CN114855283B - Pb-based coordination polymer crystal and preparation method and application thereof - Google Patents

Pb-based coordination polymer crystal and preparation method and application thereof Download PDF

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CN114855283B
CN114855283B CN202110076579.XA CN202110076579A CN114855283B CN 114855283 B CN114855283 B CN 114855283B CN 202110076579 A CN202110076579 A CN 202110076579A CN 114855283 B CN114855283 B CN 114855283B
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王观娥
徐刚
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Fujian Institute of Research on the Structure of Matter of CAS
Mindu Innovation Laboratory
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Abstract

The invention provides a Pb-based coordination polymer crystal, and a preparation method and application thereof, wherein ligands adopted in the crystal comprise terephthalyl mercaptan, p-hydroxy phenyl mercaptan, p-amino phenyl mercaptan, p-fluoro phenyl mercaptan, p-methoxy phenyl mercaptan and p-carboxyl phenyl mercaptan. After Pb-based coordination polymer crystals are prepared into nano sheets and spin-coated on a perovskite solar cell, the nano sheets play a role in surface passivation on the surface of the perovskite, so that the photoelectric conversion efficiency and stability of the cell are obviously improved.

Description

Pb-based coordination polymer crystal and preparation method and application thereof
Technical Field
The invention belongs to the technical field of crystal materials, and particularly relates to a Pb-based coordination polymer crystal, and a preparation method and application thereof.
Background
Perovskite solar cells are the hottest materials currently studied, the highest photoelectric conversion efficiency of which has exceeded 25%, but such cells have been subject to stability problems due to the nature of the materials themselves. Therefore, how to improve the photoelectric efficiency and stability of such cells is a difficulty and hot spot of current research.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a Pb-based coordination polymer crystal, in which the ligand used includes terephthalyl mercaptan, p-hydroxy phenyl mercaptan, p-amino phenyl mercaptan, p-fluoro phenyl mercaptan, p-methoxy phenyl mercaptan, and p-carboxyl phenyl mercaptan.
According to an embodiment of the invention, when the ligand is terephthal-diol, the crystal is denoted as PbBDT, which is a three-dimensional structure, the crystal is a C2/C space group, and the unit cell parameters are:
Figure BDA0002907730060000011
Figure BDA0002907730060000012
α＝90°,β＝93.042°,γ＝90°,/>
Figure BDA0002907730060000013
according to an embodiment of the invention, the ligand is p-hydroxy benzenethiol, p-amino benzenethiol, p-fluoro benzenethiol, p-methoxy benzenethiol, p-carboxy benzenethiol, which is a two-dimensional structure, and the crystal is a C2 space group.
According to an embodiment of the present invention, when the ligand is p-hydroxy phenyl mercaptan, the unit cell parameters are:
Figure BDA0002907730060000014
Figure BDA0002907730060000015
α＝90°,β＝95.47(4)°,γ＝90°,/>
Figure BDA0002907730060000016
Figure BDA0002907730060000017
according to an embodiment of the present invention, when the ligand is terephthal-thiol, the crystal has a crystal structure diagram substantially as shown in fig. 1.
According to an embodiment of the present invention, the ligand is p-hydroxy benzene thiol, p-amino benzene thiol, p-fluoro benzene thiol, p-methoxy benzene thiol, and p-carboxyl benzene thiol, and the crystal has a two-dimensional structure, and has a structure as shown in fig. 2.
The invention also provides a preparation method of the Pb-based coordination polymer crystal, which comprises the following steps: dissolving Pb-containing compound and ligand in organic solvent, heating to obtain crystal.
According to an embodiment of the invention, the mass ratio of Pb-containing compound to ligand is 1-50:1, preferably 2.1:1.
According to an embodiment of the invention, the mass to volume ratio of the ligand to the organic solvent is 1-20 (mg): 1 (mL), preferably 3 (mg): 1 (mL).
