WO2019128864A1 - Ion stabilizer-doped perovskite film, preparation method therefor and application thereof - Google Patents

Abstract

Disclosed is an ion stabilizer-doped perovskite film. The perovskite film is doped with an ion stabilizer, and the ion stabilizer has a chemical structure general formula of R1-R-R2, wherein R is an alkyl group, R1 is any one of an alkyl, aryl, hydroxy, carboxyl, alkoxy, amino, substituted amino, ester or amide group, and R2 is at least one of a halogen, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, arsenic-containing group, and carbon-containing group. Also disclosed are a preparation method for and application of the ion stabilizer-doped perovskite film. By means of ion stabilizer doping, a doped perovskite solar cell may be prepared, wherein battery performance is improved and stability of the solar cell is improved.

Description

Perovskite film doped with ion stabilizer and preparation method and application thereof Technical field

The invention belongs to the technical field of perovskite solar cells, in particular to a perovskite film doped with an ion stabilizer, a preparation method and application thereof.

Background technique

In recent years, a perovskite solar cell has been widely concerned, and this perovskite solar cell has an organic metal halide as a light absorbing layer. Perovskite is a cubic octahedral structure of ABX ₃ type, as shown in Figure 1. 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 22.7%, which is higher than the commercial crystalline silicon solar cell and has higher Big cost advantage.

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. In order to improve the quality of the films and precisely control the perovskite grains, the use of additives is an effective method. The application of the additive can assist the formation of the crystal nucleus more uniformly, and affect the crystallization process of the material and improve the stability of the crystal. 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.

However, the life of perovskite batteries is still in the range of tens of hours to hundreds of hours, and there is still a long way to go from the practical application to the 10-year service life. An important aspect affecting the service life of perovskites is that perovskite solar cells are prone to ion migration under illumination, especially the migration of halogen ions, which causes the hysteresis effect of the battery and the deterioration of device performance. The vacancies left after ion migration cause damage to the semiconductor structure of the perovskite, which makes it impossible to reverse the service life of the device.

The existing perovskite film additives mainly include polymers, fullerenes, metal halide salts, inorganic acids, solvents, organic halogen salts, nanoparticles and other kinds of additives, which are obtained by regulating the crystallization process of perovskites. The surface is dense and smooth, which improves the performance of the perovskite battery, and a few of them can increase the life of the perovskite battery in a small amount.

The prior art needs to be further improved and improved.

technical problem

The technical problem to be solved by the present invention is to provide a perovskite film doped with an ion stabilizer and a preparation method and application thereof. One end of the ion stabilizer can interact with the metal oxide, and the other end can be combined with the perovskite. The ionic interaction causes the ion stabilizer to form a certain concentration gradient in the perovskite active layer, thereby inhibiting ion migration in the perovskite active layer, thereby improving the long-term stability of the perovskite battery.

Technical solution

The present invention is achieved by providing a perovskite film doped with an ion stabilizer, wherein the perovskite film is doped with an ion stabilizer having a chemical structure of R ₁ -RR ₂ wherein R is an alkyl group, R ₁ and R ₂ are each a substituent, and R ₁ is any _one of an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group, an amino group, a substituted amino group, an ester group, and an amide group. And R ₂ is at least one of a halogen, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, and a carbon-containing group.

Further, the molecules of the ion stabilizer are incorporated into the perovskite film by a solution mixing method, a gas phase assisted deposition method, a co-evaporation method, or an anti-solvent method.

Further, the ion stabilizer forms a certain concentration gradient in the perovskite film.

The present invention is achieved by the method of preparing a perovskite film doped with an ion stabilizer as described above, comprising the steps of:

Step S11, preparing a perovskite solution;

Step S12, adding an ion stabilizer to the perovskite solution, heating and stirring at 70 ° C for 2 h to obtain a perovskite stabilizer mixture;

Step S13, coating the perovskite stabilizer mixture 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 a film layer of the stabilizer mixture, and annealing the film layer to obtain a perovskite film layer doped with an ion stabilizer;

In step S11, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ 0 to 300%;

In step S12, the amount of the ion stabilizer incorporated is 0.01 to 20% of the molar amount of the precursor BX ₂ .

