CN107163942A - Small particle cerium dropped yttrium aluminum garnet fluorescent material and method and application prepared by a kind of coprecipitation - Google Patents
Small particle cerium dropped yttrium aluminum garnet fluorescent material and method and application prepared by a kind of coprecipitation Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorescent material, small particle cerium dropped yttrium aluminum garnet fluorescent material and method and application prepared by a kind of coprecipitation are disclosed.Methods described is that yttrium nitrate, aluminum nitrate and cerous nitrate are configured to metal ion solution by (1) using water according to stoichiometric proportion；(2) metallic ion mixed liquor and precipitant solution are added drop-wise in surfactant alone simultaneously, the pH of control reaction solution is maintained at 7~9；(3) continue to stir after metal ion solution is dripped, ultrasonic disperse, ageing, suction filtration is washed, and is dried, calcining obtains presoma；(4) presoma and cosolvent are subjected to ball milling；In reducing atmosphere, the product after ball milling is calcined in 1200~1600 DEG C, washed, dries, obtains fluorescent material.The fluorescent material of the present invention has the advantages that grain diameter is small, pattern is regular, good dispersion, luminous efficiency high, stable chemical performance, for white light LEDs.
Description
Technical field
The invention belongs to the technical field of fluorescent material, it is related to a kind of fluorescent material that can be effectively excited by ultraviolet light and blue light
Preparation method, small particle cerium dropped yttrium aluminum garnet fluorescent material and its method that more particularly to prepared by a kind of coprecipitation, institute
State fluorescent material and be widely used in field of photovoltaic materials.
Background technology
Japanese Ya chemical companies realize breakthrough in blue light GaN technologies within 1993, next will in 1996
YAG:Ce3+Fluorescent material, which is coated on GaN blue leds, prepares white LED lamp, then by industrialization.Its preparation process be
Coating has certain thickness YAG on blue-light LED chip:Ce3+Fluorescent material, the blue light part that blue-ray LED is sent can excite Huang
Color fluorescent material excites obtained gold-tinted to be combined with that a part of blue light through fluorescent material and obtains white light so as to send gold-tinted.It is glimmering
Light powder is the critical material for preparing white light LEDs, therefore development of the progress to white light LEDs of fluorescent material technology of preparing plays crucial work
With.At present, YAG is prepared:Ce3+The method of fluorescent material mainly has solid phase method, sol-gal process, solvent-thermal method, combustion synthesis method, spray
Mist pyrolysismethod and coprecipitation.Solid phase method has technique simple to operation, the advantage that can be mass-produced；But lack there is also some
Point, such as requirement to material purity is high, calcining heat is high and time length, light-emitting phosphor intensity are low.Sol-gal process can
So that metal ion to be mixed in atom or molecular dimension, the thinner high-purity fluorescent material of prepared sizes at a lower temperature,
But the metal alkoxide needed for this method is expensive so that cost is significantly lifted and metal alkoxide has larger poison
Property, human and environment is caused harm in operating process；The volume of gel is excessive in preparation process, and small lot can only be carried out every time
Production, yield is relatively low.Solvent-thermal method can prepare YAG at a lower temperature:Ce3+Fluorescent material, it is to avoid its other party
High-temperature burning process in method, so that the agglomeration between alleviating powder, can prepare pattern rule, good dispersion and grain
The uniform fluorescent material in footpath, but the luminous intensity of its fluorescent material prepared is weaker, and hyperbaric environment is needed during simultaneous reactions,
This requirement just to equipment is higher, is unfavorable for mass production.Synthesis temperature required for combustion synthesis method synthetizing phosphor powder
Low, the diameter of particle prepared is smaller and is evenly distributed, synthetizing phosphor powder it is simple to operate, the reaction time is short, but use combustion
Burning method, which prepares fluorescent material and there is also some problems at present, to be needed to solve, such as easily reduces luminous intensity containing carbon in product, instead
The more unexpected and time that should be carried out is shorter, and this process is difficult control；Experiment is only suitable for the production of small lot, is unfavorable for industry
Metaplasia is produced.Spray pyrolysis due to during pyrolyzing synthesis fluorescent material reactant be in units of droplet one by one carry out
Reaction, therefore the powder prepared almost does not have agglomeration, the sphericity of particle is high, and epigranular is controllable and is distributed
It is narrower, be conducive to producing in enormous quantities；But it is due to that synthesis temperature is relatively low so that light-emitting phosphor intensity is relatively low, when rise synthesis temperature
The spheric granules prepared when spending, which is also easy to produce, to be collapsed and reunites together；Other the method is higher to equipment requirement, the technique of preparation
It is more complicated to limit its industrial applications.
