CN111138185B - Eu (Eu)3+Ion activated aluminum phosphate fluorescent ceramic and preparation method and application thereof - Google Patents
Eu (Eu)3+Ion activated aluminum phosphate fluorescent ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 Ion activated aluminum phosphate Chemical class 0.000 title claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001238 wet grinding Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000012856 weighed raw material Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- 150000008040 ionic compounds Chemical class 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 238000000695 excitation spectrum Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention relates to Eu3+An ion activated aluminum phosphate fluorescent ceramic and a preparation method and application thereof, which belong to the technical field of inorganic fluorescent ceramic materials and have a chemical general formula of Li9Al3‑ 3xEu3xP8O29Wherein x is Eu3+Doped substituted Al3+X is more than or equal to 0.001 and less than or equal to 0.15. The preparation method comprises the following steps: according to the formula Li9Al3‑3xEu3xP8O29Weighing compounds containing ions of the elements according to the stoichiometric ratio of the elements, wet-grinding the weighed raw materials by respectively using acetone as a grinding aid, uniformly mixing, and calcining twice to finish the preparation; the synthesis method has the advantages of simple process, convenient operation, low requirement on equipment, energy conservation and environmental protection, and the prepared powder has high luminous efficiency and good stability. Eu according to the invention3+The ion activated red fluorescent ceramic can be widely applied to lighting and display devices.
Description
Technical Field
The invention relates to the technical field of inorganic fluorescent materials, in particular to Eu3+An ion activated aluminum phosphate fluorescent ceramic and a preparation method and application thereof.
Background
With the increasing global environmental problem and the shortage of energy, energy conservation and environmental protection become important subjects facing people at present. In the field of general illumination and luminescence, white light LED products become the focus of attention of people. The LED lamp is a novel green and environment-friendly lighting product, has the advantages of high luminous efficiency, small size, low power, long service life and the like, is considered as a new generation lighting source, and has a good development trend.
There are two main ways for white LEDs to produce white light: the first is to combine red, green and blue LEDs to produce white light; the second is to mix the LED deexcitation light conversion fluorescent ceramic to form white light, and the approach has two realization schemes, wherein the mature method is to match the blue light LED chip with the YAG: Ce yellow fluorescent ceramic to realize white light emission, but because of lack of red light, the white light obtained by compounding is cold white light, therefore, the scheme still needs to add proper red fluorescent ceramic to improve the color rendering index, and the other scheme is to combine the near-purple light LED chip (390-410nm) with the red/green/blue three primary colors fluorescent ceramic; therefore, the red fluorescent ceramic plays a significant role. The effective excitation range of the existing red fluorescent ceramic is mostly in a short-wave UV region, the luminous efficiency of the existing red fluorescent ceramic under the excitation of ultraviolet light is low, the chromaticity is not pure, the flow of the preparation method is long, the steps are complex, and the operation is difficult.
Disclosure of Invention
The invention aims to provide Eu3+The invention also aims to provide a preparation method and application of the aluminum phosphate fluorescent ceramic, wherein the preparation method has the advantages of short process flow and convenient operation, and the aluminum phosphate fluorescent ceramic can be used in the field of white light LED illumination.
In order to achieve the purpose, the invention adopts the technical scheme that: eu (Eu)3+The ion activated aluminum phosphate fluorescent ceramic has a chemical general formula of Li9Al3-3xEu3xP8O29Wherein x is Eu3+Doped substituted Al3+X is more than or equal to 0.001 and less than or equal to 0.15.
The invention also provides Eu3+The preparation method of the ion activated aluminum phosphate fluorescent ceramic is a solid-phase reaction synthesis method and comprises the following steps:
(1) according to the formula Li9Al3-3xEu3xP8O29The stoichiometric ratio of each element in the Li-containing alloy is more than or equal to 0.001 and less than or equal to 0.15, and the Li is weighed+Ionic compound, Al3+Ionic compound, Eu3+Ionic compounds and P5+The ionic compound is prepared by wet grinding the weighed raw materials by using acetone as a grinding aid respectively and uniformly mixing;
(2) calcining the mixture obtained in the step (1) for the first time in an air atmosphere, wherein the calcining temperature is 300-750 ℃, and the calcining time is 1-8 hours;
(3) naturally cooling the mixture obtained in the step (2), grinding uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 750-1200 ℃ for 1-10 hours to obtain Eu3+An ion activated aluminophosphate fluorescent ceramic.
