superposed on the buffer layer-containing layer. Forming a laminated perovskite film on the substrate;
- the buffer layer contains at least one layer of TiO 2 , ZnO, SnO 2 , PCBM, PTAA, C60, C70, ITO, AZO, CuSCN, CuGaO 2 , NiOx, WOx, MoOx and at least one of them.
- the present invention is achieved by providing a perovskite solar cell to which a perovskite-doped perovskite film as described above is applied.
- the present invention is achieved by providing a perovskite solar cell on which the calcium-titanium prepared by the method for preparing an anti-oxidant perovskite film as described above is used. Mineral film.
- the antioxidant-doped perovskite film of the present invention and the preparation method and application thereof in the preparation process of the perovskite film, incorporate an appropriate amount of antioxidant, and inhibit the loss of electrons by perovskite
- the oxidation reaction of the iodide ion is inhibited, thereby stabilizing the material itself, so that the long-term stability of the thus prepared perovskite battery is improved, in particular, the illumination stability is improved, the service life is remarkably prolonged, and industrial production is also promoted.
- 1 is a schematic view showing the molecular structure of a prior art perovskite film
- FIG. 2 is a schematic view showing the internal structure of a perovskite solar cell prepared by the preparation method of the present invention
- 3 is a volt-ampere characteristic curve of a perovskite solar cell prepared by the preparation method of the present invention.
- the invention discloses an anti-oxidant-doped perovskite film, wherein the perovskite film is doped with an antioxidant, the antioxidant is an amine, a phenol, a phosphite, a thioester. At least one of the chelating agents has a molecular weight ranging from 1,000 to 100,000.
- the use of the antioxidant disclosed in the present invention can suppress the oxidation of iodide ions, thereby improving the long-term stability of the perovskite battery.
- the antioxidant is incorporated into the perovskite film by a solution mixing method, or a co-evaporation method, or an anti-solvent method or a lamination method.
- the invention also discloses a preparation method of a doped anti-oxidant perovskite film as described above, comprising the following steps:
- Step S11 preparing a perovskite solution.
- Step S12 adding an antioxidant to the perovskite solution, and heating and stirring at 70 ° C for 2 hours to obtain a perovskite antioxidant mixture.
- Step S13 coating an anti-oxidant-containing perovskite solution on the substrate deposited with the transport layer by any one of spin coating, blade coating, slit continuous coating or spraying to form a layer containing perovskite
- the thin film layer of the antioxidant mixture is annealed to obtain an anti-oxidant perovskite film layer.
- the perovskite solution contains at least one divalent metal halide precursor BX 2 , at least one solution of the monovalent reactant AX, at least one solvent additive and a main solvent, B Is a divalent metal cation: lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, antimony, Any one of cations, X is at least any one of iodine, bromine, chlorine, and hydrazine, and A is lithium, sodium, potassium, rubidium, cesium, amine, sulfhydryl, and hydrazine-containing organic compounds.
- At least one of the main solvents is an amide solvent capable of dissolving metal halides and other antioxidants, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, and a ketone.
- a solvent-like solvent, an ether solvent, and an aromatic hydrocarbon solvent may be mainly N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), One of ⁇ -butyrolactone (GBL).
- the solvent additive may be at least any one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon.
- an amide solvent a sulfone/sulfoxide solvent
- an ester solvent a hydrocarbon
- a halogenated hydrocarbon solvent an alcohol solvent
- a ketone solvent an ether solvent
- an aromatic hydrocarbon for example, one or more of DMSO, NMP, 1,8-diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), chlorobenzene (CB), and toluene.
- DIO 1,8-diiodooctane
- CHP N-cyclohexyl-2-pyrrolidone
- CB chlorobenzene
- the concentration of the precursor BX 2 solution is 0.5-2 mol/L
- the volume ratio of the solvent additive to the main solvent is 0-50%.
- the amount of the antioxidant is incorporated into the precursor BX 2 molar amount of 0.01 to 25%.
- Repeating step 13 as needed provides a multilayered doped antioxidant perovskite film layer.
- the invention also discloses a preparation method of the second anti-oxidant-doped perovskite film as described above, comprising the following steps:
- Step S21 preparing an antioxidant-containing precursor BX 2 mixed solution: adding an antioxidant to the precursor BX 2 solution, and heating and stirring at 70 ° C for 2 h.
- Step S22 coating the mixed solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a precursor BX 2 film containing an antioxidant.
- the layer is subjected to annealing treatment to obtain an antioxidant-doped calcium BX 2 film layer.
- Step S23 the precursor of the doped antioxidant BX 2 film obtained in step S22 is placed in the film forming cavity, and the degree of vacuum in the film forming cavity is controlled between 10 -5 Pa - 10 5 Pa.
- Step S24 heating the reactant AX powder previously placed in the film forming cavity at a heating temperature range of 100-200 ° C, so that the precursor BX 2 film layer containing the antioxidant is placed in the vapor environment of the reactant AX while giving The substrate is heated, the heating temperature of the substrate is controlled at 30 ° C ⁇ 150 ° C, the reaction time is controlled from 10 min to 120 min, and the reactant AX gas molecules react with the precursor BX 2 molecules to form an anti-oxidant perovskite film to form calcium. Titanium ore active layer.
