A glass and a method of making the same

Abstract

The present application relates to a kind of glass and its preparation method, the component of the glass includes cerium dioxide and titanium dioxide;The mass percentage content of the titanium dioxide is more than 4 times the mass percentage content of the cerium dioxide.This application provides glass on the basis of existing low iron glass formula adds functional component, without equipment modification, can quickly realize large-scale production;And by the specific setting of the content of cerium dioxide and titanium dioxide, reduce the UVB band ultraviolet light transmittance, and improve the average transmittance of visible light and near infrared band, meet the optical performance requirements of photovoltaic, photo-thermal power generation, ensure the optical performance stability of glass, prolong the service life of solar power generation system.

Description

Technical Field

[0001] This invention belongs to the field of solar energy technology, and relates to a device suitable for solar cells, and more particularly to a glass and its preparation method. Background Technology

[0002] Solar energy, as a clean and renewable energy source, is a core support for the global energy transition. Its large-scale utilization is mainly divided into photovoltaic (PV) power generation and concentrated solar power (CSP). Among them, PV power generation has undergone three generations of technological iteration: the first-generation crystalline silicon PV power generation and the second-generation cadmium telluride thin-film PV power generation have achieved highly mature industrial applications, especially crystalline silicon PV power generation, which has become the mainstream technology route in the global PV market; the third-generation perovskite PV power generation, with its advantages of low preparation cost and high theoretical upper limit of photoelectric conversion efficiency, has received widespread attention from academia and industry and is the core development direction of the next generation of PV technology.

[0003] Whether it's the transparent conductive oxide (TCO) glass substrate essential for second- and third-generation photovoltaic power generation, or the cover glass for crystalline silicon photovoltaic modules and the substrate glass for reflectors in solar thermal power generation systems, their optical properties directly determine the energy conversion efficiency of the power generation system. The response wavelengths of these various types of solar power generation are mainly concentrated in the visible to near-infrared band of 400nm to 1200nm. Therefore, improving the transmittance of glass in this target wavelength band is one of the core paths to improving the conversion efficiency of solar power generation systems.

[0004] Meanwhile, ultraviolet (UV) irradiation is a core bottleneck restricting the long-term stability and service life of perovskite photovoltaic cells. UVB light in the 280nm–320nm band has an extremely strong ability to break chemical bonds. When it irradiates perovskite materials, it directly breaks key chemical bonds such as metal-oxygen bonds in the perovskite lattice, causing disordered oxide ion migration, lattice structure distortion, and consequently generating numerous structural defects, accelerating the decomposition and phase separation of the perovskite material. This irreversible damage to the lattice structure directly leads to a significant decrease in the separation and extraction efficiency of photogenerated carriers in the perovskite material, ultimately resulting in a continuous decline in the cell's photoelectric conversion efficiency, deterioration in long-term stability, and a drastically shortened service life.

[0005] For concentrated solar power (CSP) technology, solar radiation energy is mainly concentrated in the visible and infrared bands, while the energy in the ultraviolet band accounts for less than 5% of the total solar radiation energy. It does not significantly improve the photothermal conversion efficiency and may even cause aging and degradation of the reflector substrate and surface film. Therefore, improving the transmittance of glass in the visible-near-infrared band and reducing the transmittance of ultraviolet light are also of great significance to improving the efficiency and long-term service stability of CSP systems.

[0006] In summary, high transmittance in the visible to near-infrared band plays a decisive role in the energy conversion efficiency of both photovoltaic and solar thermal power generation systems. Ultraviolet light, however, not only causes severe aging and damage to perovskite photovoltaic cells but also offers no significant benefit to other solar power generation technologies, and may even have negative effects. Therefore, developing a solar power glass with high transmittance in the 400nm–1200nm visible to near-infrared band, while simultaneously possessing efficient shielding against ultraviolet light (especially the 280nm–320nm UVB band), is a pressing technical problem that needs to be solved in this field. This is of great significance for promoting the industrialization of perovskite photovoltaic technology and improving the conversion efficiency and long-term operational stability of various solar power generation systems. Summary of the Invention

[0007] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a glass and its preparation method. The glass provided by this invention can reduce the transmittance of ultraviolet light in the UVB band and increase the average transmittance of visible light and near-infrared bands, meet the optical performance requirements of photovoltaic and solar thermal power generation, ensure the stability of the optical performance of the glass, and extend the service life of solar power generation systems.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a glass, the composition of which, based on oxides, includes cerium dioxide and titanium dioxide;

[0010] The mass percentage of titanium dioxide is more than four times the mass percentage of cerium dioxide.

