CN114774115B - LED fluorescent powder and preparation method and application thereof - Google Patents
LED fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229940104869 fluorosilicate Drugs 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 40
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000004806 packaging method and process Methods 0.000 abstract description 13
- -1 hexafluoro manganate Chemical compound 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 27
- 239000011591 potassium Substances 0.000 description 27
- 239000013078 crystal Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
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- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ZDLRUHBQIZPTMS-UHFFFAOYSA-M [Mn](=O)(=O)([O-])F.[K+] Chemical compound [Mn](=O)(=O)([O-])F.[K+] ZDLRUHBQIZPTMS-UHFFFAOYSA-M 0.000 description 1
- OJOWXSLGSMTXEO-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] Chemical compound [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] OJOWXSLGSMTXEO-UHFFFAOYSA-H 0.000 description 1
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- 229910001437 manganese ion Inorganic materials 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses LED fluorescent powder and a preparation method and application thereof, belonging to the technical field of material synthesis; the invention provides LED fluorescenceThe structural formula of the powder is A 2 (MF 6 ):Mn 4+ Of which D is 50 ＝3.5‑21.5μm，D 10 ≥1.0μm，D 90 Less than or equal to 31.65 mu m and a particle size distribution coefficient P = (D) 90 ‑D 10 )/D 50 Less than or equal to 1.0; wherein A comprises Li, na, K, rb, cs and NH 4 M comprises any one of Ge, si, sn, ti, zr and Sc; the preparation method comprises the following steps: ultrasonically stirring a hydrofluoric acid solution of fluorosilicate and a hydrofluoric acid solution of hexafluoro manganate, dropwise adding a hydrofluoric acid solution of fluorohydrogenate, and after finishing dropwise adding, ultrasonically stirring, crystallizing, quenching, aging, washing and drying to obtain LED fluorescent powder; the invention synthesizes fluorescent powder by chemical liquid phase ultrasound, introduces ultrasonic wave in the preparation process, and adopts the subsequent aging step, thereby obtaining the fluorescent powder with small particle size uniformly distributed; the preparation method provided by the invention is high in yield and simple to operate, and the fluorescent powder can be applied to LED products, so that the light efficiency and the light quality are improved, and the packaging amount is saved.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to LED fluorescent powder and a preparation method and application thereof.
Background
The LED fluorescent powder can improve the light quality and color rendering of an LED product, so that the improvement of the light efficiency and the improvement of the light color quality of an LED packaging device and the reduction of the packaging cost through the innovation of an LED fluorescent powder technology are the constant subjects of the technical development of the LED fluorescent powder.
The product granularity of fluoride LED red fluorescent powder for realizing mass production or related reports on the market at present is generally between 18 and 45 mu m, and fluorescent powder with smaller grain diameter is not available; meanwhile, the fluoride LED red fluorescent powder commercially available on the market is synthesized by a chemical precipitation method, and the particle size of the powder is difficult to control below 20 mu m according to the current preparation method because the fluoride LED red fluorescent powder crystal has the characteristic of extremely easy growth; in the current industrial production, the fluoride LED red fluorescent powder is synthesized by using a liquid phase synthesis process, but the granularity of the powder synthesized by the method generally fluctuates between 4 and 8 mu m, so that the concentration of the granularity is insufficient, and if the powder is further treated by screening, partial yield is sacrificed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the LED fluorescent powder with small particle size and high particle size concentration, and the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the structural formula of the LED fluorescent powder is A 2 (MF 6 ):Mn 4+ Of which D is 50 ＝3.5-21.5μm，D 10 ≥1.0μm，D 90 Less than or equal to 31.65 mu m and a particle size distribution coefficient P = (D) 90 -D 10 )/D 50 Less than or equal to 1.0; wherein A comprises Li, na, K, rb, cs and NH 4 M includes any one of Ge, si, sn, ti, zr, and Sc.
The LED fluorescent powder provided by the technical scheme of the invention has small granularity and concentrated granularity distribution, can be well applied to LED products, and has excellent improvement effect on the lighting effect and the light quality of the LED products.
As a preferred embodiment of the LED fluorescent powder, the structural formula of the LED fluorescent powder is K 2 Si (1-x) F 6 :Mn x Wherein x =0.045-0.070.
