CN112490367A - Perovskite solar cell and preparation method thereof - Google Patents
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Abstract
The invention discloses a perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell comprises FTO, an ion transport layer, a perovskite layer, a hole transport layer and a metal electrode layer; the perovskite battery is characterized in that an ion transport layer/a perovskite layer/a hole transport layer/a metal electrode layer are sequentially coated on clean FTO conductive glass in a spin coating mode, and the ion transport layer is a compact titanium dioxide layer/a mesoporous titanium dioxide layer; the perovskite layer is CH3NH3PbI3(MAI); the hole transport layer is a spiro-OMeTAD layer doped with an anionic metal organic framework material. The perovskite solar cell has high photoelectric conversion efficiency, and the stability of the perovskite solar cell is effectively improved by doping the indium-metal organic framework.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
The perovskite solar cell is developed from a dye-sensitized solar cell, organic dye in the dye-sensitized solar cell is replaced by organic-inorganic hybrid perovskite material, and iodine-containing electrolyte is replaced by spiro-OMeTAD. In recent 10 years, the development of perovskite solar cells has been extremely rapid, and the photoelectric conversion efficiency has increased from the first 3.8% to the present 25.2%, mainly due to the great advantages of perovskite materials, such as longer carrier lifetime and diffusion length, wider absorption range, stronger absorption coefficient, and the like.
In order to obtain solar cells with high photovoltaic performance, it is essential to reduce defects and to improve carrier extraction capability, such as at the perovskite/Hole Transport Layer (HTL) or at the interface of the perovskite/Electron Transport Layer (ETL). On one hand, halide anion vacancies and organic cation vacancies are easily generated at the surface or grain boundary of the perovskite thin film due to the low formation energy of the perovskite material, and meanwhile, the trap state-induced charge recombination accelerates the decomposition of the perovskite material, which in turn reduces the stability of the perovskite solar cell. Therefore, reduction of halide anions and organic cation vacancies is very important for improving the efficiency and stability of perovskite solar cells; on the other hand, at the interface of the functional layer is where defect states are most likely to occur, and therefore it is particularly important to reduce interface charge recombination and passivate the defect states of the perovskite by promoting the transport of charges at the interface. In the prior art, interface defects are easy to occur on a perovskite layer and a hole transport layer, so that the perovskite solar cell is low in efficiency and poor in stability.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a perovskite solar cell, which includes an FTO, an ion transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer; the perovskite battery is characterized in that an ion transport layer/a perovskite layer/a hole transport layer/a metal electrode layer are sequentially spin-coated on clean FTO conductive glass by adopting a spin-coating method; the ion transmission layer is a compact titanium dioxide layer/mesoporous titanium dioxide layer; the perovskite layer is CH3NH3PbI3(MAI); the hole transport layer is a spiro-OMeTAD layer doped with an anionic metal organic framework material.
Another object of the present invention is to provide a method for preparing a perovskite solar cell, which comprises the following steps:
s1: ultrasonically cleaning FTO conductive glass by acetone, absolute ethyl alcohol and deionized water for 25-40 min respectively in sequence, then placing the FTO conductive glass in a tube furnace, heating for 40min at 500-550 ℃, and cooling; adding tetraisopropyl titanate into n-butyl alcohol, stirring for 30-50 min, then spin-coating on FTO conductive glass, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use.
S2: adding titanium dioxide slurry into isopropanol, continuously stirring for 60-80 h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1: 22-25, and then spin-coating the titanium dioxide slurry and the isopropanol in step S1 to obtain FTO/compact TiO2And (3) coating the layer, wherein the spin coating speed is 6000rpm and the acceleration is 600rpm/s, heating at 120 ℃ for 12min, annealing at 500 ℃ for 30min, and cooling for later use.
S3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, stirring at 70-75 ℃ for 12 hours, and preparing molar concentration PbI by using the mixed solution2:CH2NH2Stirring the perovskite solution with the I of 1.12:1 at 70-75 ℃ for 12h, cooling, and spin-coating the FTO/dense TiO solution obtained in the step S22Layer/mesoporous TiO2On the layer, spin coating speed was 5000rpm, then solvent chlorobenzene was dropped on the perovskite layer, and annealing was performed at 110 ℃ for 10min for standby.