According to an embodiment of the present invention, the Pb-containing compound is selected from PbCl 2 、PbBr 2 、PbI 2 At least one of, preferably PbCl 2 。
According to an embodiment of the present invention, the ligand is selected from at least one of terephthal-dithiol, p-hydroxy-benzenethiol, p-amino-benzenethiol, p-fluoro-benzenethiol, p-methoxy-benzenethiol, p-carboxy-benzenethiol, preferably terephthal-dithiol.
According to an embodiment of the present invention, the organic solvent is one of N, N' Dimethylformamide (DMF), acetonitrile, water and ethanol.
According to an embodiment of the invention, the heating temperature is 50-140 ℃, the heating time is at least 1h, preferably 24h at 90 ℃.
The invention also provides application of the Pb-based coordination polymer to preparation of Pb-based coordination polymer nano sheets.
According to an embodiment of the present invention, the thickness of the Pb-based coordination polymer nanosheets is 5 to 100nm.
The invention also provides a preparation method of the Pb-based coordination polymer nanosheets, which comprises the following steps: and dissolving Pb-containing compound in a first solvent, dissolving ligand in a second solvent, and uniformly mixing the two solutions to prepare the Pb-based coordination polymer nano-sheet.
According to an embodiment of the present invention, the mass to volume ratio of the Pb-containing compound to the first solvent is 1 to 50 (mg): 1 (mL); preferably 4-30 (mg): 1 (mL); more preferably 7.6 (mg): 1 (mL).
According to an embodiment of the invention, the ligand to second solvent mass to volume ratio is 0.5-40 (mg): 1 (mL); preferably 1-10 (mg): 1 (mL); more preferably 1.2 (mg): 1 (mL).
According to an embodiment of the invention, the first solvent is at least one of water and DMF.
According to an embodiment of the invention, the second solvent is at least one of isopropanol, DMF, acetonitrile, propanol.
According to the embodiment of the invention, the two solutions are uniformly mixed under the ultrasonic condition, and the ultrasonic time is 1-5 hours, preferably 2 hours; the ultrasound temperature is 20-40 ℃, preferably 25 ℃.
The invention also provides application of the Pb-based coordination polymer nano-sheet, and the Pb-based coordination polymer nano-sheet is deposited on a perovskite film in a spin coating, blade coating or spray coating mode to complete assembly of a perovskite solar cell device; preferably, the Pb-based coordination polymer nano-sheet is deposited on the perovskite film in a spin coating mode, so that the assembly of the perovskite solar cell device is completed.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(1) Preparing an electron transport layer on a conductive film substrate;
(2) Preparing a perovskite film on the surface of the electron transport layer;
(3) Uniformly coating Pb-based three-dimensional coordination polymer nanosheet suspension on the surface of the perovskite substrate layer in the step (2), and annealing to prepare a perovskite solar cell precursor;
(4) And (3) preparing a hole transport layer on the surface of the perovskite solar cell precursor in the step (3), and forming an electrode on the surface of the hole transport layer to prepare the perovskite solar cell.
According to an embodiment of the invention, the conductive film substrate comprises an FTO conductive glass substrate.
According to an embodiment of the invention, the electron transport layer is selected from the group consisting of TiO 2 、SnO 2 、ZnO-MgO-EA + ZnO, mgO and NiO 2 At least one of them is preferably ZnO-MgO-EA + And TiO 2 . Wherein EA is ethanolamine.
According to an embodiment of the present invention, in step (1), the conductive film substrate is subjected to a pretreatment process before use, where the pretreatment process is: etching the conductive film substrate into an electrode pattern, respectively carrying out ultrasonic treatment on the electrode pattern by acetone, deionized water and ethanol, and carrying out primary annealing to remove surface oxides and impurities of the conductive film substrate.
According to an embodiment of the present invention, the first annealing temperature of the conductive thin film substrate is 400 to 600 ℃, preferably 500 ℃; the annealing time is 20-40min, preferably 30min.
