CN108130074B - Method for preparing high-crystallinity nano nitride fluorescent powder - Google Patents
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Abstract
The invention discloses a method for preparing high-crystallinity nano nitride fluorescent powder, which comprises the steps of firstly preparing potassium sulfate particles with nano sizes, carrying out surface modification on the potassium sulfate particles to ensure that the particles are uniformly dispersed in dimethylbenzene, and then dispersing and isolating the nano nitride fluorescent powder particles obtained by mechanical crushing in the dimethylbenzene. And drying the precipitate, calcining in an inert atmosphere, and washing with water to obtain the nano nitride fluorescent powder with high crystallization, high dispersion and excellent luminescence property. The invention can rapidly prepare high-quality nano nitride fluorescent powder in batches, and the fluorescent powder can be made into transparent fluorescent glue, thereby not only eliminating light scattering loss, but also solving the problem of inconsistent white light LED light color caused by sedimentation.
Description
Technical Field
The invention relates to a technology for preparing high-crystallinity nano nitride fluorescent powder, belonging to the technical field of luminescent materials.
Background
(Sr/Ca)AlSiN3Eu and Sr2Si5N8Eu-system nitride red fluorescent powder is widely applied to commercial white light LEDs due to high luminous efficiency and pure light color.
At present, commercial nitride fluorescent powder is prepared by a high-temperature solid phase method, the synthesis temperature is as high as 1400 ℃ to 1700 ℃, the prepared fluorescent powder has large particles, and the particle size is generally about 10-20 mu m. Since the particles are too coarse, there are two drawbacks: (1) the phosphor particles are much higher than liquid packaging adhesive in specific gravity in the packaging process, and are settled in the packaging adhesive, so that the packaging process is difficult to control accurately, the phosphor particles are not distributed uniformly, the light color consistency of the white light LED is difficult to ensure, the light color is not uniform, and the yield is low. In order to ensure that the sedimentation degrees of all batches of fluorescent powder particles are consistent, higher requirements on the precision of the packaging process are necessarily put forward, and the packaging process cost is greatly increased; (2) the fluorescent powder particles have strong light scattering on the excitation light and the emitted light, light scattering loss is caused, and partial light returns to the LED chip, so that internal reflection loss is caused, and the light emitting efficiency of the white light LED is influenced.
To eliminate the light loss of the phosphor particles, the light scattering can be completely eliminated by reducing the size of the phosphor particles to less than 100nm and uniformly dispersing the phosphor particles in the packaging adhesive to reach a transparent state. That is, the preparation of dispersed nano-nitride phosphor is the only way to eliminate the light scattering loss. In addition, if the phosphor particles can be made to be less than 100 nanometers, the sedimentation speed of the phosphor particles in the packaging adhesive is reduced by 10000 times, and the phenomenon of nonuniform light color caused by the sedimentation of the particles can be basically eliminated.
Due to the extremely high synthesis temperature, the nano nitride fluorescent powder is difficult to prepare by the conventional means. If mechanical crushing methods such as ball milling, jet milling and the like are used for reducing the size of the nitride fluorescent powder particles to the nanometer scale, the crystallinity of the fluorescent powder particles can be seriously damaged, and the great reduction of the luminous efficiency is brought. If the mechanically pulverized nano nitride fluorescent powder is calcined at high temperature for two times, although the crystallinity of the nano nitride fluorescent powder can be recovered, the nano nitride fluorescent powder can cause the re-sintering growth of nano particles. To date, there have been no reports on highly crystalline dispersed nano-nitride particles and transparent nitride fluorescent gels.
Disclosure of Invention
The technical problem is as follows: the invention provides a method for preparing high-crystallinity nano nitride fluorescent powder, which can quickly prepare nano nitride particles with good dispersibility in batches and solve the problems of agglomeration and sintering of the nano particles, can stably prepare the nano particles with the particle size of less than 100nm, and can prepare the prepared high-dispersibility nano nitride fluorescent powder into transparent fluorescent glue with organic silicon resin, silica gel or epoxy resin, thereby eliminating light loss caused by light scattering, improving the light-emitting efficiency of a white light LED and basically avoiding the problem of inconsistent light color of the white light LED caused by sedimentation.
