Rare-earth-based environment-friendly clarifying agent for ultrathin photovoltaic glass and preparation method thereof

Abstract

The invention provides a rare-earth-based environment-friendly clarifying agent and a preparation method thereof.The method comprises the steps that S1, CeO2 and Y2O3 are ground and mixed to be uniform, and composite rare earth oxide powder is obtained; s2, uniformly mixing the obtained composite rare earth oxide powder, SiO2, Al2O3, CaO, MgO, Na2O and K2O, ball-milling and mixing, pre-sintering the basic powder, cooling, and crushing to obtain a pre-sintered material; s3, SnO2, Sb2O3 and a pore forming agent are added into the pre-sintered material, ball milling and mixing are conducted, and mixed powder is further pressed into a blank; s4, performing high-temperature sintering, cooling and crushing on the blank body to obtain a clarifying agent precursor; and S5, coating the surface of the clarifying agent precursor with a SiO2 nano film by adopting a sol-gel method to obtain the rare-earth-based environment-friendly clarifying agent. According to the clarifying agent, through non-bridge oxygen combination of rare earth ions and a glass network, the network polymerization degree is enhanced, the mechanical strength of glass is improved, and energy saving and mechanical properties are both considered.

Description

Technical Field

[0001] This invention relates to the field of glass manufacturing technology, and provides a rare earth-based environmentally friendly clarifying agent for ultra-thin photovoltaic glass and its preparation method. Background Technology

[0002] With the increasing demands for lightweight, high-transmittance, and high-reliability photovoltaic modules, ultra-thin photovoltaic glass with a thickness of ≤1.1 mm has become a research hotspot in the industry. However, when ultra-thin glass is melted at high temperatures of 1450~1550 ℃, the melt viscosity increases significantly, making it difficult for traditional clarifying agents to fully release the decomposition products of gases such as SO3 and CO2. This results in high bubble density and large average diameter in the finished product, directly reducing light transmittance and weakening mechanical strength. Existing technologies generally use clarifying agents containing arsenic and antimony heavy metals such as As2O3 and Sb2O3. Although the clarifying effect is acceptable, these agents are highly toxic and pose significant environmental hazards, and are subject to strict restrictions under EU regulations such as RoHS and REACH. In addition, traditional clarifying agents have poor dispersibility and short action time in the low-alkali, high-alumina formulation of ultra-thin glass, which easily leads to local over-clarification or secondary bubbles, causing optical distortion and a decrease in yield.

[0003] Therefore, developing a novel clarifying agent that combines high efficiency in clarifying, environmental friendliness, and adaptability to low-melting-point and high-stability formulations for ultra-thin photovoltaic glass has become a key technical challenge that urgently needs to be addressed in this field. Summary of the Invention

[0004] To address the problems mentioned in the background section, the main objective of this invention is to provide a rare-earth-based environmentally friendly clarifying agent for ultra-thin photovoltaic glass and its preparation method. This invention aims to solve key technical problems encountered during the melting process of ultra-thin photovoltaic glass, such as decreased light transmittance and insufficient mechanical strength due to high viscosity at high temperatures and difficulty in fully escaping bubbles, as well as environmental pollution caused by the presence of arsenic and antimony heavy metals in traditional clarifying agents. The invention strives to provide a clarifying agent that combines high-efficiency clarifying performance with green and environmentally friendly characteristics.

[0005] In a first aspect, the present invention provides a rare earth-based environmentally friendly clarifying agent for ultrathin photovoltaic glass, comprising CeO2, Y2O3, SiO2, Al2O3, CaO, MgO, Na2O, K2O, SnO2 and Sb2O3.

[0006] In some embodiments, the chemical composition of the rare earth-based environmentally friendly clarifying agent, by mass percentage, includes: CeO2 1~5 wt%, Y2O3 0.5~5 wt%, SiO2 55~75 wt%, Al2O3 1~8 wt%, CaO 5~15 wt%, MgO 0~5 wt%, Na2O 5~15 wt%, K2O 0~5 wt%, SnO2 0.01~5 wt%, Sb2O3 0.01~5 wt%.