According to the embodiment of the present invention, the volumes of acetone, deionized water and ethanol are not particularly limited, and the conductive film substrate can be immersed, wherein the conductive film substrate can be washed with acetone, deionized water and ethanol, respectively, a plurality of times.
According to an embodiment of the invention, in step (1), the ultrasound time is between 10 and 20 minutes, preferably 10 minutes.
According to an embodiment of the present invention, the electron transport layer is TiO 2 The specific preparation step of the step (1) is that ZnO-MgO-EA + Spin-coating the solution on an FTO conductive glass substrate, heating for the second time for annealing, and heating for the third time for annealing to obtain compact ZnO-MgO-EA + The layer was cooled to room temperature and TiCl was then introduced into the solution 4 Heating the solution, taking out and drying, and then adding TiO 2 Spin-coating the isopropanol solution of the slurry on the surface of the substrate, heating for the fourth annealing, and depositing mesoporous TiO on the FTO conductive glass substrate 2 A layer.
According to an embodiment of the invention, znO-MgO-EA + The solution was prepared by mixing 169mg ofZinc acetate and 49.3mg of magnesium acetate were dissolved in 2.5mL of dimethoxy ethanol and 60uL of ethanol amine to prepare the composition.
According to an embodiment of the present invention, the ZnO-MgO-EA + The thickness of the layer is 30-50nm.
According to an embodiment of the invention, znO-MgO-EA + The spin-coating speed of the solution is 2500-3000rpm, and the spin-coating time is 20-25s. Preferably 2800rpm,25s.
According to an embodiment of the invention, the temperature of the second annealing is between 90 and 110 ℃, preferably 100 ℃; the second annealing time is 3-5min, preferably 3min; the temperature of the third annealing is 480-510 ℃, preferably 500 ℃; the time for the third annealing is 40-50min, preferably 40min.
According to an embodiment of the invention, tiCl 4 The concentration of the solution is 25-45mmol/L, preferably 40mmol/L.
According to an embodiment of the invention, in TiCl 4 The temperature of heating in the solution is 60-90deg.C, heating time is 12-18min, preferably 70deg.C for 15min.
According to an embodiment of the invention, tiO 2 The mass ratio of the slurry to the isopropanol solution is 1:3-10, preferably 1:8.
according to an embodiment of the invention, tiO 2 The spin-coating speed of the isopropanol solution of the slurry is 4000-5000rpm, and the spin-coating time is 20-25s. Preferably 5000rpm,25s.
According to an embodiment of the invention, the temperature of the fourth annealing is 480-500 ℃, preferably 500 ℃; the time for the fourth annealing is 35-40min, preferably 40min.
According to an embodiment of the present invention, the specific steps of step (2) are: uniformly coating a perovskite precursor solution on a conductive film substrate with an electron transport layer as an outer layer, quickly dripping at least one solution of toluene, chlorobenzene or diethyl ether on the substrate to obtain an intermediate film, and annealing the intermediate film for the fifth time to prepare the perovskite film.
According to an embodiment of the invention, the perovskite precursor solution is PbI 2 ，PbBr 2 CsI, iodoformamidine (FAI) andbromomethylamine (MABr) was dissolved in a mixed solution of DMF and DMSO.
According to an embodiment of the invention, pbI 2 ，PbBr 2 The molar ratio of CsI, iodoformamidine and bromomethylamine is 6-24:2-14:1-3:1-9:1, e.g., 21.6:3.3:1.4:7.7:1; for example 8.4:8:1.6:1.6:1.
The volume ratio of DMF to DMSO is 6-10:1, preferably 8.6:1;
the mass volume ratio of bromomethylamine to DMSO is 1:3-5, preferably 1:4.
According to an embodiment of the invention, the perovskite precursor solution is applied by spin coating.
According to an embodiment of the invention, the spin-coating speed of the perovskite precursor solution is 5500-6200rpm and the spin-coating time is 30-35s, preferably 6000rpm,35s.