The present invention is achieved by the method of preparing a perovskite film doped with an ion stabilizer as described above, comprising the steps of:

Step S21, preparing a precursor stabilizer mixture: adding an ion stabilizer to the perovskite precursor solution, heating and stirring at 70 ° C for 2 h;

Step S22, coating the precursor stabilizer 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 the precursor stabilizer mixture. a thin film layer, and annealing the thin film layer to obtain a perovskite precursor film layer doped with an ion stabilizer;

Step S23, the substrate of the perovskite precursor film layer doped with the ion stabilizer prepared in step S22 is placed in the film forming cavity, and the degree of vacuum in the film forming cavity is controlled at 10 ^-5 Pa to 10 ⁵ Pa. between;

Step S24, heating the reactant AX powder previously placed in the film forming cavity, and heating at a temperature ranging from 100 to 200 ° C, so that the perovskite precursor film layer is placed in the vapor environment of the reactant AX, and the substrate is heated at the same time. 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 a perovskite film with doping ion stabilizer to form perovskite activity. Floor;

In step S21, the perovskite precursor solution is mixed with a solution containing at least one divalent metal halide precursor BX ₂ and an organic solvent, and B is a divalent metal cation: lead, tin, tungsten, copper, zinc. , any one of gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine, bromine, chlorine At least any one of an anion, a thiocyanate, and an acetate, the organic solvent comprising a main solvent and a solvent additive, the main solvent being a soluble metal halide and other additives, an amide solvent, a sulfone/sulfoxide Any one of a solvent, an ester solvent, a hydrocarbon, a halogenated 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 sulfone/Asia At least one of a sulfone solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; in the perovskite precursor solution, a precursor The concentration of the BX ₂ solution is 0.5~2mol/L, and the ionic stabilizer is mixed. The amount of precursor BX ₂ molar amount of 0.01 to 20% solvent additive precursor molar ratio of BX ₂ is 0 to 300%;

In step S24, A of the reactant AX is at least any one of ruthenium, osmium, amine group, sulfhydryl group or alkali group, and the amount of the reactant AX added is 0 to 100% of the molar amount of the precursor BX ₂ .

The present invention is achieved by the method of preparing a perovskite film doped with an ion stabilizer 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 ion stabilizer in different evaporation sources, the evaporation rate of AX is 0.1~10Å/s, the evaporation rate of BX ₂ is 0.1~10Å/s, and the ion is stable. The evaporation rate of the agent is 0.05~5Å/s, so that the precursor BX ₂ , the reactant AX and the ion stabilizer react with each other to form a perovskite film doped with an ion stabilizer to form a perovskite active layer;

In step S32, 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 an anthracene, an anthracene, an amine group, a mercapto group or an alkali group.

The present invention is achieved by the method of preparing a perovskite film doped with an ion stabilizer as described above, comprising the steps of:

Step S41, dissolving the ion stabilizer in the anti-solvent, heating and stirring at 60 ° C for 2 h, to prepare a mixture of anti-solvent stabilizer;

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 stabilizer mixture onto 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 is performed. a perovskite film layer doped with an ion stabilizer;

In step S41, 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; the concentration of the ion stabilizer in the antisolvent stabilizer mixture is 0.01 to 3 mol/L;

In step S42, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ It is 0~300%.

The present invention is achieved by providing a perovskite solar cell to which a perovskite film doped with an ion stabilizer as described above is applied.

The present invention is achieved by providing a perovskite solar cell on which the calcium prepared by the method for preparing a perovskite film doped with an ion stabilizer as described above is used. Titanium ore film.