[0011] This invention adds titanium dioxide and cerium dioxide to the glass composition, with the titanium dioxide content being more than four times that of cerium dioxide. This creates a complementary absorption and synergistic enhancement mechanism between cerium dioxide and titanium dioxide in the ultraviolet band. Cerium dioxide leverages its strong absorption advantage in the mid-to-short-wave ultraviolet, while titanium dioxide achieves precise shielding through its ultraviolet absorption peak, which is highly matched to the ultraviolet band. This significantly reduces ultraviolet light transmittance, significantly delays the ultraviolet aging of perovskite photovoltaic cells, and improves cell stability and lifespan, while maximizing the preservation of high transmittance of the glass in the 400nm~1200nm visible and near-infrared bands. Furthermore, this invention introduces only the two functional components in specific proportions while maintaining the basic composition of conventional glass. It is highly compatible with existing low-iron glass production processes, enabling industrial-scale mass production without significant adjustments to the production line. The process modification cost is low, and the implementation is highly feasible. It improves the optical uniformity and production stability of the glass, adapting to the needs of photovoltaic and solar thermal power generation applications, and possesses significant technical advantages and industrialization value.

[0012] In some embodiments, the cerium dioxide content in the glass composition is less than 2 wt%, preferably less than 0.5 wt%, and more preferably 0.05 wt% to 0.3 wt%, by mass percentage.

[0013] In some embodiments, the glass composition, based on oxides, includes 68wt% to 75wt% SiO2, 12wt% to 17wt% Na2O, 6wt% to 12wt% CaO, less than 6wt% MgO, less than 3wt% Al2O3, less than 400ppm Fe2O3, with the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

[0014] In some embodiments, the glass composition, based on oxides, includes 70wt% to 73wt% SiO2, 13wt% to 15wt% Na2O, 8wt% to 10wt% CaO, 1wt% to 4wt% MgO, 0.5wt% to 2wt% Al2O3, less than 400ppm Fe2O3, with the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

[0015] Secondly, the present invention provides a method for preparing glass, the method comprising the following steps:

[0016] The raw materials are mixed in the formula, melted and clarified to obtain a glass melt; the glass melt is homogenized, shaped and annealed to obtain the glass described in the first aspect.

[0017] In some embodiments, the cerium source in the raw materials includes any one or a combination of at least two of cerium-containing slag, cerium dioxide, cerium carbonate, cerium oxalate, or cerium powder.

[0018] In some embodiments, the titanium source in the raw materials includes any one or a combination of at least two of titanium-containing slag, titanium dioxide, titanium dioxide, titanium carbonate, or titanates.

[0019] In some embodiments, the forming method includes float forming or calendering.

[0020] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] This invention adds titanium dioxide and cerium dioxide to the glass composition, with the titanium dioxide content being more than four times that of cerium dioxide. This creates a complementary absorption and synergistic enhancement mechanism between cerium dioxide and titanium dioxide in the ultraviolet band. Cerium dioxide leverages its strong absorption advantage in the mid-to-short-wave ultraviolet, while titanium dioxide achieves precise shielding through its ultraviolet absorption peak, which is highly matched to the ultraviolet band. This significantly reduces ultraviolet light transmittance, significantly delays the ultraviolet aging of perovskite photovoltaic cells, and improves cell stability and lifespan, while maximizing the preservation of high transmittance of the glass in the 400nm~1200nm visible and near-infrared bands. Furthermore, this invention introduces only the two functional components in specific proportions while maintaining the basic composition of conventional glass. It is highly compatible with existing low-iron glass production processes, enabling industrial-scale mass production without significant adjustments to the production line. The process modification cost is low, and the implementation is highly feasible. It improves the optical uniformity and production stability of the glass, adapting to the needs of photovoltaic and solar thermal power generation applications, and possesses significant technical advantages and industrialization value. Detailed Implementation

