Composite glass-ceramic for high-power leds with concave-convex surface and method for manufacturing same

Abstract

A kind of composite glass-ceramic for high-power LED with concave-convex surface and its preparation method, the composite glass-ceramic includes transparent ceramic and glass layer formed by glass powder coated on transparent ceramic;The chemical formula of transparent ceramic is Y 3‑x Al5O 12 : xCe 3+ ; glass powder is low melting point glass powder of MgO-Al2O3-SiO2-B2O3-RO system, wherein, R is one or more of Ca, Sr, Ba, Zn. Preparation method: YAG: Ce transparent ceramic is prepared by vacuum sintering method;Glass melting method is used to prepare precursor glass powder, and precursor glass powder is obtained after ball milling, then it is mixed with glue, and precursor glass powder is coated on transparent ceramic by silk screen printing technology, and composite glass-ceramic is obtained after sintering. The method can improve the extraction efficiency of transparent ceramic and improve the emission color;The composite glass-ceramic prepared can have the characteristics of high luminous efficiency and high color rendering index.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of inorganic luminescent materials, and particularly relates to a composite glass-ceramic for high-power LED with concave-convex surface and a preparation method thereof. BACKGROUND

[0002] White light emitting diodes (WLEDs) are considered to be good general lighting devices due to their energy saving, high energy efficiency, long service life and other excellent performances. Yellow Y3Al5O 12 :Ce (YAG:Ce) fluorescent powder is blended with organic resin and combined with blue light emitting InGaN / GaN chip, and white light is obtained due to its wide emission spectrum, high quantum efficiency, good thermal quenching and good chemical stability. However, due to the low thermal conductivity of organic resin or organosilicon, the organic resin or organosilicon is easy to turn yellow under high irradiance and high temperature of high-power LED, and the interaction between the fluorescent powder and the gel interface will also cause serious carbonization, thereby reducing the luminous efficiency, causing obvious color shift and shortening the service life. At the same time, the high scattering and reflection loss emitted by the micro-size fluorescent powder layer also limits the conversion efficiency and luminous efficiency. YAG:Ce transparent ceramic is developed for improving the performance of white light LED due to its superior optical performance and thermal conductivity.

[0003] Document "Tang Y, Zhou S, Chen C, et al. Composite phase ceramic phosphor of Al2O3-Ce:YAG for high efficiency light emitting [J]. Optics Express, 2015, 23(14): 17923-17928", document "Sai Q, Zhao Z, Xia C, et al. Ce-doped Al2O3-YAG eutectic and its application for white LEDs [J]. Optical Materials, 2013, 35(12): 2155-2159.", document "Sai Q, Xia C. Tunable colorimetric performance of Al2O3-YAG:Ce eutectic crystal by Ce 3+ doping and its application for white LEDs [J]. Optical Materials, 2013, 35(12): 2155-2159." and document "Sai Q, Xia C. Tunable colorimetric performance of Al2O3-YAG:Ce eutectic crystal by Ce 3+"Enhanced light extraction from transparent ceramics by introducing a secondary phase to change light propagation and enhance light extraction for higher device luminous efficacy", Journal of Luminescence, 2017, 186: 68-71. By introducing a secondary phase to change light propagation and enhance light extraction, higher device luminous efficacy was obtained. However, the above ceramic must be polished on both sides to increase the penetration of blue light from the chip. In this remote mode, due to the large difference in refractive index between the ceramic (n = 1.82) and air (n = 1.00), most of the yellow emission light is captured by total internal reflection (TIR) and waveguide effect, resulting in weak front light extraction. Part of the captured light is emitted from the side of the ceramic, and part is reabsorbed, then converted into heat, thereby reducing the front light emission and reducing the color uniformity, showing a typical "yellow ring effect". Therefore, it is still a challenging problem to explore a simple and further processing-free method to improve the TIR effect and waveguide effect to enhance the front light extraction, to realize the remote application of transparent ceramics in high-power light-emitting diodes. SUMMARY

[0004] The purpose of the present application is to provide a kind of composite glass-ceramic with concave-convex surface for high-power LED and its preparation method, which can realize the surface with different concave-convex structure by adjusting the size of different glass powder particle size, thereby improving the extraction efficiency of transparent ceramic, improving the emission color, and greatly promoting its industrial application in high-power LED;The prepared composite glass-ceramic can have the characteristics of high luminous efficiency and high color rendering index.