[0007] In some embodiments, the chemical composition of the rare earth-based environmentally friendly clarifying agent, by mass percentage, includes: CeO2 1~5 wt%, Y2O3 0.5~5 wt%, SiO2 60~70 wt%, Al2O3 1~5 wt%, CaO 10~15 wt%, MgO 1~5 wt%, Na2O 5~10 wt%, K2O 1~5 wt%, SnO2 1~5 wt%, Sb2O3 1~5 wt%.

[0008] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains CeO2 of 1 to 5 wt%, preferably 1 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0009] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains Y2O3 at a concentration of 0.5 to 5 wt%, preferably 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0010] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains SiO2 of 55-75 wt%, preferably 55 wt%, 60 wt%, 62 wt%, 64 wt%, 65 wt%, 66 wt%, 68 wt%, 70 wt%, 75 wt%, or any two of the above values ​​forming a range.

[0011] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains Al2O3 at a concentration of 1 to 8 wt%, preferably 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or any two of the above values ​​forming a range.

[0012] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains 5 to 15 wt% CaO, preferably 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, or any two of the above values ​​forming a range.

[0013] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains 0-5 wt% MgO, preferably 0, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0014] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains 5 to 15 wt% Na2O, preferably 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, or any two of the above values ​​forming a range.

[0015] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains K2O in a range of 0-5 wt%, preferably 0, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0016] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains SnO2 at a concentration of 0.01 to 5 wt%, preferably 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0017] In some embodiments, the rare earth-based environmentally friendly clarifying agent contains Sb2O3 at a concentration of 0.01 to 5 wt%, preferably 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any two of the above values ​​forming a range.

[0018] In some embodiments, the rare earth-based environmentally friendly clarifying agent further includes at least one of TiO2, ZrO2, and Fe2O3.

[0019] In some embodiments, the rare earth-based environmentally friendly clarifying agent further includes TiO2 at a concentration of 0.01~1.5 wt%, preferably 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or 1.5 wt%.

[0020] In some embodiments, the rare earth-based environmentally friendly clarifying agent further includes ZrO2 at a concentration of 0.01~1.5 wt%, preferably 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or 1.5 wt%.

[0021] In some embodiments, the rare earth-based environmentally friendly clarifying agent further includes Fe2O3 at a concentration of 0.01~1.5 wt%, preferably 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or 1.5 wt%.

[0022] In some embodiments, the chemical composition of the rare earth-based environmentally friendly clarifying agent, by mass percentage, includes: CeO2 1.5 wt%, Y2O3 0.5 wt%, SiO2 65 wt%, Al2O3 4 wt%, CaO 12 wt%, MgO 2 wt%, Na2O 10 wt%, K2O 2 wt%, SnO2 1.5 wt%, and Sb2O3 1.5 wt%.

[0023] In some embodiments, the chemical composition of the rare earth-based environmentally friendly clarifying agent, by mass percentage, includes: CeO2 1.5 wt%, Y2O3 0.5 wt%, SiO2 65 wt%, Al2O3 4 wt%, CaO 12 wt%, MgO 2 wt%, Na2O 10 wt%, K2O 2 wt%, SnO2 0.5 wt%, Sb2O3 0.5 wt%, TiO2 0.6 wt%, ZrO2 0.6 wt%, Fe2O3 0.8 wt%.

[0024] For specific process requirements, at least a portion of SnO2 and Sb2O3 can be replaced by one or more of TiO2, ZrO2, and Fe2O3, with a total replacement amount of ≤3 wt%. While maintaining clarification performance, the formulation can be flexibly adjusted according to glass color or UV cutoff requirements.

[0025] To precisely control particle porosity, a pore-forming agent, selected from at least one of carbon powder, starch, or polymer microspheres, can be added at 1–5 wt% of the total mass of the rare-earth-based environmentally friendly clarifying agent. This agent decomposes and volatilizes during sintering to form a microporous structure, increasing the specific surface area while preventing the introduction of impurities. The resulting clarifying agent particles have a particle size distribution D. 50 With a particle size of ≤10μm, and by spray granulation or plasma spheroidization technology, it is made into a spherical or near-spherical shape, which significantly improves the dispersion uniformity and flowability in molten glass.

[0026] In some embodiments, the rare earth-based environmentally friendly clarifying agent further includes a pore-forming agent.

[0027] In some embodiments, the pore-forming agent is selected from at least one of carbon powder, starch, or polymer microspheres.