In addition, the invention also provides a preparation method of the LED fluorescent powder, which comprises the following steps:
(1) Adding the hydrofluoric acid solution of the fluosilicate into the hydrofluoric acid solution of the hexafluoro manganate, and stirring and mixing to obtain a mixed solution;
(2) Placing the mixed solution at 2-10 ℃ for ultrasonic stirring, and dropwise adding hydrofluoric acid solution of fluorohydrogenate;
(3) And after the dropwise addition is finished, carrying out ultrasonic stirring crystallization, quenching reaction, aging, washing and drying to obtain the LED fluorescent powder.
According to the invention, the LED fluorescent powder is prepared by a chemical liquid phase ultrasonic stirring synthesis method, and ultrasonic waves with specific frequency are introduced in the preparation process, so that the characteristic that crystals of the fluorescent powder are easy to grow can be effectively inhibited, and the fluorescent powder with small granularity is prepared; in the chemical liquid phase ultrasonic stirring synthesis process, the crystal formation of the LED fluorescent powder generally comprises two stages, namely the formation of crystal nucleus and the growth of the crystal nucleus, and the prepared crystal of the fluorescent powder has smaller granularity and better distribution uniformity only when the speed of the stage is balanced; the invention can well realize the balance of the formation of crystal nucleus and the growth of crystal by selecting the mode of combining ultrasound and dripping at specific temperature, thereby achieving the aim of synthesizing the LED fluorescent powder with small granularity and high uniformity, wherein D of the synthesized LED fluorescent powder 50 ＝3.5-21.5μm，P＝(D 90 -D 10 )/D 50 ≤1.0。
In the preferred embodiment of the production method of the present invention, in the step (1), the temperature of the hydrofluoric acid solution of fluorosilicate and the hydrofluoric acid solution of hexafluoromanganate is 0 to 6 ℃.
In a preferred embodiment of the preparation method of the present invention, in the step (1), the mass-to-volume ratio of the hexafluoromanganate to the hydrofluoric acid solution is (6-9) g:2.5L.
The mass-volume ratio of the hexafluoromanganate to the hydrofluoric acid solution can be used for adjusting the concentration of tetravalent manganese ions in the luminescent center of the finished fluorescent powder product, so that the color coordinate and the luminous intensity of the fluorescent powder and the quantity of the LED product packaging powder of the fluorescent powder are adjusted, and when the mass-volume ratio of the hexafluoromanganate to the hydrofluoric acid solution is in the range, the prepared LED fluorescent powder has proper color coordinate and luminous intensity, so that the packaging cost of subsequent application can be reduced.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the fluorosilicate includes potassium fluorosilicate, sodium fluorosilicate, ammonium fluorosilicate; the hexafluoromanganate comprises potassium hexafluoromanganate.
In a preferred embodiment of the preparation method of the present invention, in the step (1), the hydrofluoric acid has a concentration of 41 to 45% by mass.
In a preferred embodiment of the production method of the present invention, in the step (1), the molar concentration of the solute in the hydrofluoric acid solution of fluorosilicate is 1.3 to 1.8mol/L.
As a preferable embodiment of the preparation method of the present invention, in the step (1), the stirring time is 1 to 4min.
As a preferable embodiment of the production method of the present invention, in the step (2), the dropping rate is 2 to 10mL/s.
As a preferable embodiment of the production method of the present invention, in the step (2), the dropping rate is 4 to 8mL/s.
When the dripping speed is 2-10mL/s, especially 4-8mL/s, the forming points of crystal nuclei can be ensured to be more dispersed, and the phenomenon that the later-stage crystal granularity is larger or the dispersion uniformity of the crystals is reduced due to the formation of the crystal nuclei is avoided; meanwhile, the impure phase in the powder forming process can be reduced, so that the luminous efficiency of the prepared powder is ensured.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the frequency of the ultrasound is 5 to 50kHz.
In the process of ultrasonic stirring, the introduction of ultrasonic waves with ultrasonic frequency can inhibit the excessive growth of phosphor powder crystal nuclei, thereby ensuring the small granularity of the prepared phosphor powder; if the frequency of the ultrasound is insufficient, the synthesized particle size is too large, and if the frequency of the ultrasound is too large, the formed crystal nuclei are destroyed, so that the phosphor powder with a certain shape cannot be formed, and the effect of the subsequent application is reduced.
In the step (2), the molar concentration of the fluorohydrogenate in the hydrofluoric acid solution of the fluorohydrogenate is 1.8 to 2.2mol/L.
