CN110571336A - Method for improving photoelectric conversion rate of two-dimensional perovskite solar cell - Google Patents
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Abstract
The invention belongs to the technical field of photovoltaic materials, and particularly relates to a method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell, wherein the solar cell comprises the following components in sequence from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; the perovskite-type composite material is characterized in that the perovskite layer is a perovskite thin film, and the thickness of the perovskite layer is 220-320 nm; the preparation method comprises the steps of preparing a mixed solution, preparing a perovskite precursor solution, and preparing and treating the perovskite film. Compared with the prior art, the invention has the following advantages: the perovskite thin film prepared by the method has good stability, can improve the photoelectric conversion rate of the perovskite solar cell when being used for preparing the perovskite solar cell, and has good cell performance, long service life and wide application range.
Description
Technical Field
the invention belongs to the technical field of photovoltaic materials, and particularly relates to a method for improving photoelectric conversion rate of a two-dimensional perovskite solar cell.
background
Experiments show that after a metal halide material forms a perovskite structure, the perovskite structure material is very effective as an acquisition layer in a photovoltaic solar cell and can successfully convert solar energy into electric energy, based on the discovery, in 2009, the perovskite structure material is formally applied to a thin film solar cell, and in the following years, the perovskite structure material has been greatly developed in the photovoltaic field, the photoelectric conversion rate is continuously improved, particularly, the metal halide perovskite material is generally made of cheap lead, halogen and amine salt, the source is wide, the manufacturing cost is lower than that of the conventional silicon-based material, in the aspect of the photoelectric conversion rate, the perovskite material is developed from the initial 3.8% to 15.9% only in less than 5 years, and the efficiency of the silicon-based photovoltaic material is gradually approached, at present, the efficiency of perovskite solar cells is up to 23.7% after being authenticated, so that the solar cells using the photovoltaic materials with the perovskite structures can completely replace the traditional solar cells using silicon photovoltaic materials; however, the problems of low repeatability, poor stability and the like of the perovskite solar cell are still the biggest obstacles to the commercial application process of the perovskite solar cell, the perovskite is unstable at room temperature due to moisture absorption, chemical reaction can occur in an oxygen environment to further damage a crystal structure, and obvious efficiency attenuation can occur after the perovskite is used for a period of time.
Disclosure of Invention
The invention aims to provide a method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell, aiming at the problem that the existing two-dimensional perovskite material has better stability but lower performance than that of a three-dimensional perovskite cell.
the invention is realized by the following technical scheme: a method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell comprises the following steps from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; wherein the perovskite layer is a perovskite thin film, and the thickness is 220-320 nm; the preparation method comprises the following steps:
(1) Preparing a mixed solvent, namely mixing dimethyl sulfoxide, gamma-butyrolactone, ethylenediamine and tetrapropyl ammonium bromide in a volume ratio of 16-20:6-8:6-8:1, and stirring for 10-15 minutes to obtain the mixed solvent;
(2) preparing a perovskite precursor solution, namely mixing 0.6-0.8 part of stannous iodide, 1.4-1.6 parts of cobalt carbonyl, 3.5-4.5 parts of methyl ammonium bromide and 0.2-0.3 part of vanadium difluoride with 30-40 parts of a mixed solvent in parts by weight, stirring for 3.5-4.5 hours at the temperature of 105-115 ℃, and uniformly mixing to obtain the perovskite precursor solution;
(3) Preparing a perovskite film, heating a perovskite precursor solution to 100 ℃, spin-coating on a TiO2 mesoporous layer to prepare a film, standing for 20 minutes after the film is finished, treating for 5 minutes at 120 ℃, adjusting the temperature to 105 ℃, continuing to treat for 15 minutes, and naturally cooling to room temperature after the film is finished;
(4) And (2) treating the perovskite film, namely uniformly mixing 2-3 parts of 1, 8-diiodooctane, 0.6-1.2 parts of cationic surfactant and 100 parts of isopropanol by weight to obtain a composite treating fluid, then soaking the perovskite film into the composite treating fluid for treating for 20-30 minutes, washing with isopropanol after the treatment is finished, and then drying for 20 minutes in a nitrogen atmosphere at 100 ℃ to obtain the perovskite film.
Wherein the thickness of the compact layer is 30-50nm, the thickness of the TiO2 mesoporous layer is 300-500nm, the thickness of the hole transport layer is 60-180nm, and the thickness of the electrode layer is 60-180 nm.
Wherein the square resistance of the FTO conductive glass is 14 omega/cm, and the transmittance is greater than 80%.
