A lead-leakage-inhibited perovskite solar cell and a preparation method thereof

Abstract

The application discloses a kind of inhibiting lead leakage perovskite solar cell and preparation method thereof, it is related to perovskite solar cell field, the modified perovskite light-absorbing layer of perovskite solar cell is prepared using APUS molecular doping;The modified perovskite light-absorbing layer is prepared by using APUS molecular doping in the application, the adsorption of lead can be realized, so as to effectively inhibit the lead leakage of perovskite film, the film prepared by using APUS molecule is used to externally package the cell, and the inhibition of lead leakage is realized simultaneously inside and outside. The biocompatibility of organic-inorganic hybrid perovskite solar cell is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of perovskite solar cells, in particular to a perovskite solar cell for inhibiting lead leakage and a preparation method thereof. BACKGROUND

[0002] In recent years, organic-inorganic hybrid perovskite solar cells (PSCs) have attracted extensive attention due to their excellent photoelectric conversion efficiency (25.7%), simple preparation process and low manufacturing cost, and have become one of the photovoltaic technologies with commercial application prospects. However, extreme weather conditions such as hail, high temperature and running water, and sudden events such as fire can cause the perovskite thin film to leak out PbI2, PbBr2 and PbCl2, and other toxic heavy metal products containing PbO, which poses a serious threat to the ecological system and human health. 0 With PbO and other toxic heavy metal products containing PbO, which poses a serious threat to the ecological system and human health. SUMMARY

[0003] In view of the above shortcomings of the prior art, the present application provides a perovskite solar cell for inhibiting lead leakage and a preparation method thereof.

[0004] To achieve the above-mentioned application purposes, the technical solutions adopted by the present application are as follows:

[0005] A perovskite solar cell for inhibiting lead leakage is provided, wherein the modified perovskite light-absorbing layer of the perovskite solar cell is prepared by doping with APUS molecules, and the molecular structure of the APUS is shown in Formula I.

[0006] .

[0007] Further, the perovskite solar cell is externally packaged with a thin film prepared from APUS molecules.

[0008] Further, the thickness of the thin film prepared from APUS molecules is 3mm.

[0009] The present application also provides a preparation method of the above-mentioned perovskite solar cell for inhibiting lead leakage, comprising the following specific steps:

[0010] S1: preparing a SnO2 electron transport layer on an ITO glass substrate;

[0011] S2: preparing a modified perovskite light-absorbing layer on the SnO2 electron transport layer by a two-step method, first preparing a PbI2 thin film on the SnO2 electron transport layer;

[0012] S3: further prepare a modified film on the PbI2 film, specifically: dissolve methylamine chloride, methylamine bromide and formamidine hydroiodide into isopropyl alcohol at room temperature to obtain a mixed solution A; dissolve APUS molecules in dimethylacetamide at room temperature to obtain a mixed solution B; mix the mixed solution B and the mixed solution A uniformly at a volume ratio of 1:100, spin coating on the PbI2 film, and annealing on a hot stage at 140°C for 10 min to obtain a modified perovskite light absorption layer;

[0013] S4: prepare a Spiro-OMeTAD hole transport layer on the surface of the modified perovskite light absorption layer;

[0014] S5: evaporate a metal electrode on the surface of the Spiro-OMeTAD hole transport layer.

[0015] Further, the mass ratio of methylamine chloride, methylamine bromide and formamidine hydroiodide in the mixed solution A is 6:6:60, and the dosage ratio of methylamine chloride to isopropyl alcohol is 6 mg:1 mL; the dosage ratio of APUS molecules to dimethylacetamide in the mixed solution B is 10 mg:1 mL.

[0016] Further, the volume ratio of the mixed solution after mixing the mixed solution B and the mixed solution A to the area of the PbI2 film is 130 μL / 256 mm 2 .

[0017] Further, step S1 is specifically:

[0018] S11: ultrasonically disperse a SnO2 water-soluble colloid with a mass fraction of 12% into deionized water to obtain a SnO2 aqueous solution; the volume ratio of the SnO2 water-soluble colloid to the deionized water is 1:6;

[0019] S12: filter the SnO2 aqueous solution using a polyether sulfone filter with a filter diameter of 0.22 μm to obtain a SnO2 filtrate;

[0020] S13: drop the SnO2 filtrate on an ITO glass substrate, spin coating at a rotation speed of 4000 rpm / s for 30 s, and annealing at 180°C for 20 min to obtain a SnO2 electron transport layer.