YAG is produced in industry:Ce3+Fluorescent material, which has that particle diameter is big and uneven, calcining heat is high, luminous efficiency is low lacks
Point, therefore the requirement of white light LEDs is not well positioned to meet, also need further to improve luminous efficiency, reduction diameter of particle.The present invention
Cerium dropped yttrium aluminum garnet (the YAG that selection is prepared using coprecipitation:Ce3+) fluorescent material can preferably meet white light LEDs
It is required that.
The content of the invention
The technical problems to be solved by the invention are that have that particle diameter is big, granulated for the fluorescent material sold in the market
The deficiency that looks are irregular and luminous efficiency is low can produce the method for cerium dropped yttrium aluminum garnet fluorescent material in enormous quantities there is provided a kind of
That is coprecipitation.Fluorescent powder grain particle diameter (the D of this method production50) 2~5 μm, granule-morphology rule, good dispersion, luminous effect
It rate height, stable chemical performance, can effectively be excited by blue light, the complexity of technique can be reduced during white light LEDs enfeoffment dress,
Improve its yields.
Another object of the present invention is to provide the cerium dropped yttrium aluminum garnet fluorescent material prepared by the above method.
It is still another object of the present invention to provide the application of above-mentioned cerium dropped yttrium aluminum garnet fluorescent material.The cerium dopping yttrium
Aluminium garnet fluorescent material is used for white light LEDs.
The purpose of the present invention is achieved through the following technical solutions：
It is a kind of to be co-precipitated the method for preparing small particle cerium dropped yttrium aluminum garnet fluorescent material, comprise the following steps：
(1) preparation of metal ion solution：Using water by yttrium nitrate, aluminum nitrate and cerous nitrate according to Y2.96Ce0.04Al5O12
Middle stoichiometric proportion is configured to metallic ion mixed liquor；In step (1) purity of yttrium nitrate, aluminum nitrate and cerous nitrate be 3~
4N, the molar concentration of metal ion mixed liquor is 0.1~1.5molL-1；
(2) preparation of precipitating reagent：Ammoniacal liquor is mixed with ammonium bicarbonate soln, precipitant solution is obtained；The ammoniacal liquor
Concentration with ammonium bicarbonate soln is all 1~4molL-1, the volume ratio of the ammoniacal liquor and ammonium bicarbonate soln is 1:(1~3)；
(3) precipitant solution in the metallic ion mixed liquor in step (1) and step (2) is added drop-wise to alone simultaneously
In surfactant, by controlling the rate of addition of precipitant solution so that the pH of reaction solution is maintained at 7~9, metal ion
Mixed solution rate of addition is 5~15mLmin-1, react at normal temperatures；
(4) continue to stir 1~4h after metallic ion mixed liquor is dripped, then ultrasonic disperse, ageing, suction filtration, washing,
Dry, calcining obtains presoma；The temperature of the calcining is 500~800 DEG C；
(5) presoma and cosolvent are placed in ball-grinding machine and carry out ball milling, obtain the product after ball milling；In reducing atmosphere
In, the product after ball milling is calcined in 1200~1600 DEG C, washed, dries, obtains small particle cerium dropped yttrium aluminum garnet
Fluorescent material.
Surfactant described in step (3) is at least one in polyethylene glycol, ammonium sulfate and neopelex
Kind；The consumption of the surfactant is the 0.5~3% of yttrium nitrate, aluminum nitrate and cerous nitrate gross mass.
The condition of ultrasonic disperse described in step (4) be in 150~400W, 10~60min of ultrasonic disperse, be preferably in
250W ultrasonic disperses 30min, the time of the ageing is 8~12h；
The temperature dried described in step (4) is 50~120 DEG C, preferably 80 DEG C；
Calcination time described in step (4) is 1~3h.
Rotational speed of ball-mill described in step (5) is 100~500 revs/min, preferably 300 revs/min.
Ball-milling Time described in step (5) is 10~60min, and calcination time described in step (5) is 2~6h.
The temperature dried described in step (5) is 50~120 DEG C, preferably 90 DEG C.
