Preparation method and application of copper-doped indium hydroxide nano material

Abstract

The invention discloses a preparation method and application of a copper-doped indium hydroxide nano material, and belongs to the technical field of novel solar cells. The preparation method of the copper-doped indium hydroxide nano material comprises the following specific steps: preparing a polyether P123 solution, preparing a KOH solution, adding indium nitrate and copper nitrate, adding ethylene glycol, heating in an air dry oven at 220 DEG C, and the like. The prepared copper-doped indium hydroxide nano material can be used as an interface modification layer to be applied to a carbon-based perovskite solar cell. The copper-doped indium hydroxide nano material is prepared by adopting a simple, convenient and efficient synthesis process, good operability and repeatability are achieved, and the carbon-based perovskite solar cell based on the copper-doped indium hydroxide interface modification layer not only has high photoelectric conversion efficiency, but also shows good stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of novel solar cells, and relates to a preparation method of an inorganic metal hydroxide nanomaterial and its application in carbon-based perovskite solar cells. Background Art

[0002] Perovskite solar cells have become a research hotspot in the photovoltaic field due to their high light absorption coefficient, excellent photoelectric conversion efficiency, low-cost preparation process, and flexible bandgap adjustment ability. However, the inherent high cost, scarcity of noble metals, and complexity of vacuum evaporation coating process severely restrict the large-scale commercial application of PSCs. The carbon electrode has the characteristics of strong conductivity, low cost, and strong stability, and is undoubtedly an excellent choice to replace the metal electrode. At present, blade coating method, screen printing method, and lamination method are the main methods for fabricating the carbon electrode of perovskite solar cells. However, the first two usually use organic solutions as solvents, which will damage the underlying materials and affect the optoelectronic properties. A large number of pores will be generated due to solution replacement during the preparation of the carbon film by the lamination method, affecting the interface contact. In addition, compared with gold and silver electrodes, there are some problems in the energy level matching of the carbon electrode.

[0003] The preparation of inorganic metal hydroxides is simple, and the raw materials required are also relatively abundant and cheap. However, at present, inorganic metal hydroxides are usually used as charge transport layer materials in the field of carbon-based perovskite solar cells, and the research on using inorganic metal hydroxides as interface modification layers is still less. At the same time, when used as an interface modification layer, the particle size of inorganic metal hydroxides will also affect the modification effect. Large particle inorganic metal hydroxides have poor dispersibility and are prone to loose accumulation when prepared into an interface modification layer, making it difficult to form a dense interface modification layer, resulting in poor interface contact and increasing the charge transport resistance. Therefore, how to prepare nanoparticles is also a difficult point. Summary of the Invention

[0004] The purpose of the present invention is to improve the deficiencies existing in the preparation of carbon electrodes by the lamination method, and to provide a copper-doped indium hydroxide nanomaterial, which is used as an interface modification layer in carbon-based perovskite solar cells, and good photoelectric conversion efficiency has been achieved.

[0005] The above technical problems are achieved through the following technical solutions:

[0006] A preparation method of a copper-doped indium hydroxide nanomaterial, the specific steps are as follows:

[0007] (1) Use deionized water to prepare a polyether P123 solution with a concentration of 50 mg / mL, and stir well at room temperature until completely dissolved;

[0008] (2) Prepare a KOH solution with deionized water at a concentration of 0.875 M, and stir well at room temperature until completely dissolved;

[0009] (3) Weigh indium nitrate and copper nitrate successively. The molar amount of copper is 25% - 100% of that of indium. Then add them to the solution in step (1). For every 1 mmol of In 3+ Use 8 mL of polyether P123 solution;

[0010] (4) Add ethylene glycol to the solution in step (3). Use 0.875 mL of ethylene glycol for every 1 mL of the solution in step (3);

[0011] (5) Add the KOH solution in step (2) to the solution obtained in step (4). Use 0.67 mL of KOH solution for every 1 mL of the solution in step (4);

[0012] (6) Add the solution obtained in step (5) to a reaction kettle, and then place the reaction kettle in a forced-air drying oven and heat it at 220 °C for 3 h;

[0013] (7) Wash the product obtained in step (6) with dilute ammonia water and ethanol respectively, and finally obtain copper-doped indium hydroxide nanomaterials.

[0014] The preferred molar ratio of copper to indium described in step (3) is 50%.

