CN112864329B - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a perovskite solar cell and a preparation method thereof. The preparation method comprises the following steps: mixing an additive with the perovskite material solution to prepare a precursor mixed solution; the additive is 4,4' -bipyridine; spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite film; coating a mixed solution containing a hole transport material on the perovskite film to form a hole transport layer; and evaporating a metal film on the hole transport layer to serve as a back electrode, so as to obtain the perovskite solar cell. The perovskite solar cell containing the specific additive has excellent photoelectric conversion rate and stability.
Description
Technical Field
The invention relates to a solar cell, in particular to a perovskite solar cell, and belongs to the technical field of solar cells.
Background
Organic-inorganic hybrid perovskite materials have a high light absorption coefficient (10 5 cm -1 ) The characteristics of large electron/hole diffusion length (up to 1 μm), easy band gap adjustment (1-2.5 eV), small exciton binding energy (about 40 meV), low-cost solution processing and the like enable the rapid development of the polycrystalline perovskite solar cell. Currently, the photoelectric conversion efficiency of polycrystalline perovskite solar cells has exceeded 25%, and is widely appreciated by various countries and solar cell fields.
During solution preparation of the polycrystalline perovskite thin film, conventional solution processing and annealing techniques can lead to disorder of part of the structure, volatilization of components and degradation of the photoactive layer, thereby generating uncomplexed lead ions (Pb) 2+ ) And lead clusters (Pb clusters) (chem.soc.rev.2019, 48,3842). The migration of part of halogen ions and the rapid film crystallization mode can generate the problems of vacancy and gap defects, hollows, pinholes and the like. The final perovskite thin film has obvious internal and surface defects, causes more non-radiative recombination centers and energy loss, and seriously affects the device efficiency (Science 2017,355,722; science,2019,364,833; adv. Mater.2015, 27, 1837). Thus, the high quality perovskite thin film directly determines the performance of the polycrystalline perovskite cell.
Additive engineering is an effective method for preparing high quality perovskite thin films (adv. Energy Mater.2019, 1902579). Han et al added urea to the perovskite solution to adjust the crystal growth and morphology, and prepared a large-sized perovskite thin film (Solar RRL 2018,2,1800054) with higher quality. Jen et al added additive DIO to the precursor solution to give a perovskite thin film with high crystallinity and uniform surface (adv. Mater.,2014,26,3748). Recently, new molecular additives such as NH have been developed through molecular design 2 -R-NH 2 And the coexistence structure of N-H and c=o can effectively realize defect passivation of the perovskite thin film (sci.adv.2019, 5,eaav8925;Science 2019,366,1509).
However, most of the molecular additives currently contain long alkyl chains, and their insulation properties are disadvantageous for the maintenance and improvement of the carrier mobility of the perovskite thin film. Therefore, finding out a functionalized molecular additive from the aspect of finding out a unique molecular structure can effectively passivate the defects of the perovskite thin film and enhance the carrier mobility thereof, so that the improvement of the photoelectric performance of the device is promoted, and the method still has great challenges.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a perovskite solar cell with higher photoelectric conversion efficiency and device stability and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for manufacturing a perovskite solar cell, comprising the steps of:
mixing an additive with the perovskite material solution to prepare a precursor mixed solution; wherein the additive is 4,4' -bipyridine;
spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite film;
coating a mixed solution containing a hole transport material on the perovskite film to form a hole transport layer;
and evaporating a metal film on the hole transport layer to serve as a back electrode, so as to obtain the perovskite solar cell.
In the perovskite solar cell of the present invention, 4 '-bipyridine is used as an additive, and the chemical structure of 4,4' -bipyridine (BPY [4,4 ]) is as follows:
the two pyridine rings are connected through a para-position structure to form a symmetrical structure, the left end and the right end are N atoms, and the two pyridine rings are conjugated structures.