[0005] The technical scheme adopted by the present application is as follows: the present application provides a kind of composite glass-ceramic with concave-convex surface for high-power LED, which includes transparent ceramic and glass layer formed by glass powder coated on the transparent ceramic;

[0006] The chemical formula of the transparent ceramic is Y 3-x Al5O 12 : xCe 3+ , wherein x is the mole percentage of Ce 3+ substituting Y 3+ , 0.001≤x≤0.004;

[0007] The glass powder is a low-melting-point glass powder of MgO-Al2O3-SiO2-B2O3-RO system composed of 14-20wt% MgO, 24-28wt% Al2O3, 46-49wt% SiO2, 3-8wt% H2BO3 and 3-5wt% RO, wherein R is one or more of Ca, Sr, Ba and Zn.

[0008] Preferably, the glass powder is a low-melting-point glass powder of MgO-Al2O3-SiO2-B2O3-ZnO system.

[0009] To achieve the above-mentioned purposes, the application further provides a preparation method of the composite glass-ceramic with concave-convex surface for high-power LED, comprising the following steps:

[0010] S1, preparing transparent ceramic Y 3-x Al5O 12 : xCe 3+ ;

[0011] S1-1, taking Y2O3, Al2O3 and CeO2 as raw material powders, and taking each raw material according to the stoichiometric ratio of corresponding elements in the chemical formula Y 3-x Al5O 12 : xCe 3+ , wherein x is the molar percentage of Ce 3+ substituting Y 3+ , 0.001≤x≤0.004; then adding 0.5-0.8wt.% MgO and 0.05-0.20wt.% TEOS as sintering aids to the total mass of the raw material powders, and ball-milling to obtain a mixed slurry;

[0012] S1-2, drying and sieving the mixed slurry, and dry-pressing to obtain a green body;

[0013] S1-3, placing the green body into a vacuum sintering furnace and vacuum pre-sintering at 1740-1800℃ for 3-6h, and finally polishing both sides to obtain a transparent ceramic;

[0014] S2, taking MgO, Al2O3, SiO2, H2BO3 and RO as raw material powders, and taking each raw material according to the mass percentage of each raw material in MgO-Al2O3-SiO2-B2O3-RO, wherein R is one or more of Ca, Sr, Ba and Zn, grinding each raw material powder in an agate mortar for 0.5-2h to obtain a mixed powder;

[0015] S3, placing the mixed powder prepared in step S2 into an up-and-down furnace and melting at 1480-1540℃ for 0.5-2h, and then taking out and water-quenching to obtain a glass precursor;

[0016] S4, placing the glass precursor prepared in step S3 into a ball mill tank and wet ball-milling using zirconia balls at a rotation speed of 220-280r / min for 18-30h, drying, and then sieving through 200-500 meshes to obtain a precursor glass powder with a particle size of 2-9um;

[0017] S5, mixing the precursor glass powder prepared in step S3 with glue according to a mass ratio of 1:(1-1.6), coating the precursor glass powder on the transparent ceramic prepared in step S1 by a screen printing technology, and placing in a muffle furnace to be kept at 600-660 DEG C for 0.5-2h to obtain a composite glass-ceramic.

[0018] Preferably, in step S1-1, the ball milling time is 16-22h, and the ball milling rotation speed is 160-220r / min.

[0019] Preferably, in step S1-2, the drying temperature is 50-65 DEG C, the drying time is 12-18h, the mesh number of sieving is 100-160 meshes, and the pressure of dry pressing is 2-8MPa.

[0020] Compared with the prior art, the present application has the following beneficial effects:

[0021] 1. The present application adopts a vacuum sintering method to prepare high-quality YAG:Ce transparent ceramic, and by adjusting and controlling the particle size of different glass powders, the glass powders are fused on the YAG:Ce transparent ceramic to form a concave-convex surface structure, the light propagation is changed, and the extraction efficiency of a packaged high-power LED device is improved, as shown in FIG. 1. Figure 1

[0022] 2. The composite glass-ceramic of the present application has a maximum luminous efficiency of 141-152lm / W, a color rendering index of 68-76, and a light extraction rate of 50-80% when the laser excitation power is 3W.

