Rare earth doped phosphate luminescent glass, preparation method and application thereof, photovoltaic glass backboard material and application thereof

Abstract

The invention relates to the technical field of glass, and discloses rare earth doped phosphate luminescent glass and a preparation method and application thereof, and a photovoltaic glass backboard material and application thereof, and the rare earth doped phosphate luminescent glass is prepared from the following raw material composition in percentage by mass: 30 to 60 percent of P2O5, 10 to 25 percent of CaO, 5 to 15 percent of Na2O, 5 to 15 percent of K2O, 1 to 10 percent of Al2O3, 1 to 5 percent of SrO, 0 to 1 percent of BaO, 0 to 1 percent of SiO2, 0.1 to 2 percent of Eu2O3 and 0.1 to 2 percent of Dy2O3. Wherein the sum of the mass percentage contents of CaO, Al2O3 and SiO2 is 12-26%; the sum of the mass percentage contents of CaO, Eu2O3 and Dy2O3 is 11 to 22 percent. The rare earth doped phosphate luminescent glass prepared by the invention has excellent properties of long afterglow time and uniform color.

Description

Technical Field

[0001] The present invention relates to the field of glass technology, and in particular to a rare earth doped phosphate luminescent glass and a preparation method and application thereof, a photovoltaic glass back panel material and an application thereof. Background Art

[0002] Glass is a uniform and transparent medium whose structure is short-range ordered but long-range disordered. The doping amount of luminescent material in glass can be relatively high. Therefore, glass becomes a good luminescent matrix material.

[0003] However, traditional luminescent materials encapsulated with materials such as epoxy resin have poor heat dissipation effects. The large amount of heat energy accumulated can easily cause the phosphor to deteriorate and lose its luminous performance. In addition, the luminous efficiency is low and the color reproduction is not good enough.

[0004] Rare earth materials are excellent luminescent matrices. The luminescence of rare earth ions is based on the transition of their 4f electrons within the ff configuration or between the fd configurations. The spectrum of rare earth ions or atoms with unfilled 4f shells covers the visible region of 390-760nm. Rare earth luminescence has bright colors, strong light absorption ability, high conversion efficiency, and a wide distribution area of ​​emission wavelengths. Rare earth ion-doped luminescent glass combines the rich and stable luminescence of rare earth ions with the good physical, chemical and thermal stability of glass. It has outstanding advantages in controlling costs, simplifying production processes, and being more environmentally friendly, and has attracted the attention of more and more researchers.

[0005] Luminous glass has potential application value in the field of photovoltaic glass due to its unique transparency. Photovoltaic backplane glass is used for the back packaging of photovoltaic modules to protect solar cells from the influence of the external environment. With the continuous advancement of technology and the continuous expansion of the market, the performance of photovoltaic backplane glass has been diversified. Photovoltaic glass backplane materials are used in the construction / transportation field to provide safety warnings for pedestrians and vehicles without lighting tools at night. This "reflective self-luminous" technology is not only low-carbon and environmentally friendly, but also relatively low in cost. It has good development prospects.

[0006] CN103936281A discloses a rare earth doped luminescent glass and a preparation method thereof. The main components of the glass matrix of the luminescent glass are B2O3, Al2O3, ZnO, CaF2, CaO and Na2O, and the rare earth ion Tb 3+ 、Sm 3+ 、Eu 3+ 、Dy 3+ and Tm 3+As the luminescent center, rare earth ions are singly, doped, or tri-doped in a glass matrix, and combined with an ultraviolet LED chip to emit visible light; the luminescent glass is prepared by a melt cooling method; the luminescent glass disclosed in the invention can be excited by 350-400nm ultraviolet light to produce visible light. However, the glass involved in the scheme is a borate glass system, which has poor optical uniformity and a high softening temperature, which is not conducive to molding. In addition, the glass composition contains CaF2. During the melting process of the glass, the glass melt will corrode the crucible, and during industrial production, the glass melt will corrode the refractory material of the kiln.

[0007] Therefore, it is of great significance to develop a rare earth-doped luminescent glass with a long afterglow time, simple preparation process and suitable for photovoltaic backplane materials to meet the requirements of the photovoltaic technology field. Summary of the invention

[0008] The purpose of the present invention is to provide a rare earth doped phosphate luminescent glass with long afterglow time and uniform color.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a rare earth doped phosphate luminescent glass, wherein the raw material composition for forming the rare earth doped phosphate luminescent glass comprises: in terms of mass percentage, P2O5: 30-60%, CaO: 10-25%, Na2O: 5-15%, K2O: 5-15%, Al2O3: 1-10%, SrO: 1-5%, BaO: 0-1%, SiO2: 0-1%, Eu2O3: 0.1-2%, Dy2O3: 0.1-2%;

[0010] Among them, the sum of the mass percentages of CaO, Al2O3 and SiO2 is 12-26%; the sum of the mass percentages of CaO, Eu2O3 and Dy2O3 is 11-22%.

