Perovskite solar cell module, cell and preparation method and application thereof

Abstract

The invention discloses a perovskite solar cell module, a cell and a preparation method and application thereof. Relates to the technical field of solar cells. The perovskite solar cell module comprises a substrate layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer and an electrode layer which are stacked in sequence, and the passivation layer is formed by a salt material containing trifluoromethyl benzene sulfonate. According to the invention, through the combination of the sequentially stacked functional structure and the specific passivation layer material, the problems of poor stability and difficulty in batch production of the large-area perovskite solar cell module are effectively solved, and the large-area perovskite solar cell module is adapted to the industrial batch production requirement.

Description

Technical Field

[0001] This invention relates to the field of solar cell technology, and in particular to a perovskite solar cell module, cell, its preparation method and application. Background Technology

[0002] Perovskite solar cells, as a rapidly emerging photovoltaic technology in recent years, have demonstrated broad development prospects and enormous commercial value in the global energy transition wave due to their superior performance and significant economic advantages. Compared with traditional crystalline silicon cells, perovskite solar cells not only possess higher theoretical photoelectric conversion efficiency potential, but can also further break through the efficiency ceiling through stacking technology. Simultaneously, their raw material costs are lower, and energy consumption in the production process is significantly reduced, making their cost advantage even more prominent in large-scale mass production. Furthermore, these cells can maintain stable power generation performance even in low-light environments such as cloudy weather, sunrise, and sunset. This high low-light effect gives them irreplaceable unique advantages in distributed photovoltaic systems and building-integrated photovoltaics (BIPV), better adapting to diverse application scenarios. Therefore, perovskite solar cells are considered a core development direction for next-generation photovoltaic technology, and their commercial application is crucial for promoting the popularization of renewable energy. However, to achieve the commercial production of perovskite solar cells, developing large-area perovskite solar cell technology is essential. Only by overcoming the technical bottlenecks of large-area cells can we truly propel them from laboratory research to large-scale industrial applications.

[0003] Currently, the large-scale mass production of large-area perovskite solar cells still faces many challenges, the most critical being the poor stability of the perovskite layer. This issue is directly related to the inherent shortcomings of the perovskite film itself. As the area of ​​the perovskite film increases, internal defects inevitably expand, leading to a decrease in the consistency of cell performance. Simultaneously, the edge regions of large-area perovskite films are prone to uneven or excessive coating of perovskite material, resulting in cracks. These edge defects further exacerbate the decline in perovskite layer stability, severely impacting cell lifespan and long-term reliability. To address these issues, industry researchers and technology developers are modifying and optimizing the perovskite layer through various methods to enhance its stability and explore effective methods for improving the stability of large-area perovskite films. After all, obtaining large-area perovskite films that can be stably stored for extended periods with consistent performance is a crucial prerequisite for the commercial production of perovskite solar cells.

[0004] Starting from the optimization of the perovskite layer itself, current strategies for improving the stability of perovskite thin films mainly include the following categories: First, introducing new salt substances to change the chemical composition of the perovskite and form new perovskite structures, thereby improving structural stability; second, using ion doping technology to replace some constituent ions in the perovskite structure, adjusting the internal ion distribution and bonding state, and enhancing the film's resistance to degradation; third, using dimensional engineering to construct two-dimensional and three-dimensional composite perovskite structures, utilizing the stability of the two-dimensional structure to improve the overall film performance; and fourth, introducing a functional film on the surface of the perovskite layer. This film not only acts as a waterproof layer, isolating the perovskite layer from external moisture erosion, but also effectively passivates surface defects, reduces charge recombination, and improves battery stability and efficiency. These strategies have been well applied and verified in small-area perovskite thin films, significantly improving the stability and performance of small-area films and laying the foundation for the development of perovskite solar cell technology.

[0005] However, existing strategies for improving the stability of perovskite thin films still have significant limitations in their application on large-area perovskite films, and mature, scalable solutions have not yet been developed. On the one hand, optimization strategies for small-area films are difficult to directly transfer to large-area applications. As the film area increases, existing modification methods cannot effectively address the problems of defect propagation and uneven edge coating in large-area films, resulting in the inability of large-area films to meet the stability and performance consistency requirements for commercial production. On the other hand, current research on the stability of large-area perovskite thin films is still in the exploratory stage, lacking universally applicable methods and strategies. Different technical routes suffer from poor compatibility, high costs, or complex processes, making it difficult to adapt to the needs of large-scale mass production. With the accelerated industrialization of perovskite solar cells, the market demand for efficient, stable, and low-cost large-area perovskite solar cell modules is becoming increasingly urgent. Developing universally applicable technologies that can effectively improve the stability of large-area perovskite thin films has become a core technical problem that urgently needs to be solved in the perovskite photovoltaic field, which is of vital importance to promoting the commercial application of perovskite solar cells. Summary of the Invention

[0006] A perovskite solar cell module includes a substrate layer, a hole transport layer, a perovskite absorber layer, a passivation layer, an electron transport layer, and an electrode layer stacked sequentially; the passivation layer is formed of a salt material containing trifluoromethylbenzenesulfonate.

