CN105295906B - The preparation method and product of LED red fluorescence powders and combinations thereof and application - Google Patents
The preparation method and product of LED red fluorescence powders and combinations thereof and application Download PDFInfo
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- CN105295906B CN105295906B CN201510885206.1A CN201510885206A CN105295906B CN 105295906 B CN105295906 B CN 105295906B CN 201510885206 A CN201510885206 A CN 201510885206A CN 105295906 B CN105295906 B CN 105295906B
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Abstract
The present invention provides a kind of preparation method of LED red fluorescence powders, which is represented by general formula I：A2M1‑xF6:xMn4+(I), wherein, A is selected from one or both of K and Na, and M is selected from one or both of Si and Ti, x=0.02~0.3；The preparation method includes the following steps：(1) by A2MnF6It is dissolved in hydrofluoric acid, obtains solution containing Mn；(2) by A2MF6It is added in the solution containing Mn that step (1) obtains, adds in dispersant, cool down ageing after abundant heating stirring, and solid is obtained by filtration, and then the solid described in a small amount of pure water and organic solvent washing, drying obtain the LED red fluorescence powders successively.The preparation method of the composition containing the fluorescent powder is additionally provided, uses LED red fluorescence powders made from this method or the purposes containing its composition and the fluorescent powder or containing its composition in LED backlight element or equipment.
Description
Technical field
The present invention relates to a kind of preparation methods of fluorescent powder, and in particular to a kind of preparation method of LED red fluorescence powders contains
There is the preparation method of the composition of the LED red fluorescence powders, using LED red fluorescence powders made from above-mentioned preparation method or contain
The composition of the LED red fluorescence powders and the LED red fluorescence powders in LED backlight element or are set containing its composition
Purposes in standby.
Background technology
Light emitting diode (Light-Emitting Diode, referred to as LED) is a kind of to convert electrical energy into the half of luminous energy
Conducting electrons element.This electronic component occurred early in 1962, can only send out the feux rouges of low luminosity in early days, develop it later
His monochromatic version, the light that can be sent out even to this day have spread visible ray, infrared ray and ultraviolet light, range be also raised to compared with
High level is referred to as " forth generation light source ".It is extensive since it has many advantages, such as energy-saving and environmental protection, safety, long lifespan
Applied to the various aspects in industry and life, including indicating, showing, decorating, the fields such as backlight, general lighting.
For the wide white LED lamp of application, at present there are mainly three types of the methods of realization white light LEDs：(1) in indigo plant
Optical chip yellow fluorescent powder applied over, mainly YAG:Ce is mixed into white light using blue light and yellow light；(2) by red, green, blue
The chip portfolio encapsulation of three kinds of colors, chip, which shines, is directly mixed into white light；(3) red, green, blue is excited with black light chip
The fluorescent powder of three kinds of colors is mixed into white light.In these three methods, the 1st kind of method is presently most ripe and mainstream side
Method, but the product colour rendering index of this method is relatively low, generally 70 or so, colour temperature is higher, generally in more than 5500K, with human eye
There are certain deviations for optimum visual requirement, it is therefore desirable to mix a certain amount of red fluorescence powder.And other two methods are also required to
Using red fluorescence powder, to send out required feux rouges.In addition to this, also can in the LED light source or device of many other types
Use red fluorescence powder.Therefore, there are the larger market demands for red fluorescence powder for LED industry.
Currently on the market better performances, using more mature red fluorescence powder be mainly rear-earth-doped nitride or nitrogen oxygen
Compound fluorescent powder.But this fluorescent powder needs rear-earth-doped, ingredient requirement is more special, usually high temperature and pressure is needed to prepare, system
Standby condition is harsh.Not only high energy consumption, yield rate is also relatively low, thus its production cost is high, price is very expensive.Therefore, exploitation is new
It the red fluorescence powder of component and improves the synthetic method of red fluorescence powder at this stage and receives the extensive concern of people.