[0021] Further, the specific steps for preparing a PbI2 film on the SnO2 electron transport layer are as follows:

[0022] S21: dissolve PbI2 in a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide at 60°C, and heat and stir for 3 h; the volume ratio of dimethyl sulfoxide to N,N-dimethylformamide is 50:950; the dosage ratio of PbI2 to dimethyl sulfoxide is 0.6 g:50 μL;

[0023] S22: After the reaction is completed, the temperature is decreased to room temperature, and PbI2 solution is obtained by filtering through PTFE with a filter size of 0.22 μm;

[0024] S23: The PbI2 solution is added dropwise on the SnO2 electron transport layer, and spin coating is performed at a rotation speed of 1500 rpm / s for 30 s, and the PbI2 film is obtained after annealing at 65 DEG C for 1 min; the area ratio of the PbI2 solution to the SnO2 electron transport layer is 50 μL / 256 mm 2 .

[0025] Further, the step S4 is specifically as follows:

[0026] S41: After Spiro-OMeTAD is dissolved in chlorobenzene, tributyl phosphate and a lithium salt solution are added, and stirring reaction is performed for 2 h;

[0027] S42: After the reaction is completed, Spiro-OMeTAD solution is obtained by filtering through PTFE with a filter size of 0.22 μm;

[0028] S43: The Spiro-OMeTAD solution is added dropwise on the surface of the modified perovskite light absorption layer, and spin coating is performed at a rotation speed of 4500 rpm for 30 s, and the Spiro-OMeTAD hole transport layer is obtained.

[0029] Further, the metal evaporated on the surface of the Spiro-OMeTAD hole transport layer in the step S5 is Au or Ag, when the metal to be evaporated is Au, the metal electrode with a thickness of 70 nm is evaporated on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s; when the metal to be evaporated is Ag, the metal electrode with a thickness of 100 nm is evaporated on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s.

[0030] The present application has the following beneficial effects:

[0031] The present application can realize the adsorption of lead by adopting the APUS molecular doping to prepare the modified perovskite light absorption layer, thereby effectively inhibiting the lead leakage of the perovskite film, and the film prepared by using the APUS molecule is used for external packaging of the battery, thereby realizing the inhibition of lead leakage from the inside and the outside at the same time, and the biocompatibility of the organic-inorganic hybrid perovskite solar cell is improved. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 It is an XPS spectrum comparison chart of the perovskite film with or without APUS doping;

[0033] Figure 2 It is an FTIR spectrum comparison chart of whether APUS is combined with PbI2 or not;

[0034] Figure 3Raman spectra comparison of whether APUS binds to PbI2;

[0035] Figure 4 Comparison of PL spectra of perovskite thin films with and without APUS doping;

[0036] Figure 5 A schematic diagram of the perovskite solar cell structure with APUS internal and external co-encapsulation.

[0037] Figure 6 This is a comparison chart of Pb ion content in polluted water after acid rain simulation tests of the four sets of devices in Example 2;

[0038] Figure 7 A comparison chart showing the efficiency of batteries with and without APUS doping. Detailed Implementation

[0039] The specific embodiments of the present invention are described below to enable those skilled in the art to understand the present invention. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various changes are obvious as long as they are within the spirit and scope of the present invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0040] Example 1: Preparation of APUS-doped modified perovskite light-absorbing layer

[0041] The specific steps are as follows:

[0042] S1: A SnO2 electron transport layer was prepared on an ITO glass substrate purchased from South China Xiangcheng Technology Co., Ltd.; the ITO glass substrate had a size of 6Ωsq. -1 Before preparing the SnO2 electron transport layer, the ITO glass substrate (16.1mm × 16.1mm) was cleaned. Specifically, a cotton swab dipped in a detergent solution was used to vigorously scrub the substrate surface to remove oil and impurities. The cleaned substrate was then placed in a PTFE basket and sonicated for 20 minutes in detergent solution, DI solution, and ethanol solution, respectively, to remove impurities and residual organic matter. Finally, a nitrogen gun was used to purge the ethanol from the substrate surface, resulting in a clean ITO glass substrate.

