CN114497390A - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

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Publication number
CN114497390A
CN114497390A CN202210024588.9A CN202210024588A CN114497390A CN 114497390 A CN114497390 A CN 114497390A CN 202210024588 A CN202210024588 A CN 202210024588A CN 114497390 A CN114497390 A CN 114497390A
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perovskite
layer
solar cell
interface modification
spin
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李晓毅
焦博新
全子威
刘丰珍
车志刚
孙丰垒
王梓臣
吴汶泽
胡堃
王涛
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University of Chinese Academy of Sciences
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • Y02E10/549—Organic PV cells

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Abstract

The invention belongs to the technical field of new energy materials and devices, and particularly relates to a perovskite solar cell and a preparation method thereof. The perovskite solar cell comprises a conductive glass layer, an electron transmission layer, an interface modification layer, a perovskite light absorption layer, a hole transmission layer and a metal electrode layer, wherein a film of the perovskite light absorption layer is doped with arginine with a certain concentration and is subjected to annealing process treatment, the interface modification layer is a sodium alginate film layer, the perovskite light absorption layer film shows stronger crystallinity and a smoother surface after being doped with arginine, and in combination with interface modification of sodium alginate, a dangling bond on the surface of the perovskite layer between the electron transmission layer and the perovskite light absorption layer interface can be passivated, so that the constraint of deep level defects on current carriers is reduced, the contact between the electron transmission layer and the hole transmission layer is effectively reduced, leakage current is reduced, the photoelectric conversion efficiency is improved, oxygen permeation is favorably blocked, and the oxidation of perovskite materials is reduced.

Description

Perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of new energy materials and devices, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
In recent years, the demand for electric power has sharply increased in humans, but the reserves of conventional fossil energy sources have been far from sufficient. And thus solar cells are increasingly emphasized. Perovskite solar cells are expected as new solar cells due to their excellent photovoltaic characteristics and great development potential, but the perovskite solar cells have relatively poor photoelectric characteristics such as photoelectric conversion efficiency and stability and are difficult to industrialize, which has been a technical bottleneck that restricts their wide application. One important factor affecting the photoelectric properties of perovskite structured materials is the presence of microscopic defects.
The existing research and technology show that the perovskite solar cell is excited to generate excitons (electron-hole pairs) under the illumination condition, and the excitons are separated into electrons and holes and then move to the two sides of the cell under the action of an electric field built in a p-n junction due to weak exciton binding energy and high carrier mobility of the perovskite material. The operation principle of the perovskite solar cell is that photogenerated holes move to a p region, photogenerated electrons move to an n region, and thus current is formed in a closed path. The common perovskite solar cell structure sequentially comprises conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode. Due to a plurality of interference factors existing in the actual crystallization process, a large number of defects exist in the crystal of the perovskite light absorption layer, the defects mainly include interface defects between layers and defects of counter ions, grain boundaries and the like existing in the perovskite light absorption layer, and the defects can capture free charges to reduce the photoelectric performance of the device. Many studies have shown that doping with certain substances can effectively passivate defects.
The interface modification method is mainly adopted aiming at the interface defects.
Aiming at the defects in the perovskite light absorption layer, Lewis acid/alkali (such as micromolecule organic matters and the like) and metal ions and other substances are added to reduce the influence caused by the defects, so that the actual photoelectric property and the stability of a battery device are improved.
In the practical preparation of the traditional perovskite solar cell, titanium dioxide (TiO2) or tin dioxide (SnO2) is mainly used as an electron transport layer, a spiro-MeOTAD material is mainly used as a hole transport layer, and a silver electrode or a gold electrode is commonly used as a metal electrode. In a practical perovskite solar cell. CH3NH3PbI3(MAPbI3) is a commonly used perovskite light-absorbing layer material having a perovskite-type crystal structure. Researches show that the perovskite material is doped with aminopropionic acid hydrochloride (APAC) or nickel ions (Ni2+) for passivation, so that the photoelectric conversion efficiency of the perovskite solar cell can be improved, but the perovskite material is relatively high in price, heavy metals are harmful to human bodies and the environment, and the difficulty in practical use is relatively high due to relatively high operation precision of controlling the dosage.