According to an embodiment of the invention, the toluene or chlorobenzene or diethyl ether is added dropwise for a period of 12 to 16s, preferably 15s. The amount of toluene or chlorobenzene or diethyl ether added is 300 to 500. Mu.L, preferably 400. Mu.L.
According to an embodiment of the invention, the temperature of the fifth annealing is 100-160 ℃, preferably 150 ℃; the fifth annealing time is 12-16min, preferably 15min.
According to an embodiment of the present invention, in step (3), the Pb-based coordination polymer nanosheet suspension is prepared by dispersing Pb-based coordination polymer nanosheets in chlorobenzene; the concentration of the chlorobenzene suspension of PbBDT is 2-15mg/mL, and may be, for example, 2mg/mL, 2.5mg/mL, 5mg/mL, 10mg/mL, 15mg/mL.
According to the embodiment of the invention, the chlorobenzene suspension of PbBDT adopts a spin coating mode.
According to the embodiment of the invention, the spin coating speed of the chlorobenzene suspension of PbBDT is 2500-3000rpm, and the time is 20-30s; preferably 2800rpm,25s.
According to an embodiment of the invention, the annealing temperature in step (3) is 100-130 ℃ for 8-12min; preferably 120℃for 10min.
According to an embodiment of the present invention, the specific preparation steps in step (4) are: and uniformly coating the hole transport material solution on the outer layer of the perovskite solar cell precursor, drying, and depositing an electrode by adopting a vacuum evaporation mode to prepare the cell.
According to an embodiment of the present invention, the hole transport material is spin coated at a spin speed of 3800-4200rpm, preferably 4000rpm.
According to an embodiment of the invention, the hole transporting material is a solution of Spiro-OMeTAD in chlorobenzene at a concentration of 70-76mg/1mL, preferably 72mg/1mL.
According to an embodiment of the present invention, the hole transport material further includes an additive, wherein the additive is acetonitrile solution containing lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI) and 4-tert-butylpyridine (TBP), and the volume ratio of the acetonitrile solution containing Li-TFSI to the 4-tert-butylpyridine is 1:1-3; preferably 1:1.6.
According to an embodiment of the invention, the concentration of the acetonitrile solution of Li-TFSI is 480-520, preferably 520mg/mL.
According to an embodiment of the invention, the drying is carried out at room temperature for a drying time of 4 to 6 hours, preferably 5 hours.
According to an embodiment of the present invention, the electrode may be an Au or Ag electrode.
According to an embodiment of the invention, the thickness of the electrode is 60-120nm, preferably 80nm.
The invention also provides a perovskite solar cell prepared by adopting the preparation method.
Advantageous effects
(1) The invention combines Pb ion and coordination compound to obtain a novel Pb-based coordination polymer crystal.
(2) After the Pb-based coordination polymer crystal is prepared into the nano-sheet and spin-coated on the perovskite solar cell, the nano-sheet plays a role in surface passivation on the surface of the perovskite, so that the photoelectric conversion efficiency and stability of the cell are obviously improved.
Drawings
Fig. 1 is a diagram showing the structure of PbBDT crystals in example 1;
FIG. 2 is a schematic diagram of a crystal in two dimensions;
fig. 3 is an SEM image of PbBDT nanoplatelets in example 2;
FIG. 4 shows the short-circuit current (J) of the solar cell device of example 3 at different concentrations sc ) A figure;
FIG. 5 shows the short-circuit current (J) of the solar cell device of example 4 at different concentrations sc ) A drawing.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Single crystal synthesis and single crystal structure of Pb-based three-dimensional coordination polymer (PbBDT, BDT refers to terephthalyl alcohol)
PbCl 2 0.038g of BDT ligand 0.018g and 6ml of N, N' -Dimethylformamide (DMF) in a 10ml glass bottle, the bottle cap was screwed on, and the bottle cap was kept at a constant temperature of 90℃for 1 day and naturally cooled to obtain red and black flaky crystals.