In the preferred embodiment of the production method of the present invention, in the step (2), the molar concentration of the fluorohydrogenate in the hydrofluoric acid solution of the fluorohydrogenate is 2mol/L.
The molar concentration of selecting above-mentioned scope carries out the dropwise add, can with dropwise add speed cooperation to guarantee that the formation of crystal nucleus is comparatively dispersed relatively, can not too concentrate the problem that the crystal size that leads to later stage crystal nucleus overlapping is too big or the homogeneity that distributes descends, also can avoid the problem that miscellaneous looks increase, the light efficiency that brings of the concentration of the fluorine hydride salt that adds descends.
As a preferred embodiment of the preparation method, the mass ratio of the fluorohydridate to the fluoromanganate is (6-9): 1.
as a preferable embodiment of the preparation method of the present invention, in the step (3), the frequency of the ultrasound is 5 to 50kHz; the crystallization temperature is 2-10 deg.C, and the crystallization time is 8-12min.
Maintaining the above ultrasonic frequency, crystallization temperature and crystallization time at the crystallization stage enables the rate of growth of the crystal nuclei formed in step (2) to be controlled, avoiding the formation of larger crystals or uneven distribution of the particle size of the formed crystals.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the aging temperature is 2-10 ℃ and the aging time is 2-8min.
After quenching reaction and before washing, a proper aging condition is provided for the crystal, the crystallinity of the particle can be further improved, the particle size distribution is further concentrated, and the crystallization yield can be ensured.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the quenching reaction is to add hydrogen peroxide to the reaction system for quenching; the mass concentration of the hydrogen peroxide is 25-40%; the adding amount of the hydrogen peroxide is that the hydrogen peroxide is added to the system to change the color.
In a preferred embodiment of the preparation method of the present invention, in the step (3), the solvent used for washing is acetone, and the sign of the end of washing is that the pH of the system is 6.8-7.2.
As a preferable embodiment of the preparation method of the present invention, in the step (3), the drying is performed by vacuum drying at a temperature of 70 to 90 ℃.
In addition, the invention also provides application of the LED fluorescent powder in LED products.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the method comprises the following steps: the technical scheme of the invention provides LED fluorescent powder, and D thereof 50 =3.5-21.5 μm, particle size distribution coefficient P = (D) 90 -D 10 )/D 50 The LED fluorescent powder provided by the invention has narrow particle size distribution and high uniformity, so that excellent lighting effect and light quality can be provided for LED products, and meanwhile, the packaging efficiency of the LED products can be improved, and the packaging cost can be reduced;
secondly, the method comprises the following steps: in the preparation process of the LED fluorescent powder, a chemical liquid phase ultrasonic stirring synthesis method is adopted, and the dropwise addition mixing, the specific mixing and crystallization temperature, the appropriate crystallization time and the subsequent aging time of reaction raw materials are matched, so that the crystal nucleus formation and the crystal growth rate of the fluorescent powder are relatively balanced in the crystal formation process, and the subsequent aging can further stabilize the crystals and reduce the particle size distribution range, so that the advantage of high particle size distribution concentration is achieved;
thirdly, the method comprises the following steps: in the preparation process of the LED fluorescent powder, ultrasonic waves are introduced, and the inhibition of the crystal growth in different degrees is realized by controlling the power of the ultrasonic waves and the positions and the number of energy overflow outlets in a preparation system, so that the aim of preparing the fluorescent powder in a specific small particle size range is fulfilled;
fourthly: the LED fluorescent powder provided by the invention is simple in preparation process, simple and convenient to operate, and suitable for actual production.