[0028] In some embodiments, the pore-forming agent is 0.01~5 wt% based on the total mass of the rare earth-based environmentally friendly clarifying agent, preferably 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.45wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, or any two of the above values ​​forming any one of the ranges.

[0029] Secondly, this invention provides a method for preparing a rare earth-based environmentally friendly clarifying agent, comprising the following steps: S1. Grind and mix CeO2 and Y2O3 evenly to obtain composite rare earth oxide powder; S2. After the obtained composite rare earth oxide powder, SiO2, Al2O3, CaO, MgO, Na2O and K2O are mixed evenly, the mixture is ball-milled and the base powder is pre-calcined. After cooling, it is crushed to obtain the pre-calcined material. S3. Add SnO2, Sb2O3 and pore-forming agent to the pre-calcined material, ball mill and mix, and further press the mixed powder into a blank. S4. The preform is sintered at high temperature, cooled, and pulverized to obtain the clarifying agent precursor; S5. A rare earth-based environmentally friendly clarifying agent is obtained by coating the surface of the clarifying agent particles with a SiO2 nanofilm using the sol-gel method.

[0030] In some embodiments, in step S1, the grinding and mixing time is 30 to 90 minutes, preferably 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, or any two of the above values ​​forming a range.

[0031] In some embodiments, in step S1, the grinding and mixing is carried out in a planetary ball mill with a rotation speed of 300 rpm to 500 rpm, preferably 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, or any two of the above values ​​forming a range.

[0032] In some embodiments, in step S1, the D of the composite rare earth oxide powder 50 ≤10μm, preferably 8μm.

[0033] In some embodiments, in step S2, the mixing is carried out in a three-dimensional mixer for a mixing time of 40-70 min, preferably 40 min, 50 min, 60 min, 70 min, or any two of the above values ​​forming a range.

[0034] In some embodiments, the pre-firing temperature is 800~1000℃, and the pre-firing time is 1~3h. Preferably, the temperature is any one of 800, 850, 900, 950, 1000℃ or any two of the above values, and the time is any one of 1h, 1.5h, 2h, 2.5h, 3h or any two of the above values.

[0035] In some embodiments, the preheating heating rate is 1~10℃ / min, preferably 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min or 10℃ / min.

[0036] In some embodiments, the crushing refers to crushing the pre-burned material using a crusher, and the resulting pre-burned material can be passed through a 100-mesh sieve.

[0037] In some embodiments, in step S2, the D of the ball-milled mixed powder 50 ≤10μm.

[0038] In some embodiments, in step S2, the cooling is natural cooling to room temperature. In this invention, room temperature refers to a temperature of 15~35°C.

[0039] In some embodiments, in step S3, the ball milling mixing time is 30~60min, preferably 30min, 40min, 45min, 50min, 60min, or any two of the above values ​​forming a range.

[0040] In some embodiments, in step S3, the mixed powder is further pressed into a preform under cold isostatic pressing conditions of 100-200 MPa. Preferably, the cold isostatic pressing is any one of the following ranges: 100 MPa, 120 MPa, 150 MPa, 170 MPa, 200 MPa, or any two of the above values.

[0041] In some embodiments, in step S4, the high-temperature sintering temperature is 1000~1500℃, the sintering time is 1~5h, and the heating rate is 1~5℃ / min. Preferably, the temperature is any one of the ranges formed by any two of the values ​​1000℃, 1100℃, 1200℃, 1250℃, 1300℃, 1400℃, 1500℃. Preferably, the sintering time is any one of the ranges formed by any two of the values ​​1h, 2h, 3h, 4h, 5h. Preferably, the heating rate is any one of the ranges formed by any two of the values ​​1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min.

[0042] In some embodiments, step S4 involves air jet milling, resulting in a pore size of 5-15% for the clarifying agent precursor. 50 =40μm, sphericity ≥0.85.

[0043] In some embodiments, in step S5, the clarifying agent precursor is dispersed in a solution, tetraethyl orthosilicate is added dropwise, and after the reaction is complete, the mixture is centrifuged, washed, dried, and calcined to obtain a rare earth-based environmentally friendly clarifying agent.

[0044] In some embodiments, in step S5, the solution is a mixed solution of ethanol-water-ammonia water, with a mass ratio of 1:1:1.

