CN115197690B - Orange-red fluorescent powder and preparation method thereof - Google Patents

Orange-red fluorescent powder and preparation method thereof Download PDF

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CN115197690B
CN115197690B CN202210824084.5A CN202210824084A CN115197690B CN 115197690 B CN115197690 B CN 115197690B CN 202210824084 A CN202210824084 A CN 202210824084A CN 115197690 B CN115197690 B CN 115197690B
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orange
fluorescent powder
red fluorescent
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黄咏怡
李云锋
丁雪梅
黄瑞甜
陈岱
万国江
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Jiangmen Kanhoo Industry Co ltd
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Abstract

The invention belongs to the field of fluorescent powder for LEDs, and particularly relates to orange-red fluorescent powder and a preparation method thereof. The orange red fluorescent powder has the chemical formulaIs E 1‑x D y Q z N 3 :xEu 2+ Wherein, the element E comprises at least one of Sr, ba, mg, ca and Li, the element D comprises at least one of Al, B, ga, la, gd and Y, the element Q comprises at least one of Si, ge, sb and As, and x is more than or equal to 0.001 and less than or equal to 0.01; y is more than or equal to 0.5 and less than or equal to 2; z is more than or equal to 0.5 and less than or equal to 2. The method for preparing the orange red fluorescent powder adopts a wet mixing method and a high-pressure weak reducing atmosphere sintering method to ensure that Eu is used 3+ More rapid and complete reduction to Eu 2+ And the activator is more fully reduced, and the performance of the fluorescent powder can be obviously improved. The orange-red fluorescent powder has the advantages of emission wavelength of 580-600nm, short emission wavelength and excellent thermal stability.

Description

Orange-red fluorescent powder and preparation method thereof
Technical Field
The invention belongs to the field of fluorescent powder for LEDs, and particularly relates to orange-red fluorescent powder and a preparation method thereof.
Background
At present, the fluorescent powder with the peak wavelength of 580-600nm on the market is mainly (Ba, sr) 3 SiO 5 :Eu 2+ The silicate orange-red fluorescent powder. The fluorescent powder has poor thermal stability, is easy to hydrolyze, and cannot be applied to environments with high long-term temperature and easy deliquescence, so the application of the fluorescent powder is limited. In the existing fluorescent powder for the LED, the peak wavelength of the silicon-aluminum based red fluorescent powder is closer to 600nm, and the thermal stability and the hydrolysis resistance of the silicon-aluminum based red fluorescent powder are far better than those of silicate orange red fluorescent powder. At present, the preparation process of the silicon-aluminum-based red fluorescent powder is quite mature, and the peak wavelength of the prepared product is 605-680 nm.
The silicon-aluminum based red fluorescent powder with the waveband of 580-600nm is generally prepared when the element proportion difference is large and the addition amount of an activator is very small, but the sintering atmosphere of the original silicon-aluminum based red fluorescent powder preparation is insufficient to reduce all trivalent activators into divalent to enter crystal lattices, so that the performance of the product is reduced. The prior art for preparing the silicon-aluminum-based red fluorescent powder cannot develop the high-stability silicon-aluminum-based red fluorescent powder with the wavelength less than 600nm, so the prior art for preparing the silicon-aluminum-based red fluorescent powder cannot meet the requirement of luminescence at the wavelength less than 600 nm.
In addition, in the process for preparing the silicon-aluminum-based red fluorescent powder in the prior art, because the raw materials used for preparing the silicon-aluminum-based red fluorescent powder need to isolate water and oxygen, a dry mixing mode is usually adopted in an inert gas environment, but static electricity is easy to appear in the dry mixing mode, so that raw materials are agglomerated and mixed unevenly, and further, the crystal defects of products are more, the yield is low, the performance is poor, and the particle size concentration is poor in the sintering process. Meanwhile, the product is crushed by external force, and the crystal form of the powder is damaged by the mode, so that the luminous performance and the stability of the product are reduced. Although the stability of the silica-alumina-based red fluorescent powder is better than that of silicate orange-red fluorescent powder, the problem of color bleaching still exists in some extreme use environments. The reason for the color drift is that the powder is cracked due to the erosion of the external water vapor to the crystal, so that the failure of the fluorescent powder is caused. Therefore, the development of high-performance low-waveband silicon-aluminum-based red fluorescent powder is still needed to meet the market demand for high-performance low-waveband red fluorescent powder.