The crystal is crystallized in the C2/C space group, and the unit cell parameter is that
Figure BDA0002907730060000081
Figure BDA0002907730060000082
α＝90°,β＝93.042°,γ＝90°,/>
Figure BDA0002907730060000083
Fig. 1 is a diagram showing the structure of PbBDT crystals in example 1.
Example 2
Preparation method of Pb-based three-dimensional coordination polymer (PbBDT) nanosheets
0.038g of lead chloride was dissolved in 5ml of water, 0.036g of terephthal-thiol was dissolved in 30ml of isopropanol, and the solution of terephthal-thiol was mixed with the lead chloride solution under ultrasonic conditions. And continuing ultrasonic treatment for 2 hours to obtain a thin sheet with the thickness of about ten nanometers, namely the PbBDT nano sheet.
Fig. 3 is an SEM image of PbBDT nanoplatelets in example 2.
Example 3
Battery preparation process
(1) Substrate treatment and electron transport layer preparation: after the FTO conductive glass substrate is etched into an electrode pattern by a laser etching machine, respectively carrying out ultrasonic treatment by using acetone, deionized water and ethanol for 10min, airing the FTO conductive glass substrate, and then annealing at 500 ℃ for 30min to remove surface oxides and impurities. After cooling to room temperature, 40uL of ZnO-MgO-EA was deposited using a spin coater 2800rpm for 25 seconds + The solution is spin-coated on the surface of the FTO conductive glass substrate, and is annealed at 100 ℃ for 3min and then at 500 ℃ for 40min to obtain a compact ZnO-MgO-EA+ layer. Cooling to room temperature, placing the FTO conductive glass substrate into TiCl with the concentration of 40mmol/L 4 In solution (TiCl) 4 The solution can be added by immersing glass), heating at 70deg.C for 15min, taking out, drying, and coating with spin coater at 5000rpm for 25 seconds 2 Spin-coating isopropanol solution (mass ratio of 1:8) of slurry (Dyesol DSL 18 NR-T) on the surface of the substrate, and then annealing at 500 ℃ for 40min to deposit mesoporous TiO on the pretreated FTO conductive glass substrate 2 A layer.
(2) Perovskite thin film preparation: spin-coating perovskite precursor solution at 600 rpm for 35s on TiO with mesoporous pores 2 And 400uL of toluene is required to be quickly dripped onto the rotating substrate at 15s to obtain an intermediate film, and the intermediate film is annealed on a heating plate at 150 ℃ for 15min to obtain a black compact perovskite film.
Wherein the perovskite precursor solution is PbI 2 484.05mg、PbBr 2 73.4mg, csI 32.475mg, iodoformamidine (FAI) 171.97mg and bromomethylamine (MABr) 22.4mg were dissolved in DMF750 uL and DMSO 87.5 uL.
(3) Post-treatment process: the PbBDT nanosheets are fully dispersed in chlorobenzene by ultrasound to prepare chlorobenzene suspensions with the concentration of 2.5mg/ml, 5mg/ml and 10mg/ml of Pb-BDT respectively. Uniformly distributing the uniformly dispersed Pb-BDT chlorobenzene suspension on the surface of the perovskite film in the step (2), wherein the rotating speed is 2800rpm, and the time is 25s; and then annealing at 120 ℃ for 10min to prepare the perovskite solar cell precursor.
(4) Preparing a hole transport layer and an electrode: after the perovskite thin film is cooled to room temperature, the hole transport material solution is spin-coated on the perovskite solar cell precursor outer layer at 4000rpm for 25s. And (3) activating for 5 hours in a drying box at room temperature, and depositing an Au electrode battery with the thickness of 80nm on the hole transport layer by adopting a vacuum evaporation method.