[0011] Preferably, the raw material composition for forming the rare earth-doped phosphate luminescent glass includes: in terms of mass percentage, P2O5: 45-55%, CaO: 12-20%, Na2O: 8-13%, K2O: 8-13%, Al2O3: 2-5%, SrO: 3-5%, BaO: 0.1-0.5%, SiO2: 0.1-0.5%, Eu2O3: 0.5-1.5%, and Dy2O3: 0.5-1.5%.

[0012] Further preferably, the afterglow duration of the rare earth-doped phosphate luminescent glass is ≥12 h.

[0013] The second aspect of the present invention provides a method for preparing the rare earth-doped phosphate luminescent glass according to the first aspect, the method comprising:

[0014] The raw material composition for forming the rare earth doped phosphate luminescent glass is sequentially subjected to melting treatment, forming treatment and annealing treatment to obtain the rare earth doped phosphate luminescent glass.

[0015] Preferably, the conditions of the melt treatment include: a temperature of 900-1000° C. and a time of 1-3 h.

[0016] Preferably, the annealing treatment conditions include: temperature of 300-400° C. and time of 1-5 h.

[0017] The third aspect of the present invention provides the use of the rare earth doped phosphate luminescent glass described in the first aspect in photovoltaic glass back panel materials.

[0018] The fourth aspect of the present invention provides a photovoltaic glass back panel material, which includes a luminescent glass layer, an adhesive layer, and a tempered glass layer stacked in sequence; the luminescent glass layer is the rare earth-doped phosphate luminescent glass described in the first aspect.

[0019] Preferably, the thickness of the luminescent glass layer is 0.2-1 mm.

[0020] Preferably, the adhesive layer includes at least one of a PVB layer, an EVA layer and a POE layer.

[0021] Preferably, the thickness of the tempered glass layer is 1.5-3 mm.

[0022] The fifth aspect of the present invention provides application of the photovoltaic glass backboard material described in the fourth aspect in a photovoltaic module.

[0023] The present invention uses phosphate glass as a matrix, which has a wide glass formation range and can be doped with a large number of network modifying ions. With the change of conditions, vitrification can be achieved from network structure to chain to orthophosphate. It has a large capacity for rare earth elements, and the prepared luminescent glass has excellent properties of high luminescent brightness, long afterglow time, and uniform color distribution. In addition, the rare earth-doped phosphate luminescent glass provided by the present invention, when used in the preparation of photovoltaic glass backplane materials, meets the performance requirements in the fields of photovoltaic technology and the like.

[0024] The method for preparing the rare earth-doped phosphate luminescent glass provided by the invention is simple and is conducive to large-scale production. DETAILED DESCRIPTION

[0025] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0026] As mentioned above, the first aspect of the present invention provides a rare earth doped phosphate luminescent glass, wherein the raw material composition for forming the rare earth doped phosphate luminescent glass comprises: in terms of mass percentage, P2O5: 30-60%, CaO: 10-25%, Na2O: 5-15%, K2O: 5-15%, Al2O3: 1-10%, SrO: 1-5%, BaO: 0-1%, SiO2: 0-1%, Eu2O3: 0.1-2%, Dy2O3: 0.1-2%;

[0027] Among them, the sum of the mass percentages of CaO, Al2O3 and SiO2 is 12-26%; the sum of the mass percentages of CaO, Eu2O3 and Dy2O3 is 11-22%.

[0028] Preferably, the sum of the mass percentages of CaO, Al2O3 and SiO2 is 21-24%; the sum of the mass percentages of CaO, Eu2O3 and Dy2O3 is 18-22%. The inventors of the present invention have found that under this preferred condition, the rare earth doped phosphate luminescent glass prepared by the present invention has the excellent characteristics of higher afterglow brightness and more uniform luminescent color.

[0029] Preferably, the raw material composition for forming the rare earth-doped phosphate luminescent glass includes: in terms of mass percentage, P2O5: 45-55%, CaO: 12-20%, Na2O: 8-13%, K2O: 8-13%, Al2O3: 2-5%, SrO: 3-5%, BaO: 0.1-0.5%, SiO2: 0.1-0.5%, Eu2O3: 0.5-1.5%, and Dy2O3: 0.5-1.5%.

[0030] Further preferably, the afterglow duration of the rare earth-doped phosphate luminescent glass is ≥12 h.