Disclosure of Invention
Aiming at the problems of poor stability, color bleaching and defects of a preparation process of silicon-aluminum based red fluorescent powder in the prior art, the invention provides orange red fluorescent powder and a preparation method thereof.
In order to achieve the purpose, the method specifically comprises the following technical scheme:
orange-red fluorescent powder with the chemical formula of E 1-x D y Q z N 3 :xEu 2+ Wherein, the element E comprises at least one of Sr, ba, mg, ca and Li, the element D comprises at least one of Al, B, ga, la, gd and Y, the element Q comprises at least one of Si, ge, sb and As, and x is more than or equal to 0.001 and less than or equal to 0.01; y is more than or equal to 0.5 and less than or equal to 2; z is more than or equal to 0.5 and less than or equal to 2.
The orange-red fluorescent powder has the advantages of emission wavelength of 580-600nm, short emission wavelength and excellent thermal stability.
Preparation method of orange-red fluorescent powder and bagComprising the following steps, according to E 1-x D y Q z N 3 :xEu 2+ Taking required raw materials according to a metering ratio, mixing the raw materials to obtain a solid-phase material, sintering the solid-phase material, and cooling to obtain orange-red fluorescent powder; the sintering conditions are as follows: the temperature is 1500-2000 deg.C, pressure is 0.05-5.0MPa, heat preservation time is 5-30 hr, and atmosphere is CO and H 2 And N 2 The mixed gas of (1).
The sintering condition has obvious influence on the formation process of the fluorescent powder, and the invention introduces CO/H with a certain proportion in the sintering process 2 Gas, adopting a high-pressure weak reducing atmosphere sintering method to enable Eu to be 3+ More rapid and complete reduction to Eu 2+ And the activator is more fully reduced, and the performance of the fluorescent powder can be obviously improved.
In a preferred embodiment of the present invention, the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the content of CO in the mixed gas is as follows: h 2 ：N 2 Is 2%:1%:97 percent.
Under the sintering conditions, the obtained orange-red fluorescent powder has more excellent luminous performance.
As a preferable embodiment of the invention, an organic solvent is also added during the mixing; the organic solvent comprises at least one of n-hexane and n-heptane; the mixing time is 1-3 h.
As a further preferable embodiment of the invention, the mixing time is 3h.
According to the invention, a wet mixing mode is adopted, all raw materials are put into the solvent for mixing, so that static electricity caused by dry mixing is avoided, and the fluidity among the raw materials is effectively increased, thereby improving the uniformity of mixing and achieving the effect of uniform mixing.
As a preferred embodiment of the invention, the orange-red fluorescent powder is further subjected to dispersing, cleaning, surface coating and drying treatment in sequence.
As a preferred embodiment of the present invention, the dispersion is an acid-washing crushing dispersion, and the acid includes at least one of nitric acid, hydrochloric acid, and sulfuric acid; the cleaning is carried out by alternately washing with cold water and hot water, wherein the temperature of the hot water is 70-90 ℃, the temperature of the cold water is 15-30 ℃, and the washing is carried out until the conductivity is less than 10 mu s.
As a preferred embodiment of the present invention, the surface coating comprises the following steps: adding the orange red fluorescent powder into an ethanol water solution of a silane coupling agent for coating the silane coupling agent, then adding silica sol for inorganic coating, removing a solvent, drying, and then sequentially adding ethanol and a carbon black dispersing agent for organic coating.
The invention carries out surface coating on the prepared product, adopts a coupling agent-inorganic matter-organic matter multiple coating process, coats a coating layer on the surface of the powder on the premise of not influencing the luminous performance of the powder, and improves the thermal stability of the powder through the multiple surface coating process.
As a preferable embodiment of the invention, the silane coupling agent comprises at least one of KH-570 and KH-792; the carbon black dispersant comprises DP108; the inorganic coating time is 1-6 h, and the temperature is 60-90 ℃; the temperature of the silane coupling agent coating is 60-90 ℃.