[0023] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0024] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0025] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0026] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0027] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0028] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0029] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0030] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0031] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0032] Currently, low-iron ultra-clear glass is commonly used in solar power generation to reduce the negative impact of iron impurities on the transmittance of the target wavelength. The iron in the glass is mainly in the oxidized state of Fe. 3+ and reduced Fe 2+ Two valence states exist. Among them, Fe 3+ It exhibits strong absorption in the ultraviolet band, but has little impact on visible light transmittance; Fe 2+ This results in strong absorption in the visible to near-infrared wavelength range, significantly reducing the transmittance of the target wavelength. Based on these characteristics, existing technologies typically optimize the glass melting process to convert as much iron as possible into Fe in low-iron glass. 3+ To balance transmittance in the target wavelength band and UV shielding performance, this is achieved. However, limited by the upper limit of iron content in low-iron ultra-clear glass (the national standard requires its Fe2O3 mass fraction to be no higher than 0.015%, i.e., 150ppm), even if the iron element in the glass is entirely Fe... 3+ While the form exists, its ability to shield against ultraviolet light (especially the UVB band of 280nm~320nm) is still insufficient to meet the stringent performance requirements of perovskite photovoltaic cells for long-term resistance to ultraviolet aging, and it cannot achieve a balance between high visible light-near infrared transmittance and efficient ultraviolet shielding performance.

[0033] One embodiment of the present invention provides a glass, the composition of which, based on oxides, includes cerium dioxide and titanium dioxide;

[0034] The mass percentage of titanium dioxide is more than 4 times the mass percentage of cerium dioxide, for example, it can be 4 times, 4.2 times, 4.5 times, 4.8 times or 5 times, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] This invention adds titanium dioxide and cerium dioxide to the glass composition, with the titanium dioxide content being more than four times that of cerium dioxide. This creates a complementary absorption and synergistic enhancement mechanism between cerium dioxide and titanium dioxide in the ultraviolet band. Cerium dioxide leverages its strong absorption advantage in the mid-to-short-wave ultraviolet, while titanium dioxide achieves precise shielding through its ultraviolet absorption peak, which is highly matched to the ultraviolet band. This significantly reduces ultraviolet light transmittance, significantly delays the ultraviolet aging of perovskite photovoltaic cells, and improves cell stability and lifespan, while maximizing the preservation of high transmittance of the glass in the 400nm~1200nm visible and near-infrared bands. Furthermore, this invention introduces only the two functional components in specific proportions while maintaining the basic composition of conventional glass. It is highly compatible with existing low-iron glass production processes, enabling industrial-scale mass production without significant adjustments to the production line. The process modification cost is low, and the implementation is highly feasible. It improves the optical uniformity and production stability of the glass, adapting to the needs of photovoltaic and solar thermal power generation applications, and possesses significant technical advantages and industrialization value.

[0036] The ultraviolet transmittance of glass decreases with increasing cerium dioxide content, but not linearly. At lower cerium dioxide content, the ultraviolet blocking effect is better. As the content continues to increase, the improvement in blocking effect is no longer significant, but the influence on the content of other components begins to increase.

[0037] In some embodiments, the cerium dioxide content in the glass composition, by mass percentage, is less than 2 wt%, for example, it can be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, or 2 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably less than 0.5 wt%, and more preferably 0.05 wt% to 0.3 wt%.