[0015] An application of copper-doped indium hydroxide nanomaterials, used as an interfacial modification layer in carbon-based perovskite solar cells. The specific steps are as follows:

[0016] (1) Cut the conductive glass into 1.5 cm × 1.5 cm squares, and ultrasonically clean them with isopropyl alcohol, deionized water, and ethanol for 30 min in sequence, and then treat them with ultraviolet ozone for 15 min;

[0017] (2) Prepare a TiO2 precursor solution. Add isopropyl titanate and hydrochloric acid to n-butanol to form a mixed solution. The concentrations of isopropyl titanate and hydrochloric acid in the mixed solution are both 0.125 M;

[0018] (3) Spin-coat the TiO2 precursor solution on the conductive glass at a speed of 3000 rpm for 30 s, and heat it at 80 °C and 120 °C for 20 min and 15 min respectively; wait for the glass to cool to room temperature and then soak it in a TiCl4 dilution solution at 70 °C for 30 min. Finally, sinter it in a muffle furnace at 500 °C for 1 h to obtain a TiO2 dense layer. The concentration of the TiCl4 dilution solution is 0.025 M;

[0019] (4) Weigh the TiO2 porous layer slurry and dilute it with ethanol. Use 7.59 mL of ethanol for every 1 g of the TiO2 porous layer slurry. Spin-coat this slurry onto the TiO2 dense layer under the conditions of 6000 rpm for 30 s, and then heat it at 80 °C for 20 min and 120 °C for 15 min successively. Finally, sinter it in a muffle furnace at 500 °C for 30 min;

[0020] (5) Dissolve lead iodide and formamidinium iodide in a mixed solvent of DMSO and DMF with a volume ratio of 4:1 to prepare a formamidinium lead iodide solution. Use 668 mg of lead iodide and 227 mg of formamidinium iodide for every 1 mL of the mixed solvent. Dissolve lead bromide and methylammonium bromide in a mixed solvent of DMSO and DMF with a volume ratio of 4:1 to prepare a methylammonium lead bromide solution. Use 160 mg of lead bromide and 49 mg of methylammonium bromide for every 1 mL of the mixed solvent. Then prepare a cesium iodide solution by using 380 mg of cesium iodide for every 1 mL of DMSO. Mix the formamidinium lead iodide solution, methylammonium lead bromide solution, and cesium iodide solution in a volume ratio of 1:0.2:0.06 to obtain a perovskite precursor solution;

[0021] (6) First, treat the TiO2 layer with ultraviolet ozone for 10 min and then spin-coat to prepare the perovskite layer. The parameters for the first step are 2000 rpm for 10 s, and the parameters for the second step are 7000 rpm for 30 s. At the 11th second from the end of the second step, drop 100 μL of chlorobenzene antisolvent at the center of the substrate. After the dropping is completed, anneal it at 100 °C for 1 h;

[0022] (7) Dissolve Spiro-OMeTAD (i.e., 2,2',7,7'-tetrakis(N,N'-bis(4-methoxyphenyl)amino)-9,9'-spirobifluorene) in chlorobenzene, and then add Li-TFSI and 4-tert-butylpyridine successively. Heat the mixture overnight at 70 °C. Among them, the concentration of Li-TFSI is 520 mg / mL. Use 72.5 mg of Spiro-OMeTAD, 19 μL of Li-TFSI, and 29 μL of 4-tert-butylpyridine for every 1 mL of chlorobenzene. Take 38 μL of the above mixed solution and spin-coat it under the conditions of 4500 rpm for 30 s to form a hole transport layer;

[0023] (8) Use commercial conductive carbon paste as the raw material and uniformly coat it on the cleaned carbon paper. Then soak the wet carbon film in ethanol for 30 min. After soaking, take out the carbon film and place it flat in a dry environment to dry;

[0024] (9) Disperse the copper-doped indium hydroxide nanomaterial in a mixed solution of DMSO and IPA with a volume ratio of 1:1 to obtain a dispersion with a concentration of 15 mg / mL;

[0025] (10) Take 200 - 800 μL of the dispersion obtained in step (9) and form a uniform and smooth interfacial modification layer on the carbon film obtained in step (8) by spraying method, and then dry it at 40 °C for 3 h;

[0026] (11) Thermally press the modified carbon film in step (10) onto the hole transport layer to finally obtain a carbon-based perovskite solar cell with a copper-doped indium hydroxide interfacial modification layer.

[0027] The amount of the dispersion used in step (10) is preferably 400 μL.

