A Li- and Cu-codoped NiO x Inverse perovskite battery and preparation method thereof

Abstract

The present application discloses a method based on Li and Cu co-doped NiO x The invention relates to an inverse perovskite solar cell and a preparation method thereof. The preparation process of the solar cell is as follows: (1) depositing Li and Cu co-doped NiO on a clean ITO electrode; x Hole transport layer; (2) Li and Cu co-doped NiO x Prepare a urea interface modification layer on the hole transport layer; (3) deposit a diblock copolymer [(PEO) 150 ‑(PPO) 30 ] modified Cs 0.1‑x Rb x MA 0.63 FA 0.27 Pb(I 1‑y Br y )3 perovskite photosensitive layer, the value range of x is 0.02~0.06, and the value range of y is 0.05~0.30; (4) preparing a PCBM / BCP electron transport layer on the perovskite photosensitive layer; (5) evaporating an Ag layer counter electrode on the PCBM / BCP electron transport layer to obtain.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar cells, and specifically relates to a Li- and Cu-codoped NiO x Inverse perovskite battery and preparation method thereof. Background Art

[0002] Solar cells are a crucial technological foundation for the large-scale conversion of solar energy into electricity. Their development is a "green" new technology that can alleviate the conflict between economic development, energy, and the environment. Currently, solar cell research is exploring the following new directions: 1. Developing top or bottom cells compatible with crystalline silicon cells to construct tandem cells with theoretical efficiencies exceeding 33%; 2. Developing flexible, lightweight, and multicolored new cells to complement crystalline silicon cells and meet diverse market application needs; and 3. Exploring new photosensitive materials (e.g., simple, non-toxic, low-cost, and abundant) to fabricate novel solar cells. A new research hotspot in the photovoltaic field is organic-inorganic hybrid perovskite solar cells, which have achieved significant improvements in device performance and have surpassed the highest efficiencies of semiconductor compound solar cells (e.g., CdTe and CuInGaSn). The simplicity, low cost, and solution processability of perovskite materials suggest that this thin-film solar cell technology could replace existing photovoltaic technologies and enable cost-effective development. Improving the stability of perovskite solar cells is a key area of ​​current research. Transverse perovskite solar cells fabricated using inorganic materials exhibit superior stability and hold significant research value in promoting the commercialization of perovskite cells.

[0003] At present, most perovskite solar cells are based on the formal structure of TiO2 or SnO2, in which the hole transport layer is mostly doped Spiro-OMeTAD. Commercial doped Spiro-OMeTAD is not only expensive, but also has parasitic absorption characteristics. The mobile ion dopants it contains can accelerate the rapid degradation of perovskite. In addition, Spiro-OMeTAD is easily degraded in an air environment, which will significantly affect the operational stability of the battery device and is not conducive to the commercial development of the device. This technology uses a low-temperature solution method to prepare Li and Cu co-doped NiO x Hole transport layer, urea is deposited on the hole transport layer to passivate the interface defect state; the diblock copolymer [(PEO) 150 -(PPO) 30 The researchers introduced a perovskite layer to passivate grain boundary defects and improve the stability of the perovskite film, resulting in an inverted perovskite solar cell device. This cell technology not only achieves high device performance and improved wet / thermal stability, but also allows for scalable fabrication based on a low-temperature, all-solution process, facilitating the commercialization of perovskite solar cells. Summary of the Invention

[0004] The purpose of the present invention is to provide a Li and Cu co-doped NiO x Inverse perovskite solar cells and their preparation methods can not only completely replace the Spiro-OMeTAD hole transport layer, reducing preparation costs, but also improve the device's stability to humidity, heat, and light intensity. These solar cells feature abundant raw material reserves, simple preparation methods, excellent stability, a wide range of applications, and are safe and environmentally friendly. They can also be prepared in large quantities using a fully low-temperature solution process, exploring experimental conditions and key technologies for the commercialization of inverse perovskite solar cells and possessing excellent application prospects.

[0005] Based on the above objectives, the present invention adopts the following technical solutions:

[0006] A Li and Cu co-doped NiO x The preparation method of the inverse perovskite battery comprises the following steps (Li, Cu co-doped NiO x The hole transport layer and urea interface modification layer were completed in an air environment, and the rest of the preparation process was completed in a glove box):

[0007] (1) Deposition of Li and Cu co-doped NiO on a clean ITO electrode x The hole transport layer is prepared by low temperature solution method and Li and Cu co-doped NiO with pH value>10. x The solution was diluted with deionized water and then spin-coated on a clean ITO electrode and annealed to obtain Li and Cu co-doped NiO. x Hole transport layer; Li, Cu co-doped NiO x Solution, deionized water volume ratio 1:3 for Li, Cu co-doped NiO x The solution is diluted;

[0008] (2) Li and Cu co-doped NiO x A urea aqueous solution is deposited on the hole transport layer and annealed to obtain a urea interface modification layer. The concentration of the urea aqueous solution is 0.1-0.8 mg / mL.