Preferably, the compound contains Li+The ionic compound being lithium sulphate Li2SO4Lithium hydroxide LiOH or lithium carbonate Li2CO3One of (1); said Al-containing component3+The ionic compound being alumina Al2O3Aluminum hydroxide Al (OH)3Or aluminum nitrate Al (NO)3)3·6H2One of O; said Eu being contained3+The ionic compound is europium oxide Eu2O3Or europium nitrate Eu (NO)3)3·6H2One of O; said compound containing P5+The ionic compound is ammonium dihydrogen phosphate NH4H2PO4Or phosphoric acid H3PO4One kind of (1).
Preferably, the calcining temperature in the step (3) is 800-950 ℃, and the calcining time is 4-8 hours.
The invention also provides Eu3+The application of the ion activated aluminum phosphate fluorescent ceramic can be used as red fluorescent ceramic for lighting and display devices.
Compared with the prior products of the same type, the Eu has the advantages of simple structure, low cost and high yield3+Activated aluminophosphate fluorescent ceramics have significant advantages:
(1) multiple cations exist in the matrix lattice, so that Eu can be controlled and adjusted3+The position and the relative intensity of the light emission can obtain the red light with pure chroma, and the light emission efficiency is high and stableThe performance is good.
(2) Compared with other red fluorescent materials, the preparation process of the matrix material has no pollution, the synthesis process is simple, the operation is convenient, the requirement on equipment is low, and the red fluorescent material is energy-saving and environment-friendly.
(3) Eu according to the invention3+The ion-activated red fluorescent ceramic can be widely applied to lighting and display devices, and is particularly suitable for being used in Eu3+Ion-based white LEDs.
Drawings
FIG. 1 shows Li prepared according to the embodiment 1 of the present invention9Al2.7Eu0.3P8O29X-ray ceramic powder diffraction pattern of (a);
FIG. 2 shows Li prepared according to example 1 of the present invention9Al2.7Eu0.3P8O29SEM images of fluorescent ceramic samples;
FIG. 3 shows Li prepared according to the embodiment 1 of the present invention9Al2.7Eu0.3P8O29Excitation spectra obtained under 622 nm light monitoring;
FIG. 4 shows Li prepared according to the embodiment 1 of the present invention9Al2.7Eu0.3P8O29Emission spectrum under 350 nm light excitation;
FIG. 5 shows Li prepared according to the embodiment 1 of the present invention9Al2.7Eu0.3P8O29Lifetime curve at 622 nm.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
According to Li9Al2.7Eu0.3P8O29In the chemical stoichiometric ratio of Li, Al, Eu and P, respectively weighing lithium carbonate Li2CO3: 3.321 g, alumina Al2O3: 1.377 g of europium oxide Eu2O3: 0.528 g and ammonium dihydrogen phosphate NH4H2PO4: 9.2 g. Reciprocating scaleAdding acetone into the raw materials to carry out wet grinding, uniformly mixing, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 750 ℃, and the calcining time is 1 hour; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at 850 ℃ for 4 hours to obtain Eu3+Ion activated red fluorescent ceramic.
Referring to the attached drawing 1, the X-ray ceramic powder diffraction pattern of the sample prepared by the technical scheme of the embodiment 1 is shown, and the XRD test result shows that the prepared sample has good crystallinity and is a pure-phase material.
Referring to fig. 2, it is an SEM image of a sample prepared according to the embodiment of the present invention 1, and the particles of the sample are uniform and loose at the nano-scale.
Referring to FIG. 3, it is a graph of the excitation spectrum of the sample prepared according to the embodiment 1, and the excitation spectrum monitored at a wavelength of 622 nm shows that the fluorescent ceramic is effectively excited in the ultraviolet region and the blue region.