[0028] Beneficial effects

[0029] 1. The present invention prepares copper-doped indium hydroxide nanomaterials by a simple and efficient synthesis process, which has good operability and repeatability.

[0030] 2. The copper-doped indium hydroxide nanomaterials in the present invention are synthesized by using raw materials with low cost and easy availability, providing strong support for the development of low-cost and high-performance optoelectronic devices.

[0031] 3. The carbon-based perovskite solar cell based on the copper-doped indium hydroxide interfacial modification layer in the present invention not only has a high photoelectric conversion efficiency but also shows good stability. Description of the drawings

[0032] Figure 1 is a process flow block diagram of the preparation of copper-doped indium hydroxide nanomaterials in the present invention.

[0033] Figure 2 is a process flow block diagram of the preparation of a carbon-based perovskite solar cell based on a copper-doped indium hydroxide interfacial modification layer in the present invention.

[0034] Figure 3 is a scanning electron microscope image of the copper-doped indium hydroxide interfacial modification layer prepared in Example 3.

[0035] Figure 4 is a scanning electron microscope image of the cross-section of the carbon-based perovskite solar cell prepared in Example 3.

[0036] Figure 5 is a transmission electron microscope image of the copper-doped indium hydroxide nanomaterials prepared in Example 3.

[0037] Figure 6 is a current density-voltage curve graph of the perovskite solar cells prepared in Examples 1 - 4.

[0038] Figure 7 is a current density-voltage curve graph of the perovskite solar cells prepared in Examples 3, 5, and 6. Specific embodiments

[0039] Example 1

[0040] A preparation method of indium hydroxide nanomaterial for carbon-based perovskite solar cells and its application in the interfacial modification layer specifically include the following steps:

[0041] Main feature: The interfacial modification layer material used in the carbon-based perovskite solar cell is an indium hydroxide nanomaterial without doped copper.

[0042] (1) A preparation method of indium hydroxide nanomaterial

[0043] Prepare a 50 mg / mL P123 solution with deionized water and stir it for dissolution for later use. Prepare a 0.875 M KOH solution with deionized water and dissolve it by ultrasonic for later use. Weigh 0.5 mmol In(NO3)3·xH2O and dissolve it in 4 mL of the previously prepared P123 solution and stir for 5 min. After dissolution, slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution in sequence and stir for more than 20 min. Transfer the precursor solution to a reaction kettle (filling rate 70%) and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, the indium hydroxide nanomaterial is obtained, denoted as In0.

[0044] (2) A method for applying the above indium hydroxide nanomaterial to carbon-based perovskite solar cells

[0045] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min, then heated at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 porous layer slurry (purchased from greatcell solar, model 30NR-D) was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution, 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution, 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. Ozone treatment for 10 min, and then 45 μL of this solution was deposited on the perovskite layer by two-step spin coating. The spin coating parameters for the first step were 2000 rpm for 10 s, and the spin coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin coating, it was annealed at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated on top of the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, and after soaking in ethanol to remove the solvent, it was air-dried overnight to obtain a carbon film. In0 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 400 μL of this dispersion was used to prepare an interfacial modification layer on the carbon film by spraying and dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 1, and the test curves are as Figure 6 shown. Under these conditions, the three parameters of the carbon-based perovskite solar cell, namely current density, fill factor, and voltage, are all poor, and the photoelectric conversion efficiency is significantly lower than that of the optimal example (Example 3).

[0046] Example 2

[0047] A preparation method of copper-doped indium hydroxide nanomaterials for carbon-based perovskite solar cells and their application in the interfacial modification layer, specifically including the following steps:

[0048] Main feature: When hydrothermally synthesizing copper-doped indium hydroxide nanomaterials, the feeding amount of copper nitrate is 25% of that of indium nitrate.

[0049] (1) A preparation method of copper-doped indium hydroxide nanomaterials

[0050] Prepare a 50 mg / mL P123 solution with deionized water and stir it for dissolution for later use. Prepare a 0.875 M KOH solution with deionized water and dissolve it by ultrasonic for later use. Weigh 0.5 mmol In(NO3)3·xH2O and 0.125 mmol Cu(NO3)2·3H2O and dissolve them in 4 mL of the previously prepared P123 solution and stir for 5 min. After dissolution, slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution in sequence and stir for more than 20 min. Transfer the precursor solution to a PPL reactor (filling rate 70%) and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, copper-doped indium hydroxide nanomaterials are obtained, denoted as In25.