Invention content
It is therefore an object of the present invention to improve the shortcoming for producing red fluorescence powder in the prior art, one kind is provided
The method for preparing LED red fluorescence powders in the short period at normal temperatures, it is simple for process, be not required to the harsh conditions such as high temperature and pressure,
It is suitble to industrialized production, and LED red fluorescence powders colour gamut obtained is wide, functional, has a extensive future.The present invention also carries
The preparation method of the composition containing the LED red fluorescence powders has been supplied, has used LED red fluorescence powders made from above-mentioned preparation method
Or composition and the LED red fluorescence powders or first in LED backlight containing its composition containing the LED red fluorescence powders
Purposes in part or equipment.
To achieve the above object, the present invention provides a kind of preparation method of LED red fluorescence powders, the LED red is glimmering
Light powder is represented by general formula I：
A2M1-xF6:xMn4+ (I)
Wherein, A be selected from one or both of K and Na, M be selected from one or both of Si and Ti, x=0.02~0.3,
Preferably, x=0.02~0.15, such as can be 0.02~0.07；
The preparation method includes the following steps：
(1) by A2MnF6It is dissolved in hydrofluoric acid, obtains solution containing Mn；
(2) by A2MF6It is added in the solution containing Mn that step (1) obtains, adds in appropriate dispersant, after abundant heating stirring
Cooling ageing, is obtained by filtration solid, and then the solid described in a small amount of pure water and organic solvent washing, drying successively, obtains described
LED red fluorescence powders；
Wherein, the A in step (1)2MnF6With the A in step (2)2MF6Between molar ratio be 0.02~0.3:1, preferably
It is 0.02~0.15:1, such as 0.02~0.07:1；A concentration of 60~80wt% of hydrofluoric acid in step (1), preferably 75
~80wt%, more preferably 80wt%.The inventors discovered that the Examples 1 to 4 of following article was shown, in other conditions not
In the case of change, the light efficiency highest of hydrofluoric acid concentration fluorescent powder obtained when being 80wt%.
Preparation in accordance with the present invention, wherein, in step (1), the A2MnF6Mass ratio with hydrofluoric acid is 1:10
~100.
Preparation in accordance with the present invention, wherein, in step (2), the dispersant can be the polymer of steric hindrance type
Dispersant, such as PVP, polyvinyl alcohol and polyethylene glycol or long-chain dispersant, such as oleic acid, neopelex
In it is one or more, but be not limited to several dispersants illustrated out；Preferably, the dispersant and A2MF6Mass ratio be
1:100~300, preferably 1:200~250.The inventors discovered that the glimmering of dispersant (such as PVP-K30) is not added with during preparation
Light powder particles are uneven, and particle is more, and package brightness is relatively low.
Preparation in accordance with the present invention, wherein, in step (2), the stirring is at 1~80 DEG C preferably 10
It at~80 DEG C, is more preferably carried out at 60 DEG C, the time of stirring is 5~60min, preferably 20~60min.Preferably, institute
It is at 1~80 DEG C to state ageing, is preferably carried out at 5 DEG C, and the time of ageing is 5~300min, preferably 60~90min.
Preparation in accordance with the present invention, wherein, in step (2), the organic solvent is selected from ethyl alcohol, isopropanol and third
It is one or more in ketone.Preferably, the temperature of the drying is 50~150 DEG C, preferably 80~100 DEG C.
Preparation in accordance with the present invention, wherein, the A in step (1)2MnF6It is to be prepared according to step (1a)：
(1a) is by AMnO4It is dissolved in hydrofluoric acid with KF, hydrogen peroxide is added dropwise, filtered, wash after reaction, drying, obtaining
A2MnF6.Wherein it is possible to be washed using organic solvent, these organic solvents can be alcohols solvent, ketones solvent and ethers
It is one or more in solvent, preferably ethyl alcohol, isopropanol, acetone etc..Drying can be in 50~100 DEG C, preferably 60~80
DEG C, such as carried out at 70 DEG C.
Preparation in accordance with the present invention, wherein, in step (1a), AMnO4Mass ratio between hydrofluoric acid is 1:
10~15, it is preferable that a concentration of 35~45wt% of the hydrofluoric acid, preferably 38wt%.