[0009] (3) Deposition of diblock copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1- x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 perovskite photosensitive layer, the value range of x is 0.02~0.06, and the value range of y is 0.05~0.30;

[0010] (4) PCBM and BCP are sequentially deposited on the perovskite photosensitive layer as electron transport layers;

[0011] (5) Evaporate an Ag layer onto the PCBM / BCP electron transport layer to obtain a counter electrode.

[0012] The Li and Cu co-doped NiO x The aqueous solution was obtained by the following method:

[0013] (a) dissolving nickel acetate tetrahydrate in deionized water to obtain a nickel acetate solution;

[0014] (b) dissolving lithium acetate in deionized water to obtain a lithium acetate solution;

[0015] (c) dissolving copper acetate monohydrate in anhydrous ethanol to obtain a copper acetate solution;

[0016] (d) sequentially measuring the nickel acetate and lithium acetate solutions obtained in steps (a) and (b), and adding them dropwise to concentrated aqueous ammonia with continuous stirring to obtain a complex of the two metals;

[0017] (e) measuring the copper acetate solution obtained in step (c) and adding it dropwise to the solution obtained in step (d) while stirring continuously to obtain a complex of the three metals;

[0018] (f) measuring the solid content of the mixed solution obtained in step (e); the pH value of the entire experimental process of steps (d) and (e) is greater than 10.

[0019] Preferably, in step (a), the concentration of nickel acetate is 1 mmol / mL; in step (b), the concentration of lithium acetate is 1.52 mmol / mL; in step (c), the concentration of copper acetate is 1 mmol / mL; in step (d), the molar ratio of nickel acetate to lithium acetate is 1:0.03; in step (e), the molar ratio of nickel acetate to copper acetate is 1:0.02; in step (d), when the amount of nickel acetate used is 5 mmol, the amount of concentrated ammonia water used is 10 mL.

[0020] The preparation process of the clean ITO electrode is as follows: a glass sheet with deposited ITO strip electrodes is selected and repeatedly scrubbed with detergent to remove oil stains on the surface of the glass sheet; the ITO conductive glass is cut into regular small pieces, such as 1 cm × 1 cm, and ultrasonicated in deionized water for 30 minutes, in an acetone solution for 30 minutes, and in an isopropanol solution for 30 minutes in sequence; the obtained ITO glass sheet is dried in an oven at 100 ° C for 30 minutes to obtain a clean ITO electrode.

[0021] Furthermore, the urea interface modification layer was prepared as follows: urea was weighed and added to deionized water, stirred to fully dissolve it, and the resulting urea solution concentration was 0.4 mg mL -1Measure 20 μL of urea solution and spin-coat it onto Li and Cu co-doped NiO x The hole transport layer was annealed at 120 °C for 20 min to obtain a urea interface modification layer.

[0022] Furthermore, the polymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y The preparation process of the )3 photosensitive layer is as follows: 0.27 mmol FAI, 0.63 mmol MAI, (1-3y / 2) mmol PbI2, 3y / 2 mmol PbBr2, (0.1-x) mmol CsI, x mmol RbI and 11.15 mg Pb(SCN)2 are weighed in sequence and added to a mixed solvent of DMF and DMSO with a volume ratio of 8:1. The mixture is stirred at 60-70°C until the solid is completely dissolved to obtain a perovskite precursor solution. The copolymer [(PEO) 150 -(PPO) 30 ] was dispersed in DMF solution, different volumes of copolymer solution were added to the perovskite precursor, the concentration of copolymer in the perovskite precursor was 1.0~8.0 mg / mL, and the mixture was stirred at room temperature for 1~2 h to obtain copolymer-modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 precursor solution; the copolymer-modified perovskite precursor solution is deposited onto the urea interface modification layer and annealed to obtain Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 Perovskite photosensitive layer.