Disclosure of Invention
The present invention aims to solve the above problems at least to some extent, and based on the discovery and recognition by the inventors of the following facts and problems, major problems that perovskite solar cells have yet to be perfected are as follows: the perovskite material of the perovskite solar cell has tiny crystal grains and dense crystal boundaries, so that the carrier transmission is greatly hindered, and the photoelectric conversion efficiency of a device is reduced; and secondly, interface defects exist between layers of the perovskite solar cell, and part of normally transported carriers are bound, so that the photoelectric conversion efficiency and the output performance of the cell device are reduced. In addition, external moisture and oxygen will reduce the stability of the perovskite solar cell due to the presence of defects at the interface.
The embodiment of the invention provides a perovskite solar cell preparation method, which comprises the following steps:
(1) preparing a stannic oxide electron transport layer on conductive glass;
(2) preparing a sodium alginate interface modification layer on the electron transmission layer;
(3) preparing a perovskite light absorption layer on the interface modification layer;
(4) preparing a hole transport layer on the perovskite light absorption layer;
(5) and sputtering the hole transport layer to prepare a metal electrode layer.
According to the perovskite solar cell preparation method, the prepared perovskite solar cell comprises a conductive glass layer, an electron transmission layer (tin dioxide layer), an interface modification layer (sodium alginate layer), a perovskite light absorption layer (arginine-doped perovskite thin film), a hole transmission layer and a metal electrode layer, wherein the film of the perovskite light absorption layer is subjected to arginine doping with a certain concentration and is subjected to annealing process treatment, and the interface modification layer is a sodium alginate thin film layer.
In some embodiments, the preparation of the sodium alginate interface modification layer on the electron transport layer includes the following steps:
(1) preparing a sodium alginate aqueous solution, wherein the mass-volume ratio concentration of the sodium alginate aqueous solution is 0.15-0.4 mg/ml, and stirring for dissolving to obtain an interface modification solution;
(2) spin-coating the interface modification liquid on the surface of the electron transport layer to form an interface modification layer;
(3) and (3) annealing the sample obtained in the step (2) to form a sodium alginate interface modification layer on the electron transmission layer.
Optionally, the spin coating speed of the interface modification liquid is 2800-3200 rpm, and the spin coating dosage is 35-45 μ L.
Optionally, the annealing process includes: heating to 130-150 ℃, and preserving heat for 4-5 minutes.
In some embodiments, the preparing the perovskite light absorption layer on the interface modification layer comprises the following steps:
(1) under the vacuum condition, dissolving arginine by using N, N-dimethylformamide as a first solvent and stirring to prepare an arginine precursor solution;
(2) taking a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide as a second solvent, wherein the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is (47-9) to (3-1), and adding PbI into the second solvent2And the arginine precursor solution is stirred to obtain a first perovskite precursor solution;
(3) dissolving mixed solutes of iodoformamidine (FAI, ForMaMidiniM Iodide), chloromethane (MACl, Methylalmmonium Chloride) and bromomethylamine (MABr, Methylalmmonium Bromide) by using isopropanol as a third solvent, and heating and stirring to prepare a second perovskite precursor solution;
(4) coating the first perovskite precursor solution on the sodium alginate interface modification layer in a spinning mode, and annealing to form a first perovskite layer;
(5) and rotationally coating the second perovskite precursor solution on the first perovskite layer, and annealing to prepare the perovskite light absorption layer.
Optionally, in the arginine precursor solution, the mass-to-volume ratio concentration of arginine: 0.04-0.1 mg/ml.
Optionally, in the second perovskite precursor solution, a mixing ratio of iodoformamidine, chloromethane, and bromomethylamine is: (9-10): 2-1): 1.