[0038] In some embodiments, the glass composition, based on oxides, includes 68wt% to 75wt% SiO2, 12wt% to 17wt% Na2O, 6wt% to 12wt% CaO, less than 6wt% MgO, less than 3wt% Al2O3, less than 400ppm Fe2O3, with the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

[0039] In some embodiments, the glass composition, based on oxides, includes 70wt% to 73wt% SiO2, 13wt% to 15wt% Na2O, 8wt% to 10wt% CaO, 1wt% to 4wt% MgO, 0.5wt% to 2wt% Al2O3, less than 400ppm Fe2O3, with the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

[0040] An embodiment of the present invention provides a method for preparing glass, the method comprising the following steps:

[0041] The raw materials are mixed according to the formula, melted and clarified to obtain a glass melt; the glass melt is homogenized, shaped and annealed to obtain the glass described in any embodiment.

[0042] The raw materials for the preparation of this invention include conventional low-iron glass raw materials, as well as persimmon and titanium sources.

[0043] In some embodiments, the cerium source in the raw materials includes any one or a combination of at least two of cerium-containing slag, cerium dioxide, cerium carbonate, cerium oxalate, or cerium powder. Typical but non-limiting combinations include a combination of cerium-containing slag and cerium dioxide, a combination of cerium carbonate and cerium oxalate, a combination of cerium carbonate, cerium oxalate, and cerium powder, or a combination of cerium-containing slag, cerium dioxide, cerium carbonate, cerium oxalate, and cerium powder.

[0044] In some embodiments, the titanium source in the raw materials includes any one or a combination of at least two of titanium-containing slag, titanium dioxide, titanium dioxide, titanium carbonate, or titanates. Typical but non-limiting combinations include combinations of titanium-containing slag and titanium dioxide, combinations of titanium dioxide and titanium carbonate, combinations of titanium dioxide, titanium dioxide, and titanates, or combinations of titanium-containing slag, titanium dioxide, titanium dioxide, titanium carbonate, and titanates.

[0045] In some embodiments, melting and clarification are carried out in an air atmosphere to ensure Fe 2+ Fully oxidized to Fe 3+ And Ce is mainly Ce 4+ The valence state exists.

[0046] In some embodiments, the melting temperature can be 1450℃~1550℃ and the time can be 4h~8h to ensure the complete melting of the raw materials.

[0047] The melting temperature is 1450℃~1550℃, for example, it can be 1450℃, 1480℃, 1500℃, 1520℃, 1540℃ or 1550℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0048] The melting time is 4h to 8h, for example, it can be 4h, 5h, 6h, 7h or 8h, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0049] In some embodiments, the clarification temperature can be 1500℃~1580℃ and the time can be 2h~4h to completely eliminate bubbles and solid impurities in the molten glass.

[0050] The clarification temperature is 1500℃~1580℃, for example, it can be 1500℃, 1510℃, 1520℃, 1540℃, 1550℃, 1560℃ or 1580℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0051] The clarification time is 2h to 4h, for example, it can be 2h, 2.5h, 3h, 3.5h or 4h, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0052] In some embodiments, the homogenization temperature can be 1350℃~1450℃ and the time can be 1h~3h, in order to eliminate the non-uniformity of the composition and temperature gradient in the glass melt, and ensure the uniformity of the optical properties of the finished glass.

[0053] The homogenization temperature can be between 1350℃ and 1450℃, for example, 1350℃, 1360℃, 1380℃, 1400℃, 1420℃ or 1450℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0054] The homogenization time can be 1 hour to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0055] In some embodiments, the forming method includes float forming or calendering.

[0056] In some embodiments, the float forming temperature can be 1050°C to 1200°C, for example, 1050°C, 1080°C, 1100°C, 1120°C, 1150°C, 1180°C or 1200°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0057] In some embodiments, the calendering temperature can be 1000°C to 1150°C, for example, 1000°C, 1030°C, 1050°C, 1080°C, 1100°C, 1120°C or 1150°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0058] In some embodiments, the annealing temperature can be 550°C to 600°C, and the holding time can be 20 min to 40 min, in order to eliminate the internal stress of the glass.