[0051] (2) A method for applying the above copper-doped indium hydroxide nanomaterials to carbon-based perovskite solar cells

[0052] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the FTO conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min and then at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 slurry was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution. 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution. 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. Ozone treatment was carried out for 10 min, and then 45 μL of this solution was deposited on the perovskite layer by two-step spin coating. The spin coating parameters for the first step were 2000 rpm for 10 s, and the spin coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin coating, annealing was carried out at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated above the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, soaked in ethanol to remove the solvent, and then air-dried overnight to obtain a carbon film. In25 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 400 μL of this dispersion was used to prepare an interfacial modification layer on the carbon film by spraying and dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 1, and the test curves are as Figure 6 shown. Under these conditions, the fill factor and voltage values of the carbon-based perovskite solar cell are relatively low, and the photoelectric conversion efficiency is lower than that of the optimal example (Example 3). However, compared with Example 1, all parameters have been improved.

[0053] Example 3

[0054] Preparation method of copper-doped indium hydroxide nanomaterial for carbon-based perovskite solar cells and its application in interface modification layer, specifically including the following steps:

[0055] Main feature: When hydrothermally synthesizing copper-doped indium hydroxide nanomaterial, the feeding amount of copper nitrate is 50% of that of indium nitrate.

[0056] (1) Preparation method of a copper-doped indium hydroxide nanomaterial

[0057] Use deionized water to prepare a 50 mg / mL P123 solution and stir it until dissolved for standby. Use deionized water to prepare a 0.875 M KOH solution and ultrasonically dissolve it for standby. Weigh 0.5 mmol In(NO3)3·xH2O and 0.25 mmol Cu(NO3)2·3H2O and dissolve them in 4 mL of the previously prepared P123 solution and stir for 5 min. After dissolution, sequentially and slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution and stir for more than 20 min. Transfer the precursor solution to a PPL reaction kettle (filling rate 70%) and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, the copper-doped indium hydroxide nanomaterial is obtained, denoted as In50. As Figure 5 shown, through this method, not only can uniform nucleation and crystal growth be achieved, but also good controllability and repeatability can be maintained under relatively mild reaction conditions, providing a green, low-energy-consuming and efficient solution for the development and preparation of inorganic nanomaterials.

[0058] (2) Method for applying the above copper-doped indium hydroxide nanomaterial to carbon-based perovskite solar cells

[0059] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the FTO conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min, then heated at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 slurry was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution. 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution. 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. Ozone treatment was carried out for 10 min, and then 45 μL of this solution was deposited on the perovskite layer by a two-step spin-coating method. The spin-coating parameters for the first step were 2000 rpm for 10 s, and the spin-coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin-coating, annealing was carried out at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated on top of the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, and after soaking in ethanol to remove the solvent, it was left to dry naturally overnight to obtain a carbon film. In50 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 400 μL of this dispersion was used to prepare an interfacial modification layer on the carbon film by spraying and dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 1, and the test curves are as Figure 6 shown. Under these conditions, the three parameters of the carbon-based perovskite solar cell, namely current density, fill factor, and voltage, are all optimal, and all three parameters have been improved to a certain extent. The carbon-based perovskite solar cell based on the copper-doped indium hydroxide interfacial modification layer in the present invention not only has a high photoelectric conversion efficiency but also exhibits good stability, providing strong support for the development of low-cost and high-performance optoelectronic devices.

[0060] Example 4

[0061] A preparation method of copper-doped indium hydroxide nanomaterials for carbon-based perovskite solar cells and their application in the interfacial modification layer, specifically including the following steps:

[0062] Main feature: When hydrothermally synthesizing copper-doped indium hydroxide nanomaterials, the feeding amount of copper nitrate is 100% of indium nitrate.

[0063] (1) A preparation method of copper-doped indium hydroxide nanomaterials

[0064] Use deionized water to prepare a 50 mg / mL P123 solution and stir it until dissolved for standby. Use deionized water to prepare a 0.875 M KOH solution and ultrasonically dissolve it for standby. Weigh 0.5 mmol In(NO3)3·xH2O and 0.5 mmol Cu(NO3)2·3H2O and dissolve them in 4 mL of the previously prepared P123 solution and stir for 5 min. After dissolution, slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution in sequence and stir for more than 20 min. Transfer the precursor solution to a PPL reaction kettle (filling rate 70%) and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, copper-doped indium hydroxide nanomaterials are obtained, denoted as In100.