Optionally, when the first perovskite precursor solution is spin-coated on the sodium alginate interface modification layer, the spin-coating speed is 1500 rpm, and the spin-coating dosage is 80-85 μ L; the annealing process comprises the following steps: heating to 65-70 ℃, and preserving heat for 10-15 seconds.
Optionally, when the second perovskite solution is spin-coated on the first perovskite layer, the spin-coating speed is 1500 rpm/sec, and the spin-coating dosage is 100-105 μ L; the annealing process comprises the following steps: heating to 150 deg.C, and maintaining the temperature for 15-16 min.
In some embodiments of the present invention, perovskite solar cells prepared by the above method are provided.
The perovskite solar cell prepared by the method has the following advantages:
according to the perovskite solar cell prepared by the method, the perovskite light absorption layer film shows stronger crystallinity and a smoother surface after being doped with arginine, and in combination with interface modification of sodium alginate, dangling bonds on the surface of the perovskite layer between the electron transmission layer and the perovskite light absorption layer interface can be passivated, so that the restraint of deep level defects on current carriers is reduced, the contact between the electron transmission layer and the hole transmission layer can be effectively reduced, the leakage current is reduced, the photoelectric conversion efficiency is improved, the oxygen permeation is favorably blocked, and the oxidation of perovskite materials is reduced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic view of a defect passivated perovskite solar cell in example 1 according to the present invention.
Fig. 2 is a current density-voltage (J-V) curve test chart of the perovskite solar cell in example 1 according to the present invention and comparative example 1.
Fig. 3 is a test graph of dark state current density-voltage (J-V) curves of perovskite solar cells in example 1 according to the present invention and comparative example 1.
Fig. 4 is an X-ray diffraction spectrum of the perovskite light absorbing layer thin film in the perovskite solar cell according to example 1 and comparative example 1 of the present invention.
FIG. 5 is an EIS electrochemical impedance spectrum of perovskite solar cells in example 1 according to the invention and comparative example 1;
fig. 6 is an ultraviolet-visible absorption spectrum of the perovskite solar cell in example 1 according to the present invention and comparative example 1.
Fig. 7 is a photoelectric conversion efficiency stability test of the perovskite solar cells in example 1 according to the present invention and comparative example 1; wherein FIG. 7(a) is under room air ambient conditions, FIG. 7(b) is under a standard solar intensity illumination environment, and FIG. 7(c) is under nitrogen ambient conditions.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein the examples are given by way of illustration only and are not to be construed as limiting the invention.
The embodiment of the invention provides a perovskite solar cell preparation method, which comprises the following steps:
(1) preparing a stannic oxide electron transport layer on conductive glass;
(2) preparing a sodium alginate interface modification layer on the electron transmission layer;
(3) preparing a perovskite light absorption layer on the interface modification layer;
(4) preparing a hole transport layer on the perovskite light absorption layer;
(5) and sputtering the hole transport layer to prepare a metal electrode layer.
The structural schematic diagram of the perovskite solar cell prepared by the embodiment of the invention is shown in fig. 1.
In the step (1) of the embodiment of the invention, the conductive glass is washed by the non-woven fabric soaked with the cleaning agent, washed by deionized water and ethanol, and then ultrasonically cleaned by ethanol, deionized water, ethanol, acetone and ethanol in sequence. After the cleaning, the glass is dried by nitrogen and treated by ultraviolet-ozone. SnO2Diluting the nano-crystal solution with ultrapure water and carrying out suction filtration to prepare an electron transport layer solution, then spin-coating the electron transport layer solution on conductive glass by adopting a spin-coating method in an air environment and at room temperature, and carrying out annealing treatment to prepare the electron transport layer.