[0023] Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 The perovskite photosensitive layer is specifically Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br0.10 )3, the specific preparation process is as follows: 0.27 mmol FAI, 0.63 mmol MAI, 0.85 mmol PbI2, 0.15 mmol PbBr2, 0.05 mmol CsI, 0.05 mmol RbI and 11.15 mg Pb(SCN)2 were weighed in sequence and added to a mixed solvent of 560 μL DMF and 70 μL DMSO. The solution was stirred at 65 °C for 12 h until the solid was completely dissolved; 250 mg copolymer [(PEO) 150 -(PPO) 30 ], added to 1 mL DMF solution, stirred for 2-3 h to obtain a copolymer solution with a concentration of 250 mg / mL, and 6.3 μL of polymer solution was added to 630 μL of perovskite precursor. The copolymer [(PEO) 150 -(PPO) 30 ] in the perovskite precursor solution at a concentration of 2.5 mg / mL and stirred at room temperature for 1~2 h to obtain copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 precursor solution; take 70 μL of copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 The precursor solution was deposited on the urea interface modification layer. During spin coating, the first step was 500 rpm for 5 s, and the second step was 4500 rpm for 50 s. 10 s before the end of the second step, 650 μL of ether was spin-coated and annealed to obtain Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 Perovskite photosensitive layer. The annealing during the preparation of the perovskite photosensitive layer refers to annealing at 60°C for 3 minutes and then annealing at 100°C for 6 minutes.

[0024] The PCBM / BCP electron transport layer was prepared as follows: 0.4 mg of PCBM and 0.3 mg of BCP were weighed, dispersed separately in 1 mL of chlorobenzene solution, and stirred continuously to fully dissolve to obtain a clear solution. 20 μL of the PCBM solution was spin-coated onto the perovskite photoactive layer and annealed at 75°C for 5 minutes. Then, 15 μL of the BCP solution was spin-coated onto the PCBM layer and annealed at 60°C for 5 minutes to form the PCBM / BCP bilayer electron transport layer.

[0025] The annealing in step (1) refers to annealing at 180°C for 90 min.

[0026] Furthermore, the urea-modified Li and Cu co-doped NiO prepared by the above method x The inverted perovskite solar cell with a hole transport layer includes an ITO substrate, and Li and Cu co-doped NiO on the substrate layer from bottom to top. x Hole transport layer, urea interface modification layer, Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 photosensitive layer, PCBM / BCP electron transport layer, Ag counter electrode layer, among which Li and Cu co-doped NiO x The thickness of the hole transport layer is about 30 nm, the thickness of the urea interface modification layer is about 2~5 nm, and the thickness of the Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3The thickness of the photosensitive layer is about 600 nm, the thickness of the PCBM / BCP electron transport layer is about 15 and 10 nm, respectively, and the thickness of the Ag counter electrode layer is about 110 nm.

[0027] The present invention uses nickel acetate tetrahydrate, lithium acetate and copper acetate monohydrate as raw materials to prepare Li and Cu co-doped NiO based on a full low-temperature solution process. x Aqueous solution, spin coating deposition to obtain the hole transport layer, the method is simple and can be expanded. x The dangling bonds and dislocations on its surface can generate a large number of defect states, which will cause serious non-radiative recombination of photogenerated charges. The urea aqueous solution is deposited on Li and Cu co-doped NiO. x On the hole transport layer, the NH2 groups contained in urea can be co-doped with Li and Cu to form NiO x and perovskite interaction, promoting the transfer of photogenerated charges from perovskite to Li and Cu co-doped NiO xRapid transmission and improved photogenerated charge separation efficiency. 150 -(PPO) 30 When introduced into the perovskite precursor, the polymer forms a uniform, dense interface layer that passivates perovskite grain boundary defects and promotes efficient extraction of photogenerated charges. By optimizing the cell device fabrication process, device stability and photovoltaic response characteristics can be significantly improved.

[0028] Compared with the prior art, the present invention has the following advantages:

[0029] Prepared ITO / Li, Cu co-doped NiO x / urea / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Ag inverse-structure perovskite solar cells have abundant raw material reserves, simple preparation methods, good stability, safety and environmental protection, and have good prospects for commercial development. The average photoelectric conversion efficiency of the corresponding battery devices has reached 20.03%. By optimizing the device preparation process, the highest photoelectric conversion efficiency has reached 21.12%; under non-encapsulation conditions, the best device prepared was continuously illuminated for 800 hours, and its photoelectric conversion efficiency remained above 95% of the initial efficiency. This inverse-structure perovskite battery can not only improve the photoelectric conversion efficiency, but also significantly improve the device's stability to humidity, heat, and light intensity. Combined with the battery assembly process, quantitative preparation can be achieved based on the all-low-temperature solution process, and large-scale preparation can be achieved by using processes such as scraping, spraying, and roll-to-roll, reducing manufacturing costs. It has good application prospects and provides experimental and key technologies for the commercialization of inverse-structure perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 (a) is the Li and Cu co-doped NiO prepared in Example 1 x Film surface morphology; (b) ITO / Li, Cu co-doped NiO prepared in Example 1 x / urea / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 ) Schematic diagram of the structure of a 3 / PCBM / BCP / Ag inverse solar cell;