[0045] In some embodiments, in step S5, the reaction is carried out at 15~35°C for 5~10 hours. Preferably, the reaction temperature is any one of the ranges of 15°C, 20°C, 25°C, 30°C, 35°C, or any two of the above values. Preferably, the reaction time is any one of the ranges of 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or any two of the above values.

[0046] In some embodiments, the drying temperature in step S5 is 75~85°C. Preferably, the temperature is any one of 75°C, 80°C, 85°C, or any two of the above values.

[0047] In some embodiments, the calcination temperature in step S5 is 500~700℃. Preferably, the temperature is any one of the ranges of 500℃, 550℃, 600℃, 650℃, 700℃, or any two of the above values.

[0048] In some embodiments, the calcination time in step S5 is 1 to 5 hours. Preferably, the time is any one of the ranges of 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or any two of the above values.

[0049] In some embodiments, in step S5, the mass ratio of the clarifying agent precursor to the solution is 1:5 to 10, preferably 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10.

[0050] In some embodiments, in step S5, the mass ratio of the clarifying agent precursor to tetraethyl orthosilicate is 1:5.

[0051] In some embodiments, the clarifying agent precursor is externally coated with a dense silica coating layer. In some embodiments, the silica coating layer is 50-200 nm, preferably 100-110 nm.

[0052] In some embodiments, the particle size D of the rare earth-based environmentally friendly clarifying agent 50 ≤10μm, with particle shape being spherical or near-spherical.

[0053] Thirdly, the present invention provides the application of the rare earth-based environmentally friendly clarifying agent described in the present invention or the rare earth-based environmentally friendly clarifying agent prepared by the method described in the present invention in the preparation of materials for photovoltaic cover glass, front panel of double glass module and substrate glass of flexible thin film battery.

[0054] The rare earth-based environmentally friendly clarifying agent of this invention combines with the non-bridging oxygen of the glass network through rare earth ions in the molten glass, thereby increasing Q... 2 / Q 3 The ratio is increased by 10-30%, enhancing the network aggregation degree, thereby reducing the melting temperature by ≥30 ℃ while increasing the mechanical strength of ultra-thin photovoltaic glass to ≥120 MPa, taking into account both energy saving and mechanical performance, and achieving a unity of efficient clarification, green environmental protection and energy-saving enhancement.

[0055] The above-mentioned technical solutions of the present invention constitute a complete and industrially scalable environmentally friendly clarification system, which can be widely used in the production of photovoltaic cover glass with a thickness of ≤1.1 mm, front panel of double glass module and substrate glass of flexible thin film battery.

[0056] Compared with the prior art, one of the above technical solutions has the following advantages or beneficial effects: (1) The rare earth-based environmentally friendly clarifying agent of the present invention uses rare earth oxides as the core active components. By precisely controlling the content of at least one of Ce and Y oxides to be 0.5~5 wt%, it can quickly release active oxygen in the melting temperature range of 1450~1550 ℃, which promotes the rapid diffusion, aggregation and floating discharge of residual SO3, CO2 and other gas decomposition products in the glass melt, thereby stabilizing the number of bubbles to ≤5 / kg and the average diameter of the bubbles to ≤0.2 mm, which is significantly better than the existing arsenic / antimony-based clarifying agents.

[0057] (2) The basic glass network forming agents of the rare earth-based environmentally friendly clarifying agent of the present invention are SiO2 and Al2O3, and CaO, MgO, Na2O and K2O are introduced to form a low-melting-point, highly chemically stable aluminosilicate system, which not only ensures the flexibility required for ultra-thin glass, but also provides a uniformly dispersed carrier for the core active components of rare earth oxides. To further improve the clarifying efficiency and reduce the melting temperature, SnO2 and Sb2O3 are introduced into the formula as synergistic clarifying aids. At high temperatures, they form multi-element redox couples with rare earth oxides, enhancing oxygen release kinetics while inhibiting the formation of secondary bubbles.