- the precursor BX 2 solution contains at least one divalent metal halide precursor BX 2 , at least one solvent additive and a main solvent
- B is a divalent metal cation: lead, tin, tungsten , copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine And at least any one of bromine, chlorine and hydrazine
- the main solvent is an amide solvent capable of dissolving a metal halide and other antioxidants, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogen Any one of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, and may be mainly N,N-dimethylformamide (DM)
- the solvent additive may be at least any one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon.
- an amide solvent a sulfone/sulfoxide solvent
- an ester solvent a hydrocarbon
- a halogenated hydrocarbon solvent an alcohol solvent
- a ketone solvent an ether solvent
- an aromatic hydrocarbon for example, one or more of DMSO, NMP, 1,8-diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), chlorobenzene (CB), and toluene.
- DIO 1,8-diiodooctane
- CHP N-cyclohexyl-2-pyrrolidone
- CB chlorobenzene
- the amount of the antioxidant is incorporated into the precursor BX 2 molar amount of 0.01 to 25%; BX 2 in the precursor solution, the precursor solution is a concentration of 2 BX 0.5-2mol / L, the main solvent additive solvent
- the volume ratio is 0-50%.
- a of the reactant AX is at least any one of lithium, sodium, potassium, rubidium, cesium, an amine group, a fluorenyl group, and a hydrazine nitrogen-containing organic compound.
- a multi-layer doped antioxidant perovskite film can be formed to form a multilayered perovskite active layer.
- the invention also discloses a preparation method of the third anti-oxidant-doped perovskite film as described above, comprising the following steps:
- Step S31 placing the substrate on which the transport layer is deposited in the film forming cavity, and controlling the vacuum degree in the film forming cavity to be between 10 -8 Pa and 10 5 Pa, and simultaneously heating the substrate, the heating temperature of the substrate Controlled at 30 ° C ⁇ 150 ° C.
- Step S32 placing the precursor BX 2 , the reactant AX, and the antioxidant in different evaporation sources, the evaporation rate of the reactant AX is 0.1-10 ⁇ /s, and the evaporation rate of the precursor BX 2 is 0.1-10 ⁇ /s.
- the evaporation rate of the antioxidant is 0.05-5 ⁇ /s, so that the precursor BX 2 , the reactant AX and the antioxidant react with each other to form an anti-oxidant perovskite film to form a perovskite active layer.
- B of the precursor BX 2 is a divalent metal cation: lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, antimony Any one of cations of cerium, platinum, gold, mercury, cerium, lanthanum, cerium, and X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and the reactant AX A in the middle is at least any one of lithium, sodium, potassium, rubidium, cesium, an amine group, a fluorenyl group, and a hydrazine nitrogen-containing organic compound.
- a multi-layer doped antioxidant perovskite film layer can be obtained to form a perovskite active layer.
- the invention also discloses a fourth preparation method of the anti-oxidant-doped perovskite film as described above, comprising the following steps:
- Step S41 dissolving the antioxidant in the anti-solvent, and heating and stirring at 60 ° C for 2 h to prepare an anti-solvent solution.
- Step S42 preparing a perovskite solution.
- Step S43 coating the perovskite solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer of perovskite film.
- Step S44 applying the anti-solvent solution to the substrate on which the perovskite film layer is deposited by any one of spin coating, blade coating, slit continuous coating or spraying, and annealing to obtain doping Anti-oxidant perovskite film layer.
- the anti-solvent is benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3- At least one of dichlorobenzene, 1,4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, and pentanol, and the concentration of the antioxidant in the antisolvent solution is 0.01 to 3 mol/L.
- the perovskite solution contains at least one divalent metal halide precursor BX 2 , at least one solution of the monovalent reactant AX, at least one solvent additive and a main solvent, and B is divalent.
- Metal cations lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony Any one of the cations, X is at least one of iodine, bromine, chlorine, and hydrazine, and A is at least any one of lithium, sodium, potassium, rubidium, cesium, amine, sulfhydryl, and hydrazine nitrogen-containing organic compounds.
- the main solvent is an amide solvent capable of dissolving metal halides and other antioxidants, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, Any one of an ether solvent and an aromatic hydrocarbon solvent, which may be mainly N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), ⁇ -butyl One of the lactones (GBL).
- DMF N,N-dimethylformamide
- DMSO dimethyl sulfoxide
- NMP N-methylpyrrolidone
- GBL ⁇ -butyl
- lactones GBL
- the solvent additive may be at least any one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon.
- Species such as one or more of DMSO, NMP, 1,8-diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), chlorobenzene (CB), toluene;
- concentration of the precursor BX 2 solution is 0.5-2 mol/L
- the volume ratio of the solvent additive to the main solvent is 0-50%.
- the invention also discloses a fifth preparation method of the anti-oxidant-doped perovskite film as described above, comprising the following steps:
- Step S51 depositing a buffer layer on the substrate.
- Step S52 using a method for preparing a doped antioxidant-containing perovskite film according to any one of the foregoing first to fourth embodiments, preparing an antioxidant-containing perovskite film to be superposed on the buffer layer-containing layer. On the substrate, a laminated perovskite film is formed.