[0043] The specific steps for preparing the SnO2 electron transport layer are as follows:

[0044] S11: SnO2 water-soluble colloidal with mass fraction of 12% purchased from Braite was uniformly dispersed into deionized water by ultrasonic for 30 min to obtain SnO2 aqueous solution; during the ultrasonic process, a clean ITO glass substrate was treated in a UV-ozone cleaner for 20 min to completely remove organic matter on the surface of the substrate and increase the wettability of the substrate surface; the volume ratio of SnO2 water-soluble colloidal to deionized water was 1:6;

[0045] S12: The SnO2 aqueous solution was filtered by using a polyether sulfone filter with a filter diameter of 0.22 μm to obtain a SnO2 filtrate;

[0046] S13: 150 μL of the SnO2 filtrate was dropped on the ITO glass substrate, and spin-coated at a rotation speed of 4000 rpm / s for 30 s, and then annealed at 180°C for 20 min to obtain a SnO2 electron transport layer. The SnO2 electron transport layer and the ITO glass substrate were used as an ITO / SnO2 substrate for subsequent preparation;

[0047] S2: A modified perovskite light-absorbing layer was prepared on the SnO2 electron transport layer by a two-step method. First, a PbI2 thin film was prepared on the SnO2 electron transport layer; the specific steps are as follows:

[0048] S21: 0.5993 g of PbI2 was weighed and dissolved in a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide at 60°C, and heated and stirred for 3 h; the mixed solution included 50 μL of dimethyl sulfoxide and 950 μL of N,N-dimethylformamide;

[0049] S22: After the heating reaction was completed, the temperature was lowered to room temperature, and a PTFE filter with a filter diameter of 0.22 μm was used to obtain a PbI2 solution;

[0050] S23: The prepared ITO / SnO2 substrate was treated in a UV-ozone cleaner for 5 min to improve the surface wettability and facilitate the solution spreading. 50 μL of the PbI2 solution was removed and dropped on the SnO2 electron transport layer, and spin-coated at a rotation speed of 1500 rpm / s for 30 s, and then annealed at 65°C for 1 min to obtain a PbI2 thin film.

[0051] S3: A modified thin film was prepared on the PbI2 thin film, specifically: 6 mg of methylamine chloride, 6 mg of methylamine bromide and 60 mg of formamidine hydroiodide were dissolved in 1 mL of isopropanol at room temperature to obtain a mixed solution A; and a clear solution A was obtained by PTFE filtration with a filter diameter of 0.22 μm;

[0052] Take 10 mg of APUS molecules, and the synthesis method of the APUS molecules is synthesized according to the technology disclosed in the prior art Yao W, Sui X, Yang D, et al. Versatile Photoluminescence Polymers for Printed Transparent Self-Healing Optical Devices[J]. Advanced Functional Materials, 2023, 34(17):; dissolve in 1 mL of dimethylacetamide at room temperature to obtain a mixed solution B; mix the mixed solution B and the clear solution A uniformly at a volume ratio of 1 μL: 100 μL, take out 130 μL and spin coat on the PbI2 film, and place it on a hot stage at 140°C for annealing for 10 min to obtain a modified perovskite light-absorbing layer; in specific implementation, the annealing environment is air with a humidity of 30-40%.

[0053] A control group (Control) is set, and the difference between the control group and the modified perovskite light-absorbing layer is that when the control group is prepared, dimethylacetamide and the clear solution A are directly mixed uniformly at a volume ratio of 1 μL: 100 μL, 130 μL is taken out and spin coated on the PbI2 film, and the rest of the parameters are consistent with the above steps S1-S3.

[0054] The control group and the modified perovskite light-absorbing layer are subjected to X-ray photoelectron spectroscopy (XPS) detection, and the results are shown in Figure 1 , and it can be known from Figure 1 that compared with the control group, the binding energy displacement of the Pb4f peak of the APUS modified perovskite film is lower, indicating that the electron cloud density of Pb and I is increased, and the APUS molecules are bonded in the crystallization process. This can be attributed to the rich active sites on the APUS, which effectively interact and combine with Pb 2+ , thereby achieving efficient passivation of the perovskite and anchoring of Pb 2+ .

[0055] The modified perovskite light-absorbing layer (APUS-Pb) and the APUS film are subjected to Fourier transform infrared absorption spectrum detection (FTIP), and the results are shown in Figure 2 , and it can be known from Figure 2 that after the interaction of APUS and PbI2, the stretching vibration peak of N-H in APUS is shifted, indicating that there is a strong interaction between N-H on the APUS and Pb 2+ .