[0059] The annealing temperature can be 550℃, 560℃, 570℃, 580℃, 590℃ or 600℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0060] The holding time for annealing is 20 min to 40 min, for example, it can be 20 min, 25 min, 30 min, 35 min or 40 min, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0061] As a preferred embodiment of the preparation method provided by the present invention, the preparation method includes the following steps:

[0062] (1) Prepare raw materials by mixing them according to the formula, then melt and clarify them to obtain glass melt;

[0063] The raw materials for preparation include conventional low-iron glass raw materials as well as persimmon source and titanium source; the cerium source includes any one or a combination of at least two of cerium-containing slag, cerium dioxide, cerium carbonate, cerium oxalate or cerium powder; the titanium source includes any one or a combination of at least two of titanium-containing slag, titanium dioxide, titanium dioxide, titanium carbonate or titanate.

[0064] The melting is carried out in an air atmosphere at a temperature of 1450℃~1550℃ for 4h~8h.

[0065] The clarification process involves a temperature range of 1500℃ to 1580℃ and a time range of 2 hours to 4 hours.

[0066] (2) The molten glass is homogenized, shaped and annealed to obtain the glass;

[0067] The homogenization temperature is 1350℃~1450℃, and the time is 1h~3h;

[0068] The forming method includes float forming or calendering;

[0069] The annealing temperature is 550℃~600℃, and the holding time is 20min~40min.

[0070] Example 1

[0071] This embodiment provides a glass, which, based on oxides, comprises 72.18 wt% SiO2, 14.03 wt% Na2O, 9.02 wt% CaO, 3.01 wt% MgO, 1 wt% Al2O3, 0.05 wt% CeO2, 0.25 wt% TiO2, and 400 ppm Fe2O3, along with unavoidable impurities.

[0072] The glass preparation method in this embodiment includes:

[0073] (1) Prepare raw materials by mixing them according to the formula, then melt and clarify them to obtain glass melt;

[0074] The raw materials for preparation include conventional low-iron glass materials (quartz sand, soda ash, dolomite, limestone and feldspar) as well as persimmon source and titanium source; the cerium source is cerium dioxide; the titanium source is titanium dioxide;

[0075] The melting is carried out in an air atmosphere at a temperature of 1500°C for 6 hours.

[0076] The clarification process was carried out at 1550℃ for 3 hours.

[0077] (2) The molten glass is homogenized, shaped and annealed to obtain the glass;

[0078] The homogenization temperature was 1400℃, and the time was 2 hours.

[0079] The forming method is float glass forming at a temperature of 1100℃, resulting in glass with a thickness of 2mm.

[0080] The annealing temperature is 580℃, and the holding time is 30 minutes.

[0081] Example 2

[0082] This embodiment provides a glass, which, based on oxides, comprises 70.03 wt% SiO2, 14.01 wt% Na2O, 9.00 wt% CaO, 3.00 wt% MgO, 1 wt% Al2O3, 0.1 wt% CeO2, 0.4 wt% TiO2, and 400 ppm Fe2O3, along with unavoidable impurities.

[0083] The glass preparation method in this embodiment is the same as in Example 1.

[0084] Example 3

[0085] This embodiment provides a glass, which, based on oxides, comprises 71.52 wt% SiO2, 13.91 wt% Na2O, 8.94 wt% CaO, 2.98 wt% MgO, 0.99 wt% Al2O3, 0.2 wt% CeO2, 1.0 wt% TiO2, and 400 ppm Fe2O3, along with unavoidable impurities.

[0086] The glass preparation method in this embodiment is the same as in Example 1.

[0087] Example 4

[0088] This embodiment provides a glass, which, based on oxides, comprises 70.82 wt% SiO2, 13.78 wt% Na2O, 8.86 wt% CaO, 2.95 wt% MgO, 0.98 wt% Al2O3, 0.3 wt% CeO2, 1.5 wt% TiO2, and 400 ppm Fe2O3, along with unavoidable impurities.

[0089] The glass preparation method in this embodiment is the same as in Example 1.

[0090] Example 5

[0091] This embodiment provides a glass, which, based on oxides, comprises 70.21 wt% SiO2, 13.65 wt% Na2O, 8.78 wt% CaO, 2.93 wt% MgO, 0.97 wt% Al2O3, 0.5 wt% CeO2, 2.5 wt% TiO2, and 400 ppm Fe2O3, along with unavoidable impurities.