Washing described in step (4) refers to be washed using deionized water and ethanol successively, is first washed with deionized
At least 3 times, then washed with ethanol 2~3 times.
Fluxing agent described in step (5) is sodium fluoride, calcirm-fluoride, magnesium fluoride, lithium fluoride, aluminum fluoride, ammonium fluoride, fluorination
At least one of cerium, barium fluoride, sodium molybdate and boric acid；
The consumption of fluxing agent described in step (5) is the 2~10% of cerium dropped yttrium aluminum garnet fluorescent material quality, the cerium
Doped yttrium aluminum garnet fluorescent powder quality is according to Y2.96Ce0.04Al5O12The consumption theoretical calculation of raw material obtain.
Reducing atmosphere described in step (5) be nitrogen hydrogen mixeding gas (wherein nitrogen volume is not less than 70%, not for
100%) a kind of, offer in ammonia or powdered carbon.
Washing refers to be washed using hot water described in step (5), and the temperature of hot water is 50~100 DEG C, preferably 80
℃.(80 DEG C are gone water to be easier to produce, and remaining impurity in the more high more washable deblooming powder of temperature, light-emitting phosphor performance gets over
It is good)；Washing times are 2~4 times.
The small particle cerium dropped yttrium aluminum garnet fluorescent material is obtained by above-mentioned preparation method.
When the present invention prepares fluorescent material using coprecipitation, because metal salt solution is carried out on atom or molecular level
Mixing, then uniformly precipitated in ensuing precipitation reaction, each component is uniformly mixed in obtained presoma.
Therefore it can prepare that purity is higher, particle diameter is smaller, evengranular fluorescent material at a lower temperature.Chemical coprecipitation is favourable
In improving powder reactivity, synthesis temperature is reduced, the fluorescent material of function admirable is easily prepared.
Compared with prior art, the present invention has advantages below and beneficial effect：
Because the method that the present invention prepares fluorescent material is coprecipitation, while with the addition of surfactant again so that each gold
Category ion can reach uniform mixing, the presoma uniform component of preparation on atom or molecular level；With 1500 DEG C of solid phase method
Calcining heat above is compared, and this method, which only needs 1300 DEG C or so, can obtain luminous intensity and luminous efficiency height, chemical property
Stabilization, good dispersion, granule-morphology rule and uniform, particle diameter (D50) 2~5 μm of cerium dropped yttrium aluminum garnet fluorescent material.We
The absolute luminescence efficiency of fluorescent material prepared by method reaches as high as 91%, more taller than general Commercial optical powder.In white light LEDs point
The complexity of technique can be reduced in encapsulation process, its yields is improved.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the gained cerium dropped yttrium aluminum garnet fluorescent material of embodiment 1；YAG is yttrium-aluminium-garnet in figure
Y3Al5O12；B- fluorescent material is the cerium dropped yttrium aluminum garnet fluorescent material of embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the gained cerium dropped yttrium aluminum garnet fluorescent material of embodiment 1；
Fig. 3 is the size distribution curve of the gained cerium dropped yttrium aluminum garnet fluorescent material of embodiment 1；
Fig. 4 is emission spectrum of the gained cerium dropped yttrium aluminum garnet fluorescent material of embodiment 1 under 460nm excitation wavelength.