In the perovskite solar cell, 4' -bipyridine is used as an additive, two pyridine rings are symmetrically and conjugated through the unique chemical molecular structure of the additive, and the pyridine N atoms at the left end and the right end can be well matched with uncoordinated Pb in a perovskite film 2+ Is effective in achieving defect dulling by coordinationThe conjugation performance of the 4,4' -bipyridine is connected with the grain boundary of perovskite, and plays a role in enhancing carrier mobility. 4,4' -bipyridine is also beneficial to the morphology control of perovskite film growth and is beneficial to preparing larger grain size; simultaneously pyridine N and Pb 2+ The coordination passivation effect between the perovskite thin film and the metal oxide thin film enables the prepared perovskite thin film to have good fluorescence property; the hydrophobicity of the 4,4' -bipyridine can effectively prevent the damage of water and oxygen to the perovskite film, so that a more stable perovskite film is obtained; finally, the photoelectric efficiency and the device stability of the perovskite solar cell containing the additive are improved.
In one embodiment of the invention, the molar ratio of the additive to Pb atoms in the perovskite material solution is 0.05-5:100.
in one embodiment of the present invention, the solute of the perovskite material solution employed comprises MAPbI 3 、MAPb(I,Br) 3 Or (FAMA) Pb (I, br) 3 . The method comprises the following steps: MAPbI 3 ：methyl ammonium lead iodide，CH 3 NH 3 PbI 3 ；MAPb(I,Br) 3 )：methyl ammonium lead iodide/bromide；(FAMA)Pb(I,Br) 3 : formamidinium/methyl ammonium lead iodide/bromide. The volume ratio of the solvent of the perovskite material solution is 4:1 and DMSO.
In one embodiment of the invention, the temperature of the annealing is between 100 ℃ and 150 ℃ and the time of the annealing is between 10 minutes and 15 minutes.
In one embodiment of the present invention, the mixed solution containing the hole transporting material is a Spiro-ome solution. Wherein the Spiro-OMeTAD solution is obtained by co-dissolving lithium bistrifluoromethane sulfonyl imide in chlorobenzene, spiro-OMeTAD (commercially available) and 4-tert-butylpyridine.
In a further embodiment of the invention, the Spiro-OMeTAD solution is prepared by the steps of:
dissolving 500mg-530mg of lithium bistrifluoromethane sulfonyl imide in 1mL-2mL of acetonitrile solution to form an acetonitrile solution of Li-TFSI;
15. Mu.L-25. Mu.L of Li-TFSI acetonitrile solution, 80mg-90mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are taken and dissolved in 1mL-2mL of chlorobenzene to obtain a mixed solution containing a hole transport material.
The method specifically comprises the following steps: 520mg of lithium bistrifluoromethanesulfonimide (LiTFSI) was dissolved in 1mL of acetonitrile to form an acetonitrile solution of Li-TFSI, and then 20. Mu.L of the acetonitrile solution of Li-TFSI, 85mg of Spiro-OMeTAD (2, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene) and 28. Mu.L of 4-tert-butylpyridine were taken together in 1mL of chlorobenzene to obtain a mixed solution containing a hole transporting material.
In one embodiment of the present invention, the metal film is an Au metal film; wherein the thickness of the metal film is 80-120nm.
In one embodiment of the present invention, the electron transport layer is TiO 2 An electron transport layer.
The invention also provides a perovskite solar cell, which is prepared by the preparation method of the perovskite solar cell.
The perovskite solar cell containing the specific additive has relatively excellent photoelectric conversion efficiency and stability.
Drawings
Fig. 1 is a chemical structural formula of an additive for perovskite solar cell according to the present invention and an additive in comparative example.
FIG. 2 is an ultraviolet absorbance spectrum of perovskite thin films of the invention based on different concentrations of 4,4' -bipyridine additive (comparative example 4 and examples 2-6): the concentration range is 0-5mol%.