In a preferred embodiment of the invention, the mass of the silane coupling agent is 0.1-10% of that of the orange red fluorescent powder; the mass of the carbon black dispersing agent is 0.1-10% of that of the orange red fluorescent powder; the mass of the silica gel is 0.1-10% of that of the orange-red fluorescent powder.
In a further preferred embodiment of the present invention, the mass of the silane coupling agent is 1.5% of the mass of the orange-red phosphor; the mass of the carbon black dispersing agent is 3% of that of the orange red fluorescent powder; the mass of the silica gel is 1% of that of the orange-red fluorescent powder.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a wet mixing mode, all the raw materials are put into the solvent for mixing, static electricity caused by dry mixing is avoided, and the fluidity among the raw materials is effectively increased, so that the uniformity of mixing is improved, and the effect of uniform mixing is achieved.
(2) The sintered orange-red fluorescent powder is in a block shape, so that a dispersion mode of self-separation of the powder block can be realized under an acid solution for acid pickling, crushing and dispersing, the treatment efficiency is improved, the damage of an external force to a powder crystal form is reduced, and the problem of performance reduction caused by the damage of the external force to the powder crystal form is solved.
(3) In the sintering process, CO/H with a certain proportion is introduced 2 Gas, adopting a high-pressure weak reducing atmosphere sintering method to enable Eu to be 3+ More rapid and complete reduction to Eu 2+ And the activator is more fully reduced, and the performance of the fluorescent powder can be obviously improved.
(4) The invention carries out surface coating on the prepared product, adopts a coupling agent-inorganic matter-organic matter multiple coating process, coats a coating layer on the surface of the powder on the premise of not influencing the luminous performance of the powder, and improves the thermal stability of the powder through the multiple surface coating process.
(5) The orange-red fluorescent powder has the advantages of emission wavelength of 580-600nm, short emission wavelength and excellent thermal stability.
Drawings
FIG. 1 is an optical electron diagram of the solid phase material obtained after wet mixing in step (1) in example 1.
FIG. 2 is an optical electron diagram of a mixed material obtained after dry mixing of comparative example 1.
FIG. 3 is an SEM photograph of the crushed phosphor after acid washing in step (3) of example 1.
FIG. 4 is an SEM image of the phosphor after crushing by external force in step (3) of comparative example 2.
FIG. 5 is an SEM image of the final product of example 1 before heat resistance testing.
FIG. 6 is an SEM photograph of the final product of example 1 after heat resistance test.
Fig. 7 is an SEM image of the final product of comparative example 3 before heat resistance test.
Fig. 8 is an SEM image after a heat resistance test of the final product of comparative example 3.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described by the following specific examples.
Example 1
(1) According to the chemical formula Ba 0.05 Sr 0.948 AlSiN 3 ：Eu 0.002 183.83g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank filled with n-hexane in a glove box and sealed, the mixing tank is installed on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into the glove box, the mixed raw materials are sieved, and the n-hexane and a solid-phase material are separated.
(2) Filling the uniformly mixed material in the step (1) into a crucible, and introducing CO/H 2 And N 2 And sintering the mixed gas in a sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. Wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the ratio of CO in the mixed gas is as follows: h 2 ：N 2 Is 2%:1%:97 percent.
(3) Putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushed powder on a ball mill for acid washing, crushing and dispersing, sieving the powder until no obvious particles exist, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted by ethanol =1 at 90 ℃, then adding 1.5% KH-792 silane coupling agent according to the mass of the powder, stirring uniformly, adding silica sol with the weight percentage of 3% of the powder, stirring for 4 hours to carry out inorganic coating, standing to remove the upper layer liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding 1 wt% of carbon black dispersing agent DP108 for organic coating, stopping stirring after dropwise adding, filtering, drying and sieving to finally obtain a stable orange-red fluorescent powder product.
Example 2
(1) According to chemical formulaBa 0.02 Sr 0.978 AlSiN 3 ：Eu 0.002 189.65g of strontium nitride, 2.02g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank filled with n-hexane in a glove box and sealed, the mixing tank is mounted on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into a glove box, the mixed raw materials are sieved, and the n-hexane and solid-phase materials are separated.
(2) The materials mixed evenly in the step (1) are filled in a crucible, and CO/H is introduced 2 And N 2 And sintering the mixed gas in a sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. Wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the ratio of CO in the mixed gas is as follows: h 2 ：N 2 2%:1%:97 percent.