[0023] 3. The present application adopts a solid phase reaction method and a glass melting method, the preparation method is simple and the preparation period is short, the preparation difficulty and cost are greatly reduced, the environmental pollution and resource consumption in the preparation process are reduced, the production efficiency is high, the required composite material can be quickly obtained, and the needs of rapid and large-scale preparation in industrial production are met. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 FIG. 1 is a schematic diagram of the incident light absorbed and converted by the composite glass-ceramic prepared by the present application;

[0025] Figure 2 FIG. 2 is an emission spectrum diagram of the composite glass-ceramic prepared by the present application under 460nm excitation;

[0026] Figure 3 FIG. 3 is a luminous efficiency diagram of the composite glass-ceramic prepared by the present application;

[0027] Figure 4 FIG. 4 is a color coordinate diagram of the composite glass-ceramic prepared by the present application. DETAILED DESCRIPTION​

[0028] The application will be described in further detail below with reference to the drawings and specific embodiments.

[0029] Embodiment 1

[0030] A composite glass-ceramic for high-power LED with concave-convex surface, comprising transparent ceramic and a glass layer formed by glass powder coated on the transparent ceramic; the chemical formula of the transparent ceramic is Y 2.999 Al5O 12 :0.001Ce 3+ ; the glass powder is a low-melting glass powder of MgO-Al2O3-SiO2-B2O3-ZnO system composed of 20wt% MgO, 28wt% Al2O3, 46wt% SiO2, 3wt% B2O3 and 3wt% ZnO.

[0031] The preparation method of the composite glass-ceramic for high-power LED with concave-convex surface, comprising the following steps:

[0032] S1, preparing transparent ceramic Y 2.999 Al5O 12 :0.001Ce 3+ ;

[0033] S1-1, according to the stoichiometric ratio of corresponding elements in the chemical formula Y 2.999 Al5O 12 :0.001Ce 3+ , weigh each raw material Y2O3 (34.1837g), Al2O3 (25.751g) and CeO2 (0.0522g), then add 0.5wt.% MgO (0.3g) and 0.05wt.% TEOS (0.03g) as sintering aids, and 75ml alcohol as solvent, mix the mixture by ball milling at 160r / min for 16h to obtain a mixed slurry;

[0034] S1-2, dry the mixed slurry at 50℃ for 12h, sieve through a 100 mesh sieve, and dry-press at 2MPa to obtain a green body;

[0035] S1-3, put the green body into a vacuum sintering furnace and vacuum pre-sinter at 1740℃ for 3h, and finally polish both sides to obtain the transparent ceramic;

[0036] S2, each raw material MgO (12.0012g), Al2O3 (16.8017g), SiO2 (27.6028g), H2BO3 (1.8002g), ZnO (1.8002g) is taken according to the mass percentage of each element in MgO-Al2O3-SiO2-B2O3-ZnO, and each raw material powder is ground in an agate mortar for 0.5h to obtain a mixed powder;

[0037] S3, the mixed powder prepared in step S2 is placed in an elevator furnace and melted at 1480℃ for 0.5h, then taken out and quenched in water to obtain a glass precursor;

[0038] S4, the glass precursor prepared in step S3 is placed in a ball mill tank and wet ball milled at a speed of 220r / min for 18h using zirconia balls, dried and sieved through a 200 mesh screen to obtain a precursor glass powder with a particle size of 9um;

[0039] S5, the precursor glass powder prepared in step S3 is mixed with glue at a mass ratio of 1:1, then the precursor glass powder is coated on the transparent ceramic prepared in step S1 by screen printing technology, and placed in a muffle furnace at 600℃ for 0.5h to obtain a composite glass-ceramic.

[0040] The composite glass-ceramic prepared in this example emits yellow-green light around 530nm after being packaged with 460nm blue laser light, with a light extraction efficiency of 50%, as shown in Figure 2 ; the maximum luminous efficiency is 141lm / W when the laser excitation power is 3W, as shown in Figure 3 ; the color rendering index is 68, as shown in Figure 4 .

[0041] Example 2

[0042] A composite glass-ceramic for high-power LED with concave-convex surface, comprising a transparent ceramic and a glass layer formed by a glass powder coated on the transparent ceramic; the chemical formula of the transparent ceramic is Y 2.998 Al5O 12 : 0.002Ce 3+ ; the glass powder is a low melting point glass powder of MgO-Al2O3-SiO2-B2O3-ZnO system composed of 18wt% MgO, 28wt% Al2O3, 46wt% SiO2, 5wt% B2O3, and 3wt% ZnO.

