Perovskite solar cell and preparation method and application thereof
By fabricating nickel mesh microcavity layers and multilayer structures in perovskite solar cells, the mechanical stability and efficiency issues of perovskite solar cells were solved, resulting in better wettability and interfacial bonding performance, and improving the stability and efficiency of the cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUANENG CLEAN ENERGY RES INST
- Filing Date
- 2026-01-29
- Publication Date
- 2026-04-28
AI Technical Summary
Existing perovskite solar cells suffer from poor mechanical stability and low efficiency. The metal in the flexible electrode has poor wettability to the tin oxide dispersion, which is the electron transport material, resulting in perovskite films with interfacial pores and poor adhesion.
A nickel mesh microcavity layer is prepared on the surface of a metal substrate to form a "macropore-mesoporous" multi-scale structure. The nickel mesh microcavity layer is electrodeposited using a polystyrene nanosphere template, and combined with a tin oxide electron transport layer, a perovskite layer, and a hole transport layer. Spin coating and annealing are then used to form a multilayer structure.
This improved the stability and efficiency of perovskite solar cells, and enhanced the wettability of the metal substrate to the perovskite precursor solution and the interfacial bonding performance of the perovskite thin film.
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Abstract
Description
Technical Field
[0001] This application belongs to the field of optoelectronic materials technology, specifically relating to a perovskite solar cell, its preparation method, and its application. Background Technology
[0002] Perovskite solar cells are a new type of photovoltaic device with perovskite material as the core light-absorbing layer. With their outstanding advantages such as high photoelectric conversion efficiency, low manufacturing cost, and flexibility and customizability, they have become one of the fastest-growing technologies in the photovoltaic field in the past 20 years. They are regarded as an important supplement or even a potential replacement technology for traditional crystalline silicon cells. In particular, flexible perovskite solar cells are lightweight and bendable, and are widely used in spacecraft, building-integrated photovoltaics (BIPV), portable power generation equipment and other scenarios.
[0003] Flexible electrodes are a key component of flexible perovskite solar cells. Commonly used flexible electrodes include flexible ITO electrodes based on polymer films such as PET or PEN, as well as flexible metal foils made of stainless steel, nickel, and titanium. The fabrication process for flexible ITO is relatively complex, particularly due to the weak interfacial adhesion of the ITO film, which makes it prone to failure after repeated bending. While flexible metal foil electrodes are simple to fabricate and inexpensive, they suffer from poor wettability of the metal to the electron transport material tin oxide dispersion and the perovskite precursor solution, resulting in numerous interfacial pores in the formed perovskite film. Furthermore, the poor adhesion of the perovskite film to the metal surface leads to poor mechanical stability in flexible foil electrodes. Summary of the Invention
[0004] This application provides a perovskite solar cell, its preparation method, and its application, aiming to solve the problems of poor mechanical stability and low efficiency of existing perovskite solar cells.
[0005] The first aspect of this application provides a perovskite solar cell, comprising a metal substrate layer, a nickel mesh microcavity layer, an electron transport layer, a perovskite layer, a hole transport layer, and an electrode layer stacked sequentially; the surface of the nickel mesh microcavity layer is provided with grooves.
[0006] According to some embodiments of the perovskite solar cell described in this application, the metal substrate is a nickel foil substrate.
[0007] According to some embodiments of the perovskite solar cell described in this application, the electron transport layer includes a tin oxide electron transport layer.
[0008] According to some embodiments of the perovskite solar cell described in this application, the molecular formula of the raw material contained in the perovskite layer is FA. 1-x Cs x PbI3, where 0≤x≤1.
[0009] According to some embodiments of the perovskite solar cell described in this application, the hole transport layer comprises poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA).
[0010] According to some embodiments of the perovskite solar cell described in this application, the thickness of the metal substrate layer is 10-200 μm.