[0058] (3) The rare earth-based environmentally friendly clarifying agent of the present invention is made by mixing rare earth oxides and basic oxides in a designed ratio and grinding them to D by high-energy ball milling. 50 The particle size is ≤10μm to ensure uniform diffusion of components during subsequent sintering. Then, pre-sintering is carried out at 800~1000℃ for 1~3h to allow some oxides to undergo preliminary solid-state reactions and form stable crystalline phases. After cooling, the pre-sintered product is mixed a second time with SnO2, Sb2O3, and a pore-forming agent, and then pressed under cold isostatic pressing at 100~200MPa to obtain a high-density green body. Finally, sintering is carried out at 1000~1500℃ for 1~5h. By controlling the heating rate and holding time, a uniform porosity of 5~15% is formed inside the particles, which increases the contact area with the molten glass and avoids excessively rapid dissolution of the particles, leading to localized compositional fluctuations.

[0059] (4) The rare earth-based environmentally friendly clarifying agent of the present invention, by limiting the rare earth oxides to a composite system of CeO2 and Y2O3 and controlling the mass ratio of the two to be between 1:1 and 3:1, can reduce material costs while maintaining high clarifying activity, and Ce 4+ / Ce 3+ With Y 3+ The synergistic effect can significantly inhibit Fe 2+ The effects of impurity ions on glass color are investigated. Secondly, a 50-200 nm thick SiO2 nanofilm is coated onto the surface of the clarifying agent particles. This nanofilm slowly dissolves in the molten glass, forming a protective layer that delays the release of internal active components, thereby extending the effective action time and reducing dust dispersion. Thirdly, an optical imaging system monitors the bubble density and size distribution in the molten glass in real time, and dynamically adjusts the amount of clarifying agent added based on feedback signals, achieving intelligent closed-loop control and further reducing raw material waste.

[0060] (5) The rare earth-based environmentally friendly clarifying agent of the present invention can reduce the melting temperature of glass, reduce bubble defects in the glass preparation process, and effectively improve the overall performance of ultra-thin photovoltaic glass. Attached Figure Description

[0061] Figure 1This is a bubble diagram of the ultrathin photovoltaic glass prepared in Example 5.

[0062] Figure 2 Bubble diagram of the ultrathin photovoltaic glass prepared for Comparative Example 1.

[0063] Terminology Explanation Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications, and equivalents, all of which are included within the scope of the invention as defined in the claims. Those skilled in the art will recognize that many similar or equivalent methods and materials can be used to practice the invention. The invention is by no means limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ from or contradict this application (including, but not limited to, defined terminology, application of terminology, described techniques, etc.), this application shall prevail.

[0064] It should be further appreciated that certain features of the invention, for clarity, have been described in multiple independent embodiments, but may also be provided in combination in a single embodiment. Conversely, various features of the invention, for brevity, have been described in a single embodiment, but may also be provided individually or in any suitable sub-combination.

[0065] Unless otherwise stated, all technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. All patents and publications related to this invention are incorporated herein by reference in their entirety.

[0066] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0067] In the following content, all numbers disclosed herein, whether or not they use words such as "approximately" or "about," are approximate values. The value of each number may vary by 1%, 2%, 5%, 7%, 8%, 10%, 15%, or 20%. Whenever a number with a value of N is disclosed, any numbers with values ​​of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8%, N+ / -10%, N+ / -15%, or N+ / -20% will be explicitly disclosed, where "+ / -" indicates addition or subtraction. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and techniques have also been described in many publications.

[0069] All reagents used in this invention can be purchased commercially or prepared by the methods described in this invention.

[0070] In this embodiment, SiO2 and Al2O3 are the main network oxide and intermediate oxide of the glass, respectively, and together they mainly form the glass network.

[0071] SiO2, as one of the main network oxide components of glass, is an important component in forming the Si-O tetrahedra and constructing the network structure. Al2O3 is an intermediate oxide in glass formation, which can significantly improve the thermal stability of glass. Furthermore, because [AlO4] has a larger volume than [SiO4], it provides more space for ion exchange; therefore, alumina can promote ion exchange. However, excessive Al2O3 will increase the viscosity of the glass, which is detrimental to melting.

[0072] Na₂O and K₂O, alkali metal oxides, are oxides on the outer layer of the glass network. They effectively ensure the breaking of bridging oxygen bonds within the glass, disrupting the original glass network structure and reducing glass viscosity and melting difficulty. During heat treatment, they promote glass crystallization.