Preparation in accordance with the present invention, wherein, in step (1a), a concentration of 20~40wt% of the hydrogen peroxide,
Preferably 30wt%；Preferably, the AMnO4Mass ratio with hydrogen peroxide is 1:1~2.5, preferably 1:1.2~1.5.
The present invention also provides a kind of preparation method of the composition containing fluorescent powder, the composition is included using the present invention
Above-mentioned preparation method made from LED red fluorescence powders；The preparation method includes：It is prepared using the above method of the present invention
LED red fluorescence powders and the LED red fluorescence powders are mixed with solid or liquid medium.
Solid or liquid medium in the present invention, as long as not damaging the performance of the fluorescent powder in the range of realization purpose, then
It is not particularly limited.Such as curable material can be used.Curable material is a kind of flow-like (such as liquid or gel state)
Material cures due to certain curing process.One kind can be used only in curable material, that can make in any combination with ratio
Use two or more.The curable material can also provide additional effect, such as light-emitting component (such as excitaton source) is sent out
The light gone out is guided to fluorescent powder.The curable material can be inorganic based material, such as metal alkoxide, pass through sol-gal process will
The solution that solution hydrolytie polycondensation containing ceramic precursor polymer or metal alkoxide forms, inorganic system's material after said combination curing
Expect (such as inorganic based material with siloxanes key) etc.；May be organic based material, such as thermoplastic resin, thermosetting property tree
Fat, light-cured resin are specifically as follows acrylic resins, polystyrene, the styrene-propenes such as poly- (methyl) methyl acrylate
The styrene resins such as lonitrile copolymer, polycarbonate resin, polyester resin, phenoxy resin, butyral resin, polyvinyl alcohol, ethyl
The cellulose-based resins such as cellulose, cellulose acetate, cellulose acetate-butyrate, epoxy resin, phenol resin, organic siliconresin etc..
The present invention also provides LED red fluorescence powders made from the above-mentioned preparation method for using the present invention or containing fluorescent powder
Composition, the LED red fluorescence powders have emission peak in the wave-length coverage of 610~650nm, preferably there is transmitting at 636nm
Peak.
The present invention also provides LED red fluorescence powders made from the above-mentioned preparation method for using the present invention, use the present invention
The above-mentioned preparation method composition containing fluorescent powder obtained or LED red fluorescence powders provided by the invention or the present invention provide
Purposes of the composition containing fluorescent powder in LED backlight element or device.
Technical solution provided by the invention can be efficiently synthesized LED red fluorescence powders, technique at relatively low temperatures
Simply, preparation condition is mild, easy to operate, production equipment is required relatively low.Use Mn4+Excitation is excited instead of rare earth ion, former
Material is cheap and easy to get, and compared with conventional LED nitride phosphors, production cost is greatly reduced, economic effect higher.It is prepared
LED red fluorescence powders good dispersion, transmitting peak shape it is sharp, colour gamut is wide, excitation purity is high, available for LED backlight field.This
Outside, physicochemical properties are stablized, and are easy to preserve for a long time.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail with reference to attached drawing, wherein：
Fig. 1 shows the X-ray diffractogram and standard card of LED red fluorescence powders made from embodiment 1.
Fig. 2 shows SEM (scanning electron microscope) pictures of LED red fluorescence powders made from embodiment 1.
Fig. 3 shows the spectrogram of LED red fluorescence powders made from embodiment 1.Wherein, excitation wavelength 460nm, transmitted wave
Long 636nm.The emission peak of 636nm is Mn4+'s2Eg→4A2Conversion, it was demonstrated that Mn4+Successfully adulterate.
Fig. 4 shows the SEM pictures of LED red fluorescence powders made from comparative example 1.
Fig. 5 shows the SEM pictures of LED red fluorescence powders made from comparative example 2.
Fig. 6 shows the X-ray diffractogram and standard card of LED red fluorescence powders made from embodiment 9.
Fig. 7 shows the SEM pictures of LED red fluorescence powders made from embodiment 9.
Fig. 8 shows the spectrogram of LED red fluorescence powders made from embodiment 9.