[0065] (2) A method for applying the above copper-doped indium hydroxide nanomaterials to carbon-based perovskite solar cells

[0066] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the FTO conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min and then at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 slurry was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution. 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution. 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. Ozone treatment was carried out for 10 min, and then 45 μL of this solution was deposited on the perovskite layer by two-step spin coating. The spin coating parameters for the first step were 2000 rpm for 10 s, and the spin coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin coating, annealing was carried out at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated on top of the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, and after soaking in ethanol to remove the solvent, it was air-dried overnight to obtain a carbon film. In100 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 400 μL of this dispersion was used to prepare an interface modification layer on the carbon film by spraying and dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 1, and the test curves are as Figure 6 shown. Under these conditions, the values of the current density, fill factor, and voltage of the carbon-based perovskite solar cell are all lower than those of the optimal example (Example 3), and the photoelectric conversion efficiency has decreased to a certain extent.

[0067] Example 5

[0068] Preparation method of copper-doped indium hydroxide nanomaterial for carbon-based perovskite solar cell and its application in interface modification layer, specifically including the following steps:

[0069] Main feature: Use 200 μL of In50 dispersion liquid to prepare the interface modification layer of the carbon-based perovskite solar cell.

[0070] (1) Preparation method of copper-doped indium hydroxide nanomaterial

[0071] Prepare a 50 mg / mL P123 solution with deionized water, stir and dissolve it for standby. Prepare a 0.875 M KOH solution with deionized water, ultrasonically dissolve it for standby. Weigh 0.5 mmol of In(NO3)3·xH2O and 0.25 mmol of Cu(NO3)2·3H2O and dissolve them in 4 mL of the previously prepared P123 solution, and stir for 5 min. After dissolution, slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution in sequence and stir for more than 20 min. Transfer the precursor solution to a PPL reaction kettle (filling rate 70%), and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, the copper-doped indium hydroxide nanomaterial is obtained.

[0072] (2) Method for applying the above copper-doped indium hydroxide nanomaterial to a carbon-based perovskite solar cell

[0073] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the FTO conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min and then at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 slurry was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution. 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution. 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. After ozone treatment for 10 min, 45 μL of this solution was deposited on the perovskite layer by two-step spin coating. The spin coating parameters for the first step were 2000 rpm for 10 s, and the spin coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin coating, it was annealed at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated on top of the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, and after soaking in ethanol to remove the solvent, it was air-dried overnight to obtain a carbon film. In50 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 200 μL of this dispersion was used to prepare an interfacial modification layer on the carbon film by spraying and dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 2, and the test curves are as Figure 7 shown. Under these conditions, the values of the current density, fill factor, and voltage of the carbon-based perovskite solar cell are all lower than those of the optimal example (Example 3), and the voltage gap is the most obvious, resulting in a lower photoelectric conversion efficiency.

[0074] Example 6

[0075] A preparation method of copper-doped indium hydroxide nanomaterials for carbon-based perovskite solar cells and their application in the interfacial modification layer, specifically including the following steps:

[0076] Main feature: Use 800 μL of In50 dispersion to prepare the interfacial modification layer of the carbon-based perovskite solar cell.

[0077] (1) A preparation method of copper-doped indium hydroxide nanomaterials

[0078] Prepare a 50 mg / mL P123 solution with deionized water, stir and dissolve it for later use. Prepare a 0.875 M KOH solution with deionized water, ultrasonic dissolve it for later use. Weigh 0.5 mmol of In(NO3)3·xH2O and 0.25 mmol of Cu(NO3)2·3H2O, dissolve them in 4 mL of the previously prepared P123 solution, and stir for 5 min. After dissolution, slowly add 3.5 mL of ethylene glycol and 5 mL of the previously prepared KOH solution in sequence and stir for more than 20 min. Transfer the precursor solution to a PPL reaction kettle (filling rate 70%), and react at 220 °C for 3 h. After cooling to room temperature, the product is washed with dilute ammonia water until the supernatant is transparent, and then ultrasonically washed with ethanol. After pouring out the supernatant, the copper-doped indium hydroxide nanomaterials are obtained.