- the buffer layer contains at least one layer of TiO 2 , ZnO, SnO 2 , PCBM, PTAA, C60, C70, ITO, AZO, CuSCN, CuGaO 2 , NiOx, WOx, MoOx, and at least any of them.
- the buffer layer may be composed of one or more layers of a single or a mixture, and has a function of collecting and transporting carriers.
- the present invention also discloses a perovskite solar cell on which a perovskite-doped perovskite film is applied as described above.
- the present invention also discloses another perovskite solar cell on which a perovskite film prepared by the method for preparing an anti-oxidant perovskite film as described above is used.
- Example 1 a method of preparing a first perovskite solar cell.
- a NiO x film was prepared as a hole transport layer.
- a doped PbI 2 film was prepared by slit coating using the prepared precursor liquid.
- the obtained metal halide film is placed in a film forming cavity, and the air pressure is controlled by a vacuum pump at 10 -5 Pa ⁇ 10 5 Pa, and the AX heating temperature is controlled at 100 ° C to 200 ° C, and the substrate heating temperature is controlled at At 30 ° C ⁇ 150 ° C, AX gas molecules react with BX 2 to form a doped perovskite film.
- a metal permeation layer Ag electrode is vapor-deposited to obtain a perovskite solar cell.
- Example 2 a method of preparing a second perovskite solar cell.
- a SnO 2 film was prepared as an electron transport layer.
- the prepared perovskite solution was spin-coated on the surface of the electron transport layer, and then annealed at 100 ° C for 10 minutes on a heating table to form a perovskite crystal film.
- the hole transport layer PTAA was spin-coated on a perovskite crystal film doped with an antioxidant to a thickness of 20 to 50 nm.
- An aluminum electrode of a metal conductive layer is vapor-deposited to obtain a perovskite solar cell.
- Example 3 a method of preparing a third perovskite solar cell.
- the flexible transparent conductive substrate PET was sequentially washed with detergent, deionized water, acetone, and isopropyl alcohol for 30 min, dried with N 2 , and then treated with UV O-zone for 5 min.
- a low-temperature SnO 2 film was prepared as an electron transport layer.
- the PET deposited with the transport layer is placed in the film forming cavity, and the vacuum in the film forming cavity is controlled between 10 -8 Pa-10 5 Pa, and the substrate is heated, and the heating temperature of the substrate is controlled. At 30 ° C ⁇ 150 ° C.
- the precursor BX 2 , the reactant AX and the antioxidant are respectively placed in different evaporation sources, the evaporation rate of the reactant AX is 0.1-10 ⁇ /s, and the evaporation rate of the precursor BX 2 is 0.1-10 ⁇ /s.
- the evaporation rate of the antioxidant is 0.05-5 ⁇ /s, so that the precursor BX 2 , the reactant AX and the antioxidant react with each other to form an anti-oxidant perovskite film layer.
- the hole transport layer PTAA was spin-coated on a perovskite crystal film doped with an antioxidant to a thickness of 20 to 50 nm.
- a metal-conducting layer Cu electrode is vapor-deposited to obtain a perovskite solar cell.
- Example 4 a method of preparing a fourth perovskite solar cell.
- a TiO 2 film was prepared as an electron transport layer.
- the prepared perovskite solution is spin-coated on the surface of the electron transport layer, and the anti-solvent solution is rapidly added dropwise during the spin coating process. After the spin coating is finished, the anti-oxidant-containing perovskite precursor film is placed in the heating. On the stage, annealing at 100 ° C for 20 minutes forms a perovskite crystal film.
- the hole transport layer CuSCN is scraped on a perovskite crystal film doped with an antioxidant, and has a thickness of 50-100 nm.
- Example 5 a method of preparing a fifth perovskite solar cell.
- Any solar cell is selected, including but not limited to single crystal silicon, polycrystalline silicon, amorphous silicon, copper indium gallium selenide, copper zinc tin sulfide, copper indium gallium sulfide, copper indium gallium sulfide, and cadmium telluride as a substrate.
- a laminated solar cell is constructed, wherein the perovskite battery is a top battery, that is, a battery that first receives light.
- Figure 3 is a graph showing the volt-ampere characteristic of a perovskite solar cell prepared by the method of Example 1, using the additive described in this patent. As is clear from Fig. 3, the forward scan curve and the reverse scan almost coincide, and the stability of the battery is increased without loss of efficiency.