[0073] Meanwhile, Na₂O acts as a flux during the high-temperature melting of glass, significantly lowering its melting temperature. However, excessive Na₂O content leads to a significant decrease in the chemical stability of the glass. Therefore, the ideal Na₂O mass ratio maintains both a suitable melting temperature range and ensures good ion exchange properties. K₂O can reduce the high-temperature viscosity of glass, significantly improving its formability and fluidity at high temperatures, while also significantly reducing the cracking rate. Furthermore, the addition of an appropriate amount of K₂O is beneficial for... + and Na + Ion exchange enhances the strengthening effect.

[0074] Y2O3 can improve the strength and elastic modulus of glass.

[0075] Example A rare earth-based environmentally friendly clarifying agent for ultra-thin photovoltaic glass, comprising, by mass percentage: CeO2 1~5 wt%, Y2O3 0.5~5 wt%, SiO2 55~75 wt%, Al2O3 1~8 wt%, CaO 5~15 wt%, MgO 0~5 wt%, Na2O 5~15 wt%, K2O 0~5 wt%, SnO2 0.01~5 wt%, Sb2O3 0.01~5 wt%; Preferably, 0-5 wt% of a pore-forming agent is added, based on the total mass of the rare earth-based environmentally friendly clarifying agent.

[0076] The preparation method of rare earth-based environmentally friendly clarifying agent includes the following steps: S1. CeO2 and Y2O3 are ground and mixed evenly in a planetary ball mill at a speed of 300 rpm to 500 rpm for 30 to 90 minutes to obtain D. 50 Composite rare earth oxide powder with a diameter of 8μm; S2. The obtained composite rare earth oxide powder, SiO2, Al2O3, CaO, MgO, Na2O, and K2O are mixed evenly in a three-dimensional mixer for 40-70 minutes. The mixture is then ball-milled. The D of the ball-milled powder is... 50 ≤10μm, the basic powder is pre-fired at a temperature of 800~1000℃ for 1~3h, with a heating rate of 1~10℃ / min. After naturally cooling to room temperature, the pre-fired material is crushed using a crusher and the resulting pre-fired material is passed through a 100-mesh sieve. S3. Add SnO2, Sb2O3 and pore-forming agent to the pre-burned material, ball mill and mix for 30-60 min, and then press the mixed powder into a blank under cold isostatic pressing conditions of 100-200 MPa. S4. Sinter the preform at 1000~1500℃ for 1~5h, with a heating rate of 1~5℃ / min, cool, and use airflow milling to obtain a porosity of 5~15%. 50 Clarifying agent precursors with a diameter ≤10μm and a sphericity ≥0.85; S5. Disperse the clarifying agent precursor in a mixed solution of ethanol, water, and ammonia (mass ratio 1:10), add tetraethyl orthosilicate (mass ratio of clarifying agent precursor to tetraethyl orthosilicate 1:5), and react at 15-35°C for 5-10 hours. After the reaction is complete, centrifuge, wash, dry at 75-85°C for 0.5-3 hours, and calcine at 500-700°C for 1-5 hours to obtain a rare earth-based environmentally friendly clarifying agent. In the ethanol-water-ammonia mixed solution, the mass ratio of ethanol, water, and ammonia is 1:1:1, resulting in a rare earth-based environmentally friendly clarifying agent with a dense silica coating layer; the silica coating layer is 50-200 nm, preferably 80-150 nm.

[0077] The proportions of each component are shown in Table 1 below; Table 1. Component information of each example

[0078] The specific temperatures and times during the preparation process are shown in Table 2.

[0079] Table 2 Screening of preparation process conditions

[0080] Example 4 Screening of pore-forming agent dosage The chemical composition and preparation method are the same as in Example 1, except that the amount of pore-forming agent is different, as shown in Table 3 below.

[0081] Table 3 Screening of pore-forming agents

[0082] As can be seen from the table above, different starch dosages affect the performance of clarifying agent granules. Clarifying agent granules with a porosity of 8-12% are preferred, as they can achieve a balance between clarification efficiency and granule strength.

