CN115332450A - Perovskite thin film, preparation method thereof and perovskite battery - Google Patents
Perovskite thin film, preparation method thereof and perovskite battery Download PDFInfo
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- CN115332450A CN115332450A CN202211006595.2A CN202211006595A CN115332450A CN 115332450 A CN115332450 A CN 115332450A CN 202211006595 A CN202211006595 A CN 202211006595A CN 115332450 A CN115332450 A CN 115332450A
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Abstract
A perovskite thin film, a preparation method thereof and a perovskite battery belong to the technical field of solar batteries. The preparation method of the perovskite thin film comprises the following steps: dissolving beet pigment in a perovskite precursor solution to form a mixed solution; dropping the mixed solution onto a substrate; and rotating the substrate dripped with the mixed solution to form a coating on the substrate, and performing heat treatment to prepare the perovskite thin film. The preparation method can improve the light absorption capacity of the perovskite thin film, and the prepared perovskite thin film can improve the conversion efficiency of the perovskite battery.
Description
Technical Field
The application relates to the technical field of solar cells, in particular to a perovskite thin film, a preparation method thereof and a perovskite cell.
Background
At present, fossil energy such as coal, petroleum and the like are still the main energy sources of the current society, and a great amount of pollutants such as sulfur dioxide, nitrogen dioxide, carbon monoxide, dust particles and the like are generated while fossil energy is combusted to provide power, so that the environment is seriously polluted, ecological damage is brought, and the health of people is also damaged. It is becoming increasingly appreciated that the development and utilization of renewable clean energy sources is imperative in the context of carbon peaking, carbon neutralization targets. As an effective way for utilizing solar energy resources, solar cells have become a research hotspot of researchers.
In the development process of solar cells, perovskite serving as an efficient light absorption material has the photoelectric characteristics of extremely high light absorption coefficient, excellent carrier transmission capacity, adjustable band gap and the like, and after the perovskite is firstly tried to be applied to the field of photovoltaic power generation in 2009, the energy conversion efficiency is improved to 25.2% from 3.8% in 10 years. The inventor of the present application found in research that one of the effective ways to improve the conversion efficiency of perovskite cells is to improve the light absorption capability of perovskite thin films, but how to improve the light absorption capability of perovskite thin films is a technical problem.
Disclosure of Invention
The application provides a perovskite thin film, a preparation method thereof and a perovskite battery.
The application is realized as follows:
in a first aspect, the present application provides a method for preparing a perovskite thin film, comprising:
dissolving beet pigment in the perovskite precursor solution to form a mixed solution;
dripping the mixed solution onto a substrate;
and rotating the substrate dripped with the mixed solution to form a coating on the substrate, and performing heat treatment to prepare the perovskite thin film.
In some embodiments, the betalains include betacyanin and/or betaxanthin.
In some embodiments, the betalains contain a pigment stabilizer.
In some embodiments, the pigment stabilizing agent comprises a flavonoid; optionally, the flavonoid comprises at least one of baicalin and baicalein.
In some embodiments, the perovskite precursor solution is selected to have a solute of PbI 2 And iodomethylamine, the solvent being at least one of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).
In some embodiments, the substrate surface has a dense layer; optionally, the dense layer comprises TiO 2 、SnO 2 Any one of ZnO and NiO; optionally, the dense layer has a thickness of 200 to 400nm.
Preferably, the dense layer is TiO 2 。
Preferably, the thickness of the dense layer is 300nm.
In some embodiments, the heat treatment time is 10-30min; optionally, the heat treatment time is 20min.
In some embodiments, the method of making comprises at least one of the following limitations:
a first definition: the substrate is FTO or ITO conductive glass;
the second definition: the thickness of the perovskite thin film is 400-600nm; optionally, the perovskite thin film has a thickness of 500nm;
the third limitation is that: dripping the mixed solution on a substrate with a compact layer, placing for 4-6s, and then rotating;
the fourth limitation is that: the rotating process conditions include: spin-coating at 400-600 rpm for 2-5 s, and then spin-coating at 4000-6000 rpm for 25-35 s.
In a second aspect, the present application provides a perovskite thin film which is obtained by the method for preparing a perovskite thin film according to the first aspect.