Wherein, the spin coating process in the step (3) is carried out in an inert gas protective gas box; the spin coating conditions were 2000 rpm, and the spin coating was performed for 30 seconds.
the hole transport layer comprises the following solutions in parts by weight: 3-5 parts of Spiro-OMeTAD, 0.2-0.4 part of lithium hexafluorophosphate, 20-25 parts of acetone and 50-60 parts of chlorobenzene;
And the electrode layer is obtained by coating carbon slurry on the surface of the hole transport layer in a scraping manner, standing for 30 minutes and drying at the temperature of 110 ℃ under a vacuum condition.
The perovskite crystal structure comprises organic cations, metal cations and halogen anions, and different defects of the perovskite crystal can be influenced due to changes of preparation raw materials and conditions, anion and cation vacancies meeting the electric neutral condition are formed in the crystal, the anion and cation vacancies and interstitial ions are generated in pairs, and the interstitial ions are ions which can migrate in the perovskite thin film except the halogen anions and the organic cations in the material, so that the ion mobility is improved, and the solar cell performance is improved.
Compared with the prior art, the invention has the following advantages: according to the invention, by increasing small molecular raw materials and organic additives in a perovskite precursor solution and controlling preparation conditions, the perovskite is rapidly crystallized to form a film, the grain boundary area is reduced by increasing the grain size, the internal defects of the perovskite crystal are reduced, a two-dimensional perovskite structure is obtained, then the organic small molecules are introduced again by using a composite treatment liquid, in-situ crosslinking is realized at the grain boundary to form a stable crosslinked polymer network, and the surface of the perovskite thin film is passivated, so that ions can be effectively inhibited from migrating to a hole absorption layer, the stability of the thin film is improved, and the service life of the thin film is prolonged.
drawings
FIG. 1 is a J-V plot of example 1 versus a control with current density on the ordinate and voltage V on the abscissa;
FIG. 2 is a detection result of efficiency maintaining performance of each group of perovskite solar photovoltaic cells.
Detailed Description
In order to effectively research the photoelectric conversion rate of the two-dimensional perovskite solar cell, each group of experimental data is subjected to J-V curve test on the cell prepared by each group by using a Keithley 2400 tester, and each group of experimental data is an average value obtained after 3 repeated tests are set; the invention will be further illustrated with reference to specific examples:
example 1
A method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell comprises the following steps from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; the thickness of the compact layer is 40nm, the thickness of the TiO2 mesoporous layer is 400nm, the thickness of the hole transport layer is 120nm, and the thickness of the electrode layer is 120 nm; the perovskite layer is a perovskite film, and the thickness is 280 nm;
Wherein the FTO conductive glass square resistance is 14 omega/cm, and the transmittance is greater than 80%; leaching the TiO2 compact layer for 3 times by using a 0.5mol/L diisopropoxy diacetone titanium ethanol solution, wherein the leaching rate is 0.3mm/s, standing for 10 minutes after each leaching is finished, and then drying for 20 minutes at 100 ℃ to obtain the titanium dioxide compact layer; the TiO2 mesoporous layer is obtained by adopting titanium dioxide slurry spin-coating liquid OPV-18NRT and annealing at 530 ℃ for 40 minutes after the spin-coating is finished;
The solution used for the hole transport layer comprises the following components in parts by weight: 4 parts of Spiro-OMeTAD, 0.3 part of lithium hexafluorophosphate, 22 parts of acetone and 55 parts of chlorobenzene; the electrode layer is obtained by blade-coating carbon slurry on the surface of the hole transport layer, standing for 30 minutes, and drying at 110 ℃ under a vacuum condition;
The preparation method of the perovskite layer comprises the following steps:
(1) preparing a mixed solvent, namely mixing dimethyl sulfoxide, gamma-butyrolactone, ethylenediamine and tetrapropyl ammonium bromide in a volume ratio of 18:7:7:1, and stirring for 12 minutes to obtain the mixed solvent;
(2) Preparing a perovskite precursor solution, mixing 0.7 part of stannous iodide, 1.5 parts of cobalt carbonyl, 4 parts of methyl ammonium bromide and 0.25 part of vanadium difluoride with 35 parts of a mixed solvent by weight, stirring for 4 hours at the temperature of 110 ℃, and uniformly mixing to obtain the perovskite precursor solution;
(3) Preparing a perovskite film, heating a perovskite precursor solution to 100 ℃, carrying out spin coating on a TiO2 mesoporous layer to prepare a film, carrying out the spin coating process in an inert gas protective gas box under the condition of 2000 r/min for 30s, standing for 20 minutes after the spin coating is finished, treating at 120 ℃ for 5 minutes, adjusting the temperature to 105 ℃, continuing to treat for 15 minutes, and naturally cooling to room temperature after the treatment is finished;
(4) And (2) treating the perovskite film, namely uniformly mixing 2.5 parts of 1, 8-diiodooctane, 0.9 part of cationic surfactant and 100 parts of isopropanol by weight to obtain a composite treating fluid, then soaking the perovskite film into the composite treating fluid for treating for 25 minutes, washing with the isopropanol after the treatment is finished, and then drying for 20 minutes in a nitrogen atmosphere at 100 ℃ to obtain the perovskite film.