In the step (2) of the embodiment of the present invention, sodium alginate is dissolved in ultrapure water and stirred to prepare an interface modification liquid. And (3) after the spin coating and annealing of the electron transport layer solution in the step (2) are finished, spin coating an interface modification solution on the electron transport layer prepared in the step (1), and annealing, so as to prepare the interface modification layer.
In the step (3) of the embodiment of the present invention, arginine is dissolved and stirred in N, N-dimethylformamide as a solvent under a vacuum condition to prepare an arginine precursor solution. Taking a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide as a first solvent, and adding PbI into the first solvent2And the arginine precursor solution is stirred to prepare a first perovskite precursor solution; dissolving mixed solutes of FAI, MACl and MABr in isopropanol as a solvent, heating and stirring to prepare a second perovskite precursor solution.
After stirring, spin-coating the first perovskite precursor solution on the interface modification layer prepared in the step (2) by using a spin-coating method, and annealing to form a first perovskite layer; and (3) rotationally coating the second perovskite precursor solution on the first perovskite layer under the same environment, and carrying out annealing treatment to prepare the perovskite light absorption layer.
In the step (4) of the embodiment of the invention, acetonitrile is used as a solvent to dissolve Li-TFSI (lithium bis (trifluoromethane sulfonyl) imide) so as to prepare a Li-TFSI acetonitrile solution. And dissolving Spiro-MeOTAD by using chlorobenzene as a solvent, and adding tBP and the Li-TFSI acetonitrile solution to prepare a hole transport layer solution. And (3) carrying out suction filtration on the hole transport layer solution in a vacuum environment, then carrying out spin coating on the perovskite light absorption layer obtained in the step (4) by using a spin coating method to prepare a hole transport layer, and after the spin coating is finished, placing the hole transport layer in a drying oven for oxidation for 24 hours.
In step (5) of the embodiment of the present invention, a metal electrode is sputtered on the hole transport layer by using a magnetron sputtering apparatus or an evaporation method, thereby completing the preparation of the metal sputtering electrode.
According to the perovskite solar cell prepared by the method, the perovskite light absorption layer film shows stronger crystallinity and a smoother surface after being doped with arginine, and in combination with interface modification of sodium alginate, dangling bonds on the surface of the perovskite layer between the electron transmission layer and the perovskite light absorption layer interface can be passivated, so that the restraint of deep level defects on current carriers is reduced, the contact between the electron transmission layer and the hole transmission layer can be effectively reduced, the leakage current is reduced, the photoelectric conversion efficiency is improved, the oxygen permeation is favorably blocked, and the oxidation of perovskite materials is reduced.
According to some embodiments of the invention, the preparing of the sodium alginate interface modification layer on the electron transport layer comprises the following steps:
(1) preparing a sodium alginate aqueous solution, wherein the mass-volume ratio concentration of the sodium alginate aqueous solution is 0.15-0.4 mg/ml, and stirring and dissolving to obtain an interface modification solution;
(2) spin-coating the interface modification liquid on the surface of the electron transport layer to form an interface modification layer;
(3) and (3) annealing the sample obtained in the step (2) to form a sodium alginate interface modification layer on the electron transmission layer.
According to some embodiments of the present invention, the spin speed of the interface modification liquid is 2800 to 3200 rpm, and the spin dose is 35 to 45 μ L.
According to some embodiments of the invention, the annealing process comprises: heating to 130-150 ℃, and preserving heat for 4-5 minutes.
According to some embodiments of the invention, the preparing the perovskite light absorption layer on the interface modification layer comprises the following steps:
(1) under the vacuum condition, dissolving arginine by using N, N-dimethylformamide as a first solvent and stirring to prepare an arginine precursor solution;
(2) taking a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide as a second solvent, wherein the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is (47-9) to (3-1), and adding PbI into the second solvent2And the arginine precursor solution is stirred to obtain a first perovskite precursor solution;
(3) dissolving mixed solutes of iodoformamidine (FAI, ForMaMidiniM Iodide), chloromethane (MACl, Methylalmmonium Chloride) and bromomethylamine (MABr, Methylalmmonium Bromide) by using isopropanol as a third solvent, and heating and stirring to prepare a second perovskite precursor solution;
(4) spin-coating the first perovskite precursor solution on the sodium alginate interface modification layer, and performing annealing treatment to form a first perovskite layer;
(5) and rotationally coating the second perovskite precursor solution on the first perovskite layer, and annealing to prepare the perovskite light absorption layer.