In a third aspect, the present application provides a perovskite battery comprising the perovskite thin film of the second aspect.
The application has at least the following beneficial effects:
according to the preparation method of the perovskite thin film, beet pigment is added into the perovskite precursor solution, and then the dropping and the rotation are carried out, so that the prepared perovskite thin film has better light absorption capacity.
The perovskite thin film prepared by the perovskite thin film preparation method has high photoelectric conversion efficiency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a graph showing the uv-vis absorption of the perovskite thin films of example 1 and comparative example 1 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is directed to a perovskite thin film of embodiments of the present application, a method of preparing the same, and a perovskite battery.
Specifically, the following description is made:
in a first aspect, the present application provides a method for preparing a perovskite thin film, comprising:
dissolving beet pigment in the perovskite precursor solution to form a mixed solution;
dripping the mixed solution onto a substrate;
and rotating the substrate dripped with the mixed solution to form a coating on the substrate, and performing heat treatment to prepare the perovskite thin film.
Wherein, the solute selected for the perovskite precursor solution is PbI 2 And iodomethylamine (abbreviated as MAI), wherein the solvent is at least one of N, N-dimethylformamide (abbreviated as DMF) and dimethyl sulfoxide (abbreviated as DMSO).
Optionally, the substrate is FTO or ITO conductive glass.
In some embodiments, the substrate surface has a dense layer. Under the action of the dense layer, the mixed solution can be uniformly and stably distributed on the surface of the dense layer.
Optionally, the dense layer comprises TiO 2 、SnO 2 Any one of ZnO and NiO. Optionally, the dense layer has a thickness of 200-400nm, such as 200nm, 250nm, 300nm, 350nm, or 400nm.
Further, the mixed solution is dripped on the substrate with the dense layer, placed for 4-6s and then rotated. Exemplary process conditions for rotation include: spin-coating at 400-600 rpm for 2-5 s, and then spin-coating at 4000-6000 rpm for 25-35 s. The coating is firstly carried out for a short time at a slower speed, and then is carried out for a longer time at a faster speed, so that the coating thickness of the spin coating is more uniform.
In some embodiments, the process conditions of rotation include: spin coating was performed at 500rpm for 3 seconds and then at 5000rpm for 30 seconds.
The inventor of the application finds that under the same other conditions, the perovskite precursor solution added with the betalain has better light absorption capacity and obviously stronger light absorption intensity in the range of 400-480nm compared with the titanium ore precursor solution without the betalain. Wherein the betalains comprise betacyanin and/or betaxanthin. The thickness of the perovskite thin film is 400-600nm, such as 400nm, 500nm or 600nm.
Wherein, the beet pigment can be prepared by self or purchased in the market. The betalains may be obtained by extraction from plants or may be artificially synthesized.
Illustratively, the process steps of artificially synthesized betalains include: tyrosine is reacted with tyrosinase and 4, 5-dopa dioxygenase to form betaaldehyde ammonia acid, and the betaaldehyde ammonia acid and amino acid or amine generate betaxanthin; the beet aldehyde reacts with amino acid to generate beet erythrogenin, and then the beet erythrogenin is glycosylated by glycosyl transferase to generate beet erythrogenin. Among them, the beet pigment biosynthesis pathway can be described in a paper (Fujian agriculture and forestry university, master's graduate paper: the effect of red and blue composite light on the beet pigment synthesis Cryptochrome gene expression of amaranth seedlings).
Further, a coating layer is formed on the substrate, and heat treatment is performed at a temperature of 100 to 120 ℃. The perovskite thin film prepared by heat treatment under the temperature condition has good quality and good nucleation and crystal growth conditions. Optionally, the heat treatment time is 10-30min, such as 10min, 15min, 20min, 25min or 30min. Illustratively, the temperature of the heat treatment is 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
The inventor of the present application found in research that natural betalains extracted from plants have poor thermal stability and activity is affected to some extent at high temperature. Therefore, the stability of the betalain in heat treatment can be better by adding the pigment stabilizer into natural betalain extracted from plants or adding the pigment stabilizer into artificially synthesized betalain, and the situation that the betalain is damaged in the heat treatment to influence the improvement of the light absorption capacity of the perovskite film is avoided.