Beneficial effect

Compared with the prior art, the ion-immobilized perovskite film of the invention and the preparation method and application thereof have the following characteristics: an ionic stabilizer is added to the perovskite precursor liquid to inhibit the final reaction of the perovskite Ion migration in the material, thereby stabilizing the material and extending the life of the device, preparing a doped perovskite solar cell, improving the stability of the solar energy, especially the light stability, and promoting the industrial production of the perovskite solar energy.

DRAWINGS

1 is a schematic view showing the molecular structure of a prior art perovskite film;

2 is a schematic view showing the internal structure of a perovskite solar cell prepared by the present invention;

3 is a J-V graph of a perovskite solar cell prepared by the present invention;

4 is a graph showing the stability test of a perovskite solar cell prepared according to the present invention for 1000 hours.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The invention discloses a perovskite film doped with an ion stabilizer, wherein the perovskite film is doped with an ion stabilizer, and the ion stabilizer has a chemical structure of R ₁ -RR ₂ , wherein R is an alkyl group (having a carbon number ≥ 0), R ₁ and R ₂ are each a substituent, and R ₁ is an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group, an amino group, a substituted amino group, an ester group or an amide group. Any one of R ₂ is at least one of a halogen, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, and a carbon-containing group.

The molecules of the ion stabilizer are incorporated into the perovskite film by a solution mixing method, a gas phase assisted deposition method, a co-evaporation method, or an anti-solvent method. The ionic stabilizer forms a concentration gradient in the perovskite film.

The ionic stabilizer is a kind of bifunctional organic small molecule or polymer having the following characteristics: one end is connected with a halogen, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and an arsenic-containing group. Group, carbon-containing group, this end can pass ionic bond, covalent bond, metal bond, hydrogen bond, van der Waals force, dipole action, coordination, Debye interaction, etc. The layer interacts to passivate the surface of the transport layer; the other end is connected to an electron-donating group such as an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group, an amino group, a substituted amino group, an ester group or an amide group. Ionic bond, covalent bond, metal bond, hydrogen bond, van der Waals force, dipole action, coordination, Debye interaction, etc., interact with the perovskite active layer to improve interfacial conduction Sexually, the surface defects of the active layer of the perovskite are inactivated, and the ion migration in the active layer of the perovskite is inhibited to a certain extent, thereby stabilizing the effect of the perovskite material itself.

The R1 end can interact with the perovskite active layer by one or more kinds of forces such as ionic bond, covalent bond, metal bond, hydrogen bond, van der Waals force, dipole action, coordination, Debye interaction, etc. Thereby, the interface conductivity is improved, the surface defects of the perovskite active layer are passivated, and the ion migration in the active layer of the perovskite is inhibited to a certain extent, thereby achieving the effect of stabilizing the perovskite material itself. The R2 end can interact with the transport layer by one or more forces such as ionic bond, covalent bond, metal bond, hydrogen bond, van der Waals force, dipole action, coordination, Debye interaction, and passivation transmission. The surface of the layer. The ionic stabilizer can be concentrated at the interface between the perovskite active layer and the transport layer, and the concentration is gradually increased from the perovskite to the transport layer to form a concentration gradient.

The invention also discloses a preparation method of a perovskite film doped with an ion stabilizer as described above, comprising the following steps:

Step S11, preparing a perovskite solution;

Step S12, adding an ion stabilizer to the perovskite solution, heating and stirring at 70 ° C for 2 h to obtain a perovskite stabilizer mixture;

Step S13, coating the perovskite stabilizer mixture 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 a film layer of the stabilizer mixture, and annealing the film layer to obtain a perovskite film layer doped with an ion stabilizer;

In step S11, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ It is 0~300%.

In step S12, the amount of the ion stabilizer incorporated is 0.01 to 20% of the molar amount of the precursor BX ₂ .