Preparation of hole-transporting Material solution A solution of Spiro-OMeTAD in chlorobenzene (72 mg/1 mL) was used, with additives of 17.5L of Li-TFSI in acetonitrile (520 mg/mL) and 28.8L of 4-tert-butylpyridine (TBP).
The prepared cells were subjected to open circuit voltage (Voc) and short circuit current (J) sc ) The test of the Filling Factor (FF) and the Photoelectric Conversion Efficiency (PCE) adopts the model KEITHLEY2400 of the instrument, and the solar simulator is LSH-7300ABA LED Solar Simulator.
The various performance parameters prepared are shown in table 1 below. Wherein, the sample 2 is a chlorobenzene suspension of Pb-BDT with the concentration of 2.5 mg/ml; sample 3 was a suspension of Pb-BDT in chlorobenzene at a concentration of 5 mg/ml; sample 4 was a suspension of Pb-BDT in chlorobenzene at a concentration of 10 mg/ml.
Comparative sample 1 differs from sample 2 in that the perovskite solar cell device was not treated with PbBDT.
Where Voc represents the open circuit voltage, a larger value indicates a smaller device energy loss.
FF is a fill factor, with larger values indicating better perovskite crystal quality and fewer device defects.
TABLE 1
Sample of Voc(V) J sc (mA cm -2 ) FF(％) PCE(％)
Comparative sample 1 1.12 23.56 76.40 20.21
Sample 2 1.15 23.53 78.38 21.14
Sample 3 1.15 23.35 76.70 20.62
Sample 4 1.15 23.22 76.11 20.28
FIG. 4 shows the short-circuit current (J) of the solar cell device of example 3 at different concentrations sc ) A drawing.
Example 4
Example 4 differs from example 3 in that:
the hole transporting material solution was prepared using a solution of Spiro-OMeTAD in chlorobenzene (72 mg/1 mL).
The remaining steps were the same as in example 3.
The prepared cells were subjected to electrochemical testing, and the prepared performance parameters are shown in table 2 below. Wherein, the sample 6 is a chlorobenzene suspension of Pb-BDT with the concentration of 2.5 mg/ml; sample 7 was a suspension of Pb-BDT in chlorobenzene at a concentration of 5 mg/ml; sample 8 was a suspension of Pb-BDT in chlorobenzene at a concentration of 10 mg/ml.
Comparative sample 5 differs from sample 6 in that the perovskite solar cell device was not treated with PbBDT.
TABLE 2
Sample of Voc(V) J sc (mA cm -2 ) FF％) PCE(％)
Comparative sample 5 1.05 23.40 61.64 15.14
Sample 6 1.04 22.77 69.66 16.49
Sample 7 1.06 22.98 66.80 16.31
Sample 8 1.04 23.24 70.32 16.99
FIG. 5 shows the short-circuit current (J) of the solar cell device of example 4 at different concentrations sc ) A drawing.