[0011] According to some embodiments of the perovskite solar cell described in this application, the thickness of the nickel mesh microcavity layer is 50-300 nm;
[0012] According to some embodiments of the perovskite solar cell described in this application, the thickness of the electron transport layer is 10-100 nm. According to some embodiments of the perovskite solar cell described in this application, the thickness of the perovskite layer is 100-1000 nm; According to some embodiments of the perovskite solar cell described in this application, the thickness of the hole transport layer is 10-100 nm; According to some embodiments of the perovskite solar cell described in this application, the thickness of the electrode layer is 80-200 nm.
[0013] A second aspect of this application provides a method for preparing the perovskite solar cell described in the first aspect of this application, comprising the following steps: (1) A polystyrene nanosphere template was prepared on the surface of a metal substrate to obtain a template-containing metal substrate; (2) Insert the template-containing metal substrate into the electrolyte and electrodeposit to prepare the nickel mesh microcavity layer; the electrolyte includes nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, glucose and water; (3) An electron transport layer, a perovskite layer, a hole transport layer and an electrode layer are sequentially prepared on the surface of the nickel mesh microcavity layer. After spin coating is completed, an annealing treatment is performed to obtain the perovskite solar cell.
[0014] According to some embodiments of the perovskite solar cell preparation method described in this application, in step (1), the preparation method of the polystyrene nanosphere template is as follows: mixing polystyrene nanospheres and water to obtain a mixed slurry; spin-coating the mixed slurry onto a metal substrate layer and annealing it to obtain the polystyrene nanosphere template.
[0015] According to some embodiments of the perovskite solar cell preparation method described in this application, the mass ratio of the polystyrene nanospheres to water is (0.8-1.2):1000.
[0016] According to some embodiments of the perovskite solar cell preparation method described in this application, the polystyrene nanospheres have a particle size of 100-800 nm.
[0017] According to some embodiments of the perovskite solar cell preparation method described in this application, the annealing temperature for preparing the polystyrene nanosphere template is 70-90℃ and the time is 8-12min. According to some embodiments of the perovskite solar cell fabrication method described in this application, the thickness of the polystyrene nanosphere template is 100-2000 nm.
[0018] According to some embodiments of the perovskite solar cell preparation method described in this application, the concentration of nickel sulfate hexahydrate in the electrolyte is 0.2-0.4 g / ml.
[0019] According to some embodiments of the perovskite solar cell preparation method described in this application, the mass ratio of nickel sulfate hexahydrate to nickel chloride hexahydrate in the electrolyte is 20:(2-4).
[0020] According to some embodiments of the perovskite solar cell preparation method described in this application, the mass ratio of nickel sulfate hexahydrate to boric acid in the electrolyte is 15:(1-3).
[0021] According to some embodiments of the perovskite solar cell preparation method described in this application, the mass ratio of nickel sulfate hexahydrate to glucose in the electrolyte is 30:(0.8-1.2).
[0022] According to some embodiments of the perovskite solar cell preparation method described in this application, in step (2), the electrodeposition operation steps are as follows: using platinum metal as the anode, applying a voltage of -0.80 to -0.90V for 2-10 minutes, cleaning, and then keeping warm at 380-430℃ in an inert atmosphere for 20-40 minutes.
[0023] According to some embodiments of the perovskite solar cell preparation method described in this application, in step (3), the annealing temperature is 100-120℃ and the time is 10-30min.
[0024] A third aspect of this application provides a photovoltaic module, including the perovskite solar cell described in the first aspect of this application or the perovskite solar cell obtained by the preparation method described in the second aspect of this application.
[0025] The beneficial effects of this application include: the perovskite solar cell described in this application deposits a nickel mesh microcavity layer on the surface of the metal substrate to form a "macropore-mesoporous" multi-scale structure, which improves the wettability of the metal substrate to the perovskite precursor solution and the interfacial bonding performance of the perovskite film; thus enabling the perovskite solar cell to have better stability and cell efficiency. Detailed Implementation
[0026] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.
[0027] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0028] This application provides a perovskite solar cell, comprising a metal substrate layer, a nickel mesh microcavity layer, an electron transport layer, a perovskite layer, a hole transport layer, and an electrode layer stacked sequentially; the surface of the nickel mesh microcavity layer is provided with grooves.