The technical scheme is as follows: the method for preparing the high-crystallinity nano nitride fluorescent powder comprises the following steps:
1) preparing nano potassium sulfate, and dispersing the nano potassium sulfate in ethanol to obtain nano potassium sulfate ethanol dispersion liquid;
2) adding stearic acid into the nanometer potassium sulfate ethanol dispersion liquid, and preserving the heat for more than 1 hour at the temperature of 30-60 ℃;
3) centrifuging the nano potassium sulfate ethanol dispersion liquid prepared in the step 2), and dispersing in xylene to prepare transparent nano potassium sulfate xylene dispersion liquid;
4) mechanically crushing the coarse-particle nitride fluorescent powder into nano nitride fluorescent powder, and adding the nano nitride fluorescent powder into the transparent nano potassium sulfate xylene dispersion liquid;
5) heating to 40-100 deg.c and stirring for 0.5-4 hr;
6) centrifuging, drying the centrifugate, and calcining at 1000 deg.C or below in inert atmosphere;
7) and cooling, washing with water, and drying to obtain the high-crystallinity nano nitride fluorescent powder.
Further, in the method, the nano potassium sulfate in the step 1) is prepared according to the following mode:
adding polyacrylic acid into potassium sulfate water solution, dissolving, dripping polyacrylic acid-containing potassium sulfate water solution into organic solvent under stirring, centrifuging to obtain precipitate, washing the precipitate with organic solvent for 1-2 times, and drying to obtain nanometer potassium sulfate crystal
Furthermore, in the method, the concentration of the potassium sulfate aqueous solution is 0.01mol/L to the saturated concentration.
Furthermore, in the method, the addition amount of the polyacrylic acid is 0.5-100% of the mass of the potassium sulfate.
Further, in the method of the present invention, the organic solvent is methanol, ethanol, tert-butanol, acetone or dimethylformamide.
Further, in the method of the present invention, the coarse-grained nitride phosphor in the step 4) is Ca1-x-ySryAlSiN3:EuxPhosphor or Sr2-zSi5N8:EuzPhosphor of which 0<x≤0.2，0≤y≤1-x，0.01≤z≤0.20。
Further, in the method, in the nanometer potassium sulfate ethanol dispersion liquid in the step 1), the nanometer potassium sulfate accounts for 0.1-10% of the mass of the dispersion liquid.
Further, in the method, in the step 2), the adding amount of stearic acid is 1-10% of the mass of the nanometer potassium sulfate.
Further, in the method, in the transparent nano potassium sulfate dimethylbenzene dispersion liquid prepared in the step 3), the nano potassium sulfate accounts for 1-10% of the mass of the dispersion liquid.
Further, in the method, in the step 4), the mass ratio of the added nano nitride fluorescent powder to the nano potassium sulfate in the transparent nano potassium sulfate xylene dispersion liquid is less than 1. .
The invention uses water-soluble potassium sulfate particles to be mixed with nano nitride particles obtained by mechanical crushing, the mixture is calcined at high temperature, the crystallinity of the mixture can be recovered, simultaneously, potassium sulfate particles are used as an isolation phase to prevent the nano nitride particles from agglomerating and sintering, and the potassium sulfate is removed after water washing to obtain the nano nitride fluorescent powder particles with high crystallinity.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the nano nitride fluorescent powder is difficult to prepare by the prior art. Although the size of nitride phosphor particles can be reduced to nano-scale by using a mechanical crushing method, the crystallinity of the phosphor particles is seriously damaged, and the luminous efficiency of the phosphor is greatly influenced. If the mechanically pulverized nano nitride fluorescent powder is subjected to secondary high-temperature calcination, although the crystallinity of the nano nitride fluorescent powder can be recovered, the nano particles can be sintered and grown again.
