CN104818018A - Coprecipitation preparation method for pyrophosphate phosphor containing alkali earth metal, and phosphor and application thereof - Google Patents
Coprecipitation preparation method for pyrophosphate phosphor containing alkali earth metal, and phosphor and application thereof Download PDFInfo
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Abstract
The invention provides a coprecipitation preparation method for a pyrophosphate phosphor containing alkaline earth metal. The pyrophosphate phosphor has a general formula of Mg<2-m-n-k>Ca<m>Sr<n>Ba<k>P<2>O<7>: xRE, yM, wherein m is no less than 0 and no more than 2.0, n is no less than 0 and no more than 2.0, k is no less than 0 and no more than 2.0, m+n+k is no less than 0 and no more than 2.0, x is no less than 0 and no more than 0.1, y is no less than 0 and no more than 0.2, RE is one or two selected from the group consisting of Y<3+>, La<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Sm<3+>, Eu<3+>, Eu<2+>, Gd<3+>, Tb<3+>, Dy<3+>, Ho<3+>, Er<3+>, Tm<3+>, Yb<3+> and Lu <3+>, and M is one or two selected from the group consisting of Mn<2+>, Cu<2+>, Cu<+>, Pb<2+> and Bi<3+>. The obtained phosphor has the advantages of uniform particle size distribution, stable chemical properties, good luminescence properties and capacity of being effectively excited by ultraviolet rays and is applicable to near ultraviolet chip-excited white-light LED, three-primary-color energy-saving lamps, lamps for plant growth, agricultural light-converting films, etc.
Description
Technical field
The invention belongs to field of light emitting materials, relate to the co-precipitation preparation method of the pyrophosphate phosphor of alkaline including earth metal element, fluorescent material and application thereof.
Background technology
The pyrophosphate salt system luminescent material of alkaline including earth metal due to luminous efficiency high, the plurality of advantages such as synthesis condition is simple, the low and stable chemical nature of cost are a kind of matrix well preparing fluorescent material.The Eu of bibliographical information
2+, Mn
2+the fluorescent material of the pyrophosphate salt system of codoped has wider excitation spectrum at ultraviolet region, excites lower its to have two stronger emission peaks respectively in blue region and red light region ultraviolet.Good luminosity demonstrates the fluorescent material of pyrophosphate salt system and has great application prospect in white light LEDs, in trichromatic energy saving lamp, plant growth lamp and agricultural light conversion film etc.
The method of the pyrophosphate salt system luminescent material of the synthesis alkaline including earth metal of existing report is all high temperature solid-state method, namely with (NH
4)
2hPO
4, alkaline-earth metal, the oxide compound of transition metal and rare earth element or carbonate is raw material, obtains fluorescent material product after grinding, calcining; Or first prepare the hydrophosphate of alkaline-earth metal, then with the oxide compound of the hydrophosphate of alkaline-earth metal, transition metal and rare earth element or carbonate, (NH
4)
2hPO
4for raw material, after grinding, calcining, obtain fluorescent material product.(NH is all contained in the raw material of aforesaid method
4)
2hPO
4, therefore there is following defect in crystal: a, (NH
4)
2hPO
4crystal grain is comparatively thick, raw material blending difficulty, and then causes the particle diameter of product comparatively large, and aftertreatment light decay is serious; When b, grinding, local temperature is higher, (NH
4)
2hPO
4crystal easily decomposes generation ammonia, is detrimental to health and pollution of ecological environment, especially in large-scale production process.
Summary of the invention
In order to overcome the defect of the pyrophosphate salt system luminescent material of above-mentioned high temperature solid-state method synthesis alkaline including earth metal, the invention provides a kind of method utilizing the pyrophosphate salt system luminescent material of Co deposited synthesis alkaline including earth metal, fluorescent material prepared by the present invention with one or more in rare earth ion and transition metal for activator, take alkali earth metal phosphate as matrix, blue light and ruddiness can be launched simultaneously.
The solution that the present invention solves its technical problem is: the co-precipitation preparation method providing a kind of pyrophosphate salt system luminescent material of alkaline including earth metal, particularly:
The general formula of this fluorescent material is: Mg
2-m-n-k ca
m sr
n ba
k p
2o
7:
xrE,
ym,
Wherein: 0≤
m≤ 2.0,0≤
n≤ 2.0,0≤
k≤ 2.0,0≤
m+n+k≤ 2.0,0≤
x≤ 0.1,0≤
y≤ 0.2;
RE is Y
3+, La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Eu
2+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or both;
M is Mn
2+, Cu
2+, Cu
+, Pb
2+, Bi
3+in one or both.