Wherein the pigment stabilizer comprises flavonoids. Optionally, the flavonoid comprises at least one of baicalin and baicalein. Illustratively, the mass ratio of the pigment stabilizer to the betalain is 1-3: 8 or 3.
In a second aspect, the present application provides a perovskite thin film produced by the method for producing a perovskite thin film of the first aspect. The perovskite thin film has good light absorption capacity and strong light absorption intensity within the range of 400-480 nm.
In a third aspect, the present application provides a perovskite battery comprising the perovskite thin film of the second aspect. The perovskite battery has better photoelectric conversion efficiency.
The perovskite thin film and the preparation method thereof and the perovskite battery of the present application are further described in detail with reference to examples below.
Example 1
The embodiment provides a preparation method of a perovskite thin film, which comprises the following steps:
1) Dissolving betalain containing baicalein in perovskite precursor solution, and stirring to obtain mixed solution. Wherein the concentration of the perovskite precursor solution is 1.3mol/L, pbI 2 And the molar ratio of MAI is 1.3, the volume ratio of DMF to DMSO is 3.
2) Dropwise adding the mixed solution obtained in the step 1) to TiO with the thickness of 300nm 2 The substrate of the dense layer was left for 3 seconds, spin-coated at 500rpm for 3 seconds, and then spin-coated at 5000rpm for 30 seconds.
3) After the spin coating is finished, the substrate is transferred to a high-temperature heating table in a low-humidity glove box and is subjected to heat treatment at the temperature of 120 ℃ for 20min to prepare the perovskite thin film. Wherein, the atmosphere in the low-humidity glove box is nitrogen, and the humidity is kept between 2 and 3 percent.
Example 2
The embodiment provides a preparation method of a perovskite thin film, which comprises the following steps:
1) Dissolving betalain containing baicalin in perovskite precursor solution, and stirring uniformly to obtain mixed solution. Wherein the concentration of the perovskite precursor solution is 1.3mol/L, pbI 2 And the molar ratio of MAI is 1.3, the volume ratio of DMF to DMSO is 3.
2) Mixing the mixed solution obtained in the step 1)Dropwise addition to TiO having a thickness of 300nm 2 The substrate of the dense layer was allowed to stand for 3 seconds, spin-coated at 500rpm for 3 seconds, and then spin-coated at 5000rpm for 30 seconds.
3) After the spin coating is finished, the substrate is transferred to a high-temperature heating table in a low-humidity glove box and is subjected to heat treatment at the temperature of 120 ℃ for 20min to prepare the perovskite thin film. Wherein, the atmosphere in the low-humidity glove box is nitrogen, and the humidity is kept between 2 and 3 percent.
Example 3
The embodiment provides a preparation method of a perovskite thin film, which comprises the following steps:
1) Dissolving betalain in the perovskite precursor solution, and uniformly stirring to obtain a mixed solution. Wherein the concentration of the perovskite precursor solution is 1.3mol/L, pbI 2 And MAI is 1.3, the volume ratio of DMF to DMSO is 3.
2) Dropwise adding the mixed solution obtained in the step 1) to TiO with the thickness of 300nm 2 The substrate of the dense layer was left for 3 seconds, spin-coated at 500rpm for 3 seconds, and then spin-coated at 5000rpm for 30 seconds.
3) After the spin coating is finished, the substrate is transferred to a high-temperature heating table in a low-humidity glove box and is subjected to heat treatment at the temperature of 120 ℃ for 20min to prepare the perovskite thin film. Wherein, the atmosphere in the low-humidity glove box is nitrogen, and the humidity is kept between 2 and 3 percent.
Comparative example 1
The present comparative example provides a method for preparing a perovskite thin film, comprising the steps of:
1) A perovskite precursor solution is provided. Wherein the concentration of the perovskite precursor solution is 1.3mol/L, pbI 2 And MAI at a molar ratio of 1.3, DMF and DMSO at a volume ratio of 3.
