Preparation method of carbon electrode full-inorganic perovskite solar cell

Abstract

The invention belongs to the technical field of solar cell materials, and particularly relates to a passivator, a passivation modification layer and a preparation method of a perovskite solar cell. 3-sulfydryl-1-sodium propane sulfonate is adopted to modify and improve an electron transport layer, particularly, surface defects and interface defects are effectively passivated, the transport characteristic of charge carriers is improved, and the performance of the perovskite solar cell is improved. According to the preparation method, uncoordinated lead ions and iodine vacancies of perovskite are passivated, internal defects of a thin film are reduced, erosion of water is reduced, the purpose of improving the performance of a device is achieved, and the efficiency of the prepared inorganic CsPbI3 perovskite solar cell can reach 18.44% at most.

Description

Technical Field

[0001] This invention belongs to the field of solar cell materials and technology, specifically relating to a method for preparing a passivation modification layer and a carbon electrode all-inorganic perovskite solar cell. Background Technology

[0002] The use of carbon electrodes in inorganic perovskite solar cells is gaining increasing attention, primarily due to their advantages in performance, cost, and sustainability. Compared to traditional metal electrodes (such as silver or aluminum), carbon electrodes are less expensive to produce. This advantage makes inorganic perovskite solar cells more competitive in commercial applications, especially at scale. Carbon materials are relatively environmentally friendly, with abundant and renewable sources, aligning with sustainable development principles. Using carbon electrodes helps reduce the overall environmental impact of solar cells. The good compatibility of carbon electrodes with inorganic perovskite materials allows for effective improvement in photoelectric conversion efficiency. Furthermore, carbon electrodes exhibit good stability under high temperature and humidity conditions, enabling inorganic perovskite solar cells to maintain excellent performance across a variety of applications.

[0003] Despite significant progress in CsPbI3-based perovskite solar cells over the past few years, the passivation layer, as a key component, has a crucial impact on the performance and stability of solar cells. Further improvements are needed to meet the demands of solar cell development.

[0004] Passivating agents are chemical substances used to improve the surface properties of materials, primarily by repairing or masking defects and reducing surface reactivity to enhance material performance. In perovskite solar cells, passivating agents can effectively reduce defect density and improve charge carrier recombination, thereby enhancing cell efficiency and stability.

[0005] Sodium 3-mercapto-1-propanesulfonate (MPS) is a passivating agent used in perovskite solar cells. It repairs defects in the perovskite material through a chemical reaction, reducing non-radiative recombination and improving device performance and stability. MPS is particularly effective at passivating surface and interface defects, improving charge carrier transport properties. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a perovskite passivation layer, a method for preparing a carbon electrode all-inorganic perovskite solar cell, and the resulting solar cell.

[0007] The inventors of this invention have discovered that this passivating agent can serve as a perovskite passivation layer, passivating perovskite surface defects while preventing moisture erosion, thereby improving device performance. The passivating agent used in this invention is named sodium 3-mercapto-1-propanesulfonate (MPS), with the chemical formula C3H9NaO3S2.

[0008] The technical solution provided by the present invention is as follows: The inventor of the present invention provides a method for preparing a passivation layer, comprising the following steps: preparing an electron transport layer on a substrate, then preparing an aqueous solution of MPS with a concentration of 1 mg / ml, and spin-coating it onto the electron transport layer, and then annealing it at 100°C for 3 min to obtain the passivation layer.

[0009] The inventors of this invention have discovered that MPS can be used as a passivation layer to modify the electron transport layer and improve electron transport capability.

[0010] The inventors of this invention provide a method for preparing a perovskite layer, comprising the following steps: (1) adding TEPS with a concentration of 0.001M-0.1M to a DMF / DMSO solution of DMAPbI3 and CsI, and heating and stirring at 60-80°C until clear to obtain a CsPbI3 precursor solution. (2) spin-coating the CsPbI3 precursor solution obtained in step (1) onto the modified electron transport layer, and then annealing in air at 180°C for 10 min. (3) cooling to room temperature to obtain the perovskite layer.