The invention also discloses a preparation method of a perovskite film doped with an ion stabilizer as described above, comprising the following steps:

Step S21, preparing a precursor stabilizer mixture: adding an ion stabilizer to the perovskite precursor solution, heating and stirring at 70 ° C for 2 h;

Step S22, coating the precursor stabilizer 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 the precursor stabilizer mixture. a thin film layer, and annealing the thin film layer to obtain a perovskite precursor film layer doped with an ion stabilizer;

Step S23, the substrate of the perovskite precursor film layer doped with the ion stabilizer prepared in step S22 is placed in the film forming cavity, and the degree of vacuum in the film forming cavity is controlled at 10 ^-5 Pa to 10 ⁵ Pa. between;

Step S24, heating the reactant AX powder previously placed in the film forming cavity, and heating at a temperature ranging from 100 to 200 ° C, so that the perovskite precursor film layer is placed in the vapor environment of the reactant AX, and the substrate is heated at the same time. 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 a perovskite film with doping ion stabilizer to form perovskite activity. a layer, the thickness of the prepared perovskite film layer is 200 to 800 nm;

In step S21, the perovskite precursor solution is mixed with a solution containing at least one divalent metal halide precursor BX ₂ and an organic solvent, and B is a divalent metal cation: lead, tin, tungsten, copper, zinc. , any one of gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine, bromine, chlorine At least any one of an anion, a thiocyanate, and an acetate, the organic solvent comprising a main solvent and a solvent additive, the main solvent being a soluble metal halide and other additives, an amide solvent, a sulfone/sulfoxide Any one of a solvent, an ester solvent, a hydrocarbon, a halogenated 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 sulfone/Asia At least one of a sulfone solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; in the perovskite precursor solution, a precursor The concentration of the BX ₂ solution is 0.5~2mol/L, and the ionic stabilizer is mixed. The amount of precursor BX ₂ molar amount of 0.01 to 20% solvent additive precursor molar ratio of BX ₂ is 0 to 300%.

In step S24, A of the reactant AX is at least any one of ruthenium, osmium, amine group, sulfhydryl group or alkali group, and the amount of the reactant AX added is 0 to 100% of the molar amount of the precursor BX ₂ .

The invention also discloses a preparation method of a perovskite film doped with an ion stabilizer 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 Control at 30 ° C ~ 150 ° C;

Step S32, placing the precursor BX ₂ , the reactant AX and the ion stabilizer into different evaporation sources, respectively controlling the evaporation rate of each evaporation source, the evaporation rate of AX is 0.1~10 Å/s, and the evaporation rate of BX ₂ The evaporation rate of the ion stabilizer is 0.1~10Å/s, and the evaporation rate of the ion stabilizer is 0.05~5Å/s, so that the precursor BX ₂ , the reactant AX and the ion stabilizer react with each other to form a perovskite film with doping ion stabilizer to form calcium titanium. Mineral active layer.

In step S32, 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 an anthracene, an anthracene, an amine group, a mercapto group or an alkali group.

The invention also discloses a preparation method of a perovskite film doped with an ion stabilizer as described above, comprising the following steps:

Step S41, dissolving the ion stabilizer in the anti-solvent, heating and stirring at 60 ° C for 2 h, to prepare a mixture of anti-solvent stabilizer;

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 stabilizer mixture onto 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 is performed. A perovskite film layer doped with an ionic stabilizer.

In step S41, 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; the concentration of the ion stabilizer in the antisolvent stabilizer mixture is 0.01 to 3 mol/L;

In step S42, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ 0 to 300%;

The invention also discloses a perovskite solar cell on which a perovskite film doped with an ion stabilizer is applied on the perovskite solar cell.

The invention also discloses a perovskite solar cell on which a perovskite film prepared by the method for preparing a perovskite film doped with an ion stabilizer is used on the perovskite solar cell.

Embodiments of the invention

The application of the method for preparing a perovskite-doped perovskite film of the present invention to a perovskite solar cell will be described below with reference to specific embodiments.