Specific embodiment
It is further illustrated the present invention below by specific embodiment, it should be understood, however, that, these embodiments are only
It is used for specifically describing in more detail, and is not to be construed as limiting the present invention in any form.
This part carries out general description to the material and test method that are arrived used in present invention experiment.Although it is
It is it is known in the art that still the present invention still uses up herein to realize many materials and operating method used in the object of the invention
It may detailed description.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
A used in the present invention2MnF6It can be prepared according to the method that existing technical literature is recorded, it can also be according to this hair
It is prepared by the method for bright offer.
It for example, can be according to New Experimental Chemistry Series#8, " Synthesis of
Inorganic Compound III ", Maruzen Co., page 1166, described in 1977 the step of, prepares K2MnF6：By chloroethene
The reaction vessel of olefine resin is divided into two chambers with the intermediate bulkhead of fluororesin amberplex.It is being ion exchanged what film separated
Platinum sheet is installed as anode and cathode in two chambers.Will wherein anode be sent to dissolved with the hydrofluoric acid aqueous solution of manganese (II) fluoride
In the chamber of side, and hydrofluoric acid aqueous solution is sent in cathode side cavity.By power supply be connected to electrode in the voltage of 3V and
It is electrolysed under the electric current of 0.75A.At the end of electrolysis, the hydrofluoric acid aqueous solution containing saturated level potassium fluoride is added with excessive
Enter into the reaction solution of anode side cavity, yellow solid product is consequently formed, filtered and as K2MnF6Recycling.
Embodiment 1
The present embodiment is used for the preparation method for illustrating the LED red fluorescence powders of the present invention and its using made from this method
LED red fluorescence powders.
(1a) is by 3.5g KMnO4It is dissolved in 50g 38wt% hydrofluoric acid with 1.3g KF, is added dropwise 4.5g 30wt%'s
Hydrogen peroxide is filtered after reaction, is washed using ethyl alcohol, is then dried at 70 DEG C, obtains the K of 5.2g2MnF6。
(1) 0.5g (~0.002mol) K is weighed2MnF6It is dissolved in the hydrofluoric acid of 50g 60wt%, obtains solution containing Mn.
(2) by 22.3g K2SiF6(~0.1mol) it is added to (purchased from KeYu fluorine industrial chemicals Co., Ltd of Changshu City)
It states in solution containing Mn, adds in 0.1 gram of PVP-K30,20min is stirred at 60 DEG C, is then cooled at 5 DEG C and is aged 60min, filter
Solid is obtained, then washs the solid with a small amount of pure water and ethyl alcohol successively, is dried at 90 DEG C, obtains 14.5g
K2Si0.98F6:0.02Mn4+Powder.
The XRD of the powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
Figure shows that it has and K (see Fig. 1)2SiF6Corresponding crystal structure.
It is measured using scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.)
The SEM pictures (see Fig. 2) of gained powder show the powder mainly by the cube of the relatively uniform size with about 25~30 μm
Particle is formed.
Above-mentioned powder is measured 460nm's using Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength (see Fig. 3) under excitation wavelength, there is apparent emission peak at 636nm.The emission peak of 636nm is Mn4+'s2Eg→4A2Conversion, it was demonstrated that Mn4+Successfully adulterate.
Embodiment 2
The present embodiment is used for the preparation method for illustrating the LED red fluorescence powders of the present invention and its using made from this method
LED red fluorescence powders.
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the dense of the hydrofluoric acid in step (1)
It spends for 70wt%, obtains 14.5g K2Si0.98F6:0.02Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 3
The present embodiment is used for the preparation method for illustrating the LED red fluorescence powders of the present invention and its using made from this method
LED red fluorescence powders.
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the dense of the hydrofluoric acid in step (1)
It spends for 75wt%, obtains 14.5g K2Si0.98F6:0.02Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 4
The present embodiment is used for the preparation method for illustrating the LED red fluorescence powders of the present invention and its using made from this method
LED red fluorescence powders.