S4: adding the spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12 hours In a dark condition, adding 4-tert-butylpyridine and anhydrous acetonitrile, continuing stirring for 6-10 hours In the dark condition, adding In-MOF crystal powder, performing ultrasonic treatment for 6-8 hours, and spin-coating the FTO/dense TiO crystal powder obtained In the step S32Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 80-90 nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
Preferably, the volume ratio of the tetraisopropyl titanate to the n-butyl alcohol is (0.11-0.15): 2.6-3.3); the spin coating speed in the step S1 is 2850rpm, and the acceleration is 1000 rpm/S.
Preferably, the molar concentration of the lead iodide is 1.49-1.52 mol/L.
Preferably, the mass-volume ratio of the spiroo-OMeTAD powder to the anhydrous chlorobenzene to the In-MOF is (0.07-0.079) g, (1-2.2) mL, (0.0012-0.0018) g; the volume ratio of the 4-tert-butylpyridine to the anhydrous acetonitrile is (2.5-2.9) to (1.7-1.9).
Preferably, the In-MOF is synthesized by the following method:
1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min.
2) Adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating and reacting for 24h to obtain the In-MOF.
More preferably, the mass-to-volume ratio of the 4, 4' - (1, 4-phenylenebis (pyridine-4, 2, 6-triyl)) -tetraphenylbenzoic acid, indium nitrate, N-dimethylformamide and nitric acid solution is (0.009-0.011) g, (0.006-0.008) g, (3-5) mL and (2.1-2.5) mL.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the hole transport layer is obtained by doping spiro-OMeTAD with In-MOF, and (Me) exists In the pore channel of the indium-metal organic framework material prepared In the invention2NH2)+(ii) an anionic framework metal organic framework of (Me)2NH2)+The metal organic framework can fill organic cation vacancies caused by the instability of the perovskite, further passivate the defect of the interface of the perovskite/hole transport layer, and can compensate and fix the positive charge hole transport layer to promote the transport of holes.
Drawings
FIG. 1 is an XRD pattern of MOFs prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a perovskite/hole transport layer of a perovskite solar cell fabricated in example 1 of the present invention;
fig. 3 is a graph comparing the stability of continuous output of the perovskite solar cell prepared in example 1 of the present invention and the perovskite solar cell prepared in comparative example 1 under a nitrogen atmosphere with continuous illumination at room temperature.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of a perovskite solar cell specifically comprises the following steps:
the synthesis of In-MOF adopts the following steps: 1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min.
2) Adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating for reaction for 24h to obtain In-MOF, wherein the mass-to-volume ratio of the 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid, indium nitrate, N-dimethylformamide and the nitric acid solution is 0.009g:0.006g:3mL:2.1 mL.
Preparation of perovskite solar cell:
s1: ultrasonically cleaning FTO conductive glass with acetone, absolute ethyl alcohol and deionized water for 25min respectively, then placing in a tube furnace, heating at 500 ℃ for 40min, and cooling; adding tetraisopropyl titanate into n-butanol, wherein the volume ratio of tetraisopropyl titanate to n-butanol is 0.11:2.6, stirring for 30min, then spin-coating on FTO conductive glass at the speed of 2850rpm and the acceleration of 1000rpm/s, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use.
S2: adding titanium dioxide slurry into isopropanol with stirring for 60h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1:22, and then spin-coating the titanium dioxide slurry and the isopropanol to obtain FTO/compact TiO in step S12And (3) coating the layer, wherein the spin coating speed is 6000rpm and the acceleration is 600rpm/s, heating at 120 ℃ for 12min, annealing at 500 ℃ for 30min, and cooling for later use.
S3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, wherein the content of the lead iodide isThe molar concentration is 1.49mol/L, the mixture is stirred for 12 hours at 70 ℃, and then the molar concentration PbI is prepared by the mixed solution2:CH2NH2Perovskite solution with I of 1.12:1, stirring at 70 ℃ for 12h, cooling, spin coating FTO/dense TiO at step S22Layer/mesoporous TiO2On the layer, spin coating speed was 5000rpm, then solvent chlorobenzene was dropped on the perovskite layer, and annealing was performed at 110 ℃ for 10min for standby.
S4: adding the spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12h under the condition of keeping out of the sun, then adding 4-tert-butylpyridine and anhydrous acetonitrile, wherein the volume ratio of the 4-tert-butylpyridine to the anhydrous acetonitrile is 2.5:1.7, continuing stirring for 6h under the condition of keeping out of the sun, then adding In-MOF crystal powder, carrying out ultrasonic treatment for 6h, wherein the mass-volume ratio of the spiro-OMeTAD powder, the anhydrous chlorobenzene to the In-MOF is 0.07g:1mL:0.0012g, and spin-coating the FTO/dense TiO powder obtained In the step S32Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 80nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
Example 2
A preparation method of a perovskite solar cell specifically comprises the following steps:
the synthesis of In-MOF adopts the following steps: 1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min.
2) Adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating and reacting for 24h to obtain the In-MOF, wherein the mass-to-volume ratio of the 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid, indium nitrate, N-dimethylformamide and the nitric acid solution is 0.011g:0.008g:5mL:2.5 mL.
Preparation of perovskite solar cell:
s1: ultrasonically cleaning FTO conductive glass by acetone, absolute ethyl alcohol and deionized water for 40min respectively in sequence, then placing the FTO conductive glass in a tube furnace, heating for 40min at 550 ℃, and cooling; adding tetraisopropyl titanate into n-butanol, wherein the volume ratio of tetraisopropyl titanate to n-butanol is 0.15:3.3, stirring for 50min, then spin-coating on FTO conductive glass at the speed of 2850rpm and the acceleration of 1000rpm/s, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use.
S2: adding titanium dioxide slurry into isopropanol, continuously stirring for 80h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1:25, and then spin-coating the titanium dioxide slurry and the isopropanol to obtain FTO/compact TiO in step S12And (3) coating the layer, wherein the spin coating speed is 6000rpm and the acceleration is 600rpm/s, heating at 120 ℃ for 12min, annealing at 500 ℃ for 30min, and cooling for later use.
S3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1, wherein the molar concentration of the lead iodide is 1.52mol/L, stirring at 75 ℃ for 12h, and preparing the mixed solution into molar concentration PbI2:CH2NH2Perovskite solution with I of 1.12:1, stirring at 75 ℃ for 12h, cooling, spin coating FTO/dense TiO at step S22Layer/mesoporous TiO2On the layer, spin coating speed was 5000rpm, then solvent chlorobenzene was dropped on the perovskite layer, and annealing was performed at 110 ℃ for 10min for standby.
S4: adding the spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12h under the condition of keeping out of the sun, then adding 4-tert-butylpyridine and anhydrous acetonitrile, wherein the volume ratio of the 4-tert-butylpyridine to the anhydrous acetonitrile is 2.9:1.9, continuing stirring for 10h under the condition of keeping out of the sun, then adding In-MOF crystal powder, carrying out ultrasonic treatment for 8h, wherein the mass-volume ratio of the spiro-OMeTAD powder, the anhydrous chlorobenzene to the In-MOF is 0.079g:2.2mL:0.0018g, and spin-coating the FTO/dense TiO powder obtained In the step S32Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 90nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
Example 3
A preparation method of a perovskite solar cell specifically comprises the following steps:
the synthesis of In-MOF adopts the following steps: 1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min.
2) Adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating and reacting for 24h to obtain the In-MOF, wherein the mass-to-volume ratio of the 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid, indium nitrate, N-dimethylformamide and the nitric acid solution is 0.01g:0.007g:4mL:2.2 mL.
Preparation of perovskite solar cell:
s1: ultrasonically cleaning FTO conductive glass by acetone, absolute ethyl alcohol and deionized water for 30min respectively in sequence, then placing the FTO conductive glass in a tube furnace, heating the FTO conductive glass at 500 ℃ for 40min, and cooling the FTO conductive glass; adding tetraisopropyl titanate into n-butanol, wherein the volume ratio of tetraisopropyl titanate to n-butanol is 0.12:2.8, stirring for 40min, then spin-coating on FTO conductive glass at the speed of 2850rpm and the acceleration of 1000rpm/s, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use.
S2: adding titanium dioxide slurry into isopropanol, continuously stirring for 70h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1:23, and then spin-coating the titanium dioxide slurry and the isopropanol to obtain FTO/compact TiO in step S12And (3) coating the layer, wherein the spin coating speed is 6000rpm and the acceleration is 600rpm/s, heating at 120 ℃ for 12min, annealing at 500 ℃ for 30min, and cooling for later use.
S3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1, wherein the molar concentration of the lead iodide is 1.50mol/L, stirring at 72 ℃ for 12h, and preparing the mixed solution into molar concentration PbI2:CH2NH2Perovskite solution with I of 1.12:1, stirring at 70 ℃ for 12h, cooling, spin coating FTO/dense TiO at step S22Layer/mesoporous TiO2On the layer, spin coating speed was 5000rpm, then solvent chlorobenzene was dropped on the perovskite layer, and annealing was performed at 110 ℃ for 10min for standby.
