A 380 nm ultraviolet cut-off cover plate glass for perovskite solar cell packaging and a preparation method thereof

Abstract

This invention relates to a 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation and its preparation method, characterized in that: (1) weighing the matrix components of sodium calcium silicate glass, borosilicate glass or aluminosilicate glass and the ultraviolet cutoff functional agent components: CeO2: 1%-3%, TiO2: 1%-3%, Fe2O3: 0-2%, ZnO: 0.1%-1%, V2O5: 0-1%, Sm2O3: 0-1%, Nb2O5: 0-2%, MnO2: 0-2%; (2) drying the raw materials; (3) after sieving pretreatment, accurately mixing the materials, placing the mixture in a platinum-rhodium alloy crucible, melting it at high temperature in a high-temperature furnace, casting it into shape, and then annealing and cooling it slowly. Advantages of this invention: The UV cutoff cover glass prepared has a transmittance of less than 5% at 380nm, an average transmittance of less than 0.5% between 300nm and 380nm, and an average transmittance of more than 81.5% between 400nm and 800nm; and the prepared cover glass can be further strengthened; it is suitable for use as cover glass for perovskite solar cells.

Description

Technical Field

[0001] This invention belongs to the field of special functional glass manufacturing and photovoltaic packaging technology, specifically relating to a 380nm ultraviolet cutoff cover glass for perovskite solar cell packaging and its preparation method. Background Technology

[0002] Perovskite solar cells (PSCs) are outstanding representatives of third-generation solar cells, possessing significant advantages such as high photoelectric conversion efficiency and low manufacturing cost, and are on the verge of large-scale commercial application. However, perovskite active layer materials (such as halide perovskites like methylamine lead iodine) are extremely sensitive to ultraviolet light (especially the near-ultraviolet band). Under continuous ultraviolet irradiation, perovskite materials are prone to chemical bond breakage, causing crystal structure degradation and aging, leading to a rapid decline in the cell's photoelectric conversion efficiency. Therefore, equipping perovskite cells with encapsulation cover glass with high-efficiency ultraviolet cutoff function is a necessary means to extend their long-term service life.

[0003] Currently, the common method for achieving UV cutoff in glass cover plates is to deposit a UV cutoff film (such as an organic UV-blocking coating or an inorganic semiconductor thin film titanium dioxide) onto the surface of conventional ultra-clear glass. However, this type of coated UV-cutoff glass has a fatal industry pain point: (1) The coated glass cannot be tempered. Under extreme thermal conditions, the pre-deposited UV cutoff film is prone to cracking, peeling and falling off due to the mismatch between the thermal expansion coefficient and the glass substrate, or the structure of the multivalent film material changes under high temperature and strong oxidizing atmosphere, resulting in the complete loss of UV cutoff performance. (2) If tempering is performed before coating, not only is the process complicated, but coating on the tempered glass surface with huge surface stress is prone to causing glass to spontaneously explode, and the yield is extremely low and the production cost is extremely high.

[0004] Therefore, developing a perovskite encapsulation UV-blocking cover glass that is self-blocking (without surface coating) and can fully withstand the high-temperature physical tempering thermal process has become a core engineering requirement in the current photovoltaic module encapsulation field. Summary of the Invention

[0005] The purpose of this invention is to solve the problems of perovskite active layer material degradation and aging caused by continuous ultraviolet radiation, resulting in rapid decline of photoelectric conversion efficiency of the cell, and the inability to temper ultraviolet cut-off coated glass in perovskite solar cells. The invention provides a 380nm ultraviolet cut-off cover glass for perovskite solar cell encapsulation and its preparation method.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A 380nm UV cutoff cover glass for encapsulating perovskite solar cells, comprising a glass substrate (sodium-calcium silicate glass, borosilicate glass, or aluminosilicate glass), characterized in that: a UV-cutoff functional agent is added to the glass substrate, wherein the UV-cutoff functional agent, expressed as a mass percentage based on oxides, comprises the following proportions in the glass substrate: CeO2: 1%-3%, TiO2: 1%-3%, Fe2O3: 0-2%, ZnO: 0.1%-1%, V2O5: 0-1%, Sm2O3: 0-1%, Nb2O5: 0-2%, MnO2: 0-2%.