[0031] Figure 2 (a) ITO / Li, Cu co-doped NiO prepared in Example 2 x / urea / Cs0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Ag inverse structure solar cell efficiency versus added polymer concentration curve; (b) ITO / Li, Cu co-doped NiO prepared in Example 3 x / urea / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Ag inverse structure solar cell efficiency versus deposited urea concentration curve; (c) ITO / Li, Cu co-doped NiO prepared in Example 1 x / urea / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Ag inverse structure solar cells J - V Curve (d) is ITO / Li, Cu co-doped NiO obtained in Example 1 x / urea / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Ag inverse structure solar cell external quantum efficiency spectrum (EQE);

[0032] Figure 3 (a) shows the relationship between the open circuit voltage and light intensity of the inverted solar cell with and without urea interface modification prepared in Example 1; (b) shows the relationship between the short circuit current and light intensity of the inverted solar cell with and without urea interface modification prepared in Example 1; (c) shows the relationship between the dark state of the fully perovskite solar cell with and without urea interface modification prepared in Example 1. J - V Curve (d) is the electrochemical impedance spectroscopy (EIS) of the inverse structure solar cell with / without urea interface modification prepared in Example 1;

[0033] Figure 4(a) is the inverse structure solar cell with / without urea interface modification prepared in Example 1 V OC Statistical results bar graph; (b) is the inverse structure solar cell with / without urea interface modification prepared in Example 1 J SC Statistical results bar graph; (c) is a bar graph of the FF statistical results of the trans-structure solar cell with / without urea interface modification prepared in Example 1; (d) is a bar graph of the efficiency statistical results of the trans-structure solar cell with / without urea interface modification prepared in Example 1;

[0034] Figure 5 In the figure: (a) shows the long-term operation stability of the inverse structure solar cell with / without urea interface modification prepared in Example 1; (b) shows the storage stability of the inverse structure solar cell with / without urea interface modification prepared in Example 1 under wet and hot environments. DETAILED DESCRIPTION

[0035] The technical solution of the present invention is described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto:

[0036] In the following examples [(PEO) 150 -(PPO) 30 ], urea, PCBM, BCP, nickel acetate tetrahydrate, lithium acetate, copper acetate monohydrate and ammonia were purchased from Fisher Scientific Chemical Reagent Co., Ltd., and MAI (methylamine hydroiodide), FAI (formamidine hydroiodide), PbI2, PbBr2, CsI, RbI, DMF, DMSO, Pb(SCN)2, diethyl ether, 4-tert-butylpyridine, acetonitrile, Co(III)-TFSI and Li-TFSI were purchased from Sigma Aldrich Technology Co., Ltd.

[0037] Example 1

[0038] A Li and Cu co-doped NiO x The method for preparing an inverted perovskite solar cell with a hole transport layer is as follows:

[0039] (1) Select conductive glass with deposited ITO strip electrodes. First, scrub the glass repeatedly with detergent to remove oil stains from the surface. Second, cut the ITO conductive glass into regular small pieces, such as 1 cm × 1 cm. Ultrasonicate the pieces in deionized water for 30 min, in acetone solution for 30 min, and in isopropanol solution for 30 min. Finally, dry the ITO conductive glass in an oven at 100°C for 30 min to obtain a clean ITO electrode.

[0040] (2) Li and Cu co-doped NiO x The aqueous solution preparation process is as follows: 2.5 g nickel acetate tetrahydrate (10 mmol) is added to a 25 mL glass flask, 10 mL deionized water is added, and the nickel acetate tetrahydrate powder is fully dissolved by stirring to obtain a blue-green clear solution; 0.5 g lithium acetate (anhydrous lithium acetate, 7.6 mmol) is added to a 10 mL glass flask, 5 mL deionized water is added, and the lithium acetate powder is fully dissolved by stirring to obtain a colorless clear solution; 1 g copper acetate monohydrate (5 mmol) is added to a 10 mL glass flask, 5 mL anhydrous ethanol is added, and the copper acetate powder is fully dissolved by stirring to obtain a blue-green clear solution; 10 mL ammonia water (mass percentage concentration: 28%~29%) is added to a 50 mL glass flask, sealed and set aside; 5 mL nickel acetate and 0.0987 mL of lithium acetate solution was slowly added dropwise to ammonia water in sequence. Nickel acetate and lithium acetate reacted with ammonia water to produce two hydroxides. The two hydroxides were allowed to react with excess ammonia water to produce their complexes. 0.1 mL of copper acetate solution was measured and slowly added dropwise to the mixed solution of excess ammonia water and the complex. The copper acetate reacted with ammonia water to produce hydroxides. The excess ammonia water was allowed to react with the hydroxides to produce their complexes. The mixed solution was stirred continuously to allow all hydroxides (amphoteric compounds) to fully react with the excess ammonia water to form complexes, thereby obtaining a stable, clear solution (ammonia water was in excess throughout the experiment to maintain pH>10). The solid content of the obtained mixed solution was measured to be 84.2 mg / mL. 44.8 mL of deionized water was added for dilution. The solid content of the diluted solution was 21.33 mg / mL. The solution was sealed and stored for later use.