(3) Putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushed powder on a ball mill for acid washing, crushing and dispersing, sieving the powder until no obvious particles exist, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted by ethanol =1 at 90 ℃, then adding 1.5% KH-792 silane coupling agent according to the mass of the powder, stirring uniformly, adding silica sol with the weight percentage of 3% of the powder, stirring for 4 hours to carry out inorganic coating, standing to remove the upper layer liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding a carbon black dispersing agent DP108 with the weight ratio of 1% for organic coating, stopping stirring after dropwise adding, filtering, drying and sieving to finally obtain a stable orange red fluorescent powder product.
Example 3
(1) According to the chemical formula Ba 0.05 Sr 0.949 AlSiN 3 ：Eu 0.001 184.03g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.35g of europium oxide were weighedThe raw materials are transferred into a mixing tank filled with normal hexane in a glove box and sealed, the mixing tank is arranged on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into the glove box, the mixed raw materials are sieved, and the normal hexane and solid-phase materials are separated.
(2) The materials mixed evenly in the step (1) are filled in a crucible, and CO/H is introduced 2 And N 2 And sintering the mixed gas in a sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. Wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the content of CO in the mixed gas is as follows: h 2 ：N 2 2%:1%:97 percent.
(3) Putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushed powder on a ball mill for acid washing, crushing and dispersing, sieving the powder until no obvious particles exist, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted with ethanol =1 at 90 ℃, then adding 1.5% of kh-792 silane coupling agent by mass of the powder, stirring uniformly, adding silica sol of which the weight percentage is 3% of the powder, stirring for 4 hours to perform inorganic coating, standing to remove the supernatant liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding 1 wt% of carbon black dispersing agent DP108 for organic coating, stopping stirring after dropwise adding, filtering, drying and sieving to finally obtain a stable orange-red fluorescent powder product.
Example 4
(1) According to the chemical formula Li 0.02 Sr 0.978 AlSiN 3 ：Eu 0.002 189.65g of raw materials of strontium nitride, 0.28g of lithium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank filled with n-hexane in a glove box and sealed, the mixing tank is installed on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into the glove box, and the mixed raw materials are mixedSieving to separate n-hexane and solid phase material.
(2) Charging the uniformly mixed material obtained in the step (1) into a crucible in the presence of CO/H 2 And N 2 And sintering in the mixed gas sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. Wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the content of CO in the mixed gas is as follows: h 2 ：N 2 Is 2%:1%:97 percent.
(3) Putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushed powder on a ball mill for acid washing, crushing and dispersing, sieving the powder until no obvious particles exist, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted by ethanol =1 at 90 ℃, then adding 1.5% KH-792 silane coupling agent according to the mass of the powder, stirring uniformly, adding silica sol with the weight percentage of 3% of the powder, stirring for 4 hours to carry out inorganic coating, standing to remove the upper layer liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding 1 wt% of carbon black dispersing agent DP108 for organic coating, stopping stirring after dropwise adding, filtering, drying and sieving to finally obtain a stable orange-red fluorescent powder product.
Comparative example 1
According to the chemical formula Ba 0.05 Sr 0.948 AlSiN 3 ：Eu 0.002 183.83g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank in a glove box and sealed, the mixing tank is placed on a horizontal ball mill in the glove box for dry mixing for 3 hours, and the mixed raw materials are sieved to obtain a dry-mixed material.
The electronic image of the mixed material is shown in fig. 2, and the raw materials of the dry mixing method are not uniformly mixed and have obvious large agglomerated raw materials. The solid-phase materials obtained after the wet mixing are mixed more uniformly and the particles are more uniform, as shown in figure 1.
Comparative example 2
(1) According to the chemical formula Ba 0.05 Sr 0.948 AlSiN 3 ：Eu 0.002 183.83g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide were weighed, the weighed raw materials were transferred into a mixing pot filled with n-hexane in a glove box and sealed, the mixing pot was mounted on a planetary ball mill and subjected to wet mixing for 3 hours, and then transferred into a glove box, the mixed raw materials were sieved, and n-hexane and solid-phase materials were separated.