[0031] As mentioned above, the second aspect of the present invention provides a method for preparing the rare earth-doped phosphate luminescent glass according to the first aspect, the method comprising:

[0032] The raw material composition for forming the rare earth doped phosphate luminescent glass is sequentially subjected to melting treatment, forming treatment and annealing treatment to obtain the rare earth doped phosphate luminescent glass.

[0033] According to a preferred embodiment, the conditions of the melt treatment include: a temperature of 900-1000° C. and a time of 1-3 h.

[0034] According to a preferred specific implementation manner, the molding process is performed by mold casting.

[0035] According to a more preferred embodiment, the annealing treatment conditions include: a temperature of 300-400° C. and a time of 1-5 h.

[0036] The method for preparing the rare earth-doped phosphate luminescent glass of the present invention may also include post-processing methods known in the art, such as cutting, grinding, polishing or drawing the product cooled after annealing to obtain the rare earth-doped phosphate luminescent glass that can meet various applicable scenarios. The present invention will not be described in detail here, and those skilled in the art should not be understood as limiting the present invention.

[0037] It should be noted that in the present invention, in the method for preparing the rare earth-doped phosphate luminescent glass, it is not necessary to perform a crystal phase formation operation on the obtained product, and the prepared rare earth-doped phosphate luminescent glass is a long-lasting luminescent glass-state material.

[0038] As mentioned above, the third aspect of the present invention provides the use of the rare earth doped phosphate luminescent glass described in the first aspect in photovoltaic glass back panel materials.

[0039] As mentioned above, the fourth aspect of the present invention provides a photovoltaic glass backplane material, which includes a luminescent glass layer, an adhesive layer, and a tempered glass layer stacked in sequence; the luminescent glass layer is the rare earth-doped phosphate luminescent glass described in the first aspect above.

[0040] According to a specific implementation, the thickness of the luminescent glass layer is 0.2-1 mm.

[0041] According to a preferred embodiment, the adhesive layer includes at least one of a PVB layer, an EVA layer and a POE layer. PVB is polyvinyl butyral, EVA is ethylene-vinyl acetate copolymer, and POE is a thermoplastic elastomer obtained by in-situ polymerization of ethylene and octene. The inventors have found that under this preferred embodiment, the photovoltaic glass backplane material prepared by the present invention has higher mechanical strength, and significantly better heat resistance and cold resistance.

[0042] According to a more preferred embodiment, the thickness of the tempered glass layer is 1.5-3 mm.

[0043] According to a preferred specific implementation manner, the present invention adopts a lamination process to combine the luminous glass layer and the tempered glass layer through the adhesive layer arranged in the middle, and then obtains the photovoltaic glass back panel material through autoclave treatment.

[0044] As mentioned above, the fifth aspect of the present invention provides the use of the photovoltaic glass backboard material described in the fourth aspect in a photovoltaic module.

[0045] The present invention will be described in detail below by way of examples. In the following examples and comparative examples, unless otherwise specified, the raw materials used are all commercially available products.

[0046] Unless otherwise specified, room temperature in the present invention means 25±2°C.

[0047] Preparation Example 1

[0048] (1) Weigh the raw materials according to the contents shown in Table 1, and mix them to obtain a mixed material;

[0049] (2) adding the above mixture into a crucible, placing the crucible in a heating furnace, and melting the mixture at 950° C. for 2 h to obtain molten glass;

[0050] (3) adding the above molten glass liquid into the mold for shaping and annealing, the annealing temperature is 350° C., and the annealing time is 2 h;

[0051] (4) The obtained product is cooled to room temperature, cut, polished, and drawn into rare earth-doped phosphate luminescent glass with a thickness of 0.5 mm.

[0052] Unless otherwise specified, the remaining preparation examples and comparative preparation examples were prepared using the same method as Preparation Example 1, except that the composition formulas and process parameters for preparing transparent microcrystalline glass were different, see Table 1 for details.

[0053] The rare earth-doped phosphate luminescent glasses prepared in the above-mentioned preparation examples and comparative preparation examples and their test data are shown in Table 1.

[0054] Color uniformity test: performed in accordance with the test method in T / CPIA 0028.1-2021, observed with the naked eye;

[0055] Afterglow brightness and afterglow time test: in accordance with the national standard GB / T 24981.2-2020. Table 1

[0056]

[0057] Note: 1CaO+Al2O3+SiO2 is the sum of the mass percentages of CaO, Al2O3 and SiO2;

[0058] 2 CaO+Eu2O3+Dy2O3 is the sum of the mass percentages of CaO, Eu2O3 and Dy2O3;

[0059] The excitation light source is an incandescent lamp.