[0007] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects: This invention effectively solves the problems of poor stability and difficulty in mass production of large-area perovskite solar cell modules by combining sequentially stacked functional structures with specific passivation layer materials, thus meeting the needs of industrialized mass production.

[0008] Specifically: First, the rationality of the stacked structure: the base layer provides support and conductivity, the hole transport layer and electron transport layer efficiently transport holes and electrons respectively, the perovskite absorption layer serves as the light absorption core, and the electrode layer collects charges. All layers work together to achieve the basic function of photoelectric conversion. Second, the crucial role of the passivation layer: the passivation layer, formed from a salt material containing trifluoromethylbenzenesulfonate, allows the trifluoromethylbenzenesulfonate ions in its molecules to bind with defect sites (such as lead vacancies and iodine vacancies) on the surface of the perovskite absorption layer, inhibiting ion migration within the perovskite and reducing charge recombination. Simultaneously, this passivation layer effectively blocks external moisture intrusion, inhibiting the phase transition of the perovskite from the black phase to the yellow phase, thereby improving the stability of the module. Third, this structure is suitable for large-scale production: through a reasonable stacking sequence and the selection of passivation layer materials, it avoids edge defect problems during large-area coating, providing a feasible solution for the mass production of large-scale modules.

[0009] According to one embodiment of the present invention, the passivation layer is made of sodium trifluoromethylbenzenesulfonate. The trifluoromethylbenzenesulfonate ions in the sodium trifluoromethylbenzenesulfonate molecule can tightly bind to defect sites (such as lead vacancies and iodine vacancies) on the perovskite surface, effectively inhibiting ion migration within the perovskite and reducing charge recombination loss. Furthermore, the passivation layer formed by this material can physically block the intrusion of external moisture, inhibiting the transformation of the perovskite from a black phase with excellent photoelectric properties to a yellow phase with no photoelectric activity, thereby significantly improving the stability of the component.

[0010] According to one embodiment of the present invention, the area of ​​the perovskite absorber layer is not less than 1000 × 600 mm. 2 Large-area thin films have high defect density and are easily damaged at the edges. The passivation layer of this invention can fully protect large-area thin films.

[0011] According to one embodiment of the present invention, the area of ​​the perovskite absorber layer includes 1200 × 600 mm. 2 1000×2000mm 2 and 1200×2400mm 2 One of them.

[0012] According to one embodiment of the present invention, the thickness of the perovskite absorber layer is 400-420 nm.

[0013] According to one embodiment of the present invention, the perovskite absorber layer comprises at least one of cesium iodide, lead iodide, formamidinium iodide, and methylamine chloride. Specific perovskite components are more sensitive to passivation response, and the passivating agent component of the passivation layer can form stable coordination structures with lead, halogen, and other sites in the perovskite.

[0014] According to one embodiment of the present invention, the perovskite absorber layer is composed of (CsPbI3).0.1 (FAPbI3) 0.9 .

[0015] According to one embodiment of the present invention, the substrate layer is ITO glass.

[0016] According to one embodiment of the present invention, the hole transport layer is a nickel oxide layer and is formed by a PVD process.

[0017] According to one embodiment of the present invention, the passivation layer thickness is at least 2-30 nm. Preferably, the passivation layer thickness is at least 10-15 nm.

[0018] Specifically, the technical solution adopted according to the second aspect of the present invention is as follows: A method for preparing the perovskite solar cell module includes the following steps: A substrate is provided, on which a hole transport layer and a perovskite absorber layer are sequentially formed. A passivation layer is prepared on the perovskite absorber layer, and an electron transport layer and an electrode layer are sequentially formed on the passivation layer.

[0019] According to one embodiment of the present invention, the passivation layer is prepared by a slot coating process. The slot coating process for forming the passivation layer is suitable for the mass production of large-area components, avoiding the area limitations and uneven edge coating problems of traditional spin coating processes, and ensuring the uniformity of the passivation layer within a large size range (e.g., 1200×600mm²).

[0020] According to one embodiment of the present invention, the perovskite absorber layer is prepared by a slit coating process with a coating speed of 20-40 mm / s and a pump coating speed of 150-200 μL / s.

[0021] According to one embodiment of the present invention, the coating speed is 30-40 mm / s.