[0029] The perovskite solar cell described in this application has a nickel mesh microcavity layer deposited on the surface of a metal substrate to form a "macropore-mesoporous" multi-scale structure, which improves the wettability of the metal substrate to the perovskite precursor solution and the interfacial bonding performance of the perovskite film; thus giving the perovskite solar cell better stability and cell efficiency.
[0030] In some embodiments of this application, the metal substrate is a nickel foil substrate.
[0031] In some embodiments of this application, the electron transport layer includes a tin oxide electron transport layer; In some embodiments of this application, the molecular formula of the raw material contained in the perovskite layer is FA. 1-x Cs x PbI3, where 0≤x≤1, and FA refers to amitrazine.
[0032] In some embodiments of this application, the hole transport layer comprises poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA).
[0033] In some embodiments of this application, the thickness of the metal substrate layer is 10-200 μm; for example, 10 μm, 20 μm, 50 μm, 80 μm, 120 μm, 150 μm, 180 μm, 200 μm, etc.
[0034] In some embodiments of this application, the thickness of the nickel mesh microcavity layer is 50-300nm; for example, 50nm, 80nm, 120nm, 160nm, 180nm, 220nm, 260nm, 300nm, etc.
[0035] In some embodiments of this application, the thickness of the electron transport layer is 10-100 nm, such as 10 nm, 50 nm, 80 nm, 100 nm, etc.
[0036] In some embodiments of this application, the thickness of the perovskite layer is 100-1000 nm; for example, 100 nm, 200 nm, 500 nm, 800 nm, 1000 nm, etc.
[0037] In some embodiments of this application, the thickness of the hole transport layer is 10-100nm, such as 10nm, 30nm, 50nm, 70nm, 100nm, etc.
[0038] In some embodiments of this application, the thickness of the electrode layer is 80-200nm, such as 80nm, 120nm, 160nm, 200nm, etc.
[0039] This application also provides a method for preparing the perovskite solar cell described in the first aspect of this application, comprising the following steps: (1) A polystyrene nanosphere template was prepared on the surface of a metal substrate to obtain a template-containing metal substrate; (2) Insert the template-containing metal substrate into the electrolyte and electrodeposit to prepare the nickel mesh microcavity layer; the electrolyte includes nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, glucose and water; (3) An electron transport layer, a perovskite layer, a hole transport layer and an electrode layer are sequentially prepared on the surface of the nickel mesh microcavity layer. After preparation, an annealing treatment is performed to obtain the perovskite solar cell.
[0040] The perovskite solar cells described in this application exhibit high efficiency and good mechanical stability. The polystyrene nanosphere template, electron transport layer, perovskite layer, and hole transport layer in the perovskite solar cells described in this application can be prepared using processes such as spin coating, blade coating, slot coating, and vacuum evaporation. When using spin coating, annealing is required after each spin-coated layer. The electrode layers can be prepared using magnetron sputtering.
[0041] In some embodiments of this application, in step (1), the polystyrene nanosphere template is prepared by mixing polystyrene nanospheres and water to obtain a mixed slurry; the mixed slurry is spin-coated onto a metal substrate and annealed to obtain the polystyrene nanosphere template.
[0042] In some embodiments of this application, the electron transport layer is prepared as follows: Tin oxide aqueous dispersion is diluted to 4 wt%, and spin-coated onto the surface of a nickel mesh microcavity layer at 3000 rpm for 30 seconds. After spin-coating, the layer is annealed at 100°C for 20 minutes before use. The perovskite layer is prepared as follows: 1.52 mmol FAI, 0.08 mmol CsI, and 1.6 mmol PbI2 are dissolved in 1 ml of a mixed solution of DMF and DMSO (volume ratio 4:1), stirred at 60°C for 2 hours, and then naturally cooled to room temperature; 100... m The above solution was added dropwise to the surface of the electron transport layer, and spin-coated at 2000 rpm for 20 s, then at 5000 rpm for 40 s. 50 μL of chlorobenzene was added 15 s before the end of the spin-coating. The spin-coated perovskite film was then annealed at 100°C for 30 min. The hole transport layer was prepared by dissolving PTAA in acetonitrile to obtain a solution with a concentration of 30 mg / ml, then spin-coating it onto the perovskite layer surface at 3000 rpm for 30 s. After spin-coating, the solution was annealed at 100°C for 10 min.