Embodiment
The present invention is done with reference to embodiment and accompanying drawing and is further described in detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of method that co-precipitation prepares cerium dropped yttrium aluminum garnet fluorescent material, comprises the following steps：
(1) Y is pressed2.96Ce0.04Al5O12Stoichiometric proportion weigh yttrium nitrate 17.21g, aluminum nitrate 28.61g and cerous nitrate
0.26g, three kinds of nitric acid purity salts are all 99.9%；Each nitrate is dissolved in 150ml deionized water and is made into metal ion
Solution (0.8molL-1)；
(2) by ammoniacal liquor (3molL-1) and ammonium bicarbonate soln (1molL-1) according to volume ratio be 1：2 are mixed,
Obtain precipitant solution；
(3) under conditions of stirring (rotating speed is 500 revs/min), by metal ion solution in step (1) and step (2)
Middle precipitant solution (precipitant solution makes precipitation by metallic ion complete) is alone while be added drop-wise to 0.46g polyethylene glycol (metal nitre
The 1% of hydrochlorate gross mass, molecular weight 6000) in, metal ion solution rate of addition is 10mLmin-1, reaction temperature is normal temperature
By adjusting the drop rate of precipitant solution come constant (pH=8.0) of control ph in (25 DEG C), course of reaction；Metal from
Sub- solution continues to stir 1h, then the ultrasonic disperse 30min under 250W after dripping, and is aged 8h, suction filtration, then with deionized water and
After absolute ethyl alcohol is respectively washed 3 times, (>=12h) is dried in 80 DEG C, presoma is obtained；
(4) presoma is put into high temperature furnace, 2h is calcined at 600 DEG C, the presoma after being handled；After processing
Presoma is put into progress ball milling (ball in ball grinder together with fluxing agent (0.45g sodium fluoride (account for target product quality 5%))
The time of mill is 30min), the rotating speed of ball milling is 300 revs/min, obtains well mixed powder；
(5) in nitrogen hydrogen reduction atmosphere (15v%H2/ 85v%N2) in, well mixed powder is calcined into 4h, 80 in 1300 DEG C
The washing of DEG C deionized water, (>=12h) is dried in 90 DEG C, is crossed 300 mesh sieves, is obtained cerium dropped yttrium aluminum garnet fluorescent material.This implementation
Fluorescent powder grain particle diameter (D prepared by example50) 2.5 μm, pattern rule, good dispersion, luminous efficiency height (absolute quantum efficiency QY=
91%), stable chemical performance, can effectively be excited by blue light.The knot of cerium dropped yttrium aluminum garnet fluorescent material manufactured in the present embodiment
Structure is characterized with the performance test results as shown in figures 1-4.The XRD spectrum of the cerium dropped yttrium aluminum garnet fluorescent material of the present embodiment is such as
Shown in Fig. 1, scanning electron microscope (SEM) photograph is as shown in Fig. 2 size distribution curve is as shown in figure 3, transmitting light under 460nm excitation wavelength
Spectrum is as shown in Figure 4.
As can be seen from Figure 1 fluorescent material manufactured in the present embodiment is pure YAG crystalline phases, does not contain other impurities；From Fig. 3
Understand, fluorescent material particle diameter narrow distribution manufactured in the present embodiment, particle diameter is conducive to the encapsulation of white light LEDs at 2.5 μm or so；From
In Fig. 4 understand, phosphor emission intensity manufactured in the present embodiment is higher, can effectively be stimulated by blue light and send wave-length coverage compared with
Wide gold-tinted.
Embodiment 2
A kind of method that co-precipitation prepares cerium dropped yttrium aluminum garnet fluorescent material, comprises the following steps：
(1) Y is pressed2.96Ce0.04Al5O12Stoichiometric proportion weigh yttrium nitrate 17.21g, aluminum nitrate 28.61g and cerous nitrate
0.26g, three kinds of nitric acid purity salts are all 99.9%；It is molten that metal ion is made into the deionized water that nitrate is dissolved in 150ml
Liquid (0.8molL-1)；
(2) by ammoniacal liquor (3molL-1) and ammonium bicarbonate aqueous solution (1molL-1) according to volume ratio be 1：1 is mixed
Close, obtain precipitant solution；
(3) under conditions of stirring (rotating speed is 500 revs/min), by metal ion solution in step (1) and step (2)
Middle precipitant solution (precipitant solution makes precipitation by metallic ion complete) is alone while be added drop-wise to 0.46g neopelexes
In ((the 1% of metal nitrate gross mass)), metal ion solution rate of addition is 5mLmin-1, reaction temperature is normal temperature (25
DEG C), by adjusting the drop rate of precipitating reagent come constant (pH=7.5) of control ph, metal ion solution in course of reaction
Continue to stir 1h, then the ultrasonic disperse 30min under 250W after dripping, be aged 8h, suction filtration, then with deionized water and anhydrous second
After alcohol is respectively washed 3 times, (>=12h) is dried in 80 DEG C, presoma is obtained；
(4) presoma is put into high temperature furnace, 2h is calcined at 800 DEG C, the presoma after being handled；After processing
(0.36g sodium fluoride (account for target product quality 4%) and 0.18g boric acid (accounts for target product quality to presoma with fluxing agent
2%)) it is put into together in ball grinder and carries out ball milling (time of ball milling is 30min), the rotating speed of ball milling is 300 revs/min, is mixed
Close uniform powder；
(5) in nitrogen hydrogen reduction atmosphere (15v%H2/ 85v%N2) in, well mixed powder is calcined into 4h, 80 in 1400 DEG C
The washing of DEG C deionized water, (>=12h) is dried in 90 DEG C, is crossed 300 mesh sieves, is obtained cerium dropped yttrium aluminum garnet fluorescent material, its particle
Particle diameter (D50) 4.5 μm, pattern rule, good dispersion, luminous efficiency high (absolute quantum efficiency QY=89%), chemical property it is steady
Determine, can effectively be excited by blue light.