According to some embodiments of the invention, the arginine precursor solution has a mass to volume ratio concentration of arginine: 0.04-0.1 mg/ml.
According to some embodiments of the invention, the mixing ratio of the iodoformamidine, the chloromethane, and the bromomethylamine in the second perovskite precursor solution is: (9-10): 2-1): 1.
According to some embodiments of the invention, when the first perovskite precursor solution is spin-coated on the sodium alginate interface modification layer, the spin-coating speed is 1500 rpm, and the spin-coating dosage is 80-85 μ L; the annealing process comprises the following steps: heating to 65-70 ℃, and preserving heat for 10-15 seconds.
According to some embodiments of the invention, the second perovskite solution is spin-coated on the first perovskite layer at a spin speed of 1500 rpm in an amount of 100 to 105 μ L; the annealing process comprises the following steps: heating to 150 deg.C, and maintaining the temperature for 15-16 min.
In the perovskite solar cell prepared by the method, arginine is used as a small molecular organic matter to play a role of condensation nuclei of perovskite film formation and is used for improving the film forming property of a perovskite material and increasing perovskite crystal grains to reduce the loss of current carriers, the arginine has various functional groups such as amino, carboxyl and the like, and can form coordinate bonds and hydrogen bonds with various defects in perovskite so as to optimize a lattice structure distorted due to the defects, and Lewis basic functional groups (such as amino) can be coordinated with PbI type anti-site defects (lead ions replace iodide ions) so as to offset the binding capacity of the Lewis basic functional groups on free current carriers, so that the photoelectric property of a cell device is improved compared with that of a traditional perovskite solar cell device. After the perovskite solar cell is connected with an external circuit, the structure enables the perovskite solar cell to receive illumination to form a photogenerated carrier, and the photogenerated carrier flows into the external circuit under the action of the internal potential difference formed by the structure to form stable photogenerated current.
The perovskite solar cell in the embodiment of the invention is prepared by the method in the embodiment of the invention.
Specific examples of the present invention are described in detail below. All examples are exemplary and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
1. ITO glass with sheet resistance of 15 and transmittance of 93% and substrate size of 15 × 15mm is used2And 0.7mm thick. And (3) cleaning the conductive glass by using the non-woven fabric soaked with the detergent, washing the conductive glass by using deionized water and ethanol, and then sequentially and respectively ultrasonically cleaning the conductive glass for 15 minutes by using ethanol, deionized water, ethanol, acetone and ethanol. After the cleaning, the glass is dried by nitrogen before use and then treated by ultraviolet-ozone for 15 minutes.
2. 500 μ LSnO was removed with pipette2The nanocrystal solution was added to 2.5ml of ultrapure water, which was placed in a refrigerator for use. Before use, a 1ml syringe is connected with a 0.22 mu m nylon filter head to filter the solution so as to prepare an electron transport layer solution, then a liquid transfer gun is used for taking 50 mu L of the electron transport layer solution in an air environment and at room temperature to spin-coat the electron transport layer solution on conductive glass, the spin-coating rotating speed is 3000 r/30 s, and after the spin-coating is finished, the hot platform is annealed for 30 minutes at 145 ℃ so as to prepare the electron transport layer.
3. Sodium alginate was dissolved in ultrapure water as a solvent to 0.35mg/ml, followed by stirring for 3 hours to prepare an interface modification solution. And (3) after the spin coating of the electron transport layer solution in the step (2) and the annealing are finished, spin coating 40 microliter of interface modification solution on the electron transport layer at the rotating speed of 3000 r/30 s, and then placing the electron transport layer on a hot bench for annealing at 150 ℃ for 5 minutes to prepare the interface modification layer.