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Abstract
一种掺杂抗氧化剂的钙钛矿薄膜,在所述钙钛矿薄膜内掺杂有抗氧化剂,所述抗氧化剂为胺类、酚类、亚磷酸酯类、硫代酯类、螯合剂类中的至少一种,其分子量范围为:1000-100000。还公开了一种掺杂抗氧化剂的钙钛矿薄膜的制备方法和应用,通过掺杂抗氧化剂,制备得到掺杂的钙钛矿太阳能电池,提高电池性能,并提高太阳能电池的稳定性。在钙钛矿薄膜的制备过程中,掺入适量的抗氧化剂,通过抑制碘离子的氧化反应,从而达到稳定材料本身的作用,使得由此制备的钙钛矿电池的长期稳定性得到提升,使用寿命显著延长,而且还促进工业化生产。
Description
本发明属于钙钛矿太阳能电池技术领域,特别涉及涉及一种掺杂抗氧化剂的钙钛矿薄膜及其制备方法和应用。
太阳能电池是一种光电转换器件,利用半导体的光伏效应将太阳能转化为电能。发展至今,太阳能发电已经成为除水力发电和风力发电之外最重要的可再生能源。现用于商业化的半导体有单晶硅、多晶硅、非晶硅、碲化镉、铜铟镓硒等等,但大多能耗大、成本高。
近年来,一种钙钛矿太阳能电池受到广泛关注,这种钙钛矿太阳能电池以有机金属卤化物为光吸收层。钙钛矿分子为ABX
3型的立方八面体结构,如图1所示。此种材料制备的薄膜太阳能电池工艺简便、生产成本低、稳定且转化率高,自2009年至今,光电转换效率从3.8%提升至22%以上,已高于商业化的晶硅太阳能电池且具有较大的成本优势。
钙钛矿太阳能电池中的卤素碘离子的稳定性较差,容易失去电子变成碘单质,导致器件性能的恶化。
为了进一步提高钙钛矿电池效率,有研究提出了新的电池结构,或在材料界面进行修饰,并且探索新的材料。还有研究提出,钙钛矿电池的高效率得益于材料本身的优化形貌和质量,为了提高薄膜质量并精准控制钙钛矿晶粒,使用添加剂是一种行之有效的方法。添加剂的应用可以辅助晶核更均匀的形成,并且影响材料的结晶过程。应用添加剂的好处包括可制备平整的薄膜表面,提高表面覆盖率,控制晶粒大小,从而增大钙钛矿电池的并联电阻,进而达到增加电池效率的目的。
现有的钙钛矿薄膜添加剂主要有聚合物,富勒烯,金属卤素盐,无机酸,溶剂,有机卤素盐,纳米粒子和其他种类添加剂。这些方法有效的调控了钙钛矿的结晶过程,获得表面致密光滑的薄膜,从而提高钙钛矿电池的性能和长期稳定性。但是现有的添加剂却不能碘离子发生氧化反应,不能防止钙钛矿材料的老化。
因此,现有技术有待进一步改进和完善。
本发明所要解决的技术问题在于,提供一种掺杂抗氧化剂的钙钛矿薄膜及其制备方法和应用,从化学的角度利用抗氧化剂来设计钙钛矿的结构,提供一种具有掺杂抗氧化剂的活性层的钙钛矿薄膜及钙钛矿太阳能电池。
本发明是这样实现的,提供一种掺杂抗氧化剂的钙钛矿薄膜,在所述钙钛矿薄膜内掺杂有抗氧化剂,所述抗氧化剂为胺类、酚类、亚磷酸酯类、硫代酯类、螯合剂类、复合类及其他类中的至少一种,其分子量范围为:1000-100000。
进一步地,所述抗氧化剂通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
本发明是这样实现的,还提供第一种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S11、制备钙钛矿溶液;
步骤S12、在所述钙钛矿溶液中添加抗氧化剂,70℃加热搅拌2h,得到钙钛矿抗氧化剂混合液;
步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿抗氧化剂混合液涂覆在沉积有传输层的基片上形成一层含有钙钛矿抗氧化剂混合液的薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的钙钛矿薄膜层;
在步骤S11和步骤S12中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX
2的溶液、至少一种一价反应物AX的溶液、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;在所述钙钛矿溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,反应物AX的摩尔比AX:BX
2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%;所述抗氧化剂的掺入量是前驱物BX
2摩尔量的0.01-25%。
在步骤S13中,所述掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
本发明是这样实现的,还提供第二种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S21、制备含抗氧化剂的前驱物BX
2混合液:在前驱物BX
2溶液中添加抗氧化剂,70℃加热搅拌2h;
步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该混合液涂覆在沉积有传输层的基片上形成一层含有抗氧化剂的前驱物BX
2薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的前驱物BX
2薄膜层;
步骤S23、将步骤S22制得的掺杂抗氧化剂的前驱物BX
2薄膜层基片放置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10
-5Pa-10
5Pa之间;
步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热,加热温度范围为100-200℃,使得含有抗氧化剂的前驱物BX
2薄膜层置于反应物AX的蒸汽环境中,同时给基片加热,基片的加热温度控制在30℃~150℃,反应时间控制在10min~120min,反应物AX气体分子与前驱物BX
2分子反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层;
在步骤S21和S22中,所述前驱物BX
2溶液中含有至少一种二价金属卤化物前驱物BX
2、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;所述抗氧化剂的掺入量是前驱物BX
2摩尔量的0.01-25%;在所述前驱物BX
2溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,溶剂添加剂与主溶剂的体积比为0-50%。
在步骤S24中,所述反应物AX的A为锂、钠、钾、铯、铷、胺基、脒基、胍等含氮有机化合物中的至少任意一种,所述掺杂抗氧化剂的钙钛矿薄膜的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
本发明是这样实现的,还提供第三种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S31、将沉积有传输层的基片置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10
-8Pa-10
5Pa之间,同时给基片加热,基片的加热温度控制在30℃~150℃;