[0007] Furthermore, the ultraviolet blocking functional agent, expressed as a mass percentage based on oxides, comprises the following proportions in the glass matrix: CeO2: 1.2%-2.0%, TiO2: 1.2%-2.0%, Fe2O3: 0-1.0%, ZnO: 0.2%-0.5%, V2O5: 0-0.5%, Sm2O3: 0-0.5%, Nb2O5: 0-1.8%, MnO2: 0-0.8%.

[0008] Furthermore, the sodium-calcium silicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 65-75%, Na2O: 10-25%, CaO: 5-15%, MgO: 1-5%, Al2O3: 0-3%.

[0009] Furthermore, the borosilicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 75-83%, Na2O: 1-5%, B2O3: 6-15%, CaO: 0.5-2%, Al2O3: 0-3%.

[0010] Furthermore, the aluminosilicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 60-69%, Na2O: 5-9%, Li2O: 2-5%, K2O: 1-5%, MgO: 3-9%, Al2O3: 16-24%.

[0011] Furthermore, the 380nm UV cutoff cover glass for perovskite solar cell encapsulation has a transmittance of less than 5% at 380nm and an average transmittance of more than 81.5% between 400nm and 800nm.

[0012] Furthermore, the 380nm UV cutoff cover glass for perovskite solar cell encapsulation has an average transmittance of less than 0.5% in the 300nm-380nm range.

[0013] A method for preparing a 380nm ultraviolet cutoff cover glass for encapsulating perovskite solar cells, characterized by comprising the following steps: (1) Weigh each component in the glass matrix and the UV cutoff functional agent as a mass percentage based on oxides; (2) All raw materials are dried before batching (drying at 90~120℃ for 2~5h) to remove adsorbed water on the surface of the raw materials and reduce the moisture content of the batch. By controlling the moisture content of the raw materials, the batching accuracy and mixing uniformity can be improved, and the bubbles, streaks and local component fluctuations caused by moisture evaporation during the melting process can be reduced, which is conducive to improving the optical uniformity and visible light transmittance stability of the glass. (3) After drying, the raw materials of each component are screened and pretreated, and then accurately mixed. The mixture is placed in a platinum-rhodium alloy crucible, melted and cast in a high-temperature furnace, and then annealed and cooled to obtain a low-stress 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation.

[0014] Furthermore, the melting stage temperature is 1450℃~1700℃, and the constant temperature melting is maintained for 3~7 hours to ensure uniform melting and dispersion of functional components.

[0015] Furthermore, the annealing temperature after molding is 480℃~620℃, held for 2~5 hours, and the cooling rate is no higher than 1℃ / min, with gradient cooling to room temperature.

[0016] Furthermore, the thickness of the 380nm ultraviolet cutoff cover glass for encapsulating perovskite solar cells is 0.05mm-6mm.

[0017] Furthermore, the 380nm UV cutoff cover glass for perovskite solar cell encapsulation can be chemically or physically tempered as required.