[0083] Example 5 Ultra-thin photovoltaic glass compound: SiO2 72 wt%, Al2O3 1.5 wt%, CaO 8.5 wt%, Na2O 14 wt%, K2O4 wt%. The clarifying agent prepared in Example 1 of this invention was added to the ultra-thin photovoltaic glass batch at 0.3 wt% of the total mass of the batch. The batch was melted at 1480°C and held at that temperature for 90 minutes. The preparation process and results are shown in Table 4 below. Table 4 Comparison of Example 5 and Comparative Example 1

[0084] The number and average diameter of the bubbles were measured using a microscope, and the results are as follows: Figure 1 and Figure 2 As shown; the melting temperature was determined by a high-temperature rotational viscometer when the viscosity = 10. 3 The temperature at which dPa·s is measured is denoted as the melting temperature; through 29 Si MAS-NMR determination of glass network structure Q 2 / Q 3 Ratio; Three-point bending strength was determined according to ASTM C158-20 standard, with a specimen size of 50 mm × 10 mm × 0.5 mm.

[0085] Depend on Figure 1 It can be seen that adding the clarifying agent prepared in this invention significantly reduces the number of bubbles in the resulting glass; Figure 2 It can be seen that the glass without added clarifying agent has more bubbles.

[0086] As can be seen from the data in Table 4, the addition of the clarifying agent prepared according to this invention improves all properties of the resulting glass. For example, the glass network structure Q... 2 / Q 3 An increase in the ratio indicates a decrease in network aggregation and an improvement in liquidity.

[0087] Example 6 The difference from Example 1 is that the total amount of rare earth oxides is fixed at 3 wt%, and the mass ratio of CeO2 and Y2O3 is changed to prepare the corresponding clarifying agent.

[0088] The difference from Example 5 is that the clarifying agent prepared in this example was used to prepare glass, and the relevant data were detected, as shown in Table 5 below.

[0089] Table 5 Data table for Example 6

[0090] When adding a clarifying agent to glass preparation, the bubble removal rate reaches 92%~94% when the mass ratio of CeO2 to Y2O3 is 3:1, and the glass transmittance (380~1000nm) is increased by 1.81%. When the CeO2 content is 75% (e.g., 1:1), the glass yellows. When the mass ratio of Y2O3 is greater than 50% (1:2, 1:3), the clarification efficiency of the glass prepared by the clarifying agent decreases, and the bubble removal rate is less than 80%.

[0091] Example 7 The difference from Example 1 is that the total proportion of SnO2 and Sb2O3 is reduced by 1 / 3, and at least one of TiO2, ZrO2, and Fe2O3 is used to replace them to prepare the corresponding clarifying agent, as shown in Table 6 below: The difference from Example 5 is that the clarifying agent prepared in this example was used to prepare glass, and the relevant data were detected, as shown in Table 6 below.

[0092] Table 6 Data table for Example 7

[0093] It is evident that the glass properties change after different components are substituted, and appropriate substitutions can be made according to the required glass conditions.

[0094] The method of this invention has been described through preferred embodiments. Those skilled in the art will readily be able to modify or appropriately alter and combine the methods and applications described herein within the scope, spirit, and context of this invention to implement and apply the technology of this invention. Those skilled in the art can refer to the content herein to appropriately improve process parameters. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included within the scope of this invention.

Claims

1. A rare earth based eco-friendly fining agent for ultra-thin photovoltaic glass, characterized in that, CeO2, Y2O3, SiO2, Al2O3, CaO, MgO, Na2O, K2O, SnO2 and Sb2O3.

2. The environment friendly clarifier according to claim 1, wherein The chemical components of the rare earth-based environmentally friendly clarifier include, in terms of mass percentage, CeO2 1-5 wt%, Y2O3 0.5-5 wt%, SiO2 55-75 wt%, Al2O3 1-8 wt%, CaO 5-15 wt%, MgO 0-5 wt%, Na2O 5-15 wt%, K2O 0-5 wt%, SnO2 0.01-5 wt%, and Sb2O3 0.01-5 wt%. Preferably, the chemical components of the rare earth-based environmentally friendly clarifier include, in terms of mass percentage, CeO2 1-5 wt%, Y2O3 0.5-5 wt%, SiO2 60-70 wt%, Al2O3 1-5 wt%, CaO 10-15 wt%, MgO 1-5 wt%, Na2O 5-10 wt%, K2O 1-5 wt%, SnO2 1-5 wt%, and Sb2O3 1-5 wt%.

3. The environment friendly clarifier according to claim 1, wherein The rare earth-based environmentally friendly clarifier further includes at least one of TiO2, ZrO2 and Fe2O3. Preferably, the TiO2 is 0.01-1.5 wt%, the ZrO2 is 0.01-1.5 wt%, and the Fe2O3 is 0.01-1.5 wt%.