[0079] (2) A method for applying the above copper-doped indium hydroxide nanomaterials to carbon-based perovskite solar cells

[0080] The conductive glass was cut into small pieces of 1.5 cm × 1.5 cm, cleaned, and then treated with ultraviolet ozone for 15 min. A TiO2 precursor solution was prepared, which consisted of a n-butanol solution of 0.125 M isopropyl titanate and 0.125 M hydrochloric acid. 60 μL of this solution was spin-coated on the FTO conductive glass at 3000 rpm for 30 s, heated on a hot plate at 80 °C for 20 min and then at 120 °C for 15 min. After heating, it was soaked in a TiCl4 dilution solution at 70 °C for 30 min, and finally sintered in a muffle furnace at 500 °C for 1 h to form a dense layer. The TiO2 slurry was diluted with ethanol, and 50 μL of this solution was spin-coated on the dense layer at 6000 rpm for 30 s, gradually heated again, and sintered at 500 °C for 30 min to form a porous layer. 668 mg of lead iodide and 227 mg of formamidinium iodide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2FAI3 solution. 160 mg of lead bromide and 49 mg of methylammonium bromide were dissolved in a mixed solution of DMF and DMSO with a ratio of 4:1 to prepare a Pb2MABr3 solution. 190 mg of cesium iodide was dissolved in 500 μL of DMSO to prepare a CsI solution. The Pb2FAI3 solution, Pb2MABr3 solution, and CsI solution were mixed in a ratio of 1:0.2:0.06 to obtain a perovskite precursor solution. Ozone treatment was carried out for 10 min, and then 45 μL of this solution was deposited to form a perovskite layer by a two-step spin-coating method. The spin-coating parameters for the first step were 2000 rpm for 10 s, and the spin-coating parameters for the second step were 7000 rpm for 30 s. At the same time, 100 μL of chlorobenzene was dropped at the 11th second from the end of the second step. After spin-coating, annealing was carried out at 100 °C for 1 h. 72.5 mg of Spiro-OMeTAD, 29 μL of 4-tert-butylpyridine, and 19 μL of Li-TFSI were added to 1 mL of chlorobenzene to obtain a mixed solution. 38 μL of this solution was spin-coated on top of the perovskite layer at 4500 rpm for 30 s. The conductive carbon paste was blade-coated on the carbon paper, and after soaking in ethanol to remove the solvent, it was left to dry naturally overnight to obtain a carbon film. In50 was dispersed in an 8 mL mixed solution of DMSO and IPA (ratio 1:1) to obtain a dispersion with a concentration of 15 mg / mL. 800 μL of this dispersion was used to prepare an interfacial modification layer on the carbon film by spraying and then dried. Finally, the carbon film was hot-pressed under the conditions of 0.5 MPa and 50 °C to complete the preparation of the carbon-based perovskite solar cell. The test results of this device are shown in Table 2, and the test curves are as Figure 7 shown. Under this condition, the values of the current density, fill factor, and voltage of the carbon-based perovskite solar cell all decreased to a certain extent compared with the optimal example (Example 3), and at the same time, the photoelectric conversion efficiency was lower than that of Example 5.

[0081] Table 1 Performance table of carbon-based perovskite solar cells with interfacial modification layers prepared based on different copper nitrate feeding ratios

[0082]

[0083] Table 2 Performance table of carbon-based perovskite solar cells with interface modification layers prepared based on different spray volumes

[0084]

Claims

1. A method for preparing copper-doped indium hydroxide nanomaterials, the specific steps are as follows: (1) Prepare a polyether P123 solution using deionized water with a concentration of 50 mg / mL, and stir well at room temperature until completely dissolved; (2) Prepare a KOH solution using deionized water with a concentration of 0.875 M, and stir well at room temperature until completely dissolved; (3) Weigh indium nitrate and copper nitrate successively. The molar amount of copper is 25% - 100% of that of indium. Then add them to the solution in step (1). For every 1 mmol of In 3+ Use 8 mL of polyether P123 solution; (4) Add ethylene glycol to the solution in step (3), using 0.875 mL of ethylene glycol for every 1 mL of the solution in step (3); (5) Add the KOH solution in step (2) to the solution obtained in step (4), using 0.67 mL of KOH solution for every 1 mL of the solution in step (4); (6) Add the solution obtained in step (5) to a reaction kettle, and then place the reaction kettle in a blast drying oven and heat it at 220 °C for 3 h; (7) Wash the product obtained in step (6) with dilute ammonia water and ethanol respectively, and finally obtain copper-doped indium hydroxide nanomaterials.

2. The preparation method of a copper-doped indium hydroxide nanomaterial according to claim 1, characterized in that, The molar ratio of copper to indium in step (3) is 50%.