Embodiment 3
A kind of method that co-precipitation prepares cerium dropped yttrium aluminum garnet fluorescent material, comprises the following steps：
(1) Y is pressed2.96Ce0.04Al5O12Stoichiometric proportion weigh yttrium nitrate 17.21g, aluminum nitrate 28.61g and cerous nitrate
0.26g, three kinds of nitric acid purity salts are all 99.9%；It is molten that metal ion is made into the deionized water that nitrate is dissolved in 150ml
Liquid (0.8molL-1)；
(2) by ammoniacal liquor (3molL-1) and ammonium bicarbonate soln (1molL-1) according to volume ratio be 1：2 are mixed,
Obtain precipitant solution；
(3) under conditions of stirring (rotating speed is 500 revs/min), by metal ion solution in step (1) and step (2)
Middle precipitant solution (precipitant solution makes precipitation by metallic ion complete) is alone while be added drop-wise to 0.46g polyethylene glycol ((metal nitre
Hydrochlorate gross mass 1%)) in, metal ion solution rate of addition be 5mLmin-1, reaction temperature is normal temperature (25 DEG C), reaction
During by adjusting the drop rate of precipitating reagent come constant (pH=7.5) of control ph, after metal ion solution is dripped
Continue to stir 2h, then the ultrasonic disperse 30min under 250W, be aged 10h, suction filtration, then respectively washed with deionized water and absolute ethyl alcohol
Wash after 3 times, dry (>=12h) in 80 DEG C, obtain presoma；
(4) presoma is put into high temperature furnace, the presoma after being handled after 2h is calcined at 800 DEG C；After handling
Presoma (0.36g barium fluoride (account for target product quality 4%) and 0.18g boric acid (account for target product matter with fluxing agent
Amount 2%)) be put into together in ball grinder and carry out ball milling (time of ball milling be 30min), the rotating speed of ball milling is 300 revs/min, is obtained
To well mixed powder；
(5) in nitrogen hydrogen reduction atmosphere (20v%H2/ 80v%N2) in, well mixed powder is calcined into 4h, 80 in 1500 DEG C
The washing of DEG C deionized water, (>=12h) is dried in 90 DEG C, is crossed 300 mesh sieves, is obtained cerium dropped yttrium aluminum garnet fluorescent material, its particle
Particle diameter (D50) 4.0 μm, pattern rule, good dispersion, luminous efficiency high (absolute quantum efficiency QY=93%), chemical property it is steady
Determine, can effectively be excited by blue light.
Embodiment 4
A kind of method that co-precipitation prepares cerium dropped yttrium aluminum garnet fluorescent material, comprises the following steps：
(1) Y is pressed2.96Ce0.04Al5O12Stoichiometric proportion weigh yttrium nitrate 17.21g, aluminum nitrate 28.61g and cerous nitrate
0.26g, three kinds of nitric acid purity salts are all 99.9%；It is molten that metal ion is made into the deionized water that nitrate is dissolved in 150ml
Liquid (0.8molL-1)；
(2) by ammoniacal liquor (3molL-1) and ammonium bicarbonate soln (1molL-1) according to volume ratio be 1：2 are mixed,
Obtain precipitant solution；
(3) under conditions of stirring (rotating speed is 500 revs/min), by metal ion solution in step (1) and step (2)
Middle precipitant solution (precipitant solution makes precipitation by metallic ion complete) is alone while be added drop-wise to the ((metal of polyethylene glycol containing 0.46g
Nitrate gross mass 1%)) in, metal ion solution rate of addition be 15mLmin-1, reaction temperature is normal temperature (25 DEG C),
By adjusting the drop rate of precipitating reagent come constant (pH=8.5) of control ph in course of reaction；Metal ion solution is added dropwise
Continue to stir 2h after complete, then the ultrasonic disperse 30min under 250W, is finally aged 12h, suction filtration, with deionized water and anhydrous second
Alcohol respectively washing 3 times, dry (>=12h) in 80 DEG C, obtain presoma；
(4) presoma is put into high temperature furnace, the presoma after being handled after 2h is calcined at 700 DEG C；After handling
Presoma be put into together with fluxing agent (0.54g barium fluoride (account for target product quality 6%)) in ball grinder and carry out ball milling
(time of ball milling is 30min), the rotating speed of ball milling is 300 revs/min, obtains well mixed powder；
(5) in nitrogen hydrogen reduction atmosphere (20v%H2/ 80v%N2) in, well mixed powder is calcined into 4h, 80 in 1500 DEG C
The washing of DEG C deionized water, (>=12h) is dried in 90 DEG C, is crossed 300 mesh sieves, is obtained cerium dropped yttrium aluminum garnet fluorescent material, its particle
Particle diameter (D50) 3.0 μm, pattern rule, good dispersion, luminous efficiency high (absolute quantum efficiency QY=90%), chemical property it is steady
Determine, can effectively be excited by blue light.