[0043] In some embodiments of this application, the mass ratio of the polystyrene nanospheres to water is (0.8-1.2):1000; for example, 0.8:1000, 1.0:1000, 1.2:1000, etc.
[0044] In some embodiments of this application, the polystyrene nanospheres have a particle size of 100-800 nm, such as 100 nm, 300 nm, 400 nm, 500 nm, 800 nm, etc.
[0045] In some embodiments of this application, the annealing temperature for preparing polystyrene nanosphere templates is 70-90°C, such as 70°C, 76°C, 80°C, 85°C, 90°C, etc., and the time is 8-12 min, such as 8 min, 10 min, 12 min, etc.
[0046] In some embodiments of this application, the thickness of the polystyrene nanosphere template is 100-2000 nm, such as 100 nm, 500 nm, 800 nm, 1000 nm, 1200 nm, 1500 nm, 2000 nm, etc. Limiting the template thickness facilitates obtaining nickel microcavities of a specific thickness.
[0047] In some embodiments of this application, 300 nm polystyrene nanospheres were prepared into an aqueous dispersion of 1 mg / ml, spin-coated on a nickel foil substrate at 3000 rpm for 30 s, and annealed at 80°C for 10 min to form a polystyrene nanosphere template.
[0048] In some embodiments of this application, the concentration of nickel sulfate hexahydrate in the electrolyte is 0.2-0.4 g / ml; for example, 0.2 g / ml, 0.3 g / ml, 0.4 g / ml, etc.
[0049] In some embodiments of this application, the mass ratio of nickel sulfate hexahydrate to nickel chloride hexahydrate in the electrolyte is 20:(2-4); for example, 20:2, 20:3, 20:4, etc.
[0050] In some embodiments of this application, the mass ratio of nickel sulfate hexahydrate to boric acid in the electrolyte is 15:(1-3); for example, 15:1, 15:2, 15:3, etc.
[0051] In some embodiments of this application, the mass ratio of nickel sulfate hexahydrate to glucose in the electrolyte is 30:(0.8-1.2); for example, 30:0.8, 30:1, 30:1.2, etc.
[0052] In some embodiments of this application, in step (2), the electrodeposition operation steps are as follows: using platinum metal as the anode, applying a voltage of -0.80 to -0.90V for 2-10 minutes, cleaning, and then holding at 380-430℃, for example 380℃, 400℃, 430℃, etc., in an inert atmosphere for 20-40 minutes, for example 20 minutes, 25 minutes, 30 minutes, 36 minutes, 40 minutes, etc.
[0053] In some embodiments of this application, nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, and glucose are dissolved in deionized water, and the mixture is washed after being subjected to a voltage of -0.9V for 2 minutes with platinum metal as the anode. The mixture is then kept at 400°C under an argon atmosphere for 30 minutes before being taken out for use.
[0054] In some embodiments of this application, in step (3), the annealing temperature is 100-120℃, such as 100℃, 105℃, 110℃, 120℃, etc., and the time is 10-30min, such as 10min, 20min, 25min, 30min, etc. The annealing process removes the template layer.
[0055] This application also provides a photovoltaic module, including the perovskite solar cell described in the first aspect of this application or the perovskite solar cell obtained by the preparation method described in the second aspect of this application.
[0056] The technical solution of this application will be further described below with reference to specific embodiments.