[0041] Take 30 μL of diluted Li and Cu co-doped NiO x The aqueous solution (solid content of 21.33 mg / mL) was spin-coated on an ITO conductive glass electrode and annealed at 180 °C on a hot plate for 90 min to obtain Li and Cu co-doped NiO with a thickness of about 30 nm. x Hole transport layer. Figure 1 (a) is Li and Cu co-doped NiO x Scanning electron microscope images of the hole transport layer show that Li and Cu co-doped NiO x The film is smooth, dense, has few pinholes, and achieves complete coverage, which is conducive to the efficient extraction of photogenerated charges.

[0042] (3) Deposition of urea interface modification layer: Weigh 40 mg of urea and add it to 100 mL of deionized water. Stir until it is fully dissolved. The resulting urea solution concentration is 0.4 mg mL -1Measure 20 μL of urea solution and spin-coat it onto Li and Cu co-doped NiO x The hole transport layer was annealed at 120 °C for 20 min to obtain a urea interface modification layer.

[0043] (4) Deposition of perovskite Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 Photosensitive layer: 0.27 mmol FAI, 0.63 mmol MAI, 0.85 mmol PbI2, 0.15 mmol PbBr2, 0.05 mmol CsI, 0.05 mmol RbI and 11.15 mg Pb(SCN)2 were weighed in sequence and added to a mixed solvent of 560 μL DMF and 70 μL DMSO. The solution was stirred continuously on a hot plate at 65 °C in a glove box for 12 h until the solid was completely dissolved; 250 mg copolymer [(PEO) 150 -(PPO) 30 ], added to 1 mL DMF solution, stirred continuously for 2-3 h to obtain a copolymer solution with a concentration of 250 mg / mL, 6.3 μL of polymer solution was added to 630 μL of perovskite precursor, and the copolymer [(PEO) 150 -(PPO) 30 ] in the perovskite precursor solution at a concentration of 2.5 mg / mL and stirred at room temperature for 1~2 h to obtain copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 precursor solution; take 70 μL of copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 The precursor solution was deposited onto the urea interface modification layer. During spin coating, the first step was 500 rpm for 5 s, and the second step was 4500 rpm for 50 s. 10 s before the end of the second step, 650 μL of ether was spin-coated and deposited. The mixture was annealed at 60 °C for 3 min and then at 100 °C for 6 min to obtain the copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.05 Rb 0.05 MA 0.63 FA0.27 Pb(I 0.90 Br 0.10 )3 Perovskite photosensitive layer.

[0044] (5) The preparation process of the PCBM / BCP electron transport layer is as follows: 0.4 mg of PCBM and 0.3 mg of BCP are weighed in sequence and dispersed into 1 mL of chlorobenzene solution. Stirring is continued until both are fully dissolved to obtain a clear solution. 20 μL of the PCBM solution is measured and spin-coated onto the perovskite photoactive layer and annealed at 75 °C for 5 min. 15 μL of the BCP solution is measured and spin-coated onto the PCBM layer and annealed at 60 °C for 5 min to obtain the PCBM / BCP electron transport layer.

[0045] (6) The Ag layer was deposited as the counter electrode by vacuum thermal evaporation method. The thickness of the Ag layer was about 110 nm, and ITO / Li, Cu co-doped NiO was obtained. x / Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 / PCBM / BCP / Au inverse structure perovskite solar cells. Figure 1 (b) is a schematic diagram of the inverse perovskite battery structure. This battery structure is based on a fully low-temperature solution preparation process, with rich materials, simple methods, and good application prospects. Figure 2 (c) is a perovskite solar cell J - V The response curve shows that urea interface modification can improve the photovoltaic response characteristics of the device. The optimal open circuit voltage of the photovoltaic device ( V OC =1.112 V), short-circuit current ( J SC =23.36 mAcm -2 ), fill factor (FF=0.813), and photoelectric conversion efficiency (PCE=21.12%), indicating that urea interface modification can effectively passivate interface defect states, promote efficient separation and extraction of photogenerated charges, and improve device J SC and FF. Figure 2 (d) is the EQE response spectrum of the perovskite solar cell. The external quantum efficiency (EQE) of the cell device in the visible light region of 410~790 nm is greater than 84.7%, indicating that the perovskite solar cell has a high photoelectric conversion efficiency in the entire visible light region, which can effectively promote the separation of photogenerated charges and improve the photovoltaic response characteristics of the cell device.