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the dense of the hydrofluoric acid in step (1)
It spends for 80wt%, obtains 14.6g K2Si0.98F6:0.02Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 5
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the K in step (2)2SiF6Use
It measures as 8.9g (~0.04mol), obtains 5.7g K2Si0.95F6:0.05Mn4+Powder.Pass through x-ray powder diffraction instrument (model D8-
ADVANCE, purchased from German Brooker company) XRD diagram of gained powder is measured, show that it has and K2SiF6Corresponding crystal knot
Structure.Gained powder is measured using scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.)
Last SEM pictures show that the powder is mainly made of the cubic granules of the relatively uniform size with about 25~30 μm.Using glimmering
Photothermal spectroscopic analyzer (model USB4000, purchased from Ocean Optics of the U.S.) measures hair of the above-mentioned powder under the excitation wavelength of 460nm
Ejected wave is long, there is apparent emission peak at 636nm.
Embodiment 6
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the K in step (2)2SiF6Use
It measures as 5.6g (~0.025mol), obtains 3.7g K2Si0.92F6:0.08Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 7
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the K in step (2)2SiF6Use
It measures as 4g (~0.018mol), obtains 2.6g K2Si0.89F6:0.11Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 8
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the K in step (2)2SiF6Use
It measures as 3.2g (~0.0145mol), obtains 2g K2Si0.86F6:0.14Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram shows that it has and K2SiF6Corresponding crystal structure.Use scanning electron microscope (model KYKY2800B, purchased from BeiJing ZhongKe
Tech technology Development Co., Ltd) gained powder SEM pictures are measured, show the powder mainly by having about 25~30 μm
The cubic granules of relatively uniform size are formed.It uses Fluorescence Spectrometer (model USB4000, purchased from Ocean Optics of the U.S.)
Launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent emission peak at 636nm.
Embodiment 9
The present embodiment is used for the preparation method for illustrating the LED red fluorescence powders of the present invention and its using made from this method
LED red fluorescence powders.
The preparation method that the present embodiment uses is same as Example 1, and the difference lies in the doping matrixes in step (2) to be
K2TiF6(being purchased from Nantong Venus fluorine chemistry Co., Ltd), obtains 15g K2Ti0.98F6:0.02Mn4+Powder.
Gained powder is measured by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company)
XRD diagram (see Fig. 6) shows that it has and K2TiF6Corresponding crystal structure.Using scanning electron microscope, (model KYKY2800B, is purchased from
Beijing KYKY Technology Development Co., Ltd.) measure gained powder SEM pictures (see Fig. 7), show the powder mainly by
Sheet-like particle with about 30~40 μm of relatively uniform sizes is formed.Use Fluorescence Spectrometer (model USB4000, purchased from U.S.
Ocean Optics of state) launch wavelength of the above-mentioned powder under the excitation wavelength of 460nm is measured, there is apparent hair at 634nm
Penetrate peak (see Fig. 8).
Comparative example 1
This comparative example is used to be compared with the preparation method and products obtained therefrom of embodiment.
The preparation method that this comparative example uses is same as Example 1, and the difference lies in the dense of the hydrofluoric acid in step (1)
It spends for 49wt%, obtains 14.8g K2Si0.98F6:0.02Mn4+Powder.
It is measured using scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.)
Gained powder SEM pictures (see Fig. 4) show that the powder is made of the non-uniform particle of 1~4 μ m in size, and granule-morphology is very not
Rule.
Comparative example 2
This comparative example is used to be compared with the preparation method and products obtained therefrom of embodiment.
The preparation method that this comparative example uses is same as Example 1, and the difference lies in be not added with dispersant in step (2)
PVP-K30 obtains 14.8g K2Si0.98F6:0.02Mn4+Powder.
It is measured using scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.)
Gained powder SEM pictures (see Fig. 5) show that the powder is made of the non-uniform particle of 5~30 μ m in size, and granule-morphology is very not
Rule, chopped cooked entrails of sheep particle are more.