4. Under vacuum conditions with "ultrapure water: arginine was dissolved in a mixed solution of N, N-dimethylformamide 10:1 "as a solvent to a concentration of 0.08mg/ml, and then magnetically stirred for 1 hour to prepare an arginine precursor solution. With "N, N-dimethylformamide: 1.5ml of a mixed solution of 47:3 ″, which was a solvent 1, was added to the solvent 1 to prepare a first perovskite precursor solution by adding 0.9g of PbI2 and 20 μ L of the arginine precursor solution, and the mixture was heated and stirred on a hot stage at 75 ℃ for 12 to 15 hours; a mixed solute of 0.06g of fai, 0.006g of macl, and 0.006g of mabr was added to 1ml of isopropyl alcohol as a solvent and stirred at normal temperature in a low-oxygen and dry environment for 12 to 15 hours to prepare a perovskite solution 2.
Spin-coating a first perovskite precursor solution on the interface modification layer at the rotating speed of 1500 rpm/30 seconds and the acceleration of 800m/s2 in a vacuum and dry environment, and performing hot-stage annealing at 70 ℃ for 15 seconds after the spin-coating is finished to form a perovskite layer 1; the perovskite solution 2 was spin-coated on the perovskite layer 1 at the same rotational speed, and then annealed in a hot stage at 150 ℃ for 10 minutes to prepare a perovskite light-absorbing layer.
5. 1560mg of Li-TFSI (lithium bistrifluoromethanesulfonylimide) was dissolved in 3ml of acetonitrile and stirred for 3 hours to prepare an acetonitrile solution of Li-TFSI. Weighing 72.6mg of Spiro-MeOTAD and 8mg of glycoside-chrysanthemic hydrocarbon in a reagent bottle by using an electronic balance, taking 1ml of chlorobenzene in the reagent bottle by using a liquid transfer gun, adding 29 mu L of tBP and 18.0 mu L of the Li-TFSI acetonitrile solution, and stirring for 2 hours in a nitrogen environment; the above solution was filtered in a vacuum glove box using a syringe-nylon filter head (organic) combination, spin-coated at 4000 rpm for 30 seconds to prepare a hole transport layer, the spin-coating was completed, and the resultant was put into a petri dish, and the petri dish was put into a drying oven to be oxidized for 24 hours.
6. And sputtering a metal silver (Ag) electrode on the hole transport layer by utilizing a magnetron sputtering technology, thereby completing the preparation of the metal electrode. The resulting device structure is shown in fig. 1. The photoelectric conversion efficiency of the interface modified perovskite solar cell doped with amino acid obtained by the preparation method of the embodiment is 21.4% on average and the highest photoelectric conversion efficiency is 22.08% in the simulated sunlight environment, and the current-voltage curve is shown in fig. 2. As shown in fig. 7(a) "after treatment", the photoelectric conversion efficiency after 720 hours of storage in the indoor air environment was 16.8%, and as shown in fig. 7(b) "after treatment", the photoelectric conversion efficiency after 240 hours of continuous irradiation with a standard solar intensity was 17.2%; as shown in fig. 7(c) "after treatment", the photoelectric conversion efficiency was 20.5% after storage for 720 hours in a nitrogen atmosphere.
Example 2
The procedure of example 1 was repeated except that the interface modification solution of "sodium alginate having a concentration of 0.35 mg/ml" was replaced with a solution of "0.15 mg of sodium alginate in 1ml of ultrapure water". The photoelectric conversion efficiency of the interface modified perovskite solar cell doped with amino acid obtained by the preparation method of the embodiment is averagely 20.7% and the highest photoelectric conversion efficiency is 21.6% in a simulated sunlight environment, the photoelectric conversion efficiency is 16.3% after the cell is stored in an indoor air environment for 720 hours, and the photoelectric conversion efficiency is 16.7% after the cell is continuously irradiated for 240 hours by a standard solar intensity.