[0092] The glass preparation method in this embodiment is the same as in Example 1.

[0093] Example 6

[0094] This embodiment provides a glass that, except for containing 0.2 wt% CeO2 and 1.4 wt% TiO2, has the same composition and mass ratio as in Example 3.

[0095] Comparative Example 1

[0096] This comparative example provides a glass that, except for the absence of CeO2 and TiO2, has the same composition and mass ratio as in Example 3.

[0097] Comparative Example 2

[0098] This comparative example provides a glass that, except for containing only 1 wt% TiO2 and no CeO2, has the same composition and mass ratio as in Example 3.

[0099] Comparative Example 3

[0100] This comparative example provides a glass that, except for containing only 0.2 wt% CeO2 and no TiO2, has the same composition and mass ratio as in Example 3.

[0101] Comparative Example 4

[0102] This comparative example provides a glass that, except for containing only 0.05 wt% CeO2 and not containing TiO2, has the same composition and mass ratio as in Example 3.

[0103] Comparative Example 5

[0104] This comparative example provides a glass that, except for containing 0.05 wt% TiO2 and 0.05 wt% CeO2, has the same composition and mass ratio as in Example 3.

[0105] Comparative Example 6

[0106] This comparative example provides a glass that, except for containing 0.05 wt% TiO2 and 0.1 wt% CeO2, has the same composition and mass ratio as in Example 3.

[0107] Performance Characterization

[0108] The optical properties of the glass obtained in the above embodiments and comparative examples were tested, and the results are shown in Table 1. The tests were conducted in accordance with GB / T 30984.1-2015 Solar Glass Part 1: Ultra-clear Patterned Glass and GB / T 2680-2021 Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Architectural Glass.

[0109] Table 1

[0110]

[0111] As can be seen from Examples 1 to 5 in Table 1, the photovoltaic glass provided by the present invention, when the TiO2 content is more than 4 times that of CeO2, significantly enhances the shielding effect on the 300nm~380nm ultraviolet band as the amount of CeO2 and TiO2 is increased simultaneously. At the same time, it can always maintain a high transmittance in the 380~1100nm photovoltaic response band and the 380~780nm visible light band, which can effectively delay the ultraviolet aging of perovskite photovoltaic cells, while fully taking into account the photoelectric conversion efficiency requirements of the cells.

[0112] A comparison of Comparative Examples 1, 2, and 3 with Example 3 shows that only the synergistic combination of CeO2 and TiO2 can achieve the optimal balance between efficient UV shielding and high light transmittance. Adding either functional component alone cannot achieve the technical effect of this invention. This is because the blank glass without CeO2 and TiO2 has almost no shielding capability in the UV band, with a UV transmittance as high as 87.72%, failing to provide effective UV protection. When only TiO2 is added, its single UV absorption mechanism cannot cover the entire UV band, resulting in extremely poor UV shielding, with a UV transmittance still as high as 82.49%, failing to effectively delay the UV aging degradation of the battery. When only CeO2 is added, although it can exert a strong absorption advantage in the mid- and short-wave UV, it lacks the complementary effect brought by the highly matched absorption peaks of TiO2 and the UV band, failing to form a synergistic enhancement mechanism, and the UV shielding effect is still significantly lower than that of the experimental group with the combination of both.

[0113] A comparison of Comparative Examples 4, 5, and 6 with Example 3 shows that only when the TiO2 content reaches more than four times that of CeO2 can the synergistic enhancement effect of the two be fully activated, achieving a substantial improvement in the ultraviolet shielding effect. This is because when the TiO2 content is less than four times that of CeO2, it cannot form a complementary absorption system across the entire ultraviolet band with CeO2, and the synergistic enhancement mechanism cannot be effectively utilized. Its ultraviolet light transmittance is not significantly improved compared to glass with only an equal amount of CeO2 added, and may even be slightly increased. Only when the TiO2 content is more than four times that of CeO2 can a complementary absorption and synergistic enhancement mechanism be formed with CeO2 in the ultraviolet band, significantly reducing ultraviolet light transmittance while maximizing the preservation of the glass's high transmittance in the 400nm~1200nm visible and near-infrared bands.