Concrete steps are as follows:
(1) (NH is prepared
4)
2hPO
4solution A: accurately take (NH according to the stoichiometric ratio of general formula
4)
2hPO
4crystal, is mixed with (the NH that concentration is 0.5-1.5mol/L
4)
2hPO
4water solution A.
Preferably, add tensio-active agent in described solution, described tensio-active agent is polyoxyethylene glycol, comprises PEG-200, PEG-300, PEG-400, PEG-600, PEG-800 etc.
Preferably, the add-on of described tensio-active agent is the 3-10% of the presoma throw out quality generated.
(2) preparing metal Ar ion mixing solution B: the oxide compound accurately taking rare earth element and transition metal according to the stoichiometric ratio of general formula, be mixed with the suspension liquid of rare earth oxide and oxidation of interim metal, concentrated hydrochloric acid is added in suspension liquid, be heated to oxide compound dissolve completely, then heating is continued, until stop heating when the pH value of solution reaches 6-7; Then in above-mentioned solution, add the water-soluble salt of alkaline-earth metal, be mixed with mixing solutions B; Described alkaline-earth metal water-soluble salt can be that nitrate is or/and hydrochloride.
(3) prepare presoma: under the condition of the solution A constantly stirred, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma; Preferably, described solution B introduces solution A with the speed of 2 ~ 3 drops/sec, to obtain disperseing better and that particle diameter is thinner precipitation.
(4) presoma calcining: presoma is calcined in vacuum tube furnace, naturally cools to room temperature and obtain alkaline including earth metal element pyrophosphate phosphor.The calcining of described presoma preferably, is at N
2under atmosphere, 800-900 DEG C of calcining 4-8h, then continues to heat up, at N
2-H
2900-1100 DEG C of calcining 4-8h under atmosphere.The fluorescent material crystal formation obtained like this is more complete, and particle is also thinner.
Further, present invention also offers the fluorescent material MgSrP utilizing method of the present invention to prepare
2o
7: xEu
2+, yMn
2+the excitation spectrum of this fluorescent material covers whole ultraviolet region, the two transmitting of single base can be realized under ultraviolet exciting, one of them emission band is positioned at blue light region 380-450nm, peak value is 420nm, another emission band is positioned at red light district 600-775nm, and peak value is 650nm, and this fluorescent material can be used for white light LEDs, trichromatic energy saving lamp, plant growth lamp and the agricultural light conversion film that near ultraviolet chip excites.
Further, present invention also offers the fluorescent material MgSrP utilizing method of the present invention to prepare
2o
7: xEu
2+, the excitation spectrum of this fluorescent material covers whole ultraviolet region, and excite lower emmission spectrum to be positioned at blue light region 380-450 nm ultraviolet, peak value is 420 nm.
The invention has the beneficial effects as follows: the pyrophosphate salt system luminescent material of the present invention by adopting the precipitator method to prepare alkaline including earth metal, avoids and need to use (NH
4)
2hPO
4crystal is as raw material, and raw material easily mixes, sufficient reacting, and the product cut size obtained is evenly distributed, stable chemical nature, good luminous performance, effectively can be excited by ultraviolet.And avoid the release of gas in process of lapping, decrease the pollution of harm to human body and environment.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described.Obviously, described accompanying drawing is a part of embodiment of the present invention, instead of whole embodiment, and those skilled in the art, under the prerequisite not paying creative work, can also obtain other designs and accompanying drawing according to these accompanying drawings.
Fig. 1 is the emmission spectrum of fluorescent material prepared by embodiments of the invention 1;
Fig. 2 is the emmission spectrum of fluorescent material prepared by embodiments of the invention 2;
Fig. 3 is the emmission spectrum of fluorescent material prepared by embodiments of the invention 3;
Fig. 4 is the emmission spectrum of fluorescent material prepared by embodiments of the invention 4;
Fig. 5 is the emmission spectrum of fluorescent material prepared by embodiments of the invention 5;
λ in figure
exfor excitation wavelength.