[0057] Example 1 A method for fabricating a perovskite solar cell includes the following steps: (1) A template layer was prepared on a 150 μm thick nickel foil substrate. The specific operation steps were as follows: polystyrene nanospheres with a particle size of 400 nm were dispersed in water to prepare a dispersion with a concentration of 1 mg / ml; the dispersion was spin-coated onto the nickel foil substrate at a speed of 3000 rpm for 30 s, and then annealed at 80 °C for 10 min to form a polystyrene nanosphere template layer with a thickness of 1.2 μm; (2) Dissolve 30g of nickel sulfate hexahydrate, 4.5g of nickel chloride hexahydrate, 4g of boric acid and 1g of glucose in 100g of water to obtain an electrolyte; insert the nickel foil substrate containing the template layer described in step (1) into the electrolyte as a cathode, use platinum metal as an anode, apply a voltage of -0.90V for 2min and then clean it, and then keep it at 400℃ under argon atmosphere protection for 30min and then take it out to obtain a nickel mesh microcavity layer with a thickness of 100nm; (3) Disperse tin oxide in water to prepare a dispersion with a mass concentration of 4%. Spin coat the dispersion onto the nickel mesh microcavity layer at a speed of 3000 rpm and control the spin coating time to 30 s. Then anneal at 100°C for 20 min to form an electron transport layer with a thickness of 30 nm. (4) Dissolve 0.92 mmol formamidin hydroiodate, 0.08 mmol cesium iodide, and 1.0 mmol lead iodide in a mixed solution of 1 ml DMF and DMSO (volume ratio 4:1). Stir at 60°C for 2 hours and allow to cool naturally to room temperature. Take 100 μL of the above solution and drop it onto the surface of the electron transport layer. Spin coat at 2000 rpm for 20 seconds, then at 5000 rpm for 40 seconds. Add 500 μL of chlorobenzene 15 seconds before the end of the spin coating. Then anneal the spin-coated perovskite film at 100°C for 30 minutes to form a perovskite layer with a thickness of 500 nm. The molecular formula of the raw material contained in the perovskite layer is FA. 0.92 Cs 0.08 PbI3; (5) Dissolve poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in acetonitrile to form a dispersion with a concentration of 30 mg / ml. Spin coat the dispersion onto the perovskite layer at a speed of 3000 rpm for 30 s. Then anneal at 100 °C for 10 min to form a hole transport layer with a thickness of 30 nm. (6) An ITO electrode layer with a thickness of 120 nm was prepared by magnetron sputtering.
[0058] Example 2 The only difference between the perovskite solar cell fabrication method described in Example 2 and that in Example 1 is that the thickness of the nickel mesh microcavity layer in the perovskite solar cell described in Example 2 is 200 nm.
[0059] (1) A template layer was prepared on a 150 μm thick nickel foil substrate. The specific operation steps were as follows: polystyrene nanospheres with a particle size of 400 nm were dispersed in water to prepare a dispersion with a concentration of 1 mg / ml; the dispersion was spin-coated onto the nickel foil substrate at a speed of 3000 rpm for 30 s, and then annealed at 80 °C for 10 min to form a polystyrene nanosphere template layer with a thickness of 1.2 μm; (2) Dissolve 30g of nickel sulfate hexahydrate, 4.5g of nickel chloride hexahydrate, 4g of boric acid and 1g of glucose in 100g of water to obtain an electrolyte; insert the nickel foil substrate containing the template layer described in step (1) into the electrolyte as a cathode, use platinum metal as an anode, apply a voltage of -0.90V for 4min and then clean it, and then keep it at 400℃ under argon atmosphere protection for 30min and then take it out to obtain a nickel mesh microcavity layer with a thickness of 200nm; (3) Disperse tin oxide in water to prepare a dispersion with a mass concentration of 4%. Spin coat the dispersion onto the nickel mesh microcavity layer at a speed of 3000 rpm and control the spin coating time to 30 s. Then anneal at 100°C for 20 min to form an electron transport layer with a thickness of 30 nm. (4) Dissolve 0.92 mmol formamidin hydroiodate, 0.08 mmol cesium iodide, and 1.0 mmol lead iodide in a mixed solution of 1 ml DMF and DMSO (volume ratio 4:1). Stir at 60°C for 2 hours and allow to cool naturally to room temperature. Take 100 μL of the above solution and drop it onto the surface of the electron transport layer. Spin coat at 2000 rpm for 20 seconds, then at 5000 rpm for 40 seconds. Add 500 μL of chlorobenzene 15 seconds before the end of the spin coating. Then anneal the spin-coated perovskite film at 100°C for 30 minutes to form a perovskite layer with a thickness of 500 nm. The molecular formula of the raw material contained in the perovskite layer is FA. 0.92 Cs 0.08 PbI3.