Drawings
FIG. 1 is an SEM photograph of a phosphor prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a phosphor prepared in comparative example 1 of the present invention;
FIG. 3 is an ultrasonic water bath temperature control device used in an embodiment of the present invention;
1-temperature-control circulating water outlet, 2-temperature-control circulating water outlet, 3-variable frequency ultrasonic generator, 4-stirring paddle, 5-feed liquid inlet, 6-feed opening, 7-valve, 8-variable frequency motor and 9-cooling water interlayer.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the LED fluorescent powder provided by the embodiment of the invention comprises the following steps:
(1) Preparing a hydrofluoric acid solution of potassium bifluoride: adding potassium bifluoride into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of the potassium bifluoride, wherein the molar concentration of the potassium bifluoride is 2mol/L;
(2) Preparing a hydrofluoric acid solution of potassium fluosilicate: adding potassium fluosilicate into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of potassium fluosilicate, wherein the molar concentration of the potassium fluosilicate is 1.5mol/L;
(3) Measuring 2.5L of hydrofluoric acid with the mass concentration of 41%, adding 6g of potassium fluosilicate at 3 ℃, stirring for 2-4min until the solid is completely dissolved, adding the potassium fluosilicate into 200mL of hydrofluoric acid solution of potassium fluosilicate at 3 ℃, and stirring for 2-4min to obtain a mixed solution;
(4) Placing the mixed solution in the step (3) in an ultrasonic water bath temperature control device (shown in figure 3), controlling the temperature of the water bath to be 6 ℃, simultaneously starting a stirring and ultrasonic generator, adjusting the frequency of ultrasonic waves to be 5kHz, starting to dropwise add a hydrofluoric acid solution of potassium bifluoride at the temperature of 3 ℃ after the temperature of the device is stable, wherein the dropwise adding speed is 6.5mL/s, the dropwise adding volume is 400mL, and continuously stirring and ultrasonically crystallizing for 10min at the ultrasonic frequency after the dropwise adding is finished;
(5) After crystallization is finished, dropwise adding hydrogen peroxide with the mass concentration of 25% until the system changes color, then closing the ultrasonic generator, controlling the water bath temperature to be 6 ℃, and stirring and aging for 10min;
(6) After aging is finished, washing the system by using acetone until the system becomes neutral, filtering, collecting solids, drying solid powder at the temperature of 80 ℃, and then sieving to obtain LED fluorescent powder; the structural formula is K 2 Si 0.95 F 6 :Mn 0.05 The SEM image of the obtained LED phosphor is shown in fig. 1.
Example 2
In the embodiment of the invention, the influence of the ultrasonic frequency in the step (4) is researched, 5 test examples are set in the embodiment, and the rest of operations are the same as those in the embodiment 1 except that the ultrasonic frequency in the step (4) is different; the ultrasonic frequencies of the test examples are shown in table 1;
table 1: ultrasonic frequency meter for test examples 1 to 5
| Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 |
| 10kHz | 20kHz | 30kHz | 40kHz | 50kHz |
Example 3
The influence of the addition amount of the potassium fluomanganate is researched in the embodiment of the invention, 3 test examples are set in the embodiment, and the rest operations are the same as those in the embodiment 1 except that the addition amount of the potassium fluomanganate is inconsistent; the potassium fluoromanganate of the test example is shown in table 2;
table 2: potassium fluoride addition scales for test examples 6-8
| Test example 6 | Test example 7 | Test example 8 |
| 7g | 8g | 9g |
Example 4
The embodiment of the invention researches the influence of the dropping speed, 4 test examples are set in the embodiment, and the rest of the operation is the same as that in the embodiment 1 except that the dropping speed is different; potassium fluoride of the test examples is shown in table 3;
table 3: dropping speed meter for test examples 9 to 12
| Test example 9 | Test example 10 | Test example 11 | Test example 12 |
| 2mL/s | 4mL/s | 8mL/s | 10mL/s |
Comparative example 1
The preparation method of the LED fluorescent powder of the comparative example of the invention comprises the following steps:
(1) Preparing a hydrofluoric acid solution of potassium bifluoride: adding potassium bifluoride into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of the potassium bifluoride, wherein the molar concentration of the potassium bifluoride is 2mol/L;
(2) Preparing a hydrofluoric acid solution of potassium fluosilicate: adding potassium fluosilicate into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of potassium fluosilicate, wherein the molar concentration of the potassium fluosilicate is 1.5mol/L;
(3) Measuring 2.5L of hydrofluoric acid with the mass concentration of 41%, adding 6g of potassium fluosilicate at 3 ℃, stirring for 2-4min until the solid is completely dissolved, adding the potassium fluosilicate into 200mL of hydrofluoric acid solution of potassium fluosilicate at 3 ℃, and stirring for 2-4min to obtain a mixed solution;
(4) Placing the mixed solution in the step (3) in a water bath temperature control device, controlling the temperature of the water bath to be 6 ℃, starting stirring, after the temperature of the device is stable, beginning to dropwise add a hydrofluoric acid solution of potassium bifluoride at the temperature of 3 ℃, wherein the dropwise adding speed is 6.5mL/s, the dropwise adding volume is 400mL, and after the dropwise adding is finished, continuing to stir and crystallize for 10min;
(5) After crystallization is finished, dropwise adding 25% hydrogen peroxide until the system changes color, keeping the water bath temperature at 6 ℃, and stirring and aging for 10min;
(6) After aging is finished, washing the system by using acetone until the system becomes neutral, filtering, collecting solids, drying solid powder at the temperature of 80 ℃, and then sieving to obtain LED fluorescent powder; the SEM image of the obtained LED phosphor is shown in fig. 2.