[0011] The inventors of this invention have discovered that MPS is particularly effective at passivating surface and interface defects, thereby improving the transport properties of charge carriers.

[0012] The present invention also provides a method for preparing a carbon electrode all-inorganic perovskite solar cell, comprising the following steps: (1) obtaining a clean substrate; (2) preparing an electron transport layer on the substrate obtained in step (1) using the electron transport layer preparation method described above; (3) preparing a passivation layer on the electron transport layer obtained in step (2) using the passivation layer preparation method described above; (4) preparing a perovskite layer on the passivation layer obtained in step (3) using the perovskite layer preparation method described above; and (5) preparing an electrode on the perovskite layer to obtain the perovskite solar cell.

[0013] Based on the above technical solutions, the carrier transport capacity can be improved, defects inside and on the surface of the perovskite layer can be reduced, the photogenerated charge separation capacity can be improved, and the erosion of perovskite by moisture in the air can be reduced, thereby improving the performance of perovskite solar cells.

[0014] Specifically: in step (1), the substrate is transparent conductive glass FTO; in step (2), the electron transport layer is TiO2 layer; in step (3), the passivation layer is MPS layer; in step (4), the perovskite layer is TEPS-doped CsPbI3 perovskite layer; in step (5), the electrode is C electrode.

[0015] A specific preparation process of the present invention is as follows: (1) Cleaning of FTO glass substrate: The FTO glass substrate is ultrasonically cleaned for 30 min in sequence with glass cleaning solution, deionized water, isopropanol and ethanol. Then the glass substrate is taken out and dried with a nitrogen gun, and finally placed in a plasma cleaner and cleaned with air for 5 min. (2) Preparation of electron transport layer: The FTO glass substrate is immersed in 200 mL of aqueous solution containing 4.5 mL of titanium tetrachloride, soaked at 75°C for 55 min, then rinsed with distilled water, annealed at 200°C for 30 min to prepare TiO2 layer. (3) Preparation of passivation layer: MPS crystal powder is weighed in a glass bottle, then an aqueous solution is added and allowed to stand to obtain MPS aqueous solution. Then 80 µL of MPS aqueous solution is dropped onto the upper TiO2 layer, spin-coated at 5000 rpm for 20 seconds, annealed in air at 100°C for 3 min, and naturally cooled to room temperature. (4) Preparation of perovskite solution and film: Weigh DMAPbI3 and CsI (1M) crystal powder into a glass bottle, then add DMF and DMSO solvents at a volume ratio of (4:1), stir at 70°C for two hours until the solution is clear and transparent to obtain the precursor solution. Then take 60 µL of the precursor solution and drop it onto the passivation layer, spin coat at 600 rpm for 6 seconds and at 4000 rpm for 30 seconds, anneal in air at 180°C for 10 minutes, and cool naturally to room temperature. (5) Preparation of carbon electrode: Scrape carbon paste onto the spin-coated wafer, anneal at 100°C for 10 minutes, and cool naturally to room temperature to form a carbon electrode.

[0016] The present invention has the following beneficial effects: Modifying the electron transport layer with MPS can effectively improve the electron transport capability of the electron transport layer. MPS is particularly effective in passivating surface and interface defects, improving the transport characteristics of charge carriers. This increases the short-circuit current and fill factor of the device, thereby improving the photoelectric conversion efficiency of the device. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the structure of the carbon electrode all-inorganic perovskite solar cell prepared by the present invention.

[0018] Figure 2 This is the JV curve of a device obtained by modifying the electron transport layer with MPS at a concentration of 1 mg / ml.

[0019] Figure 3 This is the JV curve of the device obtained by modifying the electron transport layer with MPS at a concentration of 0.5 mg / ml.

[0020] Figure 4 This is the JV curve of the device obtained by modifying the electron transport layer with MPS at a concentration of 2 mg / ml.

[0021] Figure 5This is the JV curve of the device obtained by modifying the electron transport layer with MPS at a concentration of 1.2 mg / ml.

[0022] Figure 6 This is the JV curve of the device obtained by modifying the electron transport layer with MPS at a concentration of 1.5 mg / ml.