FIG. 3 is a graph showing fluorescence spectra of perovskite thin films of comparative example 4 and examples 2 to 6 (substrate glass, excitation wavelength 690 nm) according to the present invention.
FIG. 4 shows the FTO/TiO structure of the pure electronic device prepared by the invention 2 Perovskite thin film/PCBM/Ag (a and c) and pure hole device FTO/PEDOT: PSS/perovskite thin film/P3 HT/Ag (b and d) tested defect state density and carrier mobility: (a, c) is the perovskite thin film produced in comparative example 4; (b, d) is the perovskite thin film produced in example 3.
FIG. 5 is a scanning electron microscope top view of a perovskite thin film prepared according to the invention: (a) is prepared in comparative example 4; (b) containing the product obtained in example 2; (c) grain size statistics; (d) X-ray diffraction pattern.
Fig. 6 is a graph of contact angle measurements of perovskite thin films prepared according to the invention: (a) Is prepared in comparative example 4, (b) is prepared in example 5.
Fig. 7 is a current-voltage plot of a perovskite cell prepared according to the invention: the reference was made in comparative example 4, the others were the cells of example 3 and comparative examples 5 to 7, each containing 0.5mol% of several other additives.
Fig. 8 is a graph of stability of perovskite batteries prepared according to the invention: (a) comparative example 4, (b) example 5.
Detailed Description
Example 1
The example provides a compound 4,4' -bipyridine (BPY [4,4 ]) for perovskite solar cell additive, the structural formula is shown in figure 1, and the structural formula is:
example 2
The example provides a preparation process of a polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 DEG C 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive 4,4' -bipyridine and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 0.1:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the mixture on a perovskite film, spin-coating the perovskite film for 30-50s at the speed of 2000-5000rpm, and then placing the perovskite film in the air for 12 hours. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Example 3
The example provides a preparation process of a polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive 4,4' -bipyridine and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 0.5:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the perovskite light absorption layer film on the layer at the speed of 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating for 10-15 minutes at the temperature of 100-150 ℃ to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Example 4
The example provides a preparation process of a polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive 4,4' -bipyridine and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 1:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Example 5
The example provides a preparation process of a polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive 4,4' -bipyridine and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 3:100 A) is provided; drop the precursor solution on TiO 2 The layer was spin-coated at 4000 rpm for 60 seconds and 130 μl of chlorobenzene solution was added dropwise as spin-coating proceeded for 40 secondsHeating at 100-150deg.C for 10-15min to obtain perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Example 6
The example provides a preparation process of a polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive 4,4' -bipyridine and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 5:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Comparative example 1
The example provides a compound 2,2' -bipyridine (BPY [2,2 ]) for perovskite solar cell additive, which has the structural formula:
comparative example 2
The present example provides a compound tert-butylpyridine (TBP) for perovskite solar cell additives having the structural formula:
comparative example 3
The example provides a comparative compound 4-Cyanopyridine (CNP) for perovskite solar cell additives having the structural formula:
comparative example 4
The example provides a preparation process of a comparative polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Perovskite material (MAPbI) 3 ) The precursor solution (solvent DMF/DMSO is added in a volume ratio of 4:1) is dripped on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Comparative example 5
The example provides a preparation process of a comparative polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 DEG C 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; the molar ratio of the additive 2,2' -bipyridine to Pb is 0.5:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Comparative example 6
The example provides a preparation process of a comparative polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Water-solubleMaintaining the solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; the molar ratio of the additive tert-butylpyridine to Pb is 0.5:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Comparative example 7
The example provides a preparation process of a comparative polycrystalline perovskite film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by ultrasonic waves, and then treating the FTO conductive glass by ozone for 15 minutes; immersing it in 40mM TiCl at 70 ℃ 4 Maintaining the mixture in the aqueous solution for 30min to form a layer of compact TiO on the surface of the FTO conductive glass 2 And (3) taking out the film, washing the FTO conductive glass with ethanol, and naturally airing. Taking additive and perovskite material (MAPbI) 3 ) The solution is mixed to prepare a precursor mixed solution (solvent DMF/DMSO is in a volume ratio of 4:1; additive 4-cyanopyridine to Pb molar ratio 0.5:100 A) is provided; drop the precursor solution on TiO 2 Spin-coating the layer at 4000 rpm for 60 seconds, dropwise adding 130 mu L of chlorobenzene solution when spin-coating is carried out for 40 seconds, and heating at 100-150 ℃ for 10-15 minutes to obtain the perovskite light absorption layer film.