Embodiment
Clear, complete description is carried out, to understand object of the present invention, characteristic sum effect fully below with reference to the technique effect of embodiment to design of the present invention and generation.Obviously; described embodiment is a part of embodiment of the present invention, instead of whole embodiment, based on embodiments of the invention; other embodiments that those skilled in the art obtains under the prerequisite not paying creative work, all belong to the scope of protection of the invention.Each technical characteristic in the invention, can combination of interactions under the prerequisite of not conflicting conflict.
The step that the precipitator method of the present invention prepare the pyrophosphate salt system luminescent material of alkaline including earth metal is as follows:
(1) (NH is prepared
4)
2hPO
4solution A: accurately take (NH4) according to the stoichiometric ratio of general formula
2hPO
4crystal, is mixed with (the NH that concentration is 0.5-1.5mol/L
4)
2hPO
4water solution A.
(2) preparing metal Ar ion mixing solution B: the oxide compound accurately taking rare earth element and transition metal according to the stoichiometric ratio of general formula, be mixed with the suspension liquid of rare earth oxide and oxidation of interim metal, concentrated hydrochloric acid is added in suspension liquid, be heated to oxide compound dissolve completely, then heating is continued, until stop heating when the pH value of solution reaches 6-7; Then in above-mentioned solution, add the water-soluble salt of alkaline-earth metal, be mixed with mixing solutions B.
(3) prepare presoma: under the condition of the solution A constantly stirred, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
(4) presoma calcining: presoma is calcined, naturally cools to room temperature and obtain alkaline including earth metal element pyrophosphate phosphor.
It is below non-limiting examples of the present invention.
example 1:ca
2p
2o
7: 0.01Eu
2+, 0.1Mn
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 0.5mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take MnO 0.355g, Eu
2o
30.352g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ca (NO is added in above-mentioned solution
3)
222.316g, be mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 4h of atmosphere, then continue to heat up, at N
2-H
2the lower 900 DEG C of calcining 5h of atmosphere.
The emmission spectrum of gained fluorescent material as shown in Figure 1.
example 2:ca
1.5mg
0.5p
2o
7: 0.01Eu
2+, 0.1Mn
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 1.0mol/L, then pipettes 10ml polyoxyethylene glycol-300 in solution A; Separately accurately take MnO 0.355g, Eu
2o
30.352g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ca (NO is added in above-mentioned solution
3)
220.316g, Mg (NO
3)
2: 6H
2o 10.306g, is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 850 DEG C of calcining 5h of atmosphere, then continue to heat up, at N
2-H
2the lower 1000 DEG C of calcining 4h of atmosphere.
The emmission spectrum of gained fluorescent material as shown in Figure 2.
example 3:ca
1.5sr
0.5p
2o
7: 0.01Eu
2+, 0.1Mn
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 0.8mol/L, then pipettes 8ml polyoxyethylene glycol-200 in solution A; Separately accurately take MnO 0.355g, Eu
2o
30.352g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ca (NO is added in above-mentioned solution
3)
220.316g, Sr (NO
3)
215.306g, be mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 8h of atmosphere, then continue to heat up, at N
2-H
2the lower 1100 DEG C of calcining 4h of atmosphere.
The emmission spectrum of gained fluorescent material as shown in Figure 3.
example 4:mgSrP
2o
7: 0.04Eu
2+, 0.125Mn
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 1.5mol/L, then pipettes 15ml polyoxyethylene glycol-600 in solution A; Separately accurately take MnO 0.355g, Eu
2o
30.352g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Mg (NO is added in above-mentioned solution
3)
2: 6H
2o 5.609g, Sr (NO
3)
25.079g, is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 850 DEG C of calcining 6h of atmosphere, then continue to heat up, at N
2-H
2the lower 1000 DEG C of calcining 6h of atmosphere.
The emmission spectrum of gained fluorescent material as shown in Figure 4.
example 5:mgSrP
2o
7: 0.04Eu
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 0.6mol/L, then pipettes 15ml PEG-4000 in solution A; Separately accurately take Eu
2o
30.352g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Mg (NO is added in above-mentioned solution
3)
2: 6H
2o 5.609g, Sr (NO
3)
25.079g, is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 950 DEG C of calcining 5h of atmosphere, then continue to heat up, at N
2-H
2the lower 950 DEG C of calcining 7h of atmosphere.