[0022] According to one embodiment of the present invention, the pump coating speed is 180-200 μL / s.

[0023] According to one embodiment of the present invention, after the perovskite absorber layer is coated in a slot coating process, it is then subjected to a flash evaporation process, which includes the steps of vacuuming and annealing.

[0024] According to one embodiment of the present invention, the vacuuming is performed by reducing the atmospheric pressure to 0.7-0.8 Pa within 30-40 seconds. This reduces solvent residue through flash evaporation.

[0025] According to one embodiment of the present invention, the annealing temperature is 120-150°C, and / or the annealing time is 15-30 min.

[0026] According to one embodiment of the present invention, the slot coating parameters for the perovskite layer are: pre-injection volume of 22-30 μL and pre-injection rate of 400-420 μL / s. Preferably, the pre-injection volume is 22 μL and the pre-injection rate is 400 μL / s. The passivation layer coating parameters are: pre-injection volume of 50 μL, pre-injection rate of 50 μL / s, coating rate of 50 mm / s, and pump coating rate of 54 μL / s. The present invention avoids edge defects through parameter control, thereby ensuring film uniformity.

[0027] According to one embodiment of the present invention, the components of the perovskite absorber layer further include Meo-2Pacz and GBA.

[0028] Among them, Meo-2Pacz (full name [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, CAS: 2377770-18-6, as a hole material, can improve the crystallinity of perovskite, modify nickel oxide substrate, and improve the perovskite / electrode interface contact. Among them, GBA (full name: chlorobenzylaminoacetic acid salt, CAS: 23256-50-0) is used as an additive to improve the crystallization quality of perovskite thin films and enhance their stability and photoelectric properties.

[0029] According to one embodiment of the present invention, the concentration of the passivating agent solution is 1-10 mM before the passivation layer is deposited. Too low a concentration results in insufficient passivation, while too high a concentration easily leads to crystallization. The present invention limits the solution concentration to ensure effective deposition of the passivating agent.

[0030] According to one embodiment of the present invention, the concentration of the passivating agent solution is 1-5 mM.

[0031] According to one embodiment of the present invention, the solvent of the passivating agent solution is selected from isopropanol or ethanol. Isopropanol or ethanol is volatile, ensuring uniform film formation of the passivation layer.

[0032] According to one embodiment of the present invention, the coating parameters of the passivating agent include: a pre-injection volume of 50-52 μL, and / or a pre-injection speed of 50-52 μL / s, and / or a coating speed of 50-52 mm / s, and / or a pump coating speed of 54-56 μL / s.

[0033] In another aspect, the present invention also provides a solar cell comprising the aforementioned perovskite solar cell module.

[0034] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the discovery. Attached Figure Description

[0035] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 The graph shows the storage performance test results of the perovskite solar cell modules prepared for the examples and comparative examples.

[0036] Figure 2 The graph shows the photoelectric conversion efficiency test results of the perovskite solar cell module prepared as an example. Detailed Implementation

[0037] The terms "preferred," "more preferred," etc., used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0038] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0039] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of the present invention.

[0040] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0041] Example A perovskite solar cell module includes an ITO glass substrate, a hole transport layer, and (CsPbI3) layers stacked sequentially. 0.1 (FAPbI3) 0.9 The perovskite absorber layer, sodium trifluoromethylbenzenesulfonate passivation layer, electron transport layer, and electrode layer are all present.

[0042] A method for preparing the perovskite solar cell module includes the following steps: ITO glass substrates are selected, washed with water, dried, and stored in a dust-free environment; A nickel oxide layer was sputtered onto an ITO glass substrate using a PVD process to obtain a hole transport layer; Weigh out cesium iodide, lead iodide, formamidine iodide, and methylamine chloride, mix them, and dissolve them in an organic solvent of DMF:NMP = 5:1. Stir at room temperature to obtain (CsPbI3) with a molar concentration of 0.8 M. 0.1 (FAPbI3) 0.9 400 mL of perovskite precursor solution was mixed with additives Meo-2Pacz (0.25 mg / mL) and GBA (2 mg / mL) to obtain a clear and transparent perovskite precursor solution. The substrate containing the nickel oxide layer was annealed at 150 °C for 15 min and then cooled and placed on the platform of a slot coater. The clear and transparent perovskite precursor solution was added to the filtration system of the coater and then filtered into the reagent tank. The slot coater parameters were set as follows: pre-injection volume of 22 μL, coating speed of 30 mm / s, pre-injection speed of 400 μL / s, and pump coating speed of 180 μL / s. After coating, the perovskite absorber was flash-evaporated using a VCD device, rapidly pumped from one atmosphere to 0.8 Pa for 40 s, and then annealed at 120 °C for 15 min to obtain a 400 nm thick perovskite absorber layer. A 5 mM sodium trifluoromethylbenzenesulfonate solution (CAS: 360-27-0, with isopropanol as solvent) was prepared and heated and stirred at 40 °C for 8 h. Subsequently, the sodium trifluoromethylbenzenesulfonate solution was deposited on the perovskite absorber layer using a slot coating process. The slot coating process parameters were: pre-injection volume of 50 uL, pre-injection speed of 50 uL / s, coating speed of 50 mm / s, and pump coating speed of 54 uL / s, resulting in a passivation layer with a thickness of about 10 nm. A 25 nm thick C60 layer was deposited on the passivation layer, followed by an atomic layer deposition of 20 nm thick SnO2. Then, laser scribing was performed on P2, copper electrodes were deposited, and laser scribing was performed on P3 to obtain the electron transport layer and the electrode layer.