[0056] The modified perovskite light-absorbing layer (APUS-Pb) and the APUS film are subjected to Raman spectrum detection (Raman), and the results are shown in Figure 3 , and it can be known from Figure 3It can be seen that the S-S bond at 500cm -1 ~600cm -1 of APUS is obviously displaced after the interaction with PbI2, indicating that there is a strong interaction between S-S of APUS and Pb 2+ .

[0057] The photoluminescence spectrum (PL) of the control group and the modified perovskite light absorption layer was detected, and the results are shown in Figure 4 . It can be seen from Figure 4 that the perovskite film prepared by doping APUS has a stronger luminescence intensity.

[0058] Example 2 Preparation of a perovskite solar cell for inhibiting lead leakage

[0059] The modified perovskite light absorption layer prepared in Example 1 is used to prepare a perovskite solar cell for inhibiting lead leakage by the following method:

[0060] S41: 72.3 mg of Spiro-OMeTAD is weighed and dissolved in 1 mL of chlorobenzene to stir uniformly. Then 28.8 μL of tributyl phosphate and 17.5 μL of lithium salt solution are added, and the reaction is stirred for 2 h; in specific implementation, the lithium salt solution is prepared by dissolving 520 mg of LiTFSI in 1 mL of acetonitrile;

[0061] S42: After the reaction is completed, a PTFE filter with a pore size of 0.22 μm is used to obtain a Spiro-OMeTAD solution;

[0062] S43: 25 μL of the filtered Spiro-OMeTAD solution is added dropwise on the surface of the modified perovskite light absorption layer, and is spin-coated at a speed of 4500 rpm for 30 s to obtain a Spiro-OMeTAD hole transport layer.

[0063] S5: The metal evaporated on the surface of the Spiro-OMeTAD hole transport layer is Au, and the metal electrode is evaporated on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s for 70 nm; in specific implementation, the metal evaporated can also be Ag, and when the metal evaporated is Ag, the metal electrode is evaporated on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s for 100 nm. The structure of the perovskite solar cell for inhibiting lead leakage obtained is shown in Figure 5 , wherein Au is the metal electrode, HTL is the Spiro-OMeTAD hole transport layer, Perovskite is the modified perovskite light absorption layer, ETL is the SnO2 electron transport layer, ITO is the ITO glass substrate, and APUS is the APUS molecular thin film attached to the upper and lower sides of the perovskite solar cell thin film device.

[0064] In specific implementation, 3mm-thick APUS molecular film can also be attached to the upper and lower sides of the perovskite solar cell to achieve external encapsulation of the device. In this embodiment, the unencapsulated cell (Control) is prepared by using the control group in Example 1 and using S41-S43 and S5; the internally encapsulated cell (I-APUS) is prepared by using S5; the externally encapsulated cell (E-APUS) is prepared by attaching 3mm-thick APUS molecular film to the upper and lower sides of the unencapsulated cell; and the internally and externally encapsulated cell (G-APUS) is prepared by attaching 3mm-thick APUS molecular film to the upper and lower sides of the internally encapsulated cell.

[0065] The four groups of devices are subjected to acid rain simulation test. Specifically, a nitric acid solution with pH = 4.2 is dropped on the damaged panel at a flow rate of 10mL / h for 1h to simulate acid rain erosion. The cells after acid rain erosion are subjected to inductively coupled plasma atomic emission spectrometry, and the results are shown in Figure 6 Figure 6 It can be seen that the Pb ion content in the contaminated water of Control, E-APUS and I-APUS is 2.09ppm, 0.65ppm and 0.49ppm, respectively, and the average lead concentration of G-APUS is reduced to 0.38ppm. The cell prepared by doping with APUS molecules (I-APUS) can effectively inhibit the leakage of lead, and the internal and external collaborative encapsulation can have a lead immobilization efficiency as high as 81.77%.

[0066] The efficiency of the unencapsulated cell (C) and the internally encapsulated cell (I-APUS) is detected, and the results are shown in Figure 7 Figure 7 It can be seen that the performance of the cell prepared by doping with APUS molecules is almost the same as that of the undoped cell, and the doping of APUS molecules does not affect the performance of the cell.​​

Claims

1. A perovskite solar cell for suppressing lead leakage, characterized in that, The modified perovskite light-absorbing layer of the perovskite solar cell is prepared by APUS molecule doping, and the APUS molecule structure is shown in Formula I. ； The perovskite solar cell is externally encapsulated using a thin film prepared with APUS molecules.