步骤S32、将前驱物BX
2、反应物AX、抗氧化剂分别置于不同的蒸发源中,反应物AX的蒸发速率为0.1-10Å/s,前驱物BX
2的蒸发速率为0.1-10Å/s,抗氧化剂的蒸发速率为0.05-5Å/s,使得前驱物BX
2、反应物AX、抗氧化剂相互反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层;
在步骤S32中,所述前驱物BX
2的B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子,所述反应物AX中的A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,最终形成的掺杂抗氧化剂的钙钛矿薄膜的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
本发明是这样实现的,还提供第四种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S41、将抗氧化剂溶解于反溶剂中,60℃加热搅拌2h,制备得到反溶剂溶液;
步骤S42、制备钙钛矿溶液;
步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层;
步骤S44、将反溶剂溶液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上,并进行退火处理得到掺杂有抗氧化剂的钙钛矿薄膜层;
在步骤S41中,所述反溶剂为苯、甲苯、1,2-二甲苯、1,3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种,所述反溶剂溶液中抗氧化剂的浓度是0.01-3mol/L;
在步骤S42中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX
2、至少一种一价反应物AX的溶液、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;在所述钙钛矿溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,反应物AX的摩尔比AX:BX
2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%;
在步骤S44中,掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
本发明是这样实现的,还提供第五种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S51、在基片上沉积缓冲层;
步骤S52、采用如前述第一种至第四种中任意一种所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法将含抗氧化剂的钙钛矿薄膜叠加地制备到上述含缓冲层的基片上,构成叠层钙钛矿薄膜;
在步骤S52中,所述的缓冲层含有至少一层由TiO
2、ZnO、SnO
2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO
2、NiOx、WOx、MoOx以及它们的至少任意两种掺杂物制成的薄膜。
本发明是这样实现的,还提供一种钙钛矿太阳能电池,在所述的钙钛矿太阳能电池上应用了如前所述的掺杂抗氧化剂的钙钛矿薄膜。
本发明是这样实现的,还提供一种钙钛矿太阳能电池,在所述的钙钛矿太阳能电池上采用了如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
与现有技术相比,本发明的掺杂抗氧化剂的钙钛矿薄膜及其制备方法和应用,在钙钛矿薄膜的制备过程中,掺入适量的抗氧化剂,通过抑制钙钛矿失去电子,抑制碘离子的氧化反应,从而达到稳定材料本身的作用,使得由此制备的钙钛矿电池的长期稳定性得到提升,尤其是提升光照稳定性,使用寿命显著延长,而且还促进工业化生产。
图1为现有技术钙钛矿薄膜中分子结构示意图;
图2为本发明的制备方法制备的钙钛矿太阳能电池内部结构示意图;
图3为本发明的制备方法制备的钙钛矿太阳能电池伏安特性曲线。
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明公开了一种掺杂抗氧化剂的钙钛矿薄膜,在所述钙钛矿薄膜内掺杂有抗氧化剂,所述抗氧化剂为胺类、酚类、亚磷酸酯类、硫代酯类、螯合剂类中的至少一种,其分子量范围为:1000-100000。
使用本发明公开的抗氧化剂可以抑制碘离子氧化,从而提高钙钛矿电池的长期稳定性。
在上述实施例中,所述抗氧化剂通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
本发明还公开了一种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S11、制备钙钛矿溶液。
步骤S12、在所述钙钛矿溶液中添加抗氧化剂,70℃加热搅拌2h,得到钙钛矿抗氧化剂混合液。
步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将含抗氧化剂的钙钛矿溶液涂覆在沉积有传输层的基片上形成一层含有钙钛矿抗氧化剂混合液的薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的钙钛矿薄膜层。
在步骤S11和步骤S12中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX
2、至少一种一价反应物AX的溶液、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,主要可为N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)中的一种。
所述溶剂添加剂可以为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种,例如DMSO、NMP、1,8-二碘辛烷(DIO)、N-环己基-2-吡咯烷酮(CHP)、氯苯(CB)、甲苯中的一种或几种。在所述钙钛矿溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,反应物的摩尔比AX:BX
2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%。所述抗氧化剂的掺入量是前驱物BX
2摩尔量的0.01-25%。
在步骤S13中,掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
按照需要重复步骤13,可以得到多层掺杂抗氧化剂的钙钛矿薄膜层。
本发明还公开了第二种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S21、制备含抗氧化剂的前驱物BX
2混合液:在前驱物BX
2溶液中添加抗氧化剂,70℃加热搅拌2h。
步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该混合液涂覆在沉积有传输层的基片上形成一层含有抗氧化剂的前驱物BX
2薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的钙BX
2薄膜层。
步骤S23、将步骤S22制得的掺杂抗氧化剂的前驱物BX
2薄膜层基片放置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10
-5Pa-10
5Pa之间。
步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热,加热温度范围为100-200℃,使得含有抗氧化剂的前驱物BX
2薄膜层置于反应物AX的蒸汽环境中,同时给基片加热,基片的加热温度控制在30℃~150℃,反应时间控制在10min~120min,反应物AX气体分子与前驱物BX
2分子反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层。
在步骤S21和S22中,所述前驱物BX
2溶液中含有至少一种二价金属卤化物前驱物BX
2、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,主要可为N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)中的一种。
所述溶剂添加剂可以为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种,例如DMSO、NMP、1,8-二碘辛烷(DIO)、N-环己基-2-吡咯烷酮(CHP)、氯苯(CB)、甲苯中的一种或几种。所述抗氧化剂的掺入量是前驱物BX
2摩尔量的0.01-25%;在所述前驱物BX
2溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,溶剂添加剂与主溶剂的体积比为0-50%。
在步骤S24中,所述反应物AX的A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种。所述掺杂抗氧化剂的钙钛矿薄膜钙钛矿活性层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
按照需要重复步骤22至步骤24,可以生成多层掺杂抗氧化剂的钙钛矿薄膜,形成多层钙钛矿活性层。
本发明还公开了第三种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S31、将沉积有传输层的基片置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10
-8Pa-10
5Pa之间,同时给基片加热,基片的加热温度控制在30℃~150℃。
步骤S32、将前驱物BX
2、反应物AX、抗氧化剂分别置于不同的蒸发源中,反应物AX的蒸发速率为0.1-10Å/s,前驱物BX
2的蒸发速率为0.1-10Å/s,抗氧化剂的蒸发速率为0.05-5Å/s,使得前驱物BX
2、反应物AX、抗氧化剂相互反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层。
在步骤S32中,所述前驱物BX
2的B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子,所述反应物AX中的A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种。最终形成的所述掺杂抗氧化剂的钙钛矿薄膜钙钛矿活性层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
按照需要重复步骤32,可以得到多层掺杂抗氧化剂的钙钛矿薄膜层,形成钙钛矿活性层。
本发明还公开了第四种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S41、将抗氧化剂溶解于反溶剂中,60℃加热搅拌2h,制备得到反溶剂溶液。
步骤S42、制备钙钛矿溶液。
步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层。
步骤S44、将反溶剂溶液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上,并进行退火处理得到掺杂有抗氧化剂的钙钛矿薄膜层。
在步骤S41中,所述反溶剂为苯、甲苯、1,2-二甲苯、1,3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种,所述反溶剂溶液中抗氧化剂的浓度是0.01-3mol/L。
在步骤S42中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX
2,至少一种一价反应物AX的溶液、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,主要可为N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)中的一种。
所述溶剂添加剂可以为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种,例如DMSO、NMP、1,8-二碘辛烷(DIO)、N-环己基-2-吡咯烷酮(CHP)、氯苯(CB)、甲苯中的一种或几种;在所述钙钛矿溶液中,前驱物BX
2溶液的浓度为0.5-2mol/L,反应物AX的摩尔比AX:BX
2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%。
在步骤S44中,掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX
2:抗氧化剂=0.9-1.1:1.0:0-0.25。
按照需要重复步骤43和步骤44,可以得到多层掺杂抗氧化剂的钙钛矿薄膜层。
本发明还公开了第五种如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,包括如下步骤:
步骤S51、在基片上沉积缓冲层。
步骤S52、采用如前述第一种至第四种中任意一种所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法将含抗氧化剂的钙钛矿薄膜叠加地制备到上述含缓冲层的基片上,构成叠层钙钛矿薄膜。
在步骤S51中,所述的缓冲层含有至少一层由TiO
2、ZnO、SnO
2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO
2、NiOx、WOx、MoOx以及它们的至少任意两种掺杂物制成的薄膜。缓冲层可以由一层或多层单一或混合物构成,具有收集和传输载流子的功能。
本发明还公开了一种钙钛矿太阳能电池,在所述的钙钛矿太阳能电池上应用了如前所述的掺杂抗氧化剂的钙钛矿薄膜。
本发明还公开了另一种钙钛矿太阳能电池,在所述的钙钛矿太阳能电池上采用了如前所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
下面结合具体实施例来进一步说明本发明。