Embodiment 5
A kind of method that co-precipitation prepares cerium dropped yttrium aluminum garnet fluorescent material, comprises the following steps：
(1) Y is pressed2.96Ce0.04Al5O12Stoichiometric proportion weigh yttrium nitrate 17.21g, aluminum nitrate 28.61g and cerous nitrate
0.26g, three kinds of nitric acid purity salts are all 99.9%；It is molten that metal ion is made into the deionized water that nitrate is dissolved in 150ml
Liquid (0.8molL-1)；
(2) by ammoniacal liquor (3molL-1) and ammonium bicarbonate soln (1molL-1) according to volume ratio be 1：1 is mixed,
Obtain precipitant solution；
(3) under conditions of stirring (rotating speed is 500 revs/min), by metal ion solution in step (1) and step (2)
Middle precipitant solution (precipitant solution makes precipitation by metallic ion complete) is alone while be added drop-wise to the ((metal of polyethylene glycol containing 0.46g
Nitrate gross mass 1%)) in, metal ion solution rate of addition be 15mLmin-1, reaction temperature is normal temperature (25 DEG C),
By adjusting the drop rate of precipitating reagent come constant (pH=8.5) of control ph in course of reaction, metal ion solution is added dropwise
Continue to stir 4h, then the ultrasonic disperse 30min under 250W after complete, be aged 12h, suction filtration, then with deionized water and absolute ethyl alcohol
After respectively washing 3 times, (>=12h) is dried in 80 DEG C, presoma is obtained；
(4) presoma is put into high temperature furnace, the presoma after being handled after 2h is calcined at 600 DEG C；After handling
Presoma be put into together with fluxing agent (0.54g barium fluoride (account for target product quality 6%)) in ball grinder and carry out ball milling
(time of ball milling is 30min), the rotating speed of ball milling is 300 revs/min, obtains well mixed powder；
(5) in nitrogen hydrogen reduction atmosphere (15v%H2/ 85v%N2) in, well mixed powder is calcined into 4h, 80 in 1450 DEG C
The washing of DEG C deionized water, (>=12h) is dried in 90 DEG C, is crossed 300 mesh sieves, is obtained cerium dropped yttrium aluminum garnet fluorescent material, its particle
Particle diameter (D50) 2.0 μm, pattern rule, good dispersion, luminous efficiency high (absolute quantum efficiency QY=92%), chemical property it is steady
Determine, can effectively be excited by blue light.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by examples detailed above
System, it is other it is any without departing from spirit of the invention and the change made under principle, modification, replacement, combine, simplification is
Effect.