Inventor is respectively packaged fluorescent powder made from above example and comparative example, and packaged type is：Using this
Fluorescent powder and the yellowish green powder hybrid package of nitrogen oxides use ultraviolet-visible-near-infrared spectrum analysis system instrument in blue chip
Device (model PMS-80, purchased from Hangzhou distant place Photoelectric Co., Ltd.) measures respectively, as a result as follows：
Colour temperature, chromaticity coordinate, light efficiency and the colour rendering index of fluorescent powder prepared by 1 embodiment and comparative example of table
| Serial number | Colour temperature (K) | CIE-X | CIE-Y | Light efficiency (lm/w) | Colour rendering index |
| Embodiment 1 | 17181 | 0.2546 | 0.2695 | 106 | 82 |
| Embodiment 2 | 17318 | 0.2539 | 0.2702 | 108 | 81 |
| Embodiment 3 | 17298 | 0.2542 | 0.2700 | 111 | 82 |
| Embodiment 4 | 17029 | 0.2545 | 0.2696 | 112 | 83 |
| Embodiment 5 | 17203 | 0.2543 | 0.2698 | 110 | 83 |
| Embodiment 6 | 17191 | 0.2547 | 0.2694 | 109 | 84 |
| Embodiment 7 | 17302 | 0.2538 | 0.2703 | 114 | 82 |
| Embodiment 8 | 17298 | 0.2540 | 0.2701 | 111 | 81 |
| Comparative example 1 | 17189 | 0.2546 | 0.2695 | 100 | 79 |
| Comparative example 2 | 17182 | 0.2544 | 0.2697 | 103 | 81 |
Data above shows that the luminous efficiency of Examples 1 to 8 is superior to the property of comparative example 1 and 2, wherein embodiment 4 and 7
It can show more prominent.It can thus be seen that the luminescent properties of fluorescent powder of the present invention can be significantly improved by improving hydrofluoric acid concentration.
In addition, Mn4+Doping also has an impact fluorescent powder performance, due to concentration quenching effect, with Mn4+The increase of doping,
Luminous efficiency first increases to be reduced afterwards.Non- bonus point powder PVP-K30 in comparative example 2, the fluorescent powder grain of preparation is uneven, particle
More, package brightness is relatively low.
Although present invention has been a degree of descriptions, it will be apparent that, do not departing from the spirit and scope of the present invention
Under the conditions of, the appropriate variation of each condition can be carried out.It is appreciated that the present invention is not limited to the embodiment, and it is attributed to right
It is required that range, include the equivalent replacement of each factor.
Claims (36)
1. a kind of preparation method of LED red fluorescence powders, which is characterized in that the LED red fluorescence powders are represented by general formula I：
A2M1-xF6:xMn4+(I)
Wherein, A is selected from one or both of K and Na, and M is selected from one or both of Si and Ti, x=0.02~0.3；
The preparation method includes the following steps：
(1) by A2MnF6It is dissolved in hydrofluoric acid, obtains solution containing Mn；
(2) by A2MF6It being added in the solution containing Mn that step (1) obtains, adds in dispersant, cool down ageing after abundant heating stirring,
Solid is obtained by filtration, then it is glimmering to obtain the LED red for the solid described in a small amount of pure water and organic solvent washing, drying successively
Light powder；
Wherein, the A in step (1)2MnF6With the A in step (2)2MF6Between molar ratio be 0.02~0.3:1；In step (1)
Hydrofluoric acid a concentration of 60~80wt%；Dispersant described in step (2) is PVP.
2. preparation method according to claim 1, which is characterized in that x=0.02~0.15.
3. preparation method according to claim 1, which is characterized in that the A in the step (1)2MnF6With in step (2)
A2MF6Between molar ratio be 0.02~0.15:1.
4. preparation method according to claim 1, which is characterized in that a concentration of 75 of hydrofluoric acid in the step (1)
~80wt%.
5. preparation method according to claim 1, which is characterized in that hydrofluoric acid in the step (1) it is a concentration of
80wt%.
6. preparation method according to claim 1, which is characterized in that in step (1), the A2MnF6With hydrofluoric acid
Mass ratio is 1:10~100.
7. preparation method according to claim 1, which is characterized in that the dispersant and A2MF6Mass ratio be 1:100
~300.