[0060] (5) Dissolve poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in acetonitrile to form a dispersion with a concentration of 30 mg / ml. Spin coat the dispersion onto the perovskite layer at a speed of 3000 rpm for 30 s. Then anneal at 100 °C for 10 min to form a hole transport layer with a thickness of 30 nm. (6) An ITO electrode layer with a thickness of 120 nm was prepared by magnetron sputtering.
[0061] Example 3 The only difference between the perovskite solar cell preparation method described in Example 3 and that in Example 1 is that the polystyrene template in the perovskite solar cell described in Example 3 has a particle size of 300 nm.
[0062] (1) A template layer was prepared on a 150 μm thick nickel foil substrate. The specific operation steps were as follows: polystyrene nanospheres with a particle size of 300 nm were dispersed in water to prepare a dispersion with a concentration of 1 mg / ml; the dispersion was spin-coated onto the nickel foil substrate at a speed of 3000 rpm for 30 s, and then annealed at 80 °C for 10 min to form a polystyrene nanosphere template layer with a thickness of 1.2 μm. (2) Dissolve 30g of nickel sulfate hexahydrate, 4.5g of nickel chloride hexahydrate, 4g of boric acid and 1g of glucose in 100g of water to obtain an electrolyte; insert the nickel foil substrate containing the template layer described in step (1) into the electrolyte as a cathode, use platinum metal as an anode, apply a voltage of -0.90V for 2min and then clean it, and then keep it at 400℃ under argon atmosphere protection for 30min and then take it out to obtain a nickel mesh microcavity layer with a thickness of 100nm; (3) Disperse tin oxide in water to prepare a dispersion with a mass concentration of 4%. Spin coat the dispersion onto the nickel mesh microcavity layer at a speed of 3000 rpm and control the spin coating time to 30 s. Then anneal at 100°C for 20 min to form an electron transport layer with a thickness of 30 nm. (4) Dissolve 0.92 mmol formamidin hydroiodate, 0.08 mmol cesium iodide, and 1.0 mmol lead iodide in a mixed solution of 1 ml DMF and DMSO (volume ratio 4:1). Stir at 60°C for 2 hours and allow to cool naturally to room temperature. Take 100 μL of the above solution and drop it onto the surface of the electron transport layer. Spin coat at 2000 rpm for 20 seconds, then at 5000 rpm for 40 seconds. Add 500 μL of chlorobenzene 15 seconds before the end of the spin coating. Then anneal the spin-coated perovskite film at 100°C for 30 minutes to form a perovskite layer with a thickness of 500 nm. The molecular formula of the raw material contained in the perovskite layer is FA. 0.92 Cs 0.08 PbI3; (5) Dissolve poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in acetonitrile to form a dispersion with a concentration of 30 mg / ml. Spin coat the dispersion onto the perovskite layer at a speed of 3000 rpm for 30 s. Then anneal at 100 °C for 10 min to form a hole transport layer with a thickness of 30 nm. (6) An ITO electrode layer with a thickness of 120 nm was prepared by magnetron sputtering.
[0063] Example 4 The only difference between the perovskite solar cell fabrication method described in Example 4 and that in Example 1 is that the thickness of the nickel mesh microcavity layer in the perovskite solar cell described in Example 4 is 1.1 μm.