3. Use of the copper-doped indium hydroxide nanomaterial prepared as claimed in claim 1, characterized in that, The copper-doped indium hydroxide nanomaterials are used as an interfacial modification layer in carbon-based perovskite solar cells, and the specific steps are as follows: (1) Cut the conductive glass into a square of 1.5 cm × 1.5 cm, ultrasonically clean it with isopropanol, deionized water, and ethanol for 30 min in sequence, and then treat it with ultraviolet ozone for 15 min; (2) Prepare a TiO2 precursor solution by adding isopropyl titanate and hydrochloric acid to n-butanol to form a mixed solution, and the concentrations of isopropyl titanate and hydrochloric acid in the mixed solution are both 0.125 M; (3) Spin-coat the TiO2 precursor solution on the conductive glass at a speed of 3000 rpm for 30 s, and heat it at 80 °C and 120 °C for 20 min and 15 min respectively; wait for the glass to cool to room temperature and then soak it in a TiCl4 dilution solution at 70 °C for 30 min, and finally sinter it in a muffle furnace at 500 °C for 1 h to obtain a TiO2 dense layer, and the concentration of the TiCl4 dilution solution is 0.025 M; (4) Weigh the TiO2 porous layer slurry and dilute it with ethanol, using 7.59 mL of ethanol for every 1 g of the TiO2 porous layer slurry, spin-coat the slurry on the TiO2 dense layer at a condition of 6000 rpm for 30 s, heat it at 80 °C and 120 °C for 20 min and 15 min respectively, and finally sinter it in a muffle furnace at 500 °C for 30 min; (5) Dissolve lead iodide and formamidinium iodide in a mixed solvent of DMSO and DMF with a volume ratio of 4:1 to prepare a formamidinium lead iodide solution, using 668 mg of lead iodide and 227 mg of formamidinium iodide for every 1 mL of the mixed solvent; dissolve lead bromide and methylammonium bromide in a mixed solvent of DMSO and DMF with a volume ratio of 4:1 to prepare a methylammonium lead bromide solution, using 160 mg of lead bromide and 49 mg of methylammonium bromide for every 1 mL of the mixed solvent; then prepare a cesium iodide solution by using 380 mg of cesium iodide for every 1 mL of DMSO; mix the formamidinium lead iodide solution, methylammonium lead bromide solution, and cesium iodide solution in a volume ratio of 1:0.2:0.06 to obtain a perovskite precursor solution; (6) First, the TiO2 layer is treated with ultraviolet ozone for 10 min and then the perovskite layer is prepared by spin coating. The parameters for the first step are 2000 rpm for 10 s, and the parameters for the second step are 7000 rpm for 30 s. At the 11th second from the end of the second step, 100 μL of chlorobenzene anti-solvent is dropped at the center of the substrate. After the dropping is completed, it is annealed at 100 °C for 1 h; (7) Spiro-OMeTAD is dissolved in chlorobenzene, and then Li-TFSI and 4-tert-butylpyridine are added in sequence. After mixing, it is heated at 70 °C overnight. Among them, the concentration of Li-TFSI is 520 mg / mL, and 72.5 mg of Spiro-OMeTAD, 19 μL of Li-TFSI and 29 μL of 4-tert-butylpyridine are used for every 1 mL of chlorobenzene; 38 μL of the above mixed solution is spin-coated under the condition of 4500 rpm for 30 s to form a hole transport layer; (8) The commercial conductive carbon paste is used as a raw material and uniformly coated on the cleaned carbon paper. Then the wet carbon film is soaked in ethanol for 30 min. After soaking, the carbon film is taken out and placed flat in a dry environment to dry; (9) The copper-doped indium hydroxide nanomaterial is dispersed in a mixed solution of DMSO and IPA with a volume ratio of 1:1 to obtain a dispersion with a concentration of 15 mg / mL; (10) 200 - 800 μL of the dispersion obtained in step (9) is taken and a uniform and smooth interfacial modification layer is formed on the carbon film obtained in step (8) by spray method, and then it is dried at 40 °C for 3 h; (11) The carbon film modified in step (10) is hot-pressed onto the hole transport layer, and finally a carbon-based perovskite solar cell with a copper-doped indium hydroxide interfacial modification layer is obtained.

4. The application of a copper-doped indium hydroxide nanomaterial according to claim 3, characterized in that, The amount of the dispersion used in step (10) is 400 μL.

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