[0043] The preparation method of the above-mentioned composite glass-ceramic for high-power LED with concave-convex surface, comprising the following steps:

[0044] S1, preparing a transparent ceramic Y 2.998 Al5O 12 : 0.002Ce3+ ;

[0045] S1-1, according to the chemical formula Y 2.998 Al5O 12 :0.002Ce 3+ The stoichiometric ratio of the corresponding elements in MgO-Al2O3-SiO2-B2O3-ZnO was used to weigh each raw material Y2O3 (34.1495 g), Al2O3 (25.751 g), CeO2 (0.1043 g), and then 0.6 wt.% MgO (0.36 g) and 0.1 wt.% TEOS (0.06 g) were added as sintering aids, 80 ml of alcohol was used as a solvent, and the mixture was ball milled at 180 r / min for 18 h to obtain a mixed slurry;

[0046] S1-2, the mixed slurry was dried at 55°C for 14h, sieved through a 120 mesh sieve, and dry pressed at 4MPa to obtain a green body;

[0047] S1-3, the green body was placed in a vacuum sintering furnace and vacuum pre-sintered at 1760°C for 4h, and then double-sided polished to obtain a transparent ceramic;

[0048] S2, each raw material MgO (10.8011 g), Al2O3 (16.8017 g), SiO2 (27.6028 g), H2BO3 (3.0003 g), and ZnO (1.8002 g) was weighed according to the mass percentage of each element in MgO-Al2O3-SiO2-B2O3-ZnO, and each raw material powder was ground in an agate mortar for 1h to obtain a mixed powder;

[0049] S3, the mixed powder prepared in step S2 was placed in an elevator furnace and melted at 1500°C for 1h, then water quenched to obtain a glass precursor;

[0050] S4, the glass precursor prepared in step S3 was placed in a ball mill tank and wet ball milled at a speed of 240 r / min for 22h using zirconia balls, then dried and sieved through a 300 mesh sieve to obtain a precursor glass powder with a particle size of 7um;

[0051] S5, the precursor glass powder prepared in step S3 was mixed with glue at a mass ratio of 1:1.2, then the precursor glass powder was coated on the transparent ceramic prepared in step S1 by screen printing technology, and then placed in a muffle furnace at 620°C for 1h to obtain a composite glass-ceramic.

[0052] The composite glass-ceramic prepared in this example emits yellow-green light around 532nm after packaging with a blue laser of 460nm, and the light extraction efficiency is 72%, which is 22% higher than that of Example 1, as shown in Figure 2 ; when the laser excitation power is 3W, the maximum luminous efficiency is 144lm / W, as shown in Figure 3; color rendering index is 72, such as Figure 4 .

[0053] Embodiment 3

[0054] A composite glass-ceramic for high-power LED with concave-convex surface, comprising transparent ceramic and glass layer formed by glass powder coated on the transparent ceramic; the chemical formula of the transparent ceramic is Y 2.997 Al5O 12 : 0.003Ce 3+ ; the glass powder is low-melting glass powder of MgO-Al2O3-SiO2-B2O3-ZnO system composed of 16wt% MgO, 26wt% Al2O3, 48wt% SiO2, 6wt% B2O3, and 4wt% ZnO.

[0055] The preparation method of the composite glass-ceramic for high-power LED with concave-convex surface, comprising the following steps:

[0056] S1, preparing transparent ceramic Y 2.997 Al5O 12 : 0.003Ce 3+ ;

[0057] S1-1, according to the stoichiometric ratio of corresponding elements in the chemical formula Y 2.997 Al5O 12 : 0.003Ce 3+ , weigh each raw material Y2O3 (34.1065g), Al2O3 (25.7444g), CeO2 (0.1565g), then add 0.7wt.% MgO (0.42g) and 0.15wt.% TEOS (0.09g) as sintering aids, 85ml alcohol as solvent, mix for 20h at 200r / min to obtain mixed slurry;

[0058] S1-2, dry the mixed slurry at 60℃ for 16h, sieve through 140 mesh, and dry-press at 6MPa to obtain a green body;

[0059] S1-3, put the green body into a vacuum sintering furnace and vacuum pre-sinter at 1780℃ for 5h, and finally polish both sides to obtain transparent ceramic;