Comparative example 2
The preparation method of the LED fluorescent powder of the comparative example of the invention comprises the following steps:
(1) Preparing a hydrofluoric acid solution of potassium bifluoride: adding potassium bifluoride into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of the potassium bifluoride, wherein the molar concentration of the potassium bifluoride is 2mol/L;
(2) Preparing a hydrofluoric acid solution of potassium fluosilicate: adding potassium fluosilicate into hydrofluoric acid with the mass concentration of 41% to prepare a hydrofluoric acid solution of potassium fluosilicate, wherein the molar concentration of the potassium fluosilicate is 1.5mol/L;
(3) Measuring 2.5L of 41% hydrofluoric acid solution, adding 6g of potassium fluosilicate at 3 ℃, stirring for 2-4min until the solid is completely dissolved, adding the potassium fluosilicate into 200mL of potassium fluosilicate hydrofluoric acid solution at 3 ℃, and stirring for 2-4min to obtain a mixed solution;
(4) Placing the mixed solution in the step (3) in ultrasonic water bath temperature control equipment, controlling the temperature of the water bath to be 6 ℃, simultaneously starting stirring and an ultrasonic generator, adjusting the frequency of ultrasonic waves to be 5kHz, starting to dropwise add a hydrofluoric acid solution of potassium bifluoride at the temperature of 3 ℃ after the temperature of the equipment is stable, wherein the dropwise adding speed is 6.5mL/s, the dropwise adding volume is 400mL, and continuously stirring and ultrasonically crystallizing for 10min at the ultrasonic frequency after the dropwise adding is finished;
(5) After crystallization is finished, dropwise adding 25% hydrogen peroxide until the system changes color, then washing with acetone until the system becomes neutral, filtering, collecting solid, drying solid powder at the temperature of 80 ℃, and then sieving to obtain the LED fluorescent powder.
Comparative example 3
The only difference between the preparation process of the LED phosphor of the comparative example of the present invention and that of example 1 is that the frequency of ultrasound was controlled to be 80kHz.
Comparative example 4
The only difference between the preparation process of the LED fluorescent powder of the comparative example of the invention and the preparation process of the LED fluorescent powder of the example 1 is that in the step (4), the temperature of the water bath is controlled to be 18 ℃.
Comparative example 5
The only difference between the preparation process of the LED fluorescent powder of the comparative example of the invention and the preparation process of the LED fluorescent powder of the example 1 is that in the step (2), the molar concentration of potassium fluosilicate in the hydrofluoric acid solution of potassium fluosilicate is 3mol/L.
Comparative example 6
The only difference between the preparation process of the LED fluorescent powder of the comparative example of the invention and the preparation process of the example 1 is that the added amount of the potassium fluomanganate is 12g.
Examples of effects
Observing and recording the LED fluorescent powder prepared in the examples 1-4 and the comparative examples 1-6 under a scanning electron microscope, simultaneously detecting the particle size distribution of the LED fluorescent powder, and simultaneously testing the luminous intensity of the obtained LED fluorescent powder and the amount of the powder for packaging the LED lamp beads, wherein the structural statistics of the test are shown in a table 4;
amount of powder for encapsulation: the method comprises the steps of using a 2835 450-457nm wavelength blue light chip, using LED aluminate yellow powder with the peak wavelength of 534nm, preparing LED fluoride red fluorescent powder and AB glue into fluorescent glue, and packaging into 2700K patch lamp beads by using packaging equipment. The using proportion of the LED fluoride red fluorescent powder in the fluorescent glue is the packaging powder amount of each embodiment of the patent, wherein the packaging powder amount of the LED fluoride red fluorescent powder of the calibration embodiment 1 is 100%.