Example 1, a preparation method of a perovskite solar cell - a solution mixing method, please refer to the internal structure diagram of the perovskite solar cell shown in FIG. 2, including the following steps:

(1) 10×10cm FTO glass plate was washed with detergent, deionized water, acetone and isopropanol for 30min, then dried with N ₂ and then treated with UV O-zone for 10min;

(2) preparing a CuSCN film as a hole transport layer;

(3) Preparation of perovskite solution: 461 mg of PbI ₂ (1 mmol), 159 mg of MAI (1 mmol) were dissolved in 1 mL of DMF solution, 70.9 uL of anhydrous DMSO was added, and 36.9 mg of tetrabutylammonium iodide was added. (0.1 mmol) as an ionic stabilizer, heated and stirred at 70 ° C for 2 h, mixed and used;

(4) preparing a doping stabilizer-like perovskite film by slit coating using a doped perovskite solution, and annealing at 60 to 150 ° C for 10 to 120 minutes, and having a thickness of 200 to 600 nm;

(5) depositing an electron transport layer PCBM on the substrate, having a thickness of 20 to 50 nm;

(6) A metal conductive layer Au electrode was vapor-deposited to prepare a perovskite solar cell.

Example 2: A method for preparing a perovskite solar cell - a gas phase assisted deposition method, please refer to the internal structure diagram of the perovskite solar cell shown in FIG. 2, including the following steps:

(1) The 5×5 cm ITO glass plate was sequentially washed with detergent, deionized water, acetone, and isopropanol for 30 min, dried with N ₂ , and then treated with UV O-zone for 10 min;

(2) preparing a NiO _x film as a hole transport layer;

(3) Preparation of a precursor stabilizer mixture: 461 mg of PbI ₂ (1 mmol) was dissolved in 1 mL of DMF solution, 70.9 uL of anhydrous DMSO was added, and 13.4 μL of phenylethanethiol (0.1 mmol) was added as an ion stabilizer. The agent is heated and stirred at 70 ° C for 2 hours, and the mixture is completely used after being used;

(4) preparing a dopant-stabilized PbI ₂ film by slit coating using the prepared stabilizer mixture;

(5) The prepared doping stabilizer PbI ₂ film substrate is placed in a film forming cavity, and the air pressure is controlled by a vacuum pump at 10 ^-5 Pa to 10 ⁵ Pa, and the heating temperature of the MAI is controlled at 100 ° C to 200 ° C. The substrate heating temperature is controlled at 30 ° C ~ 150 ° C, the MAI gas molecules react with PbI ₂ to form a doping stabilizer perovskite film, the thickness is 200 ~ 500nm;

(6) depositing an electron transport layer PCBM on the substrate, having a thickness of 20 to 50 nm;

(7) A metal permeation layer Ag electrode is vapor-deposited to obtain a perovskite solar cell. Example 3: A method for preparing a perovskite solar cell, the co-steaming method, please refer to the internal structure diagram of the perovskite solar cell shown in FIG. 2, including the following steps:

(1) The 30×40 cm ITO glass plate was sequentially washed with detergent, deionized water, acetone, and isopropanol for 30 min, dried with N ₂ , and then treated with UV O-zone for 10 min;

(2) preparing a PEDOT film as a hole transport layer;

(3) The substrate on which the transport layer is deposited is placed in the film forming cavity, and the vacuum in the film forming cavity is controlled between 10 ^-8 Pa and 10 ⁵ Pa, and the substrate is heated, and the heating temperature of the substrate is heated. Controlled at 30 ° C ~ 150 ° C; PbI ₂ , MAI, ionic stabilizer 2-naphthylthiol were placed in different evaporation sources, the evaporation rate of MAI was 0.1~10Å / s, and the evaporation rate of PbI ₂ was 0.1~ 10Å/s, the ionic stabilizer 2-naphthyl mercaptan has an evaporation rate of 0.05~5Å/s, which makes PbI ₂ , MAI and ion stabilizer 2-naphthyl mercaptan react to form a perovskite film with doping ion stabilizer. a perovskite active layer having a thickness of 200 to 600 nm;

(4) depositing an electron transport layer tin oxide on the substrate, having a thickness of 5 to 40 nm;

(5) An aluminum electrode of a metal conductive layer is vapor-deposited to obtain a perovskite solar cell.