[0064] (1) A template layer was prepared on a 150 μm thick nickel foil substrate. The specific operation steps were as follows: polystyrene nanospheres with a particle size of 400 nm were dispersed in water to prepare a dispersion with a concentration of 1 mg / ml; the dispersion was spin-coated onto the nickel foil substrate at a speed of 3000 rpm for 30 s, and then annealed at 80 °C for 10 min to form a polystyrene nanosphere template layer with a thickness of 1.2 μm; (2) Dissolve 30g of nickel sulfate hexahydrate, 4.5g of nickel chloride hexahydrate, 4g of boric acid and 1g of glucose in 100g of water to obtain an electrolyte; insert the nickel foil substrate containing the template layer described in step (1) into the electrolyte as a cathode, use platinum metal as an anode, apply a voltage of -0.90V for 10min and then clean it, and then keep it at 400℃ under argon atmosphere protection for 30min and then take it out to obtain a nickel mesh microcavity layer with a thickness of 1.1μm; (3) Disperse tin oxide in water to prepare a dispersion with a mass concentration of 4%. Spin coat the dispersion onto the nickel mesh microcavity layer at a speed of 3000 rpm and control the spin coating time to 30 s. Then anneal at 100°C for 20 min to form an electron transport layer with a thickness of 30 nm. (4) Dissolve 0.92 mmol formamidin hydroiodate, 0.08 mmol cesium iodide, and 1.0 mmol lead iodide in a mixed solution of 1 ml DMF and DMSO (volume ratio 4:1). Stir at 60°C for 2 hours and allow to cool naturally to room temperature. Take 100 μL of the above solution and drop it onto the surface of the electron transport layer. Spin coat at 2000 rpm for 20 seconds, then at 5000 rpm for 40 seconds. Add 500 μL of chlorobenzene 15 seconds before the end of the spin coating. Then anneal the spin-coated perovskite film at 100°C for 30 minutes to form a perovskite layer with a thickness of 500 nm. The molecular formula of the raw material contained in the perovskite layer is FA. 0.92 Cs 0.08 PbI3; (5) Dissolve poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in acetonitrile to form a dispersion with a concentration of 30 mg / ml. Spin coat the dispersion onto the perovskite layer at a speed of 3000 rpm for 30 s. Then anneal at 100 °C for 10 min to form a hole transport layer with a thickness of 30 nm. (6) An ITO electrode layer with a thickness of 120 nm was prepared by magnetron sputtering.
[0065] Comparative Example 1 The only difference between the perovskite solar cell fabrication method of Comparative Example 1 and Example 1 is that the perovskite solar cell of Comparative Example 1 does not contain a nickel mesh microcavity layer.
[0066] (1) Disperse tin oxide in water to prepare a dispersion with a mass concentration of 4%. Spin coat the dispersion onto nickel foil at a speed of 3000 rpm for 30 s. Then anneal at 100°C for 20 min to form an electron transport layer with a thickness of 30 nm. (2) Dissolve 0.92 mmol formamidin hydroiodate, 0.08 mmol cesium iodide, and 1.0 mmol lead iodide in a mixed solution of 1 ml DMF and DMSO (volume ratio 4:1). Stir at 60°C for 2 hours and allow to cool naturally to room temperature. Take 100 μL of the above solution and drop it onto the surface of the electron transport layer. Spin coat at 2000 rpm for 20 seconds, then at 5000 rpm for 40 seconds. Add 500 μL of chlorobenzene 15 seconds before the end of the spin coating. Then anneal the spin-coated perovskite film at 100°C for 30 minutes to form a perovskite layer with a thickness of 500 nm. The molecular formula of the raw material contained in the perovskite layer is FA. 0.92 Cs 0.08 PbI3.
[0067] (3) Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) was dissolved in acetonitrile to form a dispersion with a concentration of 30 mg / ml. The dispersion was spin-coated onto the perovskite layer at a speed of 3000 rpm for 30 s. Then, the layer was annealed at 100 °C for 10 min to form a hole transport layer with a thickness of 30 nm. (4) An ITO electrode layer with a thickness of 120 nm was prepared by magnetron sputtering.
[0068] Performance study of the perovskite solar cells described in Examples 1-4 and Comparative Example 1 of this application Research Methods: Under standard sunlight, the IV curves of the above-mentioned battery devices were tested to obtain indicators such as open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency. The IV curves were then tested again after bending the battery devices 1000 times at a curvature radius of 10 mm, and the photoelectric conversion efficiency retention rate was calculated.
[0069] The results are shown in Table 1.