[0060] It can be seen from the results in Table 1 that the rare earth-doped phosphate luminescent glass provided by the present invention has excellent properties of stable luminescent color, long afterglow time and uniform color.

[0061] Example 1

[0062] This embodiment provides a method for preparing a photovoltaic glass backplane material, the method comprising:

[0063] S1: Align and laminate the luminescent glass A1 obtained in the above-mentioned Preparation Example 1 with a tempered glass having a thickness of 2 mm through a PVB layer disposed in the middle to obtain a sample I;

[0064] S2: pre-treating sample I under the following conditions: temperature 60°C, pressure 0.2MPa, to obtain sample II;

[0065] S3: Perform high temperature pressurization treatment on sample II, and the high temperature pressurization treatment conditions are: temperature 120° C., pressure 1.0 MPa, to obtain a photovoltaic glass backplane material.

[0066] The remaining examples and comparative examples were carried out according to the method of Example 1, and the details and test results are shown in Table 2;

[0067] Among them, impact strength: refer to T / CPIA 0028.1-2021 standard, the test surface is tempered glass, the test steel ball weight is 227±2g, and the test height is 1000mm;

[0068] Thermal shock resistance: Refer to T / CPIA 0028.1-2021 standard, and the photovoltaic glass backplane material obtained by testing can withstand a temperature difference of 150°C.

[0069] Table 2

[0070] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Types of Luminous Glass A1 A2 A3 A4 D-A1 D-A2 D-A3 Adhesive layer PVB EVA POE PVB PVB PVB PVB Impact strength Not broken Not broken Not broken Not broken Not broken broken broken Thermal shock resistance Not broken Not broken Not broken Not broken broken broken broken

[0071] It can be seen from the results in Table 2 that the photovoltaic glass backplane material prepared by using the rare earth-doped phosphate luminescent glass provided by the present invention has excellent impact strength and heat shock resistance, and meets the requirements of photovoltaic modules.

[0072] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A rare earth doped phosphate luminescent glass, characterized in that: The raw material composition for forming the rare earth doped phosphate luminescent glass comprises: in terms of mass percentage, P2O5: 30-60%, CaO: 10-25%, Na2O: 5-15%, K2O: 5-15%, Al2O3: 1-10%, SrO: 1-5%, BaO: 0-1%, SiO2: 0-1%, Eu2O3: 0.1-2%, Dy2O3: 0.1-2%; Among them, the sum of the mass percentages of CaO, Al2O3 and SiO2 is 12-26%; the sum of the mass percentages of CaO, Eu2O3 and Dy2O3 is 11-22%.

2. The rare earth doped phosphate luminescent glass according to claim 1, wherein: The raw material composition for forming the rare earth-doped phosphate luminescent glass includes, by mass percentage, P2O5: 45-55%, CaO: 12-20%, Na2O: 8-13%, K2O: 8-13%, Al2O3: 2-5%, SrO: 3-5%, BaO: 0.1-0.5%, SiO2: 0.1-0.5%, Eu2O3: 0.5-1.5%, and Dy2O3: 0.5-1.5%.

3. The rare earth-doped phosphate luminescent glass according to claim 1 or 2, wherein: The afterglow duration of the rare earth-doped phosphate luminescent glass is ≥12h.

4. A method for preparing the rare earth doped phosphate luminescent glass according to any one of claims 1 to 3, characterized in that: The method includes: The raw material composition for forming the rare earth doped phosphate luminescent glass is sequentially subjected to melting treatment, forming treatment and annealing treatment to obtain the rare earth doped phosphate luminescent glass.

5. The method according to claim 4, wherein: The conditions of the melting treatment include: a temperature of 900-1000° C. and a time of 1-3 hours.

6. The method according to claim 4, wherein: The annealing treatment conditions include: temperature of 300-400° C. and time of 1-5 h.

7. Use of the rare earth doped phosphate luminescent glass according to any one of claims 1 to 3 in photovoltaic glass back panel materials.

8. A photovoltaic glass back panel material, characterized in that: The photovoltaic glass back panel material comprises a luminescent glass layer, an adhesive layer, and a tempered glass layer which are stacked in sequence; the luminescent glass layer is the rare earth doped phosphate luminescent glass as described in any one of claims 1-3.

9. The photovoltaic glass back panel material according to claim 8, wherein: The thickness of the luminescent glass layer is 0.2-1 mm; And / or, the adhesive layer includes at least one of a PVB layer, an EVA layer and a POE layer; And / or, the thickness of the tempered glass layer is 1.5-3 mm.

10. Use of the photovoltaic glass backboard material according to claim 8 or 9 in photovoltaic modules.

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