实例1,第一种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图,包括以下步骤:
(1)将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min,再用N
2吹干后经UV O-zone处理10min。
(2)制备NiO
x薄膜作为空穴传输层。
(3)制备掺杂或修饰的金属卤化物前驱液:将461mg的PbI
2(1mmol)、6.752mg甲基氯化胺(0.1mmol)溶解于1mL的DMF溶液中,并添加70.9uL的无水DMSO,60℃加热搅拌2h,加入抗氧化剂溶液,混合完全后待用。
(4)使用制备的前驱液通过狭缝涂布制备掺杂的PbI
2薄膜。
(5)将制得的金属卤化物薄膜置于薄膜成型腔体中,利用真空泵控制气压在10
-5Pa~10
5Pa,AX加热温度控制在100℃~200℃,基片加热温度控制在30℃~150℃,AX气体分子与BX
2反应生成掺杂的钙钛矿薄膜。
(6)在基片上沉积电子传输层PCBM,厚20-50nm。
(7)蒸镀金属导电层Ag电极,制得钙钛矿太阳能电池。
实例2,第二种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图,包括以下步骤:
(1)将5×5cm的FTO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min,再用N
2吹干后经UV O-zone处理30min。
(2)制备SnO2薄膜作为电子传输层。
(3)制备含抗氧化剂的钙钛矿溶液:将461mg的PbI
2(1mmol)、159mg甲基碘化胺(1mmol)溶解于1mL的DMF溶液中,并添加76uL的无水NMP,再加入抗氧化剂,掺入量是前驱物BX
2摩尔量的5%。60℃加热搅拌2h,完全溶解后过滤待用。
(4)将制备的钙钛矿溶液旋涂在电子传输层表面,然后在加热台上100℃退火10分钟,形成钙钛矿结晶薄膜。
(5)在掺入抗氧化剂的钙钛矿结晶薄膜上旋涂空穴传输层PTAA,厚20-50nm。
(6)蒸镀金属导电层Al电极,制得钙钛矿太阳能电池。
实例3,第三种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图,包括以下步骤:
(1)将柔性透明导电基底PET依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min,再用N
2吹干后经UV O-zone处理5min。
(2)制备低温SnO
2薄膜作为电子传输层。
(3)将沉积有传输层的PET置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10
-8Pa-10
5Pa之间,同时给基片加热,基片的加热温度控制在30℃~150℃。
(4)将前驱物BX
2、反应物AX、抗氧化剂分别置于不同的蒸发源中,反应物AX的蒸发速率为0.1-10Å/s,前驱物BX
2的蒸发速率为0.1-10Å/s,抗氧化剂的蒸发速率为0.05-5Å/s,使得前驱物BX
2、反应物AX、抗氧化剂相互反应生成掺杂抗氧化剂的钙钛矿薄膜层。
(5)在掺入抗氧化剂的钙钛矿结晶薄膜上旋涂空穴传输层PTAA,厚20-50nm。
(6)蒸镀金属导电层Cu电极,制得钙钛矿太阳能电池。
实例4,第四种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图,包括以下步骤:
(1)将5×5cm的FTO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min,再用N
2吹干后经UV O-zone处理30min。
(2)制备TiO
2薄膜作为电子传输层。
(3)制备钙钛矿溶液:将415mg的PbI
2(0.9mmol)、36.7mg的PbBr
2(0.1mmol)、159mg甲基碘化胺(1mmol)溶解于1mL的γ-丁内酯溶液中,并添加71uL的无水DMSO。60℃加热搅拌2h,完全溶解后过滤待用。
(4)制备掺入抗氧化剂的反溶剂溶液:将抗氧化剂溶解于甲苯,60℃加热搅拌2h,完全溶解后过滤待用,浓度为0.1 mol/L。
(5)将制备的钙钛矿溶液旋涂在电子传输层表面,在旋涂过程中,迅速滴加反溶剂溶液,待旋涂结束,将含抗氧化剂的钙钛矿前驱体薄膜置于加热台上,100℃退火20分钟,形成钙钛矿结晶薄膜。
(6)在掺入抗氧化剂的钙钛矿结晶薄膜上刮涂空穴传输层CuSCN,厚50-100nm。
(7)在空穴传输层表面磁控溅射ITO电极,制得钙钛矿太阳能电池。
实例5,第五种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图,包括以下步骤:
(1)选取任意一种太阳能电池包括但不限于单晶硅,多晶硅、非晶硅、铜铟镓硒、铜锌锡硫、铜铟镓硫、铜铟镓硫、碲化镉作为基片。
(2)在干净的基片上沉积缓冲层。
(3)采用诸如前述第一种至第四种中的任意一种掺杂抗氧化剂的钙钛矿薄膜的制备方法将含抗氧化剂的钙钛矿薄膜叠加地制备到上述含缓冲层的基片上,构成叠层太阳能电池,其中钙钛矿电池为顶电池,即先接收光的电池。
图3为由实例1中所属方法制备的钙钛矿太阳能电池的伏安特性曲线,该电池使用本专利所述添加剂。从附图3中可以清楚地看出,正向扫描曲线和反向扫描几乎重合,在不损失效率的前提下,电池的稳定性增加。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
在此处键入工业实用性描述段落。
在此处键入序列表自由内容描述段落。
Claims (13)
- 一种掺杂抗氧化剂的钙钛矿薄膜,其特征在于,在所述钙钛矿薄膜内掺杂有抗氧化剂,所述抗氧化剂为胺类、酚类、亚磷酸酯类、硫代酯类、螯合剂类、复合类及其他类中的至少一种,其分子量范围为:1000-100000。
- 如权利要求1所述的掺杂抗氧化剂的钙钛矿薄膜,其特征在于,所述抗氧化剂通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
- 一种如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:步骤S11、制备钙钛矿溶液;步骤S12、在所述钙钛矿溶液中添加抗氧化剂,70℃加热搅拌2h,得到钙钛矿抗氧化剂混合液;步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将含抗氧化剂的钙钛矿溶液涂覆在沉积有传输层的基片上形成一层含有钙钛矿抗氧化剂混合液的薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的钙钛矿薄膜层;在步骤S11和步骤S12中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX 2的溶液、至少一种一价反应物AX的溶液、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;在所述钙钛矿溶液中,前驱物BX 2溶液的浓度为0.5-2mol/L,反应物AX的摩尔比AX:BX 2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%;所述抗氧化剂的掺入量是前驱物BX 2摩尔量的0.01-25%;在步骤S13中,所述掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX 2:抗氧化剂=0.9-1.1:1.0:0-0.25。