Example 3
Except that the arginine precursor solution was replaced with "ultrapure water under vacuum: the same procedure as in example 1 was repeated, except that the mixed solution of N, N-dimethylformamide and 10: 1' was used as an arginine precursor solution in which arginine was dissolved to a concentration of 0.04 mg/ml. The photoelectric conversion efficiency of the interface modified perovskite solar cell doped with amino acid obtained by the preparation method of the embodiment is 21.1% on average, the highest photoelectric conversion efficiency is 21.8% in the simulated sunlight environment, the photoelectric conversion efficiency is 16.5% after the cell is stored in an indoor air environment for 720 hours, and the photoelectric conversion efficiency is 16.8% after the cell is continuously irradiated for 240 hours by standard sunlight intensity.
Comparative example 1
The procedure of example 1 was followed except that the "arginine doping" and "modification of the sodium alginate interface layer" steps were removed. The perovskite solar cell obtained by the preparation method of the embodiment has an average photoelectric conversion efficiency of 19.3% and a highest photoelectric conversion efficiency of 19.93% in a simulated sunlight environment. The current-voltage curve is shown in fig. 1 "before treatment". FIG. 3 is a graph showing the dark state current density-voltage (J-V) curve test of example 1 and this comparative example, which shows a significant reduction in the dark state leakage current of the devices after treatment, indicating a reduction in the loss of available current. FIG. 4 is an X-ray diffraction pattern of the perovskite light-absorbing layer thin films of example 1 and this comparative example showing an increase in the relative height of the perovskite peak and a decrease in the relative height of the lead iodide peak, indicating that the crystallinity of the perovskite light-absorbing layer is improved after treatment. FIG. 5 is an EIS electrochemical impedance spectra of example 1 and this comparative example showing that the interface transmission resistance of the device after treatment decreased from 24.4k Ω to 10k Ω, indicating less obstruction of carrier transport and passivation of defects at the interface between the electron transport layer and the perovskite light absorbing layer; FIG. 6 is a UV-VIS absorption spectrum of example 1 and this comparative example showing the enhancement of the light absorption capability of the treated perovskite light absorption layer film; as shown in fig. 7(a) "before treatment", the photoelectric conversion efficiency was 14.5% after 720 hours of storage in an indoor air environment; FIG. 7(b) "before treatment", shows a photoelectric conversion efficiency of 14.0% after 240 hours of continuous irradiation with a standard solar intensity; as shown in fig. 7(c) "before treatment", the photoelectric conversion efficiency was 16.1% after storage for 720 hours in a nitrogen atmosphere. In the figure, example 1 is shown after the treatment, and comparative example 1 is shown before the treatment.
Comparative example 2
Example 1 was followed except that the "interfacial modification with sodium alginate" step was removed. The photoelectric conversion efficiency of the interface modified perovskite solar cell doped with amino acid obtained by the preparation method of the embodiment is averagely 20.7% and the highest photoelectric conversion efficiency is 21.3% in a simulated sunlight environment, the photoelectric conversion efficiency is 16.2% after the cell is stored in an indoor air environment for 720 hours, and the photoelectric conversion efficiency is 16.4% after the cell is continuously irradiated for 240 hours by standard sunlight intensity.
The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to the above embodiment, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It will be apparent to those skilled in the art that variations and modifications can be made without departing from the principles of the invention, and these variations and modifications are to be considered within the scope of the invention.

Claims (10)

1. A perovskite solar cell preparation method is characterized by comprising the following steps:
(1) preparing a stannic oxide electron transport layer on conductive glass;
(2) preparing a sodium alginate interface modification layer on the electron transmission layer;
(3) preparing a perovskite light absorption layer on the interface modification layer;
(4) preparing a hole transport layer on the perovskite light absorption layer;
(5) and sputtering the hole transport layer to prepare a metal electrode layer.