(2) The materials mixed evenly in the step (1) are filled in a crucible, and CO/H is introduced 2 And N 2 And sintering the mixed gas in a sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. Wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the content of CO in the mixed gas is as follows: h 2 ：N 2 Is 2%:1%:97 percent.
(3) And putting the sintered orange-red fluorescent powder into a crusher to be crushed, dispersed and sieved, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted by ethanol =1 at 90 ℃, adding 1.5% kh-570 silane coupling agent by weight of the powder, stirring uniformly, adding silica sol with the weight percentage of 3% of the powder, stirring for 4 hours to carry out organic coating, standing to remove the upper layer liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding DP108 with the weight ratio of 1% for inorganic coating, stopping stirring after dropwise adding is finished, and performing suction filtration and drying to obtain the fluorescent powder.
Compared with the example 1, the crystal form of the fluorescent powder obtained in the comparative example is broken, broken and irregular by external force extrusion, and is shown in fig. 4.
Comparative example 3
(1) Root of herbaceous plantAccording to the chemical formula Ba 0.05 Sr 0.948 AlSiN 3 ：Eu 0.002 183.83g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank filled with n-hexane in a glove box and sealed, the mixing tank is installed on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into the glove box, the mixed raw materials are sieved, and the n-hexane and a solid-phase material are separated.
(2) Charging the uniformly mixed material obtained in the step (1) into a crucible in a CO/H ratio 2 And N 2 And sintering in the mixed gas sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. The sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the ratio of CO in the mixed gas is as follows: h 2 ：N 2 2%:1%:97 percent.
(3) And (3) putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushing tank on a ball mill for acid washing, crushing and dispersing, and sieving after the powder is dispersed until no obvious particles exist. And (3) alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving to obtain the final product fluorescent powder.
Comparative example 4
(1) According to the chemical formula Ba 0.05 Sr 0.948 AlSiN 3 ：Eu 0.002 183.83g of strontium nitride, 5.04g of barium nitride, 81.98g of aluminum nitride, 93.52g of silicon nitride and 0.7g of europium oxide are weighed, the weighed raw materials are transferred into a mixing tank filled with n-hexane in a glove box and sealed, the mixing tank is installed on a planetary ball mill for wet mixing for 3 hours, then the mixing tank is transferred into the glove box, the mixed raw materials are sieved, and the n-hexane and a solid-phase material are separated.
(2) The materials mixed evenly in the step (1) are filled into a crucible, and N is introduced into the crucible 2 Sintering in an atmosphere sintering furnace, and taking out the sintered product after the sintering is finished and the sintered product is cooled to room temperature to obtain the orange-red fluorescent powder. The sintering conditions are as follows: temperature of1600 ℃, 0.5MPa of pressure, 6 hours of heat preservation time and N as gas 2 。
(3) Putting the sintered orange-red fluorescent powder into a crushing tank filled with an acid solution (hydrochloric acid), placing the crushed powder on a ball mill for acid washing, crushing and dispersing, sieving the powder until no obvious particles exist, alternately washing with cold water and hot water after sieving, controlling the temperature of the hot water at 80 ℃, controlling the temperature of the cold water at 30 ℃, washing until the conductivity is less than 10 mu s, drying and sieving.
(4) Then the powder is placed in a deionized water: stirring in an ethanol solution diluted by ethanol =1 at 90 ℃, then adding 1.5% KH-792 silane coupling agent according to the mass of the powder, stirring uniformly, adding silica sol with the weight percentage of 3% of the powder, stirring for 4 hours to carry out inorganic coating, standing to remove the upper layer liquid, and drying the powder. And adding the dried powder into an ethanol solution, dropwise adding 1 wt% of carbon black dispersing agent DP108 for organic coating, stopping stirring after dropwise adding, filtering, drying and sieving to obtain the fluorescent powder.
Relative brightness and spectral data for the final products of the examples and comparative examples were measured using a HAAS-2000 high precision rapid optical performance test radiometer. The heat resistance test of the final products of examples and comparative examples specifically included the following steps: the sample was placed in an aging oven at 120 ℃ and 0.1MPa for 96 hours, and the data (relative brightness, spectrum and particle size data) before and after the sample test were compared, wherein CIEx and CIEy refer to color coordinates. The D50 of the example and comparative end products were measured by the eumech laser particle size analyzer POP 6.