[0023] Figure 7 This is the JV curve of the device obtained by annealing the electron transport layer with MPS at a concentration of 1 mg / ml at 150°C.

[0024] Figure 8 This is the JV curve of the device obtained by annealing the electron transport layer with MPS at 170°C and a concentration of 1 mg / ml.

[0025] Figure 9 This is the JV curve of the device obtained by annealing the electron transport layer with MPS at a concentration of 1 mg / ml at 200°C.

[0026] Figure 10 This is the JV curve of the device obtained by annealing the electron transport layer with MPS at 220°C and a concentration of 1 mg / m. Detailed Implementation

[0027] The principles and features of the present invention are described below. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0028] Example 1: The concentration of MPS was investigated, and the preparation method was the same as the device fabrication process described above. Example 1 utilized MPS to modify the electron transport layer. The specific process was as follows: an MPS aqueous solution with a concentration of 1 mg / ml was prepared as the modification solution for the electron transport layer, followed by spin-coating of a perovskite layer and then coating with a C electrode to complete the device fabrication.

[0029] Comparative Example 1: Comparative Example 1 is a device without MPS modification. After fabricating the electron transport layer, a perovskite layer was spin-coated, and a C electrode was then coated to complete the device fabrication. The device's photoelectric performance was tested, and the current-voltage (JV) test results are as follows: Figure 2 As shown, Comparative Example 1 achieves a basic efficiency of 13.55%, an open-circuit voltage of 1.0743V, and a current density of 17.90 mA / cm². 2 The fill factor was 70.5%. The device with the MPS-modified electron transport layer achieved a peak efficiency of 18.44%, an open-circuit voltage of 1.0903V, and a current density of 23.65 mA / cm². 2 The fill factor is 71.5%.

[0030] Example 2: The concentration of MPS was investigated. An electron transport layer was modified with 0.5 mg / ml of MPS, followed by spin-coating of a perovskite layer and then coating with a C electrode to complete device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 3 As shown, the device with MPS-modified electron transport layer achieved a yield of 15.66%, an open-circuit voltage of 1.0609 V, and a current density of 21.55 mA / cm². 2 The fill factor is 68.5%.

[0031] Example 3: The concentration of MPS was investigated. An electron transport layer was modified with MPS at a concentration of 2 mg / ml, followed by spin-coating of a perovskite layer and then coating with a C electrode to complete device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 4 As shown, the device with the MPS-modified electron transport layer achieved a purity of 16.09%, an open-circuit voltage of 1.1088V, and a current density of 19.76mA / cm². 2 The fill factor is 73.5%.

[0032] Example 4: The concentration of MPS was investigated. An electron transport layer was modified with 1.2 mg / ml of MPS, followed by spin-coating of a perovskite layer and then coating with a C electrode to complete device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 5 As shown, the device with the MPS-modified electron transport layer achieved a yield of 14.82%, an open-circuit voltage of 1.1032 V, and a current density of 18.12 mA / cm². 2 The fill factor is 74.1%.

[0033] Example 5: The concentration of MPS was investigated. An electron transport layer was modified with 1.5 mg / ml of MPS, followed by spin-coating of a perovskite layer and then coating with a C electrode to complete device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 6 As shown, the device with MPS-modified electron transport layer achieved a yield of 15.98%, an open-circuit voltage of 1.0928 V, and a current density of 19.96 mA / cm². 2 The fill factor is 73.3%.

[0034] Example 6: The annealing temperature of the perovskite layer of the device was investigated. The electron transport layer was modified with MPS at a concentration of 1 mg / ml, then the perovskite layer was spin-coated, annealed at 150°C, and the C electrode was then coated to complete the device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 7 As shown, the device annealed at 150°C achieved a yield of 15.46%, with an open-circuit voltage of 1.0517V and a current density of 21.51 mA / cm².2 The fill factor is 68.3%.