detected, the photoelectric conversion efficiency is 6.39%, the open-circuit voltage is 0.52V, the short-circuit current of the battery is 20.43mA/cm, and the fill factor is 63.41%.
Example 2
a method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell comprises the following steps from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; the thickness of the compact layer is 50nm, the thickness of the TiO2 mesoporous layer is 300nm, the thickness of the hole transport layer is 60nm, and the thickness of the electrode layer is 180 nm; the perovskite layer is a perovskite film, and the thickness is 220 nm;
Wherein the FTO conductive glass square resistance is 14 omega/cm, and the transmittance is greater than 80%; leaching the TiO2 compact layer for 3 times by using a 0.6mol/L diisopropoxy diacetone titanium ethanol solution, wherein the leaching rate is 0.3mm/s, standing for 10 minutes after each leaching is finished, and then drying for 20 minutes at 100 ℃ to obtain the titanium dioxide compact layer; the TiO2 mesoporous layer is obtained by adopting titanium dioxide slurry spin-coating liquid OPV-18NRT and annealing at 530 ℃ for 40 minutes after the spin-coating is finished;
the solution used for the hole transport layer comprises the following components in parts by weight: 5 parts of Spiro-OMeTAD, 0.2 part of lithium hexafluorophosphate, 25 parts of acetone and 60 parts of chlorobenzene; the electrode layer is obtained by blade-coating carbon slurry on the surface of the hole transport layer, standing for 30 minutes, and drying at 110 ℃ under a vacuum condition;
The preparation method of the perovskite layer comprises the following steps:
(1) preparing a mixed solvent, namely mixing dimethyl sulfoxide, gamma-butyrolactone, ethylenediamine and tetrapropyl ammonium bromide in a volume ratio of 20:8:6:1, and stirring for 15 minutes to obtain the mixed solvent;
(2) Preparing a perovskite precursor solution, mixing 0.8 part of stannous iodide, 1.4 parts of cobalt carbonyl, 3.5 parts of methyl ammonium bromide and 0.2 part of vanadium difluoride with 40 parts of a mixed solvent by weight, stirring for 3.5 hours at the temperature of 105 ℃, and uniformly mixing to obtain the perovskite precursor solution;
(3) preparing a perovskite film, heating a perovskite precursor solution to 100 ℃, carrying out spin coating on a TiO2 mesoporous layer to prepare a film, carrying out the spin coating process in an inert gas protective gas box under the condition of 2000 r/min for 30s, standing for 20 minutes after the spin coating is finished, treating at 120 ℃ for 5 minutes, adjusting the temperature to 105 ℃, continuing to treat for 15 minutes, and naturally cooling to room temperature after the treatment is finished;
(4) and (2) treating the perovskite film, namely uniformly mixing 2 parts of 1, 8-diiodooctane, 1.2 parts of cationic surfactant and 100 parts of isopropanol by weight to obtain a composite treating fluid, then soaking the perovskite film into the composite treating fluid for treating for 30 minutes, washing with the isopropanol after the treatment is finished, and then drying for 20 minutes in a nitrogen atmosphere at 100 ℃ to obtain the perovskite film.