[0060] S2, according to the mass percentage of each element in MgO-Al2O3-SiO2-B2O3-ZnO, weigh each raw material MgO (9.6009g), Al2O3 (15.6016g), SiO2 (28.8029g), H2BO3 (3.6004g), and ZnO (2.4002g), and grind each raw material powder in an agate mortar for 1.5h to obtain a mixed powder;

[0061] S3, placing the mixed powder prepared in step S2 in an elevator furnace, melting at 1520°C for 1.5h, and then taking out and quenching in water to obtain a glass precursor;

[0062] S4, placing the glass precursor prepared in step S3 in a ball mill tank, wet ball milling at a rotation speed of 260r / min for 26h using zirconia balls, drying, and then sieving through a 400 mesh screen to obtain a precursor glass powder with a particle size of 5um;

[0063] S5, mixing the precursor glass powder prepared in step S3 with glue at a mass ratio of 1:1.4, coating the precursor glass powder on the transparent ceramic prepared in step S1 by screen printing technology, and placing in a muffle furnace at 640°C for 1.5h to obtain a composite glass-ceramic.

[0064] The composite glass-ceramic prepared in this example emits yellow-green light of about 534nm after being packaged with a blue laser of 460nm, with a light extraction efficiency of 80%, which is 30% higher than that of Example 1, as shown in Figure 2 ; the maximum luminous efficiency is 152lm / W when the laser excitation power is 3W, as shown in Figure 3 ; the color rendering index is 76, as shown in Figure 4 .

[0065] Example 4

[0066] A composite glass-ceramic for a high-power LED with a concave-convex surface, comprising a transparent ceramic and a glass layer formed by a glass powder coated on the transparent ceramic; the chemical formula of the transparent ceramic is Y 2.996 Al5O 12 :0.004Ce 3+ ; the glass powder is a low-melting point glass powder of the MgO-Al2O3-SiO2-B2O3-ZnO system composed of 14wt% MgO, 24wt% Al2O3, 49wt% SiO2, 8wt% B2O3, and 5wt% ZnO.

[0067] The preparation method of the composite glass-ceramic for a high-power LED with a concave-convex surface, comprising the following steps:

[0068] S1, preparing a transparent ceramic Y 2.996 Al5O 12 :0.004Ce 3+ ;

[0069] S1-1, according to the chemical formula Y 2.996 Al5O 12 :0.004Ce 3+The raw materials Y2O3 (34.0811 g), Al2O3 (25.751 g), and CeO2 (0.2087 g) were weighed according to the stoichiometric ratio of the corresponding elements, and then 0.7 wt.% MgO (0.48 g) and 0.15 wt.% TEOS (0.12 g) were added as sintering aids, 90 ml of alcohol was used as a solvent, and the mixture was ball milled at 220 r / min for 22 h to obtain a mixed slurry;

[0070] S1-2, the mixed slurry was dried at 65°C for 18 h, sieved through a 160-mesh sieve, and dry-pressed at 8 MPa to obtain a green body;

[0071] S1-3, the green body was placed in a vacuum sintering furnace and vacuum pre-sintered at 1800°C for 6 h, and then polished on both sides to obtain a transparent ceramic;

[0072] S2, the raw materials MgO (8.4008 g), Al2O3 (14.4014 g), SiO2 (29.4029 g), H2BO3 (4.8005 g), and ZnO (3.0003 g) were weighed according to the mass percentage of each element in MgO-Al2O3-SiO2-B2O3-ZnO, and the raw material powders were ground in an agate mortar for 2 h to obtain a mixed powder;

[0073] S3, the mixed powder prepared in step S2 was placed in an up-and-down furnace and melted at 1540°C for 2 h, and then water-quenched to obtain a glass precursor;

[0074] S4, the glass precursor prepared in step S3 was placed in a ball mill tank and wet ball milled at a speed of 280 r / min for 30 h using zirconia balls, and then sieved through a 500-mesh sieve after drying to obtain a precursor glass powder with a particle size of 2 um;

[0075] S5, the precursor glass powder prepared in step S3 was mixed with glue at a mass ratio of 1:6, and then the precursor glass powder was coated on the transparent ceramic prepared in step S1 by screen printing technology, and then placed in a muffle furnace and heat-treated at 660°C for 2 h to obtain a composite glass-ceramic.