[0046] (7) The preparation of perovskite solar cells without urea interface modification is the same as steps (1) to (6) except that step (3) is omitted.

[0047] Figure 3 (a) shows the relationship between the open circuit voltage and light intensity of perovskite solar cells with and without urea interface modification. Urea interface modification can reduce the slope of the curve of the relationship between open circuit voltage and light intensity, indicating that urea interface modification can effectively hinder the interface non-radiative recombination assisted by defect states. Figure 3 (b) is the relationship curve between the short-circuit current and light intensity of perovskite solar cells with and without urea interface modification. The exponential factor of the curve after urea interface modification ( α ) is significantly higher than the exponential factor of the curve without urea interface modification. The higher exponential factor also indicates that urea interface modification can effectively inhibit the interface non-radiative recombination assisted by defect states. Figure 3 (c) is the dark state of the perovskite solar cell J - V The response curve shows that the device has smaller reverse leakage current and higher forward injection current (≥0.616 V) after urea interface modification; Figure 3 Middle (d) shows the electrochemical response impedance spectrum of perovskite solar cells with and without urea interface modification. In the low-frequency region, the urea interface modification has a larger semicircle, indicating that urea modification can passivate interface defects, increase the interface recombination impedance of photogenerated charges, and promote the efficient extraction of photogenerated charges.

[0048] Figure 4 (a), (b), (c), and (d) are bar charts of the statistical results of various parameters of perovskite solar cells with and without urea interface modification. Figure 4 (a) is the open circuit voltage response bar graph, which shows that urea interface modification can increase the open circuit voltage and reduce the voltage hysteresis response; Figure 4 (b) is a histogram of the short-circuit current response, indicating that urea interface modification can effectively increase the short-circuit current and significantly reduce the current hysteresis response; Figure 4 (c) is the filling factor response bar graph, which shows that urea interface modification can effectively improve the filling factor, reduce the series resistance and increase the parallel resistance; Figure 4 (d) is a bar graph of battery efficiency response, indicating that urea interface modification can improve device response efficiency and reduce hysteresis response.

[0049] Figure 5 (a) and (b) are the stability response curves of the battery device. Figure 5 (a) is the long-term operation stability response curve of the battery device, with / without urea interface modification, using Li and Cu co-doped NiO xThe inverse perovskite solar cells with a hole transport layer showed very excellent operating stability, and their efficiency remained above 95% of the initial efficiency after 800 h of continuous illumination. Figure 5 (b) is the response curve of the battery device to humidity and heat (65 ℃, 60∼70% humidity), with / without urea interface modification, using Li and Cu co-doped NiO x The inverse perovskite solar cells with a hole transport layer exhibited excellent wet and hot stability, and their efficiency remained above 80% of the initial efficiency after being stored in wet and hot environments for 800 h.

[0050] Example 2

[0051] For the introduced diblock copolymer [(PEO) 150 -(PPO) 30 ], gradually increasing the concentration of the copolymer in the perovskite precursor solution (0, 1 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL, 10.0 mg / mL), and the rest is the same as in Example 1. The device efficiency increases with the introduction of the copolymer ((PEO) 150 -(PPO) 30 ) concentration change curve is as follows Figure 2 In (a), Figure 2 As shown in (a), the photoelectric conversion efficiency of the corresponding perovskite solar cell shows a trend of first increasing and then decreasing. This is because when the copolymer is introduced into the perovskite precursor, the hydrophilic functional groups of the copolymer will interact with the cations of the perovskite, forming a copolymer interface layer through self-assembly. These interface layers will be evenly distributed at the boundaries of the perovskite grains or grain clusters, which can effectively passivate the perovskite grain boundary defects and promote the efficient extraction of photogenerated charges. Further improving the copolymer [(PEO) 150 -(PPO) 30 ] concentration, the copolymer forms a thicker interfacial layer, which better passivates grain boundary defects. However, due to the excellent insulating properties of the copolymer interfacial layer, a thicker interfacial layer would hinder the rapid transport and extraction of photogenerated charges, affecting the performance of the battery device. The copolymer exhibits the highest photovoltaic response at a concentration of 2.5 mg / mL in the perovskite precursor solution. This concentration allows the copolymer to form an optimal interfacial layer, effectively passivating perovskite grain boundary defects without forming a thick charge transfer barrier. This promotes the efficient separation and extraction of photogenerated charges, enhancing the optoelectronic properties of trans-structured perovskite battery devices.