Claims (10)
1. a kind of be co-precipitated the method for preparing small particle cerium dropped yttrium aluminum garnet fluorescent material, it is characterised in that：Including following step
Suddenly：
(1) preparation of metal ion solution：Using water by yttrium nitrate, aluminum nitrate and cerous nitrate according to Y2.96Ce0.04Al5O12Middleization
Learn metering ratio and be configured to metallic ion mixed liquor；
(2) preparation of precipitating reagent：Ammoniacal liquor is mixed with ammonium bicarbonate soln, precipitant solution is obtained；The ammoniacal liquor and carbon
The concentration of sour hydrogen ammonium salt solution is all 1~4molL-1, the volume ratio of the ammoniacal liquor and ammonium bicarbonate soln is 1:(1~3)；
(3) precipitant solution in the metallic ion mixed liquor in step (1) and step (2) is added drop-wise to surface simultaneously alone
In activating agent, by controlling the rate of addition of precipitant solution so that the pH of reaction solution is maintained at 7~9, metal ion mixing
Solution rate of addition is 5~15mLmin-1, react at normal temperatures；
(4) continue to stir 1~4h after metallic ion mixed liquor is dripped, then ultrasonic disperse, ageing, suction filtration, are washed, and are done
Dry, calcining obtains presoma；The temperature of the calcining is 500~800 DEG C；
(5) presoma and cosolvent are placed in ball-grinding machine and carry out ball milling, obtain the product after ball milling；In reducing atmosphere,
Product after ball milling is calcined in 1200~1600 DEG C, washed, dries, obtains small particle cerium dropped yttrium aluminum garnet fluorescence
Powder.
2. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：Surfactant described in step (3) is at least one of polyethylene glycol, ammonium sulfate and neopelex；
Fluxing agent described in step (5) is sodium fluoride, calcirm-fluoride, magnesium fluoride, lithium fluoride, aluminum fluoride, ammonium fluoride, cerium fluoride, fluorine
Change at least one of barium, sodium molybdate and boric acid.
3. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：The consumption of surfactant described in step (3) is the 0.5~3% of yttrium nitrate, aluminum nitrate and cerous nitrate gross mass；
The consumption of fluxing agent described in step (5) is the 2~10% of cerium dropped yttrium aluminum garnet fluorescent material quality, the cerium dopping
Yttrium aluminium garnet fluorescent powder quality is according to Y2.96Ce0.04Al5O12The consumption theoretical calculation of raw material obtain.
4. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：Reducing atmosphere described in step (5) is nitrogen hydrogen mixeding gas, one kind in ammonia or powdered carbon is provided；In nitrogen hydrogen mixeding gas
Nitrogen volume is not less than 70%.
5. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：Rotational speed of ball-mill described in step (5) is 100~500 revs/min；Ball-milling Time described in step (5) is 10~60min.
6. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：The molar concentration of metal ion mixed liquor described in step (1) is 0.1~1.5molL-1；
The purity of yttrium nitrate, aluminum nitrate and cerous nitrate described in step (1) is 3~4N.
7. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：The condition of ultrasonic disperse described in step (4) is in 150~400W ultrasonic disperses, 10~60min；It is old described in step (4)
The time of change is 8~12h；Calcination time described in step (4) is 1~3h；
Calcination time described in step (5) is 2~6h.
8. the method that co-precipitation prepares small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 1, its feature exists
In：The temperature dried described in step (4) is 50~120 DEG C；
The temperature dried described in step (5) is 50~120 DEG C；
Washing described in step (4) refers to be washed using deionized water and ethanol successively；
Washing refers to be washed using hot water described in step (5), and the temperature of hot water is 50~100 DEG C.
9. the small particle cerium dropped yttrium aluminum garnet fluorescence that a kind of method as described in any one of claim 1~8 is prepared
Powder.
10. the application of small particle cerium dropped yttrium aluminum garnet fluorescent material according to claim 9, it is characterised in that：It is described small
Particle diameter cerium dropped yttrium aluminum garnet fluorescent material is used for white light LEDs.
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| CN115109586A (en) * | 2021-03-22 | 2022-09-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method of mechanoluminescence material |
| CN115216297A (en) * | 2022-07-14 | 2022-10-21 | 江门市科恒实业股份有限公司 | GaYAG green phosphor, synthesis method thereof and light-emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113046068A (en) * | 2019-12-27 | 2021-06-29 | 英特美光电（苏州）有限公司 | Method for improving aging performance of aluminate fluorescent powder |
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| CN113105889A (en) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | Method for preparing europium and dysprosium co-doped strontium aluminate fluorescent powder with assistance of ultrasonic waves |
| CN115216297A (en) * | 2022-07-14 | 2022-10-21 | 江门市科恒实业股份有限公司 | GaYAG green phosphor, synthesis method thereof and light-emitting device |
| CN115216297B (en) * | 2022-07-14 | 2023-08-15 | 江门市科恒实业股份有限公司 | GaYAG green fluorescent powder, synthesis method thereof and light-emitting device |
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