Example 4, a preparation method of a perovskite solar cell - an anti-solvent method, please refer to the internal structure diagram of the perovskite solar cell shown in FIG. 2, including the following steps:

(1) The 5×5 cm ITO glass plate was sequentially washed with detergent, deionized water, acetone, and isopropanol for 30 min, dried with N ₂ , and then treated with UV O-zone for 10 min;

(2) preparing a tungsten oxide film as a hole transport layer;

(3) Preparation of perovskite solution: 461 mg of PbI ₂ (1 mmol) and 159 mg of MAI (1 mmol) were dissolved in 1 mL of DMF solution, 70.9 uL of anhydrous DMSO was added, and the mixture was heated and stirred at 70 ° C for 2 h, and the mixture was completely mixed. use;

(4) Preparation of anti-solvent stabilizer mixture: 74.6 mg of 4-phenylbutylamine (0.5 mmol) was dissolved in 1 mL of anti-solvent chlorobenzene, stirred at 60 ° C for 2 h, dissolved and used;

(5) preparing a perovskite film on the hole transport layer by a doctor blade method, and coating the prepared antisolvent stabilizer mixture on the surface of the perovskite film by a doctor blade method, heating and annealing, and heating at a temperature of 60~ 120 ° C, heating time is 2 ~ 60min, to obtain a perovskite film doped with ion stabilizer;

(6) depositing an electron transport layer PC71BM on the substrate, having a thickness of 20 to 50 nm;

(7) A metal permeation layer Ag electrode is vapor-deposited to obtain a perovskite solar cell.

3 and FIG. 4 are test data tables of an ion stabilizer-doped perovskite battery prepared by the preparation method of the present invention, which can be seen from FIG. 3 by doping the ion stabilizer in the present invention. The perovskite solar cell with excellent photoelectric conversion performance has an efficiency of 17.21% (PCE). It can be seen from Fig. 4 that the solar cell incorporating the ionic stabilizer of the present invention has excellent long-term stability, and the battery efficiency of the 1000 h light is reduced by less than 1%.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Industrial applicability

Type the industrial usability description paragraph here.

Sequence table free content

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Claims (9)

1. A perovskite film doped with an ion stabilizer, characterized in that the perovskite film is doped with an ion stabilizer, and the ion stabilizer has a chemical structure of R ₁ -RR ₂ , wherein R is an alkyl group, R ₁ and R ₂ are each a substituent, and R ₁ is an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group, an amino group, a substituted amino group, an ester group or an amide group, and R ₂ It is at least one of a halogen, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, an arsenic-containing group, and a carbon-containing group.
2. The ion stabilizer-doped perovskite film according to claim 1, wherein the ion stabilizer is incorporated into a solution mixing method, a gas phase assisted deposition method, a co-evaporation method, or an anti-solvent method. Within the perovskite film.
3. The ion stabilizer-doped perovskite film according to claim 1, wherein the ion stabilizer forms a concentration gradient in the perovskite film.
4. A method for preparing a perovskite film doped with an ion stabilizer according to claim 1 or 2 or 3, comprising the steps of:

   Step S11, preparing a perovskite solution;

   Step S12, adding an ion stabilizer to the perovskite solution, heating and stirring at 70 ° C for 2 h to obtain a perovskite stabilizer mixture;

   Step S13, coating the perovskite stabilizer mixture 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 a film layer of the stabilizer mixture, and annealing the film layer to obtain a perovskite film layer doped with an ion stabilizer;

   In step S11, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ 0 to 300%;

   In step S12, the amount of the ion stabilizer incorporated is 0.01 to 20% of the molar amount of the precursor BX ₂ .
5. A method for preparing a perovskite film doped with an ion stabilizer according to claim 1 or 2 or 3, comprising the steps of:

   Step S21, preparing a precursor stabilizer mixture: adding an ion stabilizer to the perovskite precursor solution, heating and stirring at 70 ° C for 2 h;

   Step S22, coating the precursor stabilizer 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 the precursor stabilizer mixture. a thin film layer, and annealing the thin film layer to obtain a perovskite precursor film layer doped with an ion stabilizer;

   Step S23, the substrate of the perovskite precursor film layer doped with the ion stabilizer prepared in step S22 is placed in the film forming cavity, and the degree of vacuum in the film forming cavity is controlled at 10 ^-5 Pa to 10 ⁵ Pa. between;

   Step S24, heating the reactant AX powder previously placed in the film forming cavity, and heating at a temperature ranging from 100 to 200 ° C, so that the perovskite precursor film layer is placed in the vapor environment of the reactant AX, and the substrate is heated at the same time. 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 a perovskite film with doping ion stabilizer to form perovskite activity. Floor;

   In step S21, the perovskite precursor solution is mixed with a solution containing at least one divalent metal halide precursor BX ₂ and an organic solvent, and B is a divalent metal cation: lead, tin, tungsten, copper, zinc. , any one of gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine, bromine, chlorine At least any one of an anion, a thiocyanate, and an acetate, the organic solvent comprising a main solvent and a solvent additive, the main solvent being a soluble metal halide and other additives, an amide solvent, a sulfone/sulfoxide Any one of a solvent, an ester solvent, a hydrocarbon, a halogenated 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 sulfone/Asia At least one of a sulfone solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon; in the perovskite precursor solution, a precursor The concentration of the BX ₂ solution is 0.5~2mol/L, and the ionic stabilizer is mixed. The amount of precursor BX ₂ molar amount of 0.01 to 20% solvent additive precursor molar ratio of BX ₂ is 0 to 300%;

   In step S24, A of the reactant AX is at least any one of ruthenium, osmium, amine group, sulfhydryl group or alkali group, and the amount of the reactant AX added is 0 to 100% of the molar amount of the precursor BX ₂ .
6. A method for preparing a perovskite film doped with an ion stabilizer according to claim 1 or 2 or 3, 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 ion stabilizer in different evaporation sources, the evaporation rate of AX is 0.1~10Å/s, the evaporation rate of BX ₂ is 0.1~10Å/s, and the ion is stable. The evaporation rate of the agent is 0.05~5Å/s, so that the precursor BX ₂ , the reactant AX and the ion stabilizer react with each other to form a perovskite film doped with an ion stabilizer to form a perovskite active layer;

   In step S32, 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 an anthracene, an anthracene, an amine group, a mercapto group or an alkali group.
7. A method for preparing a perovskite film doped with an ion stabilizer according to claim 1 or 2 or 3, comprising the steps of:

   Step S41, dissolving the ion stabilizer in the anti-solvent, heating and stirring at 60 ° C for 2 h, to prepare a mixture of anti-solvent stabilizer;

   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 stabilizer mixture onto 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 is performed. a perovskite film layer doped with an ion stabilizer;

   In step S41, 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; the concentration of the ion stabilizer in the antisolvent stabilizer mixture is 0.01 to 3 mol/L;

   In step S42, the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX _{2 ,} a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group. The solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, 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, or an alcohol solvent. At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon; The perovskite solution, the concentration of BX ₂ precursor solution is 0.5 ~ 2mol / L, the reaction was added in an amount AX BX ₂ precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX ₂ It is 0~300%.
8. A perovskite solar cell characterized in that the perovskite film doped with an ion stabilizer according to claim 1 or 2 or 3 is applied to the perovskite solar cell.
9. A perovskite solar cell characterized in that the method for preparing a perovskite film of the doping ion stabilizer according to claim 4 or 5 or 6 or 7 is used on the perovskite solar cell A prepared perovskite film.