Detected, the photoelectric conversion efficiency is 6.28%, the open-circuit voltage is 0.47V, the short-circuit current of the battery is 19.92mA/cm, and the fill factor is 62.07%.
example 3
A method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell comprises the following steps from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; the thickness of the compact layer is 30nm, the thickness of the TiO2 mesoporous layer is 500nm, the thickness of the hole transport layer is 180nm, and the thickness of the electrode layer is 60 nm; the perovskite layer is a perovskite film and the thickness is 320 nm;
Wherein the FTO conductive glass square resistance is 14 omega/cm, and the transmittance is greater than 80%; leaching the TiO2 compact layer for 3 times by using a 0.4mol/L diisopropoxy diacetone titanium ethanol solution, wherein the leaching rate is 0.3mm/s, standing for 10 minutes after each leaching is finished, and then drying for 20 minutes at 100 ℃ to obtain the titanium dioxide compact layer; the TiO2 mesoporous layer is obtained by adopting titanium dioxide slurry spin-coating liquid OPV-18NRT and annealing at 530 ℃ for 40 minutes after the spin-coating is finished;
the solution used for the hole transport layer comprises the following components in parts by weight: 3 parts of Spiro-OMeTAD, 0.4 part of lithium hexafluorophosphate, 20 parts of acetone and 50 parts of chlorobenzene; the electrode layer is obtained by blade-coating carbon slurry on the surface of the hole transport layer, standing for 30 minutes, and drying at 110 ℃ under a vacuum condition;
The preparation method of the perovskite layer comprises the following steps:
(1) preparing a mixed solvent, namely mixing dimethyl sulfoxide, gamma-butyrolactone, ethylenediamine and tetrapropyl ammonium bromide in a volume ratio of 16:6:8:1, and stirring for 10 minutes to obtain the mixed solvent;
(2) Preparing a perovskite precursor solution, mixing 0.6 part of stannous iodide, 1.6 parts of cobalt carbonyl, 4.5 parts of methyl ammonium bromide and 0.3 part of vanadium difluoride with 30 parts of a mixed solvent in parts by weight, stirring for 4.5 hours at the temperature of 115 ℃, and uniformly mixing to obtain the perovskite precursor solution;
(3) Preparing a perovskite film, heating a perovskite precursor solution to 100 ℃, carrying out spin coating on a TiO2 mesoporous layer to prepare a film, carrying out the spin coating process in an inert gas protective gas box under the condition of 2000 r/min for 30s, standing for 20 minutes after the spin coating is finished, treating at 120 ℃ for 5 minutes, adjusting the temperature to 105 ℃, continuing to treat for 15 minutes, and naturally cooling to room temperature after the treatment is finished;
(4) And (2) perovskite film treatment, namely taking 3 parts of 1, 8-diiodooctane, 0.6 part of cationic surfactant and 100 parts of isopropanol by weight, uniformly mixing to obtain a composite treatment liquid, then immersing the perovskite film into the composite treatment liquid for treatment for 20 minutes, washing the perovskite film with the isopropanol after the treatment is finished, and then drying the perovskite film for 20 minutes in a nitrogen atmosphere at 100 ℃ to obtain the perovskite film.
detected, the photoelectric conversion efficiency is 6.32%, the open-circuit voltage is 0.51V, the short-circuit current of the battery is 20.35mA/cm, the fill factor is 63.28%, and the energy conversion efficiency is 2.41%.
the photovoltaic performance of the perovskite solar photovoltaic cell in the application is evaluated by taking the example with the application number of 2018101540560 as a control group, wherein the photoelectric conversion efficiency of the solar cell device is 3.17%, the open-circuit voltage is 0.34V, the short-circuit current is 17.63mA/cm2, and the filling factor is 52.84%.
as shown in fig. 1, as can be seen from the results in fig. 1, the photovoltaic conversion efficiency and the short-circuit current of the perovskite solar photovoltaic cell in the examples 1 to 3 and the control group are improved to some extent, and the perovskite solar photovoltaic cell in the example has relatively good cell performance.
In order to evaluate the photovoltaic characteristics of the perovskite solar photovoltaic cells prepared by the groups, a Keithley 2400 tester is used for carrying out J-V curve test on the cells prepared by the groups, and the results are shown in FIG. 1; wherein the open-circuit voltage is 0.82V, the short-circuit current of the battery is 7.25mA/cm, the fill factor is 0.41, and the energy conversion efficiency is 2.41%.
In order to evaluate the stability of the perovskite solar photovoltaic cell, the perovskite solar photovoltaic cell prepared by the preparation method is subjected to non-packaging treatment, and is placed in a dark environment with the relative humidity of 40% and the temperature of about 25 ℃, and the change of the efficiency along with the time is tested, and the specific result is shown in fig. 2, so that after 40 days, the efficiency retention rate of the perovskite solar photovoltaic cell prepared in the application reaches 96.8-97.3%, and the initial efficiency in a control group is 95.2%, which shows that the stability of the performance of the cell in the invention is further improved compared with the stability of the cell in the prior art.