[0018] CeO2, the UV cutoff functional agent in this invention, exhibits excellent UV absorption in glass, particularly showing significant inhibition in the 300–360 nm wavelength range. As the CeO2 content increases, the UV cutoff edge of the glass gradually shifts towards longer wavelengths, enhancing UV shielding capability. However, excessive addition may adversely affect visible light transmittance and glass chromaticity. TiO2 is a crucial component in this invention for adjusting the cutoff wavelength and enhancing the steepness of the cutoff edge. TiO2 itself possesses strong near-UV absorption characteristics; when incorporated into glass, it works synergistically with CeO2 to enhance absorption in the near-UV region and improve the transition morphology of the UV cutoff curve. The inventors' experiments revealed that using only CeO2 limits the range of cutoff edge control, and some formulations exhibit a relatively slow cutoff edge transition; using only TiO2 makes it difficult to achieve the target cutoff depth while maintaining high visible light transmittance. The composite design of CeO2 and TiO2 significantly improves the UV cutoff effect and makes the cutoff wavelength easier to control precisely. The addition of ZnO enhances the Zn... 2+Once integrated into the glass network, the local oxygen coordination structure and electronic environment can be modulated, making it easier for cerium ions to maintain a high valence state distribution that is favorable for UV cutoff, and in particular, it helps to suppress Ce. 4 The transition from Fe⁺ to Ce³⁺ improves the stability and repeatability of UV cutoff performance. Fe₂O₃ is the auxiliary UV cutoff and cutoff edge redshift adjustment component in this invention. Fe₂O₃ in glass mainly exists as Fe. 3+ and a small amount of Fe 2+ It exists in form. Among them, Fe... 3+ It exhibits strong absorption in the ultraviolet and near-ultraviolet regions, particularly enhancing absorption around 350–400 nm, shifting the ultraviolet cutoff edge towards longer wavelengths. However, excessive addition may adversely affect visible light transmittance and glass chromaticity. V₂O₅ is introduced as an auxiliary ultraviolet cutoff component and a cutoff edge modulator. The V₂O₅ contains V₂O₅... 5+ It can form V-O coordination structures with oxygen in the glass network, resulting in charge transfer absorption from oxygen to the vanadium center, thereby enhancing the glass's absorption capacity in the near-ultraviolet region. However, excessive addition may adversely affect visible light transmittance and glass color. Sm₂O₃ can be used as a rare-earth auxiliary spectral modulator. 3+ With its characteristic electronic energy level structure, rare earth ions, when added in appropriate amounts, can fine-tune the absorption in the near-ultraviolet and short-wave visible regions, and help improve the spectral stability of glass under ultraviolet irradiation. However, excessive addition may adversely affect visible light transmittance and glass color. Nb₂O₅ is introduced as an auxiliary ultraviolet cutoff component, a cutoff edge adjustment component, and a glass network stabilizing component. The Nb in Nb₂O₅... 5+ Nb₂O₅ can form Nb–O coordination structures with oxygen in the glass network, resulting in charge transfer absorption from oxygen to niobium centers, thereby enhancing the glass's absorption capacity in the 300–400 nm wavelength range, especially in the near-ultraviolet region of 350–400 nm. When appropriate amounts of Nb₂O₅ are used in combination with CeO₂, TiO₂, and ZnO, a Ce–O, Ti–O, and Nb–O multi-center charge transfer absorption system can be formed, improving the ultraviolet cutoff depth of the glass and making the ultraviolet cutoff edge position easier to adjust. MnO₂ is mainly used as a redox modifier, color modifier, and auxiliary ultraviolet absorber. During the melting process, MnO₂ can participate in the redox equilibrium of the glass melt, and synergistically with nitrate components and ZnO, which helps maintain cerium ions in a high valence state that is favorable for ultraviolet cutoff, thereby improving the stability of ultraviolet cutoff performance. However, when its addition amount is too high, it may have an adverse effect on visible light transmittance and glass color.

[0019] Compared with the prior art, the present invention has the following advantages: By directly adding a UV-blocking functional agent to a glass substrate (sodium-calcium silicate glass, borosilicate glass, or aluminosilicate glass), a cover glass with UV blocking function can be directly prepared (transmittance less than 5% at 380nm, average transmittance less than 0.5% in the 300nm-380nm range, and average transmittance greater than 81.5% in the 400nm-800nm ​​range). It has excellent shielding effect and excellent visible light transmittance. Furthermore, the cover glass prepared by this invention can be further strengthened (chemical or physical tempering). It is suitable for use as a cover glass for perovskite solar cells. Attached Figure Description

[0020] Figure 1 Transmittance diagram of soda-lime-silicon glass from 400nm to 800nm; Figure 2 Transmittance diagram of borosilicate glass from 400nm to 800nm; Figure 3 Transmittance of aluminosilicate glass from 400nm to 800nm. Detailed Implementation

[0021] The technical solution of the present invention is further described below through specific embodiments, but these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0022] A method for preparing a 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation, the specific implementation steps of which are as follows: (1) First, put all raw materials into a 120℃ oven and dry them for 2 hours; (2) Weigh each raw material according to the weight percentage listed in Table 1. All raw materials used are of superior purity and have passed through a 200-mesh sieve. Mix the weighed raw materials evenly to form a mixture. Pour the mixture into a platinum-rhodium alloy crucible. Place the platinum-rhodium alloy crucible containing the mixture into a high-temperature furnace and melt it at 1600℃ for 5 hours. After the melting stage is completed, pour the glass liquid into a mold. Place the molded glass block into a muffle furnace and keep it at 550℃ for 3 hours. Then cool it to room temperature at a rate of 0.5℃ / min to obtain ultraviolet cutoff glass.