The water-soluble inorganic salt particles are mixed with the nano nitride particles obtained by mechanical crushing, the nano nitride particles are calcined at high temperature to recover the crystallinity, meanwhile, the inorganic salt particles are used as an isolation phase to prevent the agglomeration and sintering of the nano nitride particles, and the potassium sulfate salt is removed after water washing to obtain the nano nitride fluorescent powder particles with high crystallinity. However, the effective implementation of the method has two important links: (1) firstly, preparing water-soluble salt particles at a nanometer level; (2) the nano-nitride obtained by mechanical pulverization is effectively isolated and dispersed by using nano-salt particles.
When the aqueous solution of the salt is added into a water-miscible, weakly polar organic solvent, the solubility of the salt is greatly reduced, and salt particles are separated out from the organic solvent, but the separated crystals are usually in the micron order. The polyacrylic acid adopted by the invention can promote the nucleation of potassium sulfate, and after the polyacrylic acid-containing potassium sulfate aqueous solution is added into an organic solvent, the nucleation rate of the potassium sulfate is greatly improved, and thus the particle size is greatly reduced. When polyacrylic acid with the weight of more than 0.5 percent of the potassium sulfate is added, the size of potassium sulfate particles can be effectively reduced to be less than 100nm, as shown in the attached figure 1 of the specification.
The action mechanism of polyacrylic acid is not clear at present, and the concept of nucleating agent does not exist in the technical field of organic solvent precipitation method. In the field of metal solidification, the nucleating agent is solid particles and can be used as a nucleating substrate during metal solidification, so that the nucleating rate is greatly improved, and the grain size is reduced. Polyacrylic acid is a water-soluble polymer material, and the action mechanism of polyacrylic acid is obviously greatly different from that of a solid nucleating agent in the solidification process. The effect of polyacrylic acid in the present invention to promote nucleation of potassium sulfate is unpredictable based on the prior art.
The nanometer potassium sulfate prepared by the method has a melting point of 1067 ℃, is stable in chemical property, does not react with nitride at high temperature, and is very suitable for being used as an isolation phase for preparing high-crystallinity nanometer nitride fluorescent powder. The nano potassium sulfate is used for dispersing and isolating the nano nitride obtained by mechanical crushing, and the nano potassium sulfate particles and the nano nitride obtained by mechanical crushing need to be stirred and mixed in an organic solvent. However, previous researches find that when nano potassium sulfate and nano nitride obtained by mechanical crushing are directly mixed in organic solvents such as ethanol and the like, nano potassium sulfate particles are easily in an agglomerated state and cannot be dispersed, and naturally cannot be used as an isolating agent to achieve the purpose of dispersing precursor particles, so that the isolating effect is poor, and the high-dispersion nano nitride fluorescent powder is difficult to prepare by drying and then calcining at high temperature.
The invention carries out surface modification on the nano potassium sulfate by stearic acid in ethanol in advance, can well disperse the nano potassium sulfate in dimethylbenzene and obtains transparent dispersion liquid. At the moment, the nano nitride fluorescent powder obtained by mechanical crushing is added, and the dispersed nano potassium sulfate can be used as an isolation phase to disperse and isolate nano nitride fluorescent powder particles.
The dispersed nanometer nitride particles and nanometer potassium sulfate are centrifuged, dried and then calcined at high temperature in inert atmosphere such as nitrogen or argon, the crystallinity of the nanometer nitride can be recovered, meanwhile, the nanometer nitride particles are always dispersed and isolated by the nanometer potassium sulfate solid particles, so that agglomeration and sintering can not occur, the dispersed nanometer nitride particles with good crystallinity can be obtained after the potassium sulfate is removed by washing, and the luminescence performance can also be recovered to the level before mechanical crushing.
If the surface active agent is added into the xylene dispersion liquid, the isolation effect of the nano potassium sulfate can be further improved. The surfactant comprises polyethylene glycol, polyvinylpyrrolidone, carboxylic acid surfactant, silane coupling agent, aluminate coupling agent, etc.
The invention can rapidly prepare the nano nitride particles with good dispersibility in batches, solves the agglomeration and sintering problems of the nano particles, and can prepare the nitride fluorescent powder with excellent light-emitting performance after secondary reduction.