[0035] Example 7: The annealing temperature of the perovskite layer of the device was investigated. The electron transport layer was modified with MPS at a concentration of 1 mg / ml, then the perovskite layer was spin-coated, annealed at 170°C, and the C electrode was then coated to complete the device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 8 As shown, the device annealed at 170°C achieved 18.08% conductivity, with an open-circuit voltage of 1.0779V and a current density of 23.48 mA / cm². 2 The fill factor is 71.4%.

[0036] Example 8: The annealing temperature of the perovskite layer of the device was investigated. The electron transport layer was modified with MPS at a concentration of 1 mg / ml, then the perovskite layer was spin-coated, annealed at 200°C, and the C electrode was then coated to complete the device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 9 As shown, the device annealed at 200°C achieved a thermal conductivity of 18.22%, an open-circuit voltage of 1.0839V, and a current density of 23.49 mA / cm². 2 The fill factor is 71.5%.

[0037] Example 9: The annealing temperature of the perovskite layer of the device was investigated. The electron transport layer was modified with MPS at a concentration of 1 mg / ml, then the perovskite layer was spin-coated, annealed at 220°C, and the C electrode was then coated to complete the device fabrication. The photoelectric performance of the device was tested, and the current-voltage (JV) test results are as follows: Figure 10 As shown, the device annealed at 220°C achieved a hysteresis rating of 16.07%, an open-circuit voltage of 1.1088V, and a current density of 19.76 mA / cm². 2 The fill factor is 73.5%.

[0038] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A carbon electrode all-inorganic perovskite solar cell, characterized in that, The perovskite absorber layer is an all-inorganic perovskite material, and the electrode is a carbon electrode. A passivation layer containing a passivating agent is disposed at at least one interface of the perovskite layer, and the perovskite absorber layer is a perovskite light-absorbing layer containing a passivating agent. The passivating agent is sodium 3-mercapto-1-propanesulfonate (MPS). The all-inorganic perovskite layer includes CsPbX3 type perovskite material, where X is one or more combinations of Cl, Br, and I.

2. The passivating agent according to claim 1, characterized in that, The solvent is one or more mixed solvents of deionized water, ethanol, and isopropanol, with a concentration of 0.001-10 mg / mL.

3. The carbon electrode all-inorganic perovskite solar cell according to claim 1, characterized in that... The device comprises a conductive glass substrate, an electron transport layer, a passivation layer, an inorganic perovskite layer, and a carbon electrode stacked sequentially. The electron transport layer is one or more combinations of SnO2, TiO2, and ZnO. A passivation layer as described in claim 1 is disposed between the electron transport layer and the perovskite absorption layer.

4. A method for preparing a carbon electrode all-inorganic perovskite solar cell according to claims 1-3, characterized in that, The steps include: (1) preparing a TiO2 electron transport layer on a selected conductive glass substrate; immersing an FTO glass substrate in 100-200 mL of an aqueous solution containing 2-4.5 mL of titanium tetrachloride, soaking at 50-80°C for 30-60 minutes, then rinsing with distilled water, and annealing at 150-250°C for 20-60 minutes to obtain a TiO2 electron transport layer; (2) mixing sodium 3-mercapto-1-propanesulfonate (MPS) with deionized water to a concentration of 0.5-2 mg / mL to obtain the passivating agent solution, then dropping 50-100 µL of MPS aqueous solution onto the upper TiO2 layer, and using 4000-6000... Spin-coat at rpm for 10-30 seconds; anneal at 80-120°C for 2-6 minutes to obtain the passivation layer; (3) add 0.001M-0.1M TEPS to the DMF / DMSO solution of DMAPbI3 and CsI, and heat and stir at 60-80°C until clear to obtain CsPbI3 precursor solution. Then take 40-80 µL of precursor solution and drop it onto the passivation layer. Spin-coat at 400-800 rpm for 4-8 seconds and at 3000-5000 rpm for 20-60 seconds. Then anneal in air at 150-250°C for 5-20 minutes. Cool to room temperature to obtain the all-inorganic perovskite layer; (4) scrape carbon paste onto the spin-coated wafer, anneal at 80-120°C for 5-20 minutes, and cool naturally to room temperature to form a carbon electrode. The carbon electrode all-inorganic perovskite solar cell described above was obtained.

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