520mg of lithium bistrifluoromethane sulfonyl imide (LiTFSI) was then dissolved in 1mL of acetonitrile solution; then, 20. Mu.L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the Spiro-OMeTAD of the hole transport layer; dripping the solution onto perovskite film, spin-coating at 2000-5000rpm for 30-50s, and standing in air for 12 hr. Finally, evaporating a layer of Au metal film with the thickness of 80-120nm on the hole transport layer to serve as a back electrode, and obtaining the perovskite solar cell.
Comparative experiment example 1
This example provides a method for the preparation of perovskite solar cells, reference (J. Mater. Chem. A,2019,7,4977), which uses 2,2' -bipyridine as additive (1.0 wt%) introduced into perovskite material FA 0.88 Cs 0.12 PbI 3 And (5) preparing a perovskite light absorption layer film. At 25℃the sunlight was simulated using a xenon lamp with an intensity of 100mW/cm 2 Under the condition, the cell (effective area 0.0725cm 2 ) The photoelectric parameters are shown in the appendix (Table 1).
Comparative experiment example 2
This example provides a method for the preparation of perovskite solar cells, reference (J. Mater. Chem. A,2015,3,22191), which uses only the perovskite material MAPbI 3 And (5) preparing a perovskite light absorption layer film. At 25℃the sunlight was simulated using a xenon lamp with an intensity of 100mW/cm 2 Under the condition, the cell (effective area 0.0725cm 2 ) The photoelectric parameters are shown in the appendix (Table 1).
Parameters of the solar cell performance (at 25 ℃, the xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm) can be obtained through photoelectric performance test 2 Testing under the conditions (effective area 0.0725cm 2 ) See table 1).
Table 1 perovskite solar cell test tables prepared in examples 2 to 6 and comparative examples 4 to 7
FIG. 2 is an ultraviolet absorbance spectrum of perovskite thin films based on different concentrations of 4,4' -bipyridine additive (comparative example 4 and examples 2-6): the concentration range is 0-5mol%. As can be seen from fig. 2, the increase of absorbance of the 4,4' -bipyridine-based perovskite thin film is beneficial to the improvement of short-circuit current of the corresponding device.
Perovskite solar cell additive based on 4,4' -bipyridine in the above example (example 3) was selected to fabricate perovskite thin films and perovskite solar cells and compared to comparative example 4. The results show that the increase in fluorescence intensity after the addition of 4,4' -bipyridine also means a reduction in internal defects of the perovskite thin film (see fig. 3); the 4,4' -bipyridine additive can reduce the defect state density and enhance the improvement of electron and hole mobility of the perovskite thin film (see fig. 4); the 4,4' -bipyridine additive can promote the growth of the perovskite thin film, thereby obtaining larger-sized grains with higher quality (see figure 5); the contact angle test is compared, and the contact angle of the perovskite film after 4,4' -bipyridine addition is larger (see figure 6), so that the perovskite film can be better prevented from being damaged by water oxygen (the bipyridine ring has better hydrophobicity) entering the crystal boundary. For the above reasons, the 4,4' -bipyridine additive can enhance the photoelectric conversion efficiency (see fig. 7) and stability (see fig. 8) of the perovskite solar cell device. Perovskite thin films and batteries using the additives 2,2' -bipyridine (comparative example 5) and t-butylpyridine (comparative example 6) of the other examples also had better battery efficiencies than comparative example 4 (see table 1).