- 如权利要求3所述的掺杂抗氧化剂的钙钛矿薄膜,其特征在于,重复步骤13,得到多层掺杂抗氧化剂的钙钛矿薄膜层。
- 一种如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:步骤S21、制备含抗氧化剂的前驱物BX 2混合液:在前驱物BX 2溶液中添加抗氧化剂,70℃加热搅拌2h;步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该混合液涂覆在沉积有传输层的基片上形成一层含有抗氧化剂的前驱物BX 2薄膜层,并对该薄膜层进行退火处理得到掺杂抗氧化剂的前驱物BX 2薄膜层;步骤S23、将步骤S22制得的掺杂抗氧化剂的前驱物BX 2薄膜层基片放置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10 -5Pa-10 5Pa之间;步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热,加热温度范围为100-200℃,使得含有抗氧化剂的前驱物BX 2薄膜层置于反应物AX的蒸汽环境中,同时给基片加热,基片的加热温度控制在30℃~150℃,反应时间控制在10min~120min,反应物AX气体分子与前驱物BX 2分子反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层;在步骤S21和S22中,所述前驱物BX 2溶液中含有至少一种二价金属卤化物前驱物BX 2、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;所述抗氧化剂的掺入量是前驱物BX 2摩尔量的0.01-25%;在所述前驱物BX 2溶液中,前驱物BX 2溶液的浓度为0.5-2mol/L,溶剂添加剂与主溶剂的体积比为0-50%;在步骤S24中,所述反应物AX的A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述掺杂抗氧化剂的钙钛矿薄膜的组分比为:AX:BX 2:抗氧化剂=0.9-1.1:1.0:0-0.25。
- 如权利要求5所述的掺杂抗氧化剂的钙钛矿薄膜,其特征在于,重复步骤22至步骤24,生成多层掺杂抗氧化剂的钙钛矿薄膜,形成多层钙钛矿活性层。
- 一种如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:步骤S31、将沉积有传输层的基片置于薄膜成型腔体中,薄膜成型腔体内的真空度控制在10 -8Pa-10 5Pa之间,同时给基片加热,基片的加热温度控制在30℃~150℃;步骤S32、将前驱物BX 2、反应物AX、抗氧化剂分别置于不同的蒸发源中,反应物AX的蒸发速率为0.1-10Å/s,前驱物BX 2的蒸发速率为0.1-10Å/s,抗氧化剂的蒸发速率为0.05-5Å/s,使得前驱物BX 2、反应物AX、抗氧化剂相互反应生成掺杂抗氧化剂的钙钛矿薄膜,形成钙钛矿活性层;在步骤S32中,所述前驱物BX 2的B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子,所述反应物AX中的A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,最终形成的掺杂抗氧化剂的钙钛矿薄膜的组分比为:AX:BX 2:抗氧化剂=0.9-1.1:1.0:0-0.25。
- 如权利要求7所述的掺杂抗氧化剂的钙钛矿薄膜,其特征在于,重复步骤32,得到多层掺杂抗氧化剂的钙钛矿薄膜层,形成钙钛矿活性层。
- 一种如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:步骤S41、将抗氧化剂溶解于反溶剂中,60℃加热搅拌2h,制备得到反溶剂溶液;步骤S42、制备钙钛矿溶液;步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层;步骤S44、将反溶剂溶液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上,并进行退火处理得到掺杂有抗氧化剂的钙钛矿薄膜层;在步骤S41中,所述反溶剂为苯、甲苯、1,2-二甲苯、1,3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种,所述反溶剂溶液中抗氧化剂的浓度是0.01-3mol/L;在步骤S42中,所述钙钛矿溶液中含有至少一种二价金属卤化物前驱物BX 2、至少一种一价反应物AX的溶液、至少一种抗氧化剂、至少一种溶剂添加剂和主溶剂,B为二价金属阳离子:铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子,X为碘、溴、氯、砹中的至少任意一种阴离子,A为锂、钠、钾、铯、铷、胺基、脒基、胍含氮有机化合物中的至少任意一种,所述主溶剂为可溶解金属卤化物及其他抗氧化剂的酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种,所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种;在所述钙钛矿溶液中,前驱物BX 2溶液的浓度为0.5-2mol/L,反应物AX的摩尔比AX:BX 2=0.9-1.1,溶剂添加剂与主溶剂的体积比为0-50%;在步骤S44中,掺杂抗氧化剂的钙钛矿薄膜层的组分比为:AX:BX 2:抗氧化剂=0.9-1.1:1.0:0-0.25。
- 如权利要求9所述的掺杂抗氧化剂的钙钛矿薄膜,其特征在于,重复步骤43和步骤44,得到多层掺杂抗氧化剂的钙钛矿薄膜层。
- 一种如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:步骤S51、在基片上沉积缓冲层;步骤S52、采用如权利要求3至10中任意一种所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法将含抗氧化剂的钙钛矿薄膜叠加地制备到上述含缓冲层的基片上,构成叠层钙钛矿薄膜;在步骤S51中,所述的缓冲层含有至少一层由TiO 2、ZnO、SnO 2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO 2、NiOx、WOx、MoOx以及它们的至少任意两种掺杂物制成的薄膜。
- 一种钙钛矿太阳能电池,其特征在于,在所述的钙钛矿太阳能电池上应用了如权利要求1或2所述的掺杂抗氧化剂的钙钛矿薄膜。
- 一种钙钛矿太阳能电池,其特征在于,在所述的钙钛矿太阳能电池上采用了如权利要求3至11中任意一种所述的掺杂抗氧化剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
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