Relative light efficiency, the LED fluoride red fluorescent powder synthesized in the embodiment 1 is packaged into a 2700K patch lamp bead, and a light efficiency value tested by a remote photoelectric LED light, color and electricity comprehensive testing system HASS-2000 spectrometer is set as 100 percent, compared with light efficiency relative values of other embodiments.
Table 4: test data table of LED phosphors prepared in examples 1 to 4 and comparative examples 1 to 6
As can be seen from Table 4, D of the LED phosphor prepared by the technical scheme of the present invention in examples 1-4 50 The particle size of the LED fluorescent powder is 3.72-21.4 mu m, and the P value is 0.86-0.98, so that the LED fluorescent powder prepared by the invention has smaller particle size and good distribution and concentration; in addition, as can be seen from table 4, the yield of the phosphor obtained by the technical scheme provided by the invention is high, the yield is over 88.4%, the obtained product has high relative brightness, and the amount of the packaging powder is small;
in addition, it can be seen from examples 1 and 2 and comparative example 1 of the present invention that whether ultrasound is used and the frequency of the ultrasound both affect the yield of the product, the particle size and the distribution uniformity, and when ultrasound is not used, the particle size of the prepared powder is significantly increased and the distribution uniformity is significantly reduced; when the ultrasonic frequency is too high, the particle size of the product is too small, so that the structure is unstable, and the product is easily oxidized in the synthesis process to cause synthesis failure;
as can be seen from the examples 1, 3 and 6, the change of the addition amount of the potassium fluomanganate can greatly reduce the powder consumption of the product, and simultaneously can cause the quenching of the concentration of the excitation center, thus causing the serious reduction of the luminescence property of the product;
as can be seen from example 1 and comparative example 2 of the present invention, when there is no aging after the crystallization quenching reaction, the product yield is significantly decreased, and at the same time, the luminescence property of the product is severely decreased;
it can be seen from example 1 and comparative example 4 of the present invention that when the temperature of the water bath temperature control during the crystallization process is set too high, the particle size of the product will be significantly increased, the powder concentration will be significantly deteriorated, and the powder consumption of the product will also be increased;
it can be seen from example 1 and comparative example 5 of the present invention that when the molar concentration of potassium fluorosilicate in the hydrofluoric acid solution of potassium fluorosilicate is too high, the particle size of the product is reduced, but a large amount of heterogeneous phase is generated during the synthesis process, which causes a serious reduction in the luminescence properties of the product and increases the powder consumption of the finished product.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. The LED fluorescent powder is characterized in that the structural formula of the LED fluorescent powder is A 2 (MF 6 ):Mn 4+ Of which D is 50 ＝3.5-21.5μm，D 10 ≥1.0μm，D 90 Less than or equal to 31.65 mu m and a particle size distribution coefficient P = (D) 90 -D 10 )/D 50 ≤1.0；
Wherein A comprises Li, na, K, rb, cs and NH 4 M comprises any one of Ge, si, sn, ti, zr and Sc;
the preparation method of the LED fluorescent powder comprises the following steps:
(1) Adding a hydrofluoric acid solution of fluorosilicate with the temperature of 0-6 ℃ into a hydrofluoric acid solution of hexafluoromanganate with the temperature of 0-6 ℃, and stirring and mixing to obtain a mixed solution;
(2) Placing the mixed solution at 2-10 ℃ for ultrasonic stirring, and dropwise adding hydrofluoric acid solution of fluorohydrogenate at the dropwise adding speed of 2-10 mL/s;
(3) After the dropwise addition is finished, ultrasonically stirring, crystallizing, quenching, aging, washing and drying to obtain the LED fluorescent powder;
in the step (3), the ultrasonic frequency is 5-50kHz; the crystallization temperature is 2-10 ℃, and the crystallization time is 8-12min; the aging temperature is 2-10 deg.C, and the aging time is 2-8min.
2. The LED fluorescent powder as claimed in claim 1, wherein in the step (1), the mass-to-volume ratio of the hexafluoromanganate to the hydrofluoric acid solution is (6-9) g:2.5L.
3. The LED phosphor as claimed in claim 1, wherein in the step (2), the frequency of the ultrasound is 5 to 50kHz.
4. The LED phosphor as claimed in claim 1, wherein in the step (2), the molar concentration of the fluorohydrogenate in the hydrofluoric acid solution of the fluorohydrogenate is 1.8-2.2mol/L.
5. Use of the LED phosphor of claim 1 in LED products.
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