The high-dispersity nano nitride fluorescent powder prepared by the invention can be made into transparent fluorescent glue with organic silicon resin, silica gel or epoxy resin, so that the light loss caused by light scattering is eliminated, and the light-emitting efficiency of a white light LED is improved.
The high-dispersibility nano nitride fluorescent powder prepared by the invention has very slow sedimentation in organic silicon resin, silica gel or epoxy resin and other packaging adhesives, so that the problem of inconsistent white light LED light color caused by sedimentation is basically avoided.
The preparation method is simple and convenient and is easy for large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of potassium sulfate nanoparticles for isolating nitride nanoparticles according to the present invention.
FIG. 2 is a scanning electron microscope image of the nano-nitride phosphor of the present invention.
Detailed Description
The invention is further described with reference to the following examples and the accompanying drawings.
Example 1: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of nanometer potassium sulfate, dispersing the nanometer potassium sulfate in 100ml xylene, adding 10g mechanically pulverized nanometer CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 2: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. Weighing 1g of nano potassium sulfate, dispersing in 200ml of ethanol, adding 0.01 g of stearic acid, and stirring for 2 hours at 50 ℃. After the nanometer potassium sulfate ethanol dispersion liquid is centrifuged,dispersing nanometer potassium sulfate in 100ml xylene, adding 0.1g mechanically pulverized nanometer CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 3: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 5g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.1g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 4: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.2 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 5: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dripping potassium sulfate solution containing polyacrylic acid into 50L ethanol under stirring, washing precipitate with ethanol for 1-2 times, and drying to obtain sulfurAnd (4) potassium nano-crystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 1g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 6: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 20 g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 2 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 7: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 30 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 8: preparing 2L potassium sulfate solution with concentration of 0.1mol/L with deionized water, adding salt5% by mass of polyacrylic acid, and dissolving. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours under the condition of heat preservation at 60 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 9: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 4 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 10: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high junctionCrystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 11: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 12: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 13: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of the nanometer potassium sulfate, dispersing the nanometer potassium sulfate in 100ml of dimethylbenzene, and adding 5g mechanically crushed Nano CaAlSiN3Eu fluorescent powder, stirring for 2 hours at 50 ℃, centrifuging, drying, calcining for 2 hours at 1000 ℃ in nitrogen atmosphere, washing with water and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 14: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring at 100 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 15: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring for 1 hour at 80 ℃, centrifuging, drying, calcining for 2 hours at 1000 ℃ in nitrogen atmosphere, washing with water and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 16: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. Weighing 10g of nano potassium sulfate, and dividingDispersing in 200ml ethanol, adding 0.5 g stearic acid, stirring at 50 deg.C for 2 hours. Centrifuging the ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized CaAlSiN3Eu fluorescent powder, stirring for 4 hours at 80 ℃, centrifuging, drying, calcining for 2 hours at 1000 ℃ in nitrogen atmosphere, washing with water and drying to obtain high-crystallinity dispersed nano CaAlSiN3Eu fluorescent powder.
Example 17: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging the ethanol dispersion of potassium sulfate, dispersing the potassium sulfate in 100ml xylene, adding 5g mechanically pulverized nano SrAlSiN3Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, washing with water, and drying to obtain high-crystallinity dispersed nano SrAlSiN3Eu fluorescent powder.
Example 18: 2L potassium sulfate solution with the concentration of 0.1mol/L is prepared by deionized water, polyacrylic acid with the mass of 5 percent of salt is added, and the solution is dissolved clearly. Dropping polyacrylic acid-containing potassium sulfate solution into 50L of ethanol under stirring, washing the precipitate with ethanol for 1-2 times, and drying to obtain potassium sulfate nanocrystal. 10g of nano potassium sulfate is weighed and dispersed in 200ml of ethanol, 0.5 g of stearic acid is added, and the mixture is stirred for 2 hours at the temperature of 50 ℃. Centrifuging ethanol dispersion of potassium sulfate, dispersing potassium sulfate in 100ml xylene, adding 5g mechanically pulverized nanometer Sr2Si5N8Eu fluorescent powder, stirring at 80 deg.C for 2 hr, centrifuging, drying, calcining at 1000 deg.C in nitrogen atmosphere for 2 hr, water washing, and drying to obtain high-crystallinity dispersed nano Sr2Si5N8Eu fluorescent powder.