S4: adding spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12h under the condition of keeping out of the sun, and then adding 4-tert-butylPyridine and anhydrous acetonitrile, wherein the volume ratio of 4-tert-butylpyridine to anhydrous acetonitrile is 2.6:1.8, stirring is continued for 8h under the condition of keeping out of the sun, then In-MOF crystal powder is added, ultrasound is carried out for 7h, wherein the mass-volume ratio of spiro-OMeTAD powder, anhydrous chlorobenzene and In-MOF is 0.072g:1.5mL:0.0014g, and the FTO/dense TiO In the step S3 is spin-coated2Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 84nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
Example 4
A preparation method of a perovskite solar cell specifically comprises the following steps:
the synthesis of In-MOF adopts the following steps: 1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min.
2) Adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating and reacting for 24h to obtain the In-MOF, wherein the mass-to-volume ratio of the 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid, indium nitrate, N-dimethylformamide and the nitric acid solution is 0.011g:0.0075g:5mL:2.4 mL.
Preparation of perovskite solar cell:
s1: ultrasonically cleaning FTO conductive glass by acetone, absolute ethyl alcohol and deionized water for 35min respectively in sequence, then placing the FTO conductive glass in a tube furnace, heating the FTO conductive glass for 40min at 550 ℃, and cooling the FTO conductive glass; adding tetraisopropyl titanate into n-butanol, wherein the volume ratio of tetraisopropyl titanate to n-butanol is 0.14:3.1, stirring for 45min, then spin-coating on FTO conductive glass at the speed of 2850rpm and the acceleration of 1000rpm/s, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use.
S2: adding titanium dioxide slurry into isopropanol with stirring for 75h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1:24, and spin-coating the titanium dioxide slurry and the isopropanol to obtain FTO/compact TiO in step S12On a layer, wherein the spin-coating speed is 6000rpm and the acceleration is 600rpm/s, thenThen heating at 120 deg.C for 12min, annealing at 500 deg.C for 30min, and cooling.
S3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1, wherein the molar concentration of the lead iodide is 1.51mol/L, stirring at 75 ℃ for 12h, and preparing the mixed solution into molar concentration PbI2:CH2NH2Perovskite solution with I of 1.12:1, stirring at 75 ℃ for 12h, cooling, spin coating FTO/dense TiO at step S22Layer/mesoporous TiO2On the layer, spin coating speed was 5000rpm, then solvent chlorobenzene was dropped on the perovskite layer, and annealing was performed at 110 ℃ for 10min for standby.
S4: adding the spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12h under the condition of keeping out of the sun, then adding 4-tert-butylpyridine and anhydrous acetonitrile, wherein the volume ratio of the 4-tert-butylpyridine to the anhydrous acetonitrile is 2.8:1.9, continuing stirring for 9h under the condition of keeping out of the sun, then adding In-MOF crystal powder, carrying out ultrasonic treatment for 8h, wherein the mass-volume ratio of the spiro-OMeTAD powder, the anhydrous chlorobenzene to the In-MOF is 0.078g:1.8mL:0.0016g, and spin-coating the FTO/dense TiO powder obtained In the step S32Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 88nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
Comparative example 1
The preparation method of this comparative example 1 is the same as that of example 1 except that the hole transport layer is not doped with In-MOF.
Examples of the experiments
And (3) performance testing:
the perovskite solar cell prepared in the embodiment 1-4 is subjected to a current-voltage test under standard sunlight to obtain a short-circuit current (J)ac) Open circuit voltage (V)oc) Fill Factor (FF) and Photoelectric Conversion Efficiency (PCE), the results of which are shown in Table 1,
table 1 short circuit current, open circuit voltage, fill factor and photoelectric conversion efficiency results:
as can be seen from table 1, the perovskite solar cells prepared in examples 1 to 4 all have a photoelectric conversion rate of about 19.9%, and have a better photoelectric conversion efficiency than the perovskite solar cell prepared in comparative example 1; as can be seen from fig. 3, the perovskite solar cell prepared in example 1 has more excellent stability with continuous output of light irradiation at room temperature under a nitrogen atmosphere.