[0114] A comparison of Examples 3 and 6 shows that, under the premise of a fixed CeO2 addition amount and a TiO2 content of more than four times that of CeO2, appropriately increasing the proportion of TiO2 can further improve the UV shielding effect of the glass while maintaining high transmittance in the photovoltaic and visible light bands. This is because, based on the correct ratio, increasing the amount of TiO2 can further enhance its shielding effect in the UV band, forming a stronger complementary synergistic effect with the mid- and short-wave UV absorption of CeO2, while not significantly negatively impacting the transmittance in the visible and near-infrared bands. The ratio can be flexibly adjusted according to the UV protection requirements of the actual application scenario.

[0115] In summary, this invention adds titanium dioxide and cerium dioxide to the glass composition, with the titanium dioxide content being more than four times that of cerium dioxide. This creates a complementary absorption and synergistic enhancement mechanism between cerium dioxide and titanium dioxide in the ultraviolet band. Cerium dioxide leverages its strong absorption advantage in mid- and short-wave ultraviolet light, while titanium dioxide achieves precise shielding through its ultraviolet absorption peak, which is highly matched to the ultraviolet band. This significantly reduces ultraviolet light transmittance, significantly delays the ultraviolet aging of perovskite photovoltaic cells, and improves cell stability and lifespan, while maximizing the preservation of high transmittance of the glass in the 400nm~1200nm visible and near-infrared bands. Furthermore, this invention introduces only the two functional components in specific proportions while maintaining the basic composition of conventional glass. It is highly compatible with existing low-iron glass production processes, enabling industrial-scale mass production without significant adjustments to the production line. The process modification cost is low, and the feasibility is high. It improves the optical uniformity and production stability of the glass, adapting to the needs of photovoltaic and solar thermal power generation applications, and possesses significant technical advantages and industrialization value.

[0116] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A type of glass, characterized in that, The glass comprises cerium dioxide and titanium dioxide, based on oxides. The mass percentage of titanium dioxide is more than four times the mass percentage of cerium dioxide.

2. The glass according to claim 1, characterized in that, The cerium dioxide content in the glass composition is less than 2 wt% by mass percentage.

3. The glass according to claim 1, characterized in that, The glass composition contains cerium dioxide at a mass percentage of less than 0.5 wt%.

4. The glass according to claim 1, characterized in that, The glass composition contains 0.05wt% to 0.3wt% cerium dioxide by mass percentage.

5. The glass according to claim 1, characterized in that, Based on oxides, the glass composition includes 68wt%~75wt% SiO2, 12wt%~17wt% Na2O, 6wt%~12wt% CaO, less than 6wt% MgO, less than 3wt% Al2O3, less than 400ppm Fe2O3, with the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

6. The glass according to claim 1, characterized in that, Based on oxides, the glass composition includes 70wt%~73wt% SiO2, 13wt%~15wt% Na2O, 8wt%~10wt% CaO, 1wt%~4wt% MgO, 0.5wt%~2wt% Al2O3, less than 400ppm Fe2O3, and the balance being titanium dioxide, cerium dioxide, and unavoidable impurities.

7. A method for preparing glass, characterized in that, The preparation method includes the following steps: The raw materials are mixed in the formula, melted and clarified to obtain a glass melt; the glass melt is homogenized, shaped and annealed to obtain the glass according to any one of claims 1 to 6.

8. The preparation method according to claim 7, characterized in that, The cerium source in the raw materials includes any one or a combination of at least two of cerium-containing slag, cerium dioxide, cerium carbonate, cerium oxalate, or cerium powder.

9. The preparation method according to claim 7, characterized in that, The titanium source in the preparation raw materials includes any one or a combination of at least two of titanium-containing slag, titanium dioxide, titanium dioxide, titanium carbonate, or titanates.

10. The preparation method according to claim 8 or 9, characterized in that, The forming method includes float forming or calendering.

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