[0076] The composite glass-ceramic prepared in this example emits yellow-green light of about 536 nm after being packaged with a blue laser of 460 nm, and the light extraction efficiency is 76%, which is increased by 26% compared with Example 1, as shown in Figure 2 ; when the laser excitation power is 3W, the maximum luminous efficiency is 149 lm / W, as shown in Figure 3 ; the color rendering index is 74, as shown in Figure 4 .

[0077] Although the present application only lists ZnO as the sintering aid, it is well known that other divalent oxides such as CaO, SrO, BaO, etc. have similar chemical properties to ZnO, and thus other divalent oxides RO can be used in combination with MgO-Al2O3-SiO2-B2O3 as sintering aids to achieve the same effect.

[0078] The above description is merely a specific implementation of the present application, but the scope of protection of the present application is not limited thereto. Any modification, equivalent replacement, and improvement made by any person skilled in the art within the technical scope disclosed by the present application, as long as it is within the spirit and principle of the present application, shall be covered by the scope of protection of the present application.

Claims

1. A composite glass-ceramic for high-power LEDs with an uneven surface, characterized in that, The glass layer formed by the transparent ceramic and the glass powder coated on the transparent ceramic; The chemical formula of the transparent ceramic is Y 3-x Al5O 12 : xCe 3+ , wherein x is the molar percentage of Ce 3+ substituting Y 3+ , 0.001≤x≤0.004; The glass powder is a low-melting-point glass powder of a MgO-Al2O3-SiO2-B2O3-RO system composed of 14-20wt% MgO, 24-28wt% Al2O3, 46-49wt% SiO2, 3-8wt% H2BO3 and 3-5wt% RO, wherein R is one or more of Ca, Sr, Ba and Zn; and the particle size of the glass powder is 2-9um.

2. The composite glass-ceramic with concave-convex surface for high-power LED according to claim 1, characterized in that, The glass powder is a low-melting-point glass powder of a MgO-Al2O3-SiO2-B2O3-ZnO system.

3. A method of producing a composite glass-ceramic for high-power LEDs with a concave-convex surface according to claim 1 or 2, characterized in that, The method comprises the following steps: S1, Preparation of transparent ceramic Y 3-x Al5O 12 : xCe 3+ ; S1-1, Y2O3, Al2O3, CeO2 as raw material powder, according to the chemical formula Y 3-x Al5O 12 : xCe 3+ The stoichiometric ratio of the corresponding elements in the formula is x for Ce 3+ Substitute Y 3+ Mol percent, 0.001≤x≤0.004; then add 0.5-0.8wt.% MgO and 0.05-0.20wt.% TEOS as sintering aids to the total mass of the raw material powder, ball mill and mix to get the mixed slurry; S1-2, drying and sieving the mixed slurry, and dry-pressing to obtain a green body; S1-3, placing the green body into a vacuum sintering furnace and vacuum pre-sintering at 1740-1800℃ for 3-6h, and finally polishing both sides to obtain a transparent ceramic; S2, taking MgO, Al2O3, SiO2, H2BO3 and RO as raw material powders, and weighing each raw material according to the mass percentage of each raw material in the MgO-Al2O3-SiO2-B2O3-RO system, wherein R is one or more of Ca, Sr, Ba and Zn, grinding each raw material powder in an agate mortar for 0.5-2h to obtain a mixed powder; S3, placing the mixed powder prepared in step S2 into an up-and-down furnace and melting at 1480-1540℃ for 0.5-2h, and then taking out and water quenching to obtain a glass precursor; S4, placing the glass precursor prepared in step S3 into a ball mill tank and wet ball milling at a speed of 220-280r / min for 18-30h using zirconia balls, drying, and sieving through a 200-500 mesh screen to obtain a glass powder with a particle size of 2-9um; S5, mixing the glass powder prepared in step S3 with glue at a mass ratio of 1:(1-1.6), coating the glass powder on the transparent ceramic prepared in step S1 by silk screen printing technology, and placing in a muffle furnace and heat treating at 600-660℃ for 0.5-2h to obtain a composite glass-ceramic.

4. The method of claim 3, wherein the method further comprises the step of: In step S1-1, the ball milling time is 16-22h, and the ball milling speed is 160-220r / min. ​ 5. The method of claim 3 or 4, wherein the method further comprises the step of: In step S1-2, the drying temperature is 50-65℃, the drying time is 12-18h, the sieving mesh number is 100-160 mesh, and the dry-pressing pressure is 2-8MPa. ​

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