4. The environment friendly clarifier according to claim 1, wherein The rare earth-based environmentally friendly clarifier further includes a pore-forming agent. Preferably, the pore-forming agent is selected from at least one of carbon powder, starch or polymer microspheres. Preferably, the pore-forming agent is 0.01-5 wt% based on the total mass of the rare earth-based environmentally friendly clarifier.

5. A process for the preparation of the environment friendly clarifier of any one of claims 1 to 4, characterized in that, The method includes the following steps: S1, grinding and mixing CeO2 and Y2O3 uniformly to obtain a composite rare earth oxide powder; S2, mixing the obtained composite rare earth oxide powder, SiO2, Al2O3, CaO, MgO, Na2O and K2O uniformly, then ball-milling and mixing, pre-sintering the base powder, crushing after cooling to obtain pre-sintered material; S3, adding SnO2, Sb2O3 and a pore-forming agent to the pre-sintered material, ball-milling and mixing, and further pressing the mixed powder into a green body; S4, high-temperature sintering the green body, cooling and crushing to obtain a clarifier precursor; S5, coating a SiO2 nano film on the surface of the clarifier particles by a sol-gel method to obtain a rare earth-based environmentally friendly clarifier.

6. The preparation method according to claim 5, characterized in that, In step S1, the grinding and mixing time is 30-90 min. The grinding and mixing is performed in a planetary ball mill at a rotation speed of 300-500 rpm. Preferably, in step S1, the D50 of the composite rare earth oxide powder is < 10 pm, preferably 8 pm. 50 ≤10 pm, preferably 8 pm.

7. The preparation method according to claim 5, characterized in that, In step S2, the mixing is performed in a three-dimensional mixer for 40-70 min. Preferably, the pre-sintering temperature is 800-1000°C, and the pre-sintering time is 1-3 h. Preferably, the pre-sintering temperature is 800-1000°C, and the pre-sintering time is 1-3 h. Preferably, the crushing refers to crushing the pre-sintered material by a crusher, and the obtained pre-sintered material is sieved through a 100-mesh sieve. Preferably, in step S2, the D50of the mixed powder ball-milled is ≤ 10 μm. 50 ≤ 10 μm; Preferably, in step S2, the cooling is natural cooling to room temperature.

8. The preparation method according to claim 5, characterized in that, The ball milling time in step S3 is 30-60 min; Preferably, in step S3, the mixed powder is further pressed into a green body under cold isostatic pressing at 100-200 MPa; Preferably, in step S4, the high-temperature sintering temperature is 1000-1500 ℃, the sintering time is 1-5 h, and the heating rate is 1-5 ℃ / min; Preferably, in step S4, the pulverization uses air flow pulverization, and the obtained clarifier precursor has a pore size of 5-15%, D 50 ≤ 10 μm, and a sphericity ≥ 0.

85.

9. The preparation method according to claim 5, characterized in that, In step S5, the clarifier precursor is dispersed in a solution, and tetraethyl orthosilicate is added dropwise. After the reaction, the rare earth-based environmentally friendly clarifier is obtained by centrifugation, washing, drying, and calcination; Preferably, in step S5, the solution is an ethanol-water-ammonia mixed solution with a mass ratio of 1:1:1; Preferably, in step S5, the reaction is carried out at 15-35 ℃ for 5-10 h; Preferably, in step S5, the drying temperature is 75-85 ℃; Preferably, in step S5, the calcination temperature is 500-700 ℃; Preferably, in step S5, the calcination time is 1-5 h; Preferably, in step S5, the mass ratio of the clarifier precursor to the solution is 1:5-10, and the mass ratio of the clarifier precursor to tetraethyl orthosilicate is 1:5; Preferably, the clarifier precursor is coated with a dense silica coating layer, and the thickness of the silica coating layer is 50-200 nm, preferably 100-110 nm; Preferably, the particle size D of the rare earth-based environmentally friendly clarifier is 50 ≤ 10 μm, and the particle shape is spherical or spheroidal.

10. Use of the rare earth-based environmentally friendly clarifier of any one of claims 1-4 or prepared by the method of any one of claims 5-9 in the preparation of a material for photovoltaic cover glass, double-glass component front plate, and flexible thin-film battery substrate glass.

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