[0052] Example 3

[0053] For the urea interface modification layer, the deposition concentration of the urea aqueous solution was gradually increased (0.0, 0.2, 0.4, 0.6, 0.8, 1.0 mg / mL), and the other aspects were the same as in Example 1. The relationship curve between the device efficiency and the concentration of the urea aqueous solution is shown in FIG. Figure 2 As shown in (b). Figure 2 As shown in (b), the photoelectric conversion efficiency of perovskite solar cells shows a trend of first increasing and then decreasing. x Hole transport layer, NiO x Surface dangling bonds and dislocations generate a large number of defect states. Urea deposition effectively passivates interfacial defects, promoting efficient separation and extraction of photogenerated charges. The results indicate that depositing an appropriate concentration of urea (0.4 mg / mL) effectively passivates interfacial defects and promotes efficient separation of photogenerated charges. Further increasing the urea concentration, resulting in a thicker urea layer, effectively passivates interfacial defects. However, its insulating properties also form an interfacial barrier, hindering rapid charge transport and affecting the photovoltaic response characteristics of the cell device.

[0054] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications are considered to be within the scope of protection of the present invention.

Claims

1. A Li- and Cu-codoped NiO x The method for preparing an inverse perovskite battery is characterized in that: The steps include: (1) Deposition of Li and Cu co-doped NiO on a clean ITO electrode x The hole transport layer is prepared by low temperature solution method and Li and Cu co-doped NiO with pH value>10. x The solution was diluted with deionized water and then spin-coated on a clean ITO electrode and annealed to obtain Li and Cu co-doped NiO. x hole transport layer; (2) Li and Cu co-doped NiO x A urea aqueous solution is deposited on the hole transport layer and annealed to obtain a urea interface modification layer. The concentration of the urea aqueous solution is 0.1-0.8 mg / mL. (3) Deposition of diblock copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1- x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 perovskite photosensitive layer, the value range of x is 0.02~0.06, and the value range of y is 0.05~0.30; (4) PCBM and BCP are sequentially deposited on the perovskite photosensitive layer as electron transport layers; (5) Evaporate an Ag layer onto the PCBM / BCP electron transport layer to obtain a counter electrode.

2. The Li- and Cu-codoped NiO according to claim 1 x The method for preparing an inverse perovskite battery is characterized in that: The Li and Cu co-doped NiO x The aqueous solution was obtained by the following method: (a) dissolving nickel acetate tetrahydrate in deionized water to obtain a nickel acetate solution; (b) dissolving lithium acetate in deionized water to obtain a lithium acetate solution; (c) dissolving copper acetate monohydrate in anhydrous ethanol to obtain a copper acetate solution; (d) sequentially measuring the nickel acetate and lithium acetate solutions obtained in steps (a) and (b), and adding them dropwise to concentrated aqueous ammonia with continuous stirring to obtain a complex of the two metals; (e) measuring the copper acetate solution obtained in step (c) and adding it dropwise to the solution obtained in step (d) while stirring continuously to obtain a complex of the three metals; (f) Measure the solid content of the mixed solution obtained in step (e). The pH value of the entire experimental process of steps (d) and (e) is greater than 10.

3. The Li and Cu co-doped NiO according to claim 2 x The method for preparing an inverse perovskite battery is characterized in that: In step (a), the concentration of nickel acetate is 1 mmol / mL; in step (b), the concentration of lithium acetate is 1.52 mmol / mL; in step (c), the concentration of copper acetate is 1 mmol / mL; in step (d), the molar ratio of nickel acetate to lithium acetate is 1:0.03; in step (e), the molar ratio of nickel acetate to copper acetate is 1:0.02; in step (d), when the amount of nickel acetate used is 5 mmol, the amount of concentrated ammonia water used is 10 mL.

4. The Li- and Cu-codoped NiO according to claim 1 x The method for preparing an inverse perovskite battery is characterized in that: The preparation process of the urea interface modification layer is as follows: weigh urea and add it to deionized water, stirring to fully dissolve it. The concentration of the obtained urea solution is 0.4 mg mL -1 Measure 20 μL of urea solution and spin-coat it onto Li and Cu co-doped NiO x Annealing is performed on the hole transport layer to obtain a urea interface modification layer.