[0043] Comparative Example The difference between the comparative example and Example 1 is that the perovskite solar cell module in the comparative example does not contain a passivation layer.

[0044] Performance testing: The perovskite solar cell modules prepared in the examples and comparative examples were placed indoors at room temperature (25°C, 30% humidity) to test for yellowing. Figure 1 As shown, after 5 days, the color of the perovskite thin film in the comparative perovskite solar cell module changed from black to yellow (see...). Figure 1 (a) In the example, after 10 days, it was found that the color of the perovskite thin film in the perovskite solar cell module prepared in the example still had not changed (see a). Figure 1 (b) in the middle.

[0045] The photoelectric conversion efficiency of the perovskite solar cell module prepared in the examples was tested, and the test results are as follows: Figure 2 As shown, Figure 2 PCE stands for photoelectric conversion efficiency. The testing method is as follows: 145 battery modules from the embodiments were assembled into battery modules, and 145 battery modules from the comparative examples were assembled into battery modules. On days 1, 5, and 10 after preparation, the battery modules were placed under simulated sunlight (illuminance 100 mW / cm²). 2 The test was conducted in an environment with AM1.5G standard spectrum, temperature 25℃, and relative humidity 60%. During the test, the positive and negative terminals of the component were connected to the electrical test system, the power supply was turned on, and the data acquisition module was activated. The current density-voltage (JV) curve was measured using a source meter. By gradually scanning the voltage and simultaneously recording the corresponding current density, the open circuit voltage (Voc), short circuit current density (Jsc), and total battery current (I) were obtained. sc The key parameters, such as fill factor (FF) and photoelectric conversion efficiency (PCE), are shown in Table 1.

[0046] Table 1

[0047] from Figure 2 As can be seen from the test results in Table 1, the perovskite solar cell module of the embodiment still achieved a photoelectric conversion efficiency of 15.37% after 10 days of environmental exposure, while the perovskite solar cell module of the comparative example only achieved a photoelectric conversion efficiency of 9.06% under the same test conditions.

[0048] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A perovskite solar cell module, characterized in that: It includes a base layer, a hole transport layer, a perovskite absorber layer, a passivation layer, an electron transport layer, and an electrode layer stacked sequentially; the passivation layer is formed of a salt material containing trifluoromethylbenzenesulfonate.

2. The perovskite solar cell module according to claim 1, characterized in that: The passivation layer is made of sodium trifluoromethylbenzenesulfonate.

3. The perovskite solar cell module according to claim 1, characterized in that: The area of ​​the perovskite absorber layer is not less than 1000 × 600 mm. 2 .

4. The perovskite solar cell module according to claim 1, characterized in that: The thickness of the perovskite absorber layer is 400-420 nm.

5. The perovskite solar cell module according to claim 1, characterized in that: The components of the perovskite absorber layer include at least one of cesium iodide, lead iodide, formamidine iodide, and methylamine chloride.

6. A method for preparing a perovskite solar cell module as described in any one of claims 1 to 5, characterized in that: Includes the following steps: A substrate is provided, on which a hole transport layer and a perovskite absorber layer are sequentially formed. A passivation layer is prepared on the perovskite absorber layer, and an electron transport layer and an electrode layer are sequentially formed on the passivation layer.

7. The perovskite solar cell module according to claim 6, characterized in that: The passivation layer is prepared by a slot coating process.

8. The method according to claim 6, characterized in that: The perovskite absorber layer was prepared using a slit coating process with a coating speed of 20-40 mm / s and a pump coating speed of 150-200 μL / s.

9. The method according to claim 6, characterized in that: The perovskite absorber layer is subjected to a flash evaporation process after the slit coating process. The flash evaporation process includes vacuuming and annealing steps.

10. A solar cell, characterized in that: Includes the perovskite solar cell module as described in any one of claims 1 to 5.

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