From an analysis of the data in tables 1 and 2, it can be seen that Li-TFSI doped in the Spiro-OMeTAD can improve the hole mobility of the Spiro-OMeTAD in the hole transport material solution, and the device performance is different. The efficiency of the perovskite solar cell device treated by adopting the PbBDT is obviously improved, which shows the efficacy of the PbBDT in the partial replacement of Li-TFSI.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (19)

1. A method for producing a Pb-based coordination polymer crystal, characterized by comprising: dissolving Pb-containing compound and ligand in organic solvent, heating to prepare crystal;
the organic solvent is DMF;
the ligand comprises terephthalyl mercaptan, p-hydroxy phenyl mercaptan, p-amino phenyl mercaptan, p-fluoro phenyl mercaptan, p-methoxy phenyl mercaptan and p-carboxyl phenyl mercaptan;
when the ligand is terephthalyl mercaptan, the crystal is PbBDT and has a three-dimensional structure, and the crystal isC2/cSpace group, its unit cell parameters are: a= 7.383 (2) a, b= 5.209 (2) a, c= 17.429 (2) a, a=90°, b= 93.042 °, g=90°, v= 669.40 (9) a 3 ；
The ligand is p-hydroxy benzene mercaptan, p-amino benzene mercaptan, p-fluoro benzene mercaptan, p-methoxy benzene mercaptan, p-carboxyl benzene mercaptan, which has a two-dimensional structure, and the crystal isC2 space groups;
and/or, when the ligand is p-hydroxy benzene mercaptan, the unit cell parameters are as follows: a= 7.635 (2) a, b= 5.206 (2) a, c=15.135 (3) a, α=90°, β=95.47 (4) °, g=90°, v= 598.86 (30) a 3 。
2. The method according to claim 1, characterized in that the mass ratio of Pb-containing compound to ligand is 1-50:1;
and/or the mass-to-volume ratio of the ligand to the organic solvent is 1-20 (mg): 1 (mL);
and/or the Pb-containing compound is selected from PbCl 2 、PbBr 2 、PbI 2 At least one of (a) and (b);
and/or the heating temperature is 50-140 ℃ and the heating time is at least 1h.
3. Use of the Pb-based coordination polymer crystal prepared by the method of claim 1 or 2, for preparing a Pb-based coordination polymer nanosheet.
4. The use according to claim 3, wherein the thickness of the Pb-based coordination polymer nanoplatelets is 5-100nm.
5. The use according to claim 3, wherein the preparation method of the Pb-based coordination polymer nanosheets comprises: and dissolving Pb-containing compound in a first solvent, dissolving ligand in a second solvent, and uniformly mixing the two solutions to prepare the Pb-based coordination polymer nano-sheet.
6. The use according to claim 5, wherein the ratio of Pb-containing compound to the first solvent is from 1 to 50 (mg): 1 (mL);
and/or the mass-to-volume ratio of the ligand to the second solvent is 0.5-40 (mg): 1 (mL);
and/or the first solvent is at least one of water and DMF;
and/or the second solvent is at least one of isopropanol, DMF, acetonitrile and propanol;
and/or mixing the two solutions uniformly under the ultrasonic condition, wherein the ultrasonic time is 1-5h; the ultrasonic temperature is 20-40 ℃.
7. Use of the Pb-based coordination polymer nanoplatelets prepared by the use of any of claims 3 to 6, wherein the perovskite solar cell device assembly is accomplished by spin coating, knife coating or spray coating deposited on a perovskite thin film; the preparation method of the perovskite solar cell specifically comprises the following steps:
(1) ZnO-MgO-EA + Spin-coating the solution on an FTO conductive glass substrate, heating for the second time for annealing, and heating for the third time for annealing to obtain compact ZnO-MgO-EA + The layer was cooled to room temperature and TiCl was then introduced into the solution 4 Heating the solution, taking out and drying, and then adding TiO 2 Spin-coating the isopropanol solution of the slurry on the surface of the substrate, heating for the fourth annealing, and depositing mesoporous TiO on the FTO conductive glass substrate 2 A layer;
(2) Preparing a perovskite film on the surface of the electron transport layer;
(3) Uniformly coating Pb-based three-dimensional coordination polymer nanosheet suspension on the surface of the perovskite substrate layer in the step (2), and annealing to prepare a perovskite solar cell precursor;
(4) Preparing a hole transport layer on the surface of the perovskite solar cell precursor in the step (3), and forming an electrode on the surface of the hole transport layer to prepare a perovskite solar cell;
the temperature of the second annealing is 90-110 ℃; the temperature of the third annealing is 480-510 ℃; the temperature of the fourth annealing is 480-500 ℃.