8. preparation method according to claim 1, which is characterized in that the dispersant and A2MF6Mass ratio be 1:200
~250.
9. preparation method according to claim 1, which is characterized in that it is described to stir what is carried out at 1~80 DEG C, it is described to stir
The time mixed is 5~60min.
10. preparation method according to claim 1, which is characterized in that the stirring carries out at 10~80 DEG C.
11. preparation method according to claim 1, which is characterized in that the stirring carries out at 60 DEG C.
12. preparation method according to claim 1, which is characterized in that the time of the stirring is 20~60min.
13. preparation method according to claim 1, which is characterized in that the ageing carries out at 1~80 DEG C, institute
Digestion time is stated as 5~300min.
14. preparation method according to claim 1, which is characterized in that the ageing carries out at 5 DEG C.
15. preparation method according to claim 1, which is characterized in that the digestion time is 60~90min.
16. preparation method according to claim 1, which is characterized in that in step (2), the organic solvent is selected from second
It is one or more in alcohol, isopropanol and acetone.
17. preparation method according to claim 16, which is characterized in that in step (2), the temperature of the drying is 50
~150 DEG C.
18. preparation method according to claim 16, which is characterized in that in step (2), the temperature of the drying is 80
~100 DEG C.
19. the preparation method according to any one of claim 1 to 18, which is characterized in that the A in step (1)2MnF6It is
It is prepared according to step (1a)：
(1a) is by AMnO4It is dissolved in hydrofluoric acid with KF, hydrogen peroxide is added dropwise, filtered, wash after reaction, drying, obtaining
A2MnF6。
20. preparation method according to claim 19, which is characterized in that washed using organic solvent.
21. preparation method according to claim 20, which is characterized in that the organic solvent is alcohols solvent, ketone is molten
It is one or more in agent and ether solvent.
22. preparation method according to claim 20, which is characterized in that the organic solvent is ethyl alcohol, isopropanol and third
It is one or more in ketone.
23. preparation method according to claim 19, which is characterized in that the drying carries out at 50~100 DEG C.
24. preparation method according to claim 19, which is characterized in that the drying carries out at 60~80 DEG C.
25. preparation method according to claim 19, which is characterized in that in step (1a), AMnO4Between hydrofluoric acid
Mass ratio be 1:10~15.
26. preparation method according to claim 19, which is characterized in that in step (1a), the concentration of the hydrofluoric acid
For 35~45wt%.
27. preparation method according to claim 19, which is characterized in that in step (1a), the concentration of the hydrofluoric acid
For 38wt%.
28. preparation method according to claim 19, which is characterized in that in step (1a), the concentration of the hydrogen peroxide
For 20~40wt%.
29. preparation method according to claim 19, which is characterized in that in step (1a), the concentration of the hydrogen peroxide
For 30wt%.
30. preparation method according to claim 19, which is characterized in that in step (1a), the AMnO4With hydrogen peroxide
Mass ratio be 1:1~2.5.
31. preparation method according to claim 19, which is characterized in that in step (1a), the AMnO4With hydrogen peroxide
Mass ratio be 1:1.2~1.5.
32. a kind of preparation method of the composition containing fluorescent powder, which is characterized in that the composition, which includes, uses claim 1
To LED red fluorescence powders made from the preparation method described in any one of 31；The preparation method includes：Use claim 1
LED red fluorescence powders are prepared to the method described in any one of 31 and the LED red fluorescence powders and solid or liquid are situated between
Matter mixes.
33. use LED red fluorescence powders made from the preparation method described in any one of claim 1 to 31, which is characterized in that
The LED red fluorescence powders have emission peak in the wave-length coverage of 610~650nm.
34. use the composition containing fluorescent powder made from the preparation method described in claim 32, which is characterized in that the fluorescence
Compound powder has emission peak in the wave-length coverage of 610~650nm.
35. LED red fluorescence powders according to claim 33, which is characterized in that the LED red fluorescence powders are in 636nm
There is emission peak at place.
36. the composition according to claim 34 containing fluorescent powder, which is characterized in that the composition containing fluorescent powder exists
There is emission peak at 636nm.
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