[0070] Table 1
[0071] As can be seen from Table 1, when the particle size of the polystyrene nanospheres used to prepare the template is 400 nm and the thickness of the nickel mesh microcavity is 200 nm, the device achieves the best conversion efficiency and mechanical stability. This may be related to the difference in wettability of the perovskite precursor liquid caused by the morphology of the nickel mesh microcavity. When the thickness of the nickel mesh microcavity is significantly increased, i.e. when the nickel mesh microcavity has an ordered interconnected porous structure, or when there is no nickel mesh microcavity structure, the efficiency and stability are significantly reduced.
[0072] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.
Claims
1. A perovskite solar cell, characterized in that, It includes a metal substrate layer, a nickel mesh microcavity layer, an electron transport layer, a perovskite layer, a hole transport layer, and an electrode layer stacked sequentially; the surface of the nickel mesh microcavity layer is distributed with grooves.
2. The perovskite solar cell according to claim 1, characterized in that, The metal substrate layer is a nickel foil substrate layer; And / or, the electron transport layer includes a tin oxide electron transport layer; And / or, the molecular formula of the raw material contained in the perovskite layer is FA. 1-x Cs x PbI3, where 0 ≤ x ≤ 1; And / or, the hole transport layer comprises poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA).
3. The perovskite solar cell according to claim 1, characterized in that, The thickness of the metal substrate layer is 10-200 μm; And / or, the thickness of the nickel mesh microcavity layer is 50-300 nm; And / or, the thickness of the electron transport layer is 10-100 nm; And / or, the thickness of the perovskite layer is 100-1000 nm; And / or, the thickness of the hole transport layer is 10-100 nm; And / or, the thickness of the electrode layer is 80-200 nm.
4. The method for preparing the perovskite solar cell according to any one of claims 1-3, characterized in that, Includes the following steps: (1) A polystyrene nanosphere template was prepared on the surface of a metal substrate to obtain a template-containing metal substrate; (2) Insert the template-containing metal substrate into the electrolyte and electrodeposit to prepare a nickel mesh microcavity layer; the electrolyte includes nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, glucose and water; (3) An electron transport layer, a perovskite layer, a hole transport layer and an electrode layer are sequentially prepared on the surface of the nickel mesh microcavity layer. After preparation, an annealing treatment is performed to obtain the perovskite solar cell.
5. The method for preparing a perovskite solar cell according to claim 4, characterized in that, In step (1), the polystyrene nanosphere template is prepared by mixing polystyrene nanospheres and water to obtain a mixed slurry; the mixed slurry is spin-coated onto a metal substrate and annealed to obtain the polystyrene nanosphere template.
6. The method for preparing a perovskite solar cell according to claim 5, characterized in that, The mass ratio of the polystyrene nanospheres to water is (0.8-1.2):1000; And / or, the polystyrene nanospheres have a particle size of 100-800 nm; And / or, the annealing temperature for preparing polystyrene nanosphere templates is 70-90℃ and the time is 8-12 min; And / or, the thickness of the polystyrene nanosphere template is 100-2000 nm.
7. The method for preparing a perovskite solar cell according to claim 4, characterized in that, The concentration of nickel sulfate hexahydrate in the electrolyte is 0.2-0.4 g / ml; And / or, the mass ratio of nickel sulfate hexahydrate to nickel chloride hexahydrate in the electrolyte is 20:(2-4); And / or, the mass ratio of nickel sulfate hexahydrate to boric acid in the electrolyte is 15:(1-3); And / or, the mass ratio of nickel sulfate hexahydrate to glucose in the electrolyte is 30:(0.8-1.2).
8. The method for preparing a perovskite solar cell according to claim 7, characterized in that, In step (2), the electrodeposition operation steps are as follows: using platinum metal as the anode, applying a voltage of -0.80 to -0.90V for 2-10 minutes, cleaning, and then keeping warm at 380-430℃ in an inert atmosphere for 20-40 minutes.
9. The method for preparing a perovskite solar cell according to claim 4, characterized in that, In step (3), the annealing temperature is 100-120℃ and the time is 10-30min.
10. A photovoltaic module, characterized in that, This includes the perovskite solar cell according to any one of claims 1-3 or the perovskite solar cell obtained by the preparation method according to any one of claims 4-9.