8. The use according to claim 7, wherein in step (1), the conductive glass substrate is subjected to a pretreatment prior to use, the pretreatment being: etching the conductive film substrate into an electrode pattern, respectively carrying out ultrasonic treatment on the electrode pattern by acetone, deionized water and ethanol, and carrying out primary annealing to remove surface oxides and impurities of the conductive film substrate;
and/or the first annealing temperature of the conductive glass substrate is 400-600 ℃; the annealing time is 20-40min;
and/or, the ZnO-MgO-EA + The thickness of the layer is 30-50nm;
and/or ZnO-MgO-EA + The spin-coating rotating speed of the solution is 2500-3000rpm, and the spin-coating time is 20-25s;
and/or the time of the second annealing is 3-5min; the time of the third annealing is 40-50min; the fourth annealing time is 35-40min;
and/or TiCl 4 The concentration of the solution is 25-45mmol/L;
and/or in TiCl 4 Heating the solution at 60-90deg.C for 12-18min;
and/or, tiO 2 The mass ratio of the slurry to the isopropanol solution is 1:3-10;
and/or, tiO 2 The spin-coating speed of the isopropanol solution of the slurry is 4000-5000rpm, and the spin-coating time is 20-25s.
9. The use according to claim 7, wherein the specific steps of step (2) are: uniformly coating a perovskite precursor solution on a conductive film substrate with an electron transport layer as an outer layer, quickly dripping at least one solution of toluene, chlorobenzene or diethyl ether on the substrate to obtain an intermediate film, and annealing the intermediate film for the fifth time to prepare the perovskite film.
10. The use according to claim 9, wherein the perovskite precursor solution is PbI 2 ，PbBr 2 CsI, iodoformamidine and bromomethylamine were dissolved in a mixed solution of DMF and DMSO.
11. The use according to claim 10, wherein PbI 2 ，PbBr 2 The molar ratio of CsI, iodoformamidine and bromomethylamine is 6-24:2-14:1-3:1-9:1;
and/or, the volume ratio of DMF to DMSO is 6-10:1; the mass volume ratio of bromomethylamine to DMSO is 1:3-5.
12. The use according to claim 9, wherein the perovskite precursor solution is applied by spin coating; the spin-coating rotational speed of the perovskite precursor solution is 5500-6200rpm, and the spin-coating time is 30-35s.
13. Use according to claim 9, characterized in that the toluene or chlorobenzene or diethyl ether is added dropwise for a period of 12-16s; the drop amount of toluene or chlorobenzene or diethyl ether is 300-500uL;
and/or, the temperature of the fifth annealing is 100-160 ℃; the time of the fifth annealing is 12-16min.
14. The use according to claim 7, wherein in step (3), the Pb-based coordination polymer nanosheet suspension is prepared by dispersing Pb-based coordination polymer nanosheets in chlorobenzene; the concentration of the chlorobenzene suspension of PbBDT is 2-15mg/mL.
15. Use according to claim 14, characterized in that the chlorobenzene suspension of PbBDT is applied by spin-coating; the spin coating rotating speed is 2500-3000rpm, and the time is 20-30s.
16. The use according to claim 7, wherein the annealing temperature in step (3) is 100-130 ℃ for 8-12min.
17. The use according to claim 7, wherein the specific preparation steps in step (4) are: and uniformly coating the hole transport material solution on the outer layer of the perovskite solar cell precursor, drying, and depositing an electrode by adopting a vacuum evaporation mode to prepare the cell.
18. The use according to claim 17, wherein the hole transport material is spin coated at a spin speed of 3800-4200rpm;
and/or the hole transport material is a chlorobenzene solution of Spiro-OMeTAD, and the concentration is 70-76 mg/mL;
and/or the hole transport material further comprises an additive, wherein the additive is acetonitrile solution containing Li-TFSI and 4-tert-butylpyridine, and the volume ratio of the acetonitrile solution containing Li-TFSI to the 4-tert-butylpyridine is 1:1-3.
19. The use according to claim 18, wherein the concentration of the acetonitrile solution of Li-TFSI is 480-520 mg/mL;
and/or the electrode may be an Au or Ag electrode;
and/or the thickness of the electrode is 60-120nm.
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