Referring to fig. 4, it is a luminescence spectrum of a sample prepared according to the technical scheme of this example 1, and an emission spectrum under 350 nm excitation shows that the emission spectrum shows pure red light with a main peak at 595 nm.
Referring to FIG. 5, the lifetime curve at 622 nm of the sample prepared according to the embodiment of this example 1 is shown, and the emission lifetime is 2.15 ms.
Example 2
According to Li9Al2.55Eu0.45P8O29In the chemical metering ratio of Li, Al, Eu and P, lithium hydroxide LiOH is respectively weighed: 2.155 g, aluminum hydroxide Al (OH)3: 1.989 g, europium oxide Eu2O3: 0.792 g of phosphoric acid H3PO4: 7.838 g. Mixing the weighed raw materials, adding acetone, wet-grinding, uniformly mixing, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 300 ℃, and the calcining time is 7.5 hours; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at 1150 ℃ for 2 hours to obtain Eu3+Ion laserA live red fluorescent ceramic.
The structure, morphology, excitation spectrum and emission spectrum of the fluorescent ceramic sample prepared in this example are similar to those of example 1.
Example 3
According to Li9Al2.997Eu0.003P8O29In the stoichiometric ratio of Li, Al, Eu and P, respectively weighing lithium sulfate Li2SO4: 5.758 g, aluminum nitrate Al (NO)3)3·6H2O: 9.620 g, europium nitrate Eu (NO)3)3·6H2O: 1.338 g of phosphoric acid H3PO4: 7.838 g. Mixing the weighed raw materials, adding acetone for wet grinding, uniformly mixing, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 450 ℃ and the calcining time is 3.5 hours; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 750 ℃ for 8 hours to obtain Eu3+Ion activated red fluorescent ceramic.
The structure, morphology, excitation spectrum and emission spectrum of the fluorescent ceramic sample prepared in this example are similar to those of example 1.
Claims (4)
1. Eu (Eu)3+The ion activated aluminum phosphate fluorescent ceramic is characterized in that the chemical general formula is Li9Al3-3xEu3xP8O29Wherein x is Eu3+Doped substituted Al3+X is more than or equal to 0.001 and less than or equal to 0.15.
2. Eu (Eu)3+The preparation method of the ion activated aluminum phosphate fluorescent ceramic is a solid-phase reaction synthesis method and is characterized by comprising the following steps:
(1) according to the formula Li9Al3-3xEu3xP8O29The stoichiometric ratio of each element in the Li-containing alloy is more than or equal to 0.001 and less than or equal to 0.15, and the Li is weighed+Ionic compound, Al3+Ionic compound, Eu3+Ionic compounds and P5+The ionic compound is prepared by wet grinding the weighed raw materials by using acetone as a grinding aid respectively and uniformly mixing;
(2) calcining the mixture obtained in the step (1) for the first time in an air atmosphere, wherein the calcining temperature is 300-750 ℃, and the calcining time is 1-8 hours;
(3) naturally cooling the mixture obtained in the step (2), grinding uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 750-1200 ℃ for 1-10 hours to obtain Eu3+An ion activated aluminophosphate fluorescent ceramic.
3. Eu according to claim 23+The preparation method of the ion-activated aluminum phosphate fluorescent ceramic is characterized in that the ceramic contains Li+The ionic compound being lithium sulphate Li2SO4Lithium hydroxide LiOH or lithium carbonate Li2CO3One of (1); said Al-containing component3+The ionic compound being alumina Al2O3Aluminum hydroxide Al (OH)3Or aluminum nitrate Al (NO)3)3·6H2One of O; said Eu being contained3+The ionic compound is europium oxide Eu2O3Or europium nitrate Eu (NO)3)3·6H2One of O; said compound containing P5+The ionic compound is ammonium dihydrogen phosphate NH4H2PO4Or phosphoric acid H3PO4One kind of (1).
4. Eu according to claim 23+The preparation method of the ion activated aluminum phosphate fluorescent ceramic is characterized in that the calcining temperature in the step (3) is 800-950 ℃, and the calcining time is 4-8 hours.
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