5. The Li- and Cu-codoped NiO according to claim 1 x The method for preparing an inverse perovskite battery is characterized in that: The diblock copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y The preparation process of the )3 photosensitive layer is as follows: 0.27 mmol FAI, 0.63 mmol MAI, (1-3y / 2) mmol PbI2, 3y / 2 mmol PbBr2, (0.1-x) mmol CsI, x mmol RbI and 11.15 mg Pb(SCN)2 are weighed in sequence and added to a mixed solvent of DMF and DMSO with a volume ratio of 8:

1. The mixture is stirred at 60-70°C until the solid is completely dissolved to obtain a perovskite precursor solution. The copolymer [(PEO) 150 -(PPO) 30 ] was dispersed in DMF solution, different volumes of copolymer solution were added to the perovskite precursor, the concentration of copolymer in the perovskite precursor was 1.0~8.0 mg / mL, and the mixture was stirred at room temperature for 1~2 h to obtain copolymer-modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 precursor solution; The copolymer modified perovskite precursor solution was deposited onto the urea interface modification layer and annealed to obtain Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 Perovskite photosensitive layer.

6. The Li and Cu co-doped NiO according to claim 5 x The method for preparing an inverse perovskite battery is characterized in that: Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 The perovskite photosensitive layer is specifically Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3, the specific preparation process is as follows: 0.27 mmol FAI, 0.63 mmol MAI, 0.85 mmol PbI2, 0.15 mmol PbBr2, 0.05 mmol CsI, 0.05 mmol RbI and 11.15 mg Pb(SCN)2 were weighed in sequence and added to a mixed solvent of 560 μL DMF and 70 μL DMSO. The solution was stirred at 65 °C for 12 h until the solid was completely dissolved; 250 mg copolymer [(PEO) 150 -(PPO) 30 ], added to 1 mL DMF solution, stirred for 2-3 h to obtain a copolymer solution with a concentration of 250 mg / mL, and 6.3 μL of polymer solution was added to 630 μL of perovskite precursor. The copolymer [(PEO) 150 -(PPO) 30 ] in the perovskite precursor solution at a concentration of 2.5 mg / mL and stirred at room temperature for 1~2 h to obtain copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 precursor solution; Take 70 μL of copolymer-modified Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 The precursor solution was deposited on the urea interface modification layer. During spin coating, the first step was 500 rpm for 5 s, and the second step was 4500 rpm for 50 s. 10 s before the end of the second step, 650 μL of ether was spin-coated and annealed to obtain Cs 0.05 Rb 0.05 MA 0.63 FA 0.27 Pb(I 0.90 Br 0.10 )3 Perovskite photosensitive layer.

7. The Li- and Cu-codoped NiO according to claim 1 x The method for preparing an inverse perovskite battery is characterized in that: The preparation process of the PCBM / BCP electron transport layer is as follows: PCBM and BCP are dissolved in chlorobenzene respectively, with the concentration of PCBM in chlorobenzene being 0.4 mg / mL and the concentration of BCP in chlorobenzene being 0.3 mg / mL. The PCBM solution is measured and spin-coated on the perovskite photosensitive layer, and annealed at 75°C for 5 min; the BCP solution is measured and spin-coated on the PCBM layer, and annealed at 60°C for 5 min to obtain the PCBM / BCP electron transport layer.

8. The Li- and Cu-codoped NiO according to claim 1 x The method for preparing an inverse perovskite battery is characterized in that: The annealing in step (1) refers to annealing at 180°C for 90 min; the annealing in step (2) refers to annealing at 120°C for 20 min.

9. The Li- and Cu-codoped NiO according to claim 6 x The method for preparing an inverse perovskite battery is characterized in that: The annealing during the preparation of the perovskite photosensitive layer refers to annealing at 60°C for 3 minutes and then annealing at 100°C for 6 minutes.

10. Li- and Cu-codoped NiO prepared by the method according to any one of claims 1 to 9 x An inverse perovskite battery, characterized in that Including ITO substrate, Li, Cu co-doped NiO on the substrate layer from bottom to top x Hole transport layer, urea interface modification layer, diblock copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3 photosensitive layer, PCBM / BCP electron transport layer, Ag counter electrode layer, among which Li and Cu co-doped NiO x The thickness of the hole transport layer is 30 nm, the thickness of the urea interface modification layer is 2~5 nm, and the diblock copolymer [(PEO) 150 -(PPO) 30 ] modified Cs 0.1-x Rb x MA 0.63 FA 0.27 Pb(I 1-y Br y )3The thickness of the photosensitive layer is 600 nm, the thickness of the PCBM / BCP electron transport layer is 15 and 10 nm respectively, and the thickness of the Ag counter electrode layer is 110 nm.

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