2. The perovskite solar cell for suppressing lead leakage according to claim 1, characterized in that, The thickness of the film prepared by the APUS molecules is 3 mm.

3. The method for preparing a perovskite solar cell with suppressed lead leakage as described in claim 1, characterized in that, The specific steps include the following: S1: Prepare a SnO2 electron transport layer on an ITO glass substrate; S2: A modified perovskite light-absorbing layer was prepared on the SnO2 electron transport layer using a two-step method. First, a PbI2 thin film was prepared on the SnO2 electron transport layer. S3: A modified film is then prepared on the PbI2 film. Specifically, methylamine chloride, methylamine bromide and formamidin hydroiodide are dissolved in isopropanol at room temperature to obtain mixed solution A; APUS molecules are dissolved in dimethylacetamide at room temperature to obtain mixed solution B; mixed solution B and mixed solution A are mixed evenly at a volume ratio of 1:100, spin-coated onto the PbI2 film, and annealed on a hot stage at 140℃ for 10 min to obtain the modified perovskite light-absorbing layer. S4: A Spiro-OMeTAD hole transport layer was prepared on the surface of the modified perovskite light-absorbing layer; S5: Deposit a metal electrode on the surface of the Spiro-OMeTAD hole transport layer.

4. The preparation method according to claim 3, characterized in that, In the mixed solution A, the mass ratio of methylammonium chloride, methylammonium bromide, and formamidinium hydroiodate is 6:6:60, and the ratio of methylammonium chloride to isopropanol is 6 mg:1 mL; in the mixed solution B, the ratio of APUS molecules to dimethylacetamide is 10 mg:1 mL.

5. The preparation method according to claim 3, characterized in that, The volume ratio of the mixture of solution B and solution A to the area of ​​the PbI2 film is 130 μL / 256 mm². 2 .

6. The preparation method according to claim 3, characterized in that, Step S1 specifically involves: S11: A SnO2 aqueous solution is obtained by ultrasonically dispersing 12% SnO2 water-soluble colloid into deionized water; the volume ratio of SnO2 water-soluble colloid to deionized water is 1:

6. S12: SnO2 filtrate is obtained by filtering an aqueous SnO2 solution using a polyethersulfone filter with a filter diameter of 0.22 μm; S13: SnO2 filtrate was dropped onto an ITO glass substrate and spin-coated at 4000 rpm / s for 30 s. The SnO2 electron transport layer was then annealed at 180°C for 20 mins.

7. The preparation method according to claim 3, characterized in that, The specific steps for preparing PbI2 thin films on SnO2 electron transport layers are as follows: S21: PbI2 is dissolved in a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide at 60°C and heated and stirred for 3 hours; the volume ratio of dimethyl sulfoxide to N,N-dimethylformamide is 50:950; the amount ratio of PbI2 to dimethyl sulfoxide is 0.6g:50μL. S22: After the heating reaction is complete, cool to room temperature and filter through a PTFE filter with a diameter of 0.22 μm to obtain a PbI2 solution; S23: A PbI2 solution is dropped onto a SnO2 electron transport layer, spin-coated at 1500 rpm / s for 30 s, and annealed at 65°C for 1 min to obtain a PbI2 thin film; the area ratio of the PbI2 solution to the SnO2 electron transport layer is 50 μL / 256 mm². 2 .

8. The preparation method according to claim 3, characterized in that, Step S4 specifically involves: S41: After dissolving Spiro-OMeTAD in chlorobenzene, add tributyl phosphate and lithium salt solution, and stir to react for 2 hours; S42: After the reaction is complete, the solution is obtained by filtration through PTFE with a filter diameter of 0.22 μm; S43: Spiro-OMeTAD solution is dropped onto the surface of the modified perovskite light-absorbing layer and spin-coated at 4500 rpm for 30 s to obtain the Spiro-OMeTAD hole transport layer.

9. The preparation method according to claim 3, characterized in that, In step S5, the metal deposited on the surface of the Spiro-OMeTAD hole transport layer is Au or Ag. When the deposited metal is Au, a 70 nm metal electrode is deposited on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s; when the deposited metal is Ag, a 100 nm metal electrode is deposited on the surface of the Spiro-OMeTAD hole transport layer at an average evaporation rate of 0.25 Å / s.

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