Claims (7)
1. a method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell comprises the following steps from bottom to top: the structure comprises an FTO conductive glass layer, a TiO2 dense layer, a TiO2 mesoporous layer, a perovskite layer, a hole absorption layer and an electrode layer; the perovskite-type composite material is characterized in that the perovskite layer is a perovskite thin film, and the thickness of the perovskite layer is 220-320 nm; the preparation method comprises the following steps:
(1) preparing a mixed solvent, namely mixing dimethyl sulfoxide, gamma-butyrolactone, ethylenediamine and tetrapropyl ammonium bromide in a volume ratio of 16-20:6-8:6-8:1, and stirring for 10-15 minutes to obtain the mixed solvent;
(2) preparing a perovskite precursor solution, namely mixing 0.6-0.8 part of stannous iodide, 1.4-1.6 parts of cobalt carbonyl, 3.5-4.5 parts of methyl ammonium bromide and 0.2-0.3 part of vanadium difluoride with 30-40 parts of a mixed solvent in parts by weight, stirring for 3.5-4.5 hours at the temperature of 105-115 ℃, and uniformly mixing to obtain the perovskite precursor solution;
(3) Preparing a perovskite film, heating a perovskite precursor solution to 100 ℃, spin-coating on a TiO2 mesoporous layer to prepare a film, standing for 20 minutes after the film is finished, treating for 5 minutes at 120 ℃, adjusting the temperature to 105 ℃, continuing to treat for 15 minutes, and naturally cooling to room temperature after the film is finished;
(4) and (2) treating the perovskite film, namely uniformly mixing 2-3 parts of 1, 8-diiodooctane, 0.6-1.2 parts of cationic surfactant and 100 parts of isopropanol by weight to obtain a composite treating fluid, then soaking the perovskite film into the composite treating fluid for treating for 20-30 minutes, washing with isopropanol after the treatment is finished, and then drying for 20 minutes in a nitrogen atmosphere at 100 ℃ to obtain the perovskite film.
2. The method for improving the photoelectric conversion rate of the two-dimensional perovskite solar cell as claimed in claim 1, wherein the thickness of the dense layer is 30-50nm, the thickness of the TiO2 mesoporous layer is 300-500nm, the thickness of the hole transport layer is 60-180nm, and the thickness of the electrode layer is 60-180 nm.
3. the method for improving the photoelectric conversion rate of a two-dimensional perovskite solar cell according to claim 1, wherein the FTO conductive glass sheet resistance is 14 Ω/cm, and the transmittance is greater than 80%.
4. the method for improving the photoelectric conversion rate of the two-dimensional perovskite solar cell as claimed in claim 1, wherein the spin coating process of the step (3) is performed in an inert gas protective gas box.
5. the method for improving the photoelectric conversion rate of the two-dimensional perovskite solar cell as claimed in claim 1, wherein the spin coating conditions in the step (3) are 2000 rpm and 30 s.
6. The method for improving the photoelectric conversion rate of the two-dimensional perovskite solar cell as claimed in claim 1, wherein the solution used for the hole transport layer comprises the following components in parts by weight: 3-5 parts of Spiro-OMeTAD, 0.2-0.4 part of lithium hexafluorophosphate, 20-25 parts of acetone and 50-60 parts of chlorobenzene.
7. the method for improving the photoelectric conversion rate of the two-dimensional perovskite solar cell as claimed in claim 1, wherein the electrode layer is obtained by coating carbon slurry on the surface of the hole transport layer, standing for 30 minutes, and drying under vacuum at 110 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111223994A (en) * | 2020-01-17 | 2020-06-02 | 桂林电子科技大学 | All-printed mesoscopic perovskite solar cell adopting carbonyl micromolecules as additives and preparation method thereof |
| CN111628091A (en) * | 2020-06-08 | 2020-09-04 | 西北工业大学 | Method for improving quality of perovskite thin film through solvent bath auxiliary heat treatment |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111223994A (en) * | 2020-01-17 | 2020-06-02 | 桂林电子科技大学 | All-printed mesoscopic perovskite solar cell adopting carbonyl micromolecules as additives and preparation method thereof |
| CN111223994B (en) * | 2020-01-17 | 2022-06-14 | 桂林电子科技大学 | All-printed mesoscopic perovskite solar cell adopting carbonyl micromolecules as additives and preparation method thereof |
| CN111628091A (en) * | 2020-06-08 | 2020-09-04 | 西北工业大学 | Method for improving quality of perovskite thin film through solvent bath auxiliary heat treatment |
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