2) Dropwise adding the perovskite precursor solution obtained in the step 1) to TiO with the thickness of 300nm 2 The substrate of the dense layer was left for 3 seconds, spin-coated at 500rpm for 3 seconds, and then spin-coated at 5000rpm for 30 seconds.
3) After the spin coating is finished, the substrate is transferred to a high-temperature heating table in a low-humidity glove box and is subjected to heat treatment at the temperature of 120 ℃ for 20min to prepare the perovskite thin film. Wherein, the atmosphere in the low-humidity glove box is nitrogen, and the humidity is kept between 2 and 3 percent.
Test example 1
The perovskite thin films of example 1 and comparative example 1 were measured for uv-visible absorbance by a uv-visible spectrophotometer, and the results are shown in fig. 1. The perovskite thin film after the addition of the pigment is the perovskite thin film of example 1, and the original perovskite thin film is the perovskite thin film of comparative example 1.
As can be seen from FIG. 1, the perovskite thin film prepared by adding betalains in example 1 has better light absorption capacity and obviously enhanced light absorption intensity in the range of 400-480nm compared with the perovskite thin film prepared by not adding betalains in comparative example 1.
Test example 2
Perovskite solar cells were prepared from the perovskite thin films of example 1 and comparative example 1 under the same conditions, and the photocurrent and voltage of the prepared cell devices were tested under the same conditions, and the test results are shown in table 1. The battery structure comprises a cathode glass substrate, a compact layer, a perovskite light absorption layer, a hole transport layer and an anode which are sequentially stacked.
TABLE 1 Battery device Performance test results
As can be seen from the results of table 1, the perovskite solar cell made of the perovskite thin film of example 1 has higher open-circuit voltage, short-circuit current, fill factor, and photoelectric conversion efficiency than the perovskite solar cell made of the perovskite thin film of comparative example 1. The perovskite thin film prepared by the preparation method of the perovskite thin film is beneficial to improving the conversion efficiency of the perovskite solar cell.
The foregoing description is given for the purpose of illustrating particular embodiments of the present application and is not in any way intended to limit the invention, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for preparing a perovskite thin film, comprising:
dissolving beet pigment in a perovskite precursor solution to form a mixed solution;
dropping the mixed solution onto a substrate;
and rotating the substrate dripped with the mixed solution to form a coating on the substrate, and performing heat treatment to prepare the perovskite thin film.
2. The method for producing a perovskite thin film as claimed in claim 1, wherein the betalains include betacyanin and/or betaxanthin.
3. The method for producing a perovskite thin film as claimed in claim 1, wherein the betalain contains a pigment stabilizer.
4. The method for producing a perovskite thin film as claimed in claim 3, wherein the pigment stabilizer comprises a flavonoid; optionally, the flavonoid comprises at least one of baicalin and baicalein.
5. The process for producing a perovskite thin film according to any one of claims 1 to 4, wherein the solute selected for the perovskite precursor solution is PbI 2 And iodomethylamine, wherein the solvent is at least one of N, N-dimethylformamide and dimethyl sulfoxide.
6. The method for producing a perovskite thin film as claimed in any one of claims 1 to 4, wherein the substrate surface has a surface areaA compact layer is arranged; optionally, the dense layer comprises TiO 2 、SnO 2 Any one of ZnO and NiO; optionally, the dense layer has a thickness of 200 to 400nm.
7. The process for producing a perovskite thin film according to any one of claims 1 to 4, wherein the heat treatment temperature is 100 to 120 ℃; optionally, the heat treatment time is 10-30min.
8. The production method of the perovskite thin film as claimed in any one of claims 1 to 4, characterized in that the production method comprises at least one of the following limitations:
a first definition: the substrate is FTO or ITO conductive glass;
a second limitation: the thickness of the perovskite thin film is 400-600nm;
the third limitation is that: dripping the mixed solution on a substrate with a compact layer, placing for 4-6s, and then rotating;
the fourth limitation is that: the rotating process conditions include: spin-coating at 400-600 rpm for 2-5 s, and then at 4000-6000 rpm for 25-35 s.
9. A perovskite thin film which is produced by the method for producing a perovskite thin film according to any one of claims 1 to 8.
10. A perovskite battery comprising the perovskite thin film as defined in claim 9.
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