The emmission spectrum of gained fluorescent material as shown in Figure 5.
example 6:sr
2p
2o
7: 0.1Y
3+, 0.2Cu
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
415.847g, is dissolved in deionized water, and compound concentration is the solution A of 0.7mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take Y
2o
30.282g, CuO 0.4g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Sr (NO is added in above-mentioned solution
3)
28.994g, is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 5h of atmosphere, then continue to heat up, at N
2-H
2the lower 950 DEG C of calcining 7h of atmosphere.
example 7:mg
2p
2o
7: 0.1Ce
3+, 0.2Pb
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
46.603g, is dissolved in deionized water, and compound concentration is the solution A of 0.9mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take CeO
20.430g, PbO 0.278g is made into the suspension liquid of oxide compound, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Mg (NO is added in above-mentioned solution
3)
2: 6H
2o 10.897 g is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 5h of atmosphere, then continue to heat up, at N
2-H
2the lower 1000 DEG C of calcining 8h of atmosphere.
example 8:ba
2p
2o
7: 0.1Pr
3+, 0.2Bi
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
46.603g, is dissolved in deionized water, and compound concentration is the solution A of 1.0mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take Pr
6o
110.426 g, Bi
2o
31.165 g are made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continue heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ba (NO is added in above-mentioned solution
3)
2: 6H
2o 12.415g, is mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 8h of atmosphere, then continue to heat up, at N
2-H
2the lower 1050 DEG C of calcining 4h of atmosphere.
example 9:baSrP
2o
7: 0.1Nd
3+, 0.2Cu
2+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
46.603g, is dissolved in deionized water, and compound concentration is the solution A of 0.5mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take Nd
2o
30.421g, CuO 0.4g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ba (NO is added in above-mentioned solution
3)
2: 6H
2o 6.123g, Sr (NO
3)
24.112g be mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 870 DEG C of calcining 7h of atmosphere, then continue to heat up, at N
2-H
2the lower 1080 DEG C of calcining 6h of atmosphere.
example 10:baMgP
2o
7: 0.1Sm
3+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
46.603g, is dissolved in deionized water, and compound concentration is the solution A of 0.5mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take Sm
2o
30.412 g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ba (NO is added in above-mentioned solution
3)
2: 6H
2o 6.123 g, Mg (NO
3)
25.112 g are mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 4.5h of atmosphere, then continue to heat up, at N
2-H
2the lower 1100 DEG C of calcining 5.5h of atmosphere.
example 11:ca
0.6sr
0.5ba
0.2mg
0.7p
2o
7: 0.05Nd
3+, 0.05Sm
3+the synthesis of fluorescent material
Stoichiometrically precise (NH
4)
2hPO
46.603g, is dissolved in deionized water, and compound concentration is the solution A of 0.5mol/L, then pipettes 10ml PEG-4000 in solution A; Separately accurately take Sm
2o
30.206g, Nd2O3 0.210g is made into suspension liquid, in suspension liquid, add concentrated hydrochloric acid, heating, continues heating after thing to be oxidized dissolves completely, until the pH value of solution reaches 6-7 stop heating; Ba (NO is added in above-mentioned solution
3)
2: 6H
2o 3.123g, Mg (NO
3)
22.112g, Ca (NO
3)
2: 6H
2o 2.123g, Sr (NO
3)
21.112g be mixed with mixing solutions B.
Under the condition of continuous stirred solution A, solution B introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma.
By the uniform presoma of oven dry grinding, enter in crucible, at N
2the lower 800 DEG C of calcining 5h of atmosphere, then continue to heat up, at N
2-H
2the lower 1100 DEG C of calcining 6.5h of atmosphere.
Composition graphs 4 is known, MgSrP prepared by the inventive method
2o
7: xEu
2+, yMn
2+fluorescent material, its excitation spectrum covers whole ultraviolet region, the two transmitting of single base can be realized under ultraviolet exciting, one of them emission band is positioned at blue light region 380-450nm, peak value is 420nm, another emission band is positioned at red light district 600-775nm, and peak value is 650nm, and this fluorescent material can be used for white light LEDs, trichromatic energy saving lamp, plant growth lamp and the agricultural light conversion film that near ultraviolet chip excites.
Composition graphs 5 can be found out, MgSrP prepared by the inventive method
2o
7: xEu
2+fluorescent material, the excitation spectrum of this fluorescent material covers whole ultraviolet region, and excite lower emmission spectrum to be positioned at blue light region 380-450 nm ultraviolet, peak value is 420 nm.
