CN113549456A - Preparation method of rare earth-free doped room-temperature luminous multiphase lanthanum molybdate mixed luminescent material - Google Patents
Preparation method of rare earth-free doped room-