2. The perovskite solar cell preparation method according to claim 1, wherein the preparation of the sodium alginate interface modification layer on the electron transport layer comprises the following steps:
(1) preparing a sodium alginate aqueous solution, wherein the mass-volume ratio concentration of the sodium alginate aqueous solution is 0.15-0.4 mg/ml, and stirring and dissolving to obtain an interface modification solution;
(2) spin-coating the interface modification liquid on the surface of the electron transport layer to form an interface modification layer;
(3) and (3) annealing the sample obtained in the step (2) to form a sodium alginate interface modification layer on the electron transmission layer.
3. The perovskite solar cell preparation method of claim 2, wherein the spin coating speed of the interface modification liquid is 2800-3200 rpm, and the spin coating dosage is 35-45 μ L.
4. The perovskite solar cell fabrication method as claimed in claim 2, wherein the annealing process is: heating to 130-150 ℃, and preserving heat for 4-5 minutes.
5. The method for preparing a perovskite solar cell according to claim 1, wherein the step of preparing the perovskite light absorption layer on the interface modification layer comprises the following steps:
(1) under the vacuum condition, dissolving arginine by using N, N-dimethylformamide as a first solvent and stirring to prepare an arginine precursor solution;
(2) taking a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide as a second solvent, wherein the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is (47-9) to (3-1), and adding PbI into the second solvent2And the arginine precursor solution is stirred to obtain a first perovskite precursor solution;
(3) dissolving a mixed solute of iodoformamidine, chloromethane and bromomethylamine by using isopropanol as a third solvent, and heating and stirring to prepare a second perovskite precursor solution;
(4) coating the first perovskite precursor solution on the sodium alginate interface modification layer in a spinning mode, and annealing to form a first perovskite layer;
(5) and rotationally coating the second perovskite precursor solution on the first perovskite layer, and annealing to prepare the perovskite light absorption layer.
6. The perovskite solar cell manufacturing method according to claim 5, wherein the mass-to-volume ratio concentration of arginine in the arginine precursor solution is: 0.04-0.1 mg/ml.
7. The perovskite solar cell manufacturing method according to claim 5, wherein the mixing ratio of iodoformamidine, chloromethane, and bromomethylamine in the second perovskite precursor solution is: (9-10): 2-1): 1.
8. The preparation method of the perovskite solar cell according to claim 5, wherein when the first perovskite precursor solution is spin-coated on the sodium alginate interface modification layer, the spin-coating speed is 1500 rpm, and the spin-coating dosage is 80-85 μ L; the annealing treatment process comprises the following steps: heating to 65-70 ℃, and preserving heat for 10-15 seconds.
9. The perovskite solar cell preparation method according to claim 5, wherein the second perovskite solution is spin-coated on the first perovskite layer at a spin-coating speed of 1500 rpm in an amount of 100 to 105 μ L; the annealing treatment process comprises the following steps: heating to 150 deg.C, and maintaining the temperature for 15-16 min.
10. A perovskite solar cell, characterized in that it is produced by a method according to any one of claims 1 to 9.
CN202210024588.9A 2022-01-11 2022-01-11 Perovskite solar cell and preparation method thereof Pending CN114497390A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114864829A (en) * 2022-07-07 2022-08-05 中国长江三峡集团有限公司 Perovskite solar cell and preparation method thereof
CN115312665A (en) * 2022-07-28 2022-11-08 兰州大学 Solar cell and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114864829A (en) * 2022-07-07 2022-08-05 中国长江三峡集团有限公司 Perovskite solar cell and preparation method thereof
EP4304317A1 (en) * 2022-07-07 2024-01-10 China Three Gorges Co., Ltd. Perovskite solar cell and preparation method therefor
CN115312665A (en) * 2022-07-28 2022-11-08 兰州大学 Solar cell and preparation method thereof

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