Above better embodiment of the present invention is illustrated, but the invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modifications or replacement under the prerequisite without prejudice to spirit of the present invention, and these equivalent modification or replacement are all included in the application's claim limited range.
Claims (10)
1. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor, the general formula of described alkali earth metal pyrophosphate phosphor is:
Mg
2-m-n-k Ca
m Sr
n Ba
k P
2O
7：
xRE,
yM；
Wherein: 0≤
m≤ 2.0,0≤
n≤ 2.0,0≤
k≤ 2.0,0≤
m+n+k≤ 2.0,0≤
x≤ 0.1,0≤
y≤ 0.2;
RE is Y
3+, La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Eu
2+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+in one or both;
M is Mn
2+, Cu
2+, Cu
+, Pb
2+, Bi
3+in one or both;
It is characterized in that: step is as follows,
(1) (NH is prepared
4)
2hPO
4solution A: accurately take (NH according to the stoichiometric ratio of general formula
4)
2hPO
4crystal, is mixed with (the NH that concentration is 0.5-1.5mol/L
4)
2hPO
4water solution A;
(2) preparing metal Ar ion mixing solution B: the oxide compound accurately taking rare earth element and transition metal according to the stoichiometric ratio of general formula, be mixed with the suspension liquid of rare earth oxide and oxidation of interim metal, concentrated hydrochloric acid is added in suspension liquid, be heated to oxide compound dissolve completely, then heating is continued, until stop heating when the pH value of solution reaches 6-7; Then in above-mentioned solution, add the water-soluble salt of alkaline-earth metal, be mixed with mixing solutions B;
(3) prepare presoma: under the condition of continuous stirred solution A, solution B is introduced in solution A, be precipitated thing, throw out is filtered, wash 2-3 time with the hot water of 80-90 DEG C, dry grinding and evenly obtain presoma;
(4) presoma calcining: presoma is calcined, naturally cools to room temperature and obtain alkaline including earth metal element pyrophosphate phosphor.
2. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 1, is characterized in that: the water-soluble salt of the alkaline-earth metal in described step (2) is that nitrate is or/and hydrochloride.
3. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 1, is characterized in that: have tensio-active agent in described solution A.
4. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 3, is characterized in that: described tensio-active agent is polyoxyethylene glycol.
5. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 4, is characterized in that: the add-on of described tensio-active agent is the 3-10% of the presoma throw out quality generated.
6. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 1, is characterized in that: described solution B introduces solution A with the speed of 2 ~ 3 drops/sec.
7. the co-precipitation preparation method of alkaline including earth metal element pyrophosphate phosphor according to claim 1, is characterized in that: in step (4), and described presoma calcining is at N
2under atmosphere, 800-900 DEG C of calcining 4-8h, then continues to heat up, at N
2-H
2900-1100 DEG C of calcining 4-8h under atmosphere.
8., with a fluorescent material prepared by the co-precipitation preparation method described in any one of claim 1 ~ 7, its general formula is: MgSrP
2o
7: xEu
2+, yMn
2+, wherein 0 <
x≤ 0.1,0 <
y≤ 0.2, it is characterized in that: the excitation spectrum of this fluorescent material covers whole ultraviolet region, the two transmitting of single base can be realized under ultraviolet exciting, one of them emission band is positioned at blue light region 380-450nm, peak value is 420nm, and another emission band is positioned at red light district 600-775nm, and peak value is 650nm.
9. a MgSrP as claimed in claim 8
2o
7: xEu
2+, yMn
2+fluorescent material, wherein 0 <
x≤ 0.1,0 <
y≤ 0.2, can be used for white light LEDs, trichromatic energy saving lamp, plant growth lamp and agricultural light conversion film that near ultraviolet chip excites.
10. the fluorescent material MgSrP prepared with the co-precipitation preparation method described in any one of claim 1 ~ 7
2o
7: xEu
2+, 0 <
x≤ 0.1, it is characterized in that: the excitation spectrum of this fluorescent material covers whole ultraviolet region, excite lower emmission spectrum to be positioned at blue light region 380-450nm ultraviolet, peak value is 420nm.
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| CN111171816B (en) * | 2020-01-08 | 2023-02-28 | 闽南师范大学 | Yellow-green long-afterglow luminescent material and preparation method thereof |
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