[0023] The obtained glass block was cut and polished to obtain a 4mm thick sample. The transmittance was then tested, and the results are as follows:

[0024] The 380nm ultraviolet cutoff glass prepared using this invention is suitable for soda-lime silica glass, borosilicate glass, and aluminosilicate glass. As can be seen from Table 1, soda-lime silica glass has the most obvious cutoff effect in the near-ultraviolet band, but its transmittance in the visible light band is relatively low. Borosilicate glass and aluminosilicate glass have poor ultraviolet cutoff effects, but their transmittance in the visible light band is significantly higher than that of soda-lime silica glass.

[0025] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention, or modify them into equivalent embodiments, without departing from the scope of the present invention. Therefore, any simple modifications, equivalent substitutions, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention, without departing from the scope of the present invention, shall still fall within the protection scope of the present invention.

Claims

1. A 380nm UV cutoff cover glass for encapsulating perovskite solar cells, comprising a sodium-calcium silicate glass, borosilicate glass, or aluminosilicate glass substrate, characterized in that: UV-blocking functional agents are added to the glass matrix. The UV-blocking functional agents, expressed as a mass percentage based on oxides, have the following proportions in the glass matrix: CeO2: 1%-3%, TiO2: 1%-3%, Fe2O3: 0-2%, ZnO: 0.1%-1%, V2O5: 0-1%, Sm2O3: 0-1%, Nb2O5: 0-2%, MnO2: 0-2%.

2. The 380nm UV cutoff cover glass for perovskite solar cell encapsulation according to claim 1, characterized in that: The UV-blocking functional agent, expressed as a mass percentage based on oxides, comprises the following proportions in the glass matrix: CeO2: 1.2%-2.0%, TiO2: 1.2%-2.0%, Fe2O3: 0-1.0%, ZnO: 0.2%-0.5%, V2O5: 0-0.5%, Sm2O3: 0-0.5%, Nb2O5: 0-1.8%, MnO2: 0-0.8%.

3. The 380nm UV cutoff cover glass for perovskite solar cell encapsulation according to claim 1, characterized in that: The sodium-calcium silicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 65-75%, Na2O: 10-25%, CaO: 5-15%, MgO: 1-5%, Al2O3: 0-3%.

4. The 380nm UV cutoff cover glass for perovskite solar cell encapsulation according to claim 1, characterized in that: The borosilicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 75-83%, Na2O: 1-5%, B2O3: 6-15%, CaO: 0.5-2%, Al2O3: 0-3%.

5. The 380nm UV cutoff cover glass for perovskite solar cell encapsulation according to claim 1, characterized in that: The aluminosilicate glass, expressed as a mass percentage based on oxides, is composed of the following substances: SiO2: 60-69%, Na2O: 5-9%, Li2O: 2-5%, K2O: 1-5%, MgO: 3-9%, Al2O3: 16-24%.

6. A 380nm UV cutoff cover glass for encapsulating perovskite solar cells according to any one of claims 1 to 5, characterized in that: The aforementioned 380nm UV cutoff cover glass for perovskite solar cell encapsulation has a transmittance of less than 5% at 380nm and an average transmittance of greater than 81.5% between 400nm and 800nm.

7. A 380nm UV cutoff cover glass for encapsulating perovskite solar cells according to any one of claims 1 to 5, characterized in that: The 380nm UV cutoff cover glass for perovskite solar cell encapsulation has an average transmittance of less than 0.5% in the 300nm-380nm range.

8. A method for preparing a 380nm ultraviolet cutoff cover glass for encapsulating perovskite solar cells according to any one of claims 1 to 5, characterized in that... Includes the following steps: (1) Weigh each component in the glass matrix and the UV cutoff functional agent as a mass percentage based on oxides; (2) Dry all raw materials before mixing; (3) After drying, the raw materials of each component are screened and pretreated, and then accurately mixed. The mixture is placed in a platinum-rhodium alloy crucible, melted and cast in a high-temperature furnace, and then annealed and cooled to obtain a low-stress 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation.

9. The method for preparing a 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation according to claim 8, characterized in that: The melting stage temperature is 1450℃~1700℃, and the melting is carried out at a constant temperature for 3~7 hours; the annealing temperature after molding is 480℃~620℃, and the temperature is held for 2~5 hours with a cooling rate not exceeding 1℃ / min, and the temperature is gradually cooled to room temperature.

10. The method for preparing a 380nm ultraviolet cutoff cover glass for perovskite solar cell encapsulation according to claim 8, characterized in that: The thickness of the 380nm UV cutoff cover glass for perovskite solar cell encapsulation is 0.05mm-6mm, and the further operation is to perform chemical tempering or physical tempering treatment.

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