Claims (10)
1. A method for preparing high-crystallinity nano nitride fluorescent powder is characterized by comprising the following steps:
1) preparing nano potassium sulfate, and dispersing the nano potassium sulfate in ethanol to obtain nano potassium sulfate ethanol dispersion liquid;
2) adding stearic acid into the nanometer potassium sulfate ethanol dispersion liquid, and preserving the heat for more than 1 hour at the temperature of 30-60 ℃;
3) centrifuging the nano potassium sulfate ethanol dispersion liquid prepared in the step 2), and dispersing in xylene to prepare a transparent nano potassium sulfate xylene dispersion liquid;
4) mechanically crushing the coarse-particle nitride fluorescent powder into nano nitride fluorescent powder, and adding the nano nitride fluorescent powder into the transparent nano potassium sulfate xylene dispersion liquid;
5) heating to 40-100 deg.c and stirring for 0.5-4 hr;
6) centrifuging, drying the centrifugate, and calcining at 1000 deg.C or below in inert atmosphere;
7) and cooling, washing with water, and drying to obtain the high-crystallinity nano nitride fluorescent powder.
2. The method for preparing high-crystallinity nano-nitride phosphor according to claim 1, wherein the nano-potassium sulfate in step 1) is prepared as follows:
adding polyacrylic acid into potassium sulfate aqueous solution, dissolving, dripping polyacrylic acid-containing potassium sulfate aqueous solution into an organic solvent under the condition of stirring, centrifuging to obtain a precipitate, washing the precipitate for 1-2 times by using the organic solvent, and drying to obtain the nano potassium sulfate crystal.
3. The method for preparing high-crystallinity nano-nitride phosphor according to claim 2, wherein the concentration of the potassium sulfate aqueous solution is from 0.01mol/L to a saturated concentration.
4. The method for preparing high-crystallinity nano-nitride phosphor according to claim 2, wherein the polyacrylic acid is added in an amount of 0.5-100% by mass based on the potassium sulfate.
5. The method for preparing high-crystallinity nano-nitride phosphor according to claim 2, wherein the organic solvent is methanol, ethanol, tert-butanol, acetone or dimethylformamide.
6. The method for preparing high-crystallinity nanometer nitride fluorescent powder according to claim 1, 2, 3, 4 or 5, characterized in that the coarse-grain nitride fluorescent powder in the step 4) is Ca1-x-ySryAlSiN3:EuxPhosphor or Sr2-zSi5N8:EuzPhosphor of which 0<x≤0.2，0≤y≤1-x，0.01≤z≤0.20。
7. The method for preparing high-crystallinity nano-nitride phosphor according to claim 1, 2, 3, 4 or 5, wherein in the nano-potassium sulfate ethanol dispersion liquid of step 1), the nano-potassium sulfate accounts for 0.1-10% of the mass of the dispersion liquid.
8. The method for preparing high-crystallinity nano-nitride phosphor according to claim 1, 2, 3, 4 or 5, wherein in the step 2), the addition amount of stearic acid is 1-10% of the mass of the nano potassium sulfate.
9. The method for preparing high-crystallinity nano-nitride fluorescent powder according to claim 1, 2, 3, 4 or 5, wherein in the transparent nano-potassium sulfate xylene dispersion prepared in the step 3), the nano-potassium sulfate accounts for 1-10% of the mass of the dispersion.
10. The method for preparing high-crystallinity nano-nitride fluorescent powder according to claim 1, 2, 3, 4 or 5, wherein in the step 4), the mass ratio of the added nano-nitride fluorescent powder to the nano-potassium sulfate in the transparent nano-potassium sulfate xylene dispersion liquid is less than 1.
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