TABLE 1 relative brightness, spectra and D50 data before and after heat resistance test of the final products of example 1 and comparative example 3
Figure BDA0003744500050000091
As can be seen from table 1, in example 1, performance data of the orange-red phosphor prepared by triple coating (silane coupling agent-inorganic-organic) is not greatly changed before and after the heat resistance test, and the sample has good thermal stability; the data before and after the heat resistance test of the uncoated phosphor of comparative example 3 varied greatly, indicating that the uncoated phosphor had poor thermal stability.
TABLE 2 relative Brightness, spectra and D50 data for the final products of examples 1 to 4 and comparative example 4
Figure BDA0003744500050000092
Figure BDA0003744500050000101
Example 1 compared with comparative example 4, a certain proportion of CO/H was introduced 2 Gas, adopting a high-pressure weak reducing atmosphere sintering method to enable Eu to be 3+ More rapid and complete reduction to Eu 2+ And the activator is more fully reduced, and the performance of the fluorescent powder can be obviously improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The preparation method of the orange-red fluorescent powder is characterized in that the chemical formula of the orange-red fluorescent powder is E 1- x D y Q z N 3 :xEu 2+ Wherein, the element E comprises at least one of Sr, ba, mg, ca and Li, the element D comprises at least one of Al, B, ga, la, gd and Y, the element Q comprises at least one of Si, ge, sb and As, and x is more than or equal to 0.001 and less than or equal to 0.01; y is more than or equal to 0.5 and less than or equal to 2; z is more than or equal to 0.5 and less than or equal to 2;
the preparation method of the orange-red fluorescent powder comprises the following steps of 1-x D y Q z N 3 :xEu 2+ Taking required raw materials according to a metering ratio, mixing the raw materials to obtain a solid phase material, sintering the solid phase material, and cooling to obtain orange redColor phosphor;
the orange-red fluorescent powder is subjected to dispersing, cleaning, surface coating and drying treatment in sequence;
the surface coating comprises the following steps: adding the orange red fluorescent powder into an ethanol water solution of a silane coupling agent for coating the silane coupling agent, then adding silica sol for inorganic coating, removing a solvent, drying, and then sequentially adding ethanol and a carbon black dispersing agent for organic coating.
2. The method for preparing orange-red fluorescent powder according to claim 1, wherein the sintering conditions are as follows: the temperature is 1500-2000 deg.C, pressure is 0.05-5.0MPa, heat preservation time is 5-30 hr, and atmosphere is CO and H 2 And N 2 The mixed gas of (1).
3. The method of claim 2, wherein the sintering conditions are as follows: the temperature is 1600 ℃, the pressure is 0.5MPa, the heat preservation time is 6 hours, and the content of CO in the mixed gas is as follows: h 2 ：N 2 Is 2%:1%:97 percent.
4. A method as claimed in claim 2 or 3, characterized in that an organic solvent is also added during the mixing; the organic solvent comprises at least one of n-hexane and n-heptane.
5. A method according to claim 2 or 3, characterized in that the mixing time is 1-3 hours.
6. The method of claim 1, wherein the dispersion is an acid wash break dispersion, the acid comprising at least one of nitric acid, hydrochloric acid, and sulfuric acid; the cleaning is carried out by alternately washing with cold water and hot water, wherein the temperature of the hot water is 70-90 ℃, the temperature of the cold water is 15-30 ℃, and the washing is carried out until the conductivity is less than 10 mu s.
7. The method of claim 1, wherein the silane coupling agent comprises at least one of KH-570, KH-792; the carbon black dispersant comprises DP108; the inorganic coating time is 1-6 h, and the temperature is 60-90 ℃; the temperature of the silane coupling agent coating is 60-90 ℃.
8. The method of claim 1, wherein the silane coupling agent is 0.1-10% by mass of the orange-red phosphor; the mass of the carbon black dispersing agent is 0.1-10% of that of the orange red fluorescent powder; the mass of the silica sol is 0.1-10% of that of the orange-red fluorescent powder.
9. The method of claim 8, wherein the silane coupling agent is 1.5% by mass of the orange-red phosphor; the mass of the carbon black dispersing agent is 3% of that of the orange red fluorescent powder; the mass of the silica sol is 1% of that of the orange-red fluorescent powder.
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