The perovskite solar cell after the addition of 4,4' -bipyridine also had higher photoelectric conversion efficiency compared with comparative examples 1 and 2, see table 1 (the test results of other part of examples are also better than those in comparative examples 1 and 2). It can be seen that the perovskite solar cell based on the additive of this example has better cell performance than perovskite solar cells based on other kinds of additives; this is because the unique chemical molecular structure of 4,4' -bipyridine enables two pyridine rings to be symmetrical and conjugated, and the pyridine N atoms at the left and right ends can be well matched with uncoordinated Pb in the perovskite film 2+ The coordination of the perovskite material realizes effective defect passivation, and the conjugation performance of the 4,4' -bipyridine is connected with the grain boundary of perovskite, so as to play a role in enhancing carrier mobility. 4,4' -bipyridine is also beneficial to morphology control of perovskite film growthThe preparation of larger grain size is facilitated; simultaneously pyridine N and Pb 2+ The coordination passivation effect between the perovskite thin film and the metal oxide thin film enables the prepared perovskite thin film to have good fluorescence property; and finally, the photoelectric efficiency of the perovskite solar cell using the additive is improved.
Table 2 table of perovskite solar cell test prepared with additives and different perovskite materials in example 3
The perovskite solar cell additive based on 4,4' -bipyridine in example 3 was also mixed with different perovskite materials in a ratio (0.5:100), and a perovskite solar cell was prepared as described above. Parameters of the solar cell performance (at 25 ℃, the xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm) can be obtained through photoelectric performance test 2 Testing under the conditions (effective area 0.0725cm 2 ) See table 2).
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (9)
1. A method of manufacturing a perovskite solar cell, the method comprising the steps of:
mixing an additive with the perovskite material solution to prepare a precursor mixed solution; wherein the additive is 4,4' -bipyridine; the molar ratio of the additive to Pb atoms in the perovskite material solution is 0.05-5:100; the solute of the perovskite material solution comprises MAPbI 3 、MAPb(I,Br) 3 Or (FAMA) Pb (I, br) 3 ；
Spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite film;
coating a mixed solution containing a hole transport material on the perovskite film to form a hole transport layer;
and evaporating a metal film on the hole transport layer to serve as a back electrode, so as to obtain the perovskite solar cell.
2. The preparation method according to claim 1, wherein the perovskite material solution has a solvent volume ratio of 4:1 and DMSO.
3. The method according to claim 1, wherein the annealing is performed at a temperature of 100 ℃ to 150 ℃ for a time of 10 minutes to 15 minutes.
4. The preparation method according to claim 1, wherein the mixed solution containing a hole transporting material is a Spiro-ome solution.
5. The process according to claim 4, wherein the solution of Spiro-OMeTAD is obtained by co-dissolving lithium bistrifluoromethane sulfonyl imide in chlorobenzene in acetonitrile, spiro-OMeTAD and 4-tert-butylpyridine.
6. The preparation method of claim 5, wherein the Spiro-ome tad solution is prepared by:
dissolving 500mg-530mg of lithium bistrifluoromethane sulfonyl imide in 1mL-2mL of acetonitrile solution to form an acetonitrile solution of Li-TFSI;
15. Mu.L-25. Mu.L of Li-TFSI acetonitrile solution, 80mg-90mg of Spiro-OMeTAD and 28. Mu.L of 4-tert-butylpyridine were taken and dissolved in 1mL-2mL of chlorobenzene to obtain a mixed solution containing a hole transporting material.
7. The production method according to claim 1, wherein the metal thin film is an Au metal thin film; the thickness of the metal film is 80nm-120nm.
8. The method of claim 1, wherein the electron transport layer is TiO 2 An electron transport layer.
9. A perovskite solar cell prepared by the method of preparing a perovskite solar cell according to any one of claims 1 to 8.
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