Claims (7)
1. A perovskite solar cell and a preparation method thereof comprise an FTO, an ion transport layer, a perovskite layer, a hole transport layer and a metal electrode layer; the perovskite battery is characterized in that an ion transport layer/a perovskite layer/a hole transport layer/a metal electrode layer are sequentially coated on clean FTO conductive glass in a spin coating mode, and the ion transport layer is a compact titanium dioxide layer/a mesoporous titanium dioxide layer; the perovskite layer is CH3NH3PbI3(MAI); the hole transport layer is a spiro-OMeTAD layer doped with an anionic metal organic framework material.
2. The method of claim 1, comprising the steps of:
s1: ultrasonically cleaning FTO conductive glass by acetone, absolute ethyl alcohol and deionized water for 25-40 min respectively in sequence, then placing the FTO conductive glass in a tube furnace, heating for 40min at 500-550 ℃, and cooling; adding tetraisopropyl titanate into n-butyl alcohol, stirring for 30-50 min, then spin-coating on FTO conductive glass, then heating at 120 ℃ for 15min, then annealing at 500 ℃ for 30min, and cooling for later use;
s2: adding titanium dioxide slurry into isopropanol, continuously stirring for 60-80 h, wherein the mass ratio of the titanium dioxide slurry to the isopropanol is 1: 22-25, and then spin-coating the titanium dioxide slurry and the isopropanol in step S1 to obtain FTO/compact TiO2On a layer, wherein the spin coating speed is 6000rpm and the acceleration is 600rpm/s, then heating at 120 ℃ for 12min, then at 500 ℃Annealing for 30min, and cooling for later use;
s3: adding lead iodide into a mixed solvent of anhydrous N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, stirring at 70-75 ℃ for 12 hours, and preparing molar concentration PbI by using the mixed solution2:CH2NH2Stirring the perovskite solution with the I of 1.12:1 at 70-75 ℃ for 12h, cooling, and spin-coating the FTO/dense TiO solution obtained in the step S22Layer/mesoporous TiO2On the layer, spin coating at a speed of 5000rpm, then dropwise adding solvent chlorobenzene on the perovskite layer, and annealing at 110 ℃ for 10min for later use;
s4: adding the spiro-OMeTAD powder into anhydrous chlorobenzene, stirring for 12 hours In a dark condition, adding 4-tert-butylpyridine and anhydrous acetonitrile, continuing stirring for 6-10 hours In the dark condition, adding In-MOF crystal powder, performing ultrasonic treatment for 6-8 hours, and spin-coating the FTO/dense TiO crystal powder obtained In the step S32Layer/mesoporous TiO2And (3) spin-coating the layer/perovskite layer at the speed of 4000rpm, placing the layer/perovskite layer on a dryer in a dark place, standing for 10 hours, and finally evaporating 80-90 nm of silver metal by using a vacuum evaporator to obtain the perovskite solar cell.
3. The method of claim 2, wherein the volume ratio of tetraisopropyl titanate to n-butanol is (0.11-0.15): (2.6-3.3); the spin coating speed in the step S1 is 2850rpm, and the acceleration is 1000 rpm/S.
4. The method for preparing a perovskite solar cell as claimed in claim 2, wherein the molar concentration of the lead iodide is 1.49-1.52 mol/L.
5. The preparation method of the perovskite solar cell according to claim 2, wherein the mass-to-volume ratio of the spiroo-OMeTAD powder to the anhydrous chlorobenzene to the In-MOF is (0.07-0.079) g, (1-2.2) mL (0.0012-0.0018) g; the volume ratio of the 4-tert-butylpyridine to the anhydrous acetonitrile is (2.5-2.9) to (1.7-1.9).
6. The method for preparing a perovskite solar cell according to claim 2, wherein the In-MOF is synthesized by the following method:
1) adding ligand 4, 4' - (1, 4-phenylene bis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid into N, N-dimethylformamide, ultrasonically dissolving, then adding indium nitrate, and ultrasonically dissolving for 10 min;
2) adding a nitric acid solution In the step 1), then placing the mixture In an oven at 85 ℃, and heating and reacting for 24h to obtain the In-MOF.
7. The method for preparing the perovskite solar cell as claimed in claim 6, wherein the mass-to-volume ratio of the 4, 4' - (1, 4-phenylenebis (pyridine-4, 2, 6-triyl)) -tetraphenyl formic acid, indium nitrate, N-dimethyl formamide and nitric acid solution is (0.009-0.011) g, (0.006-0.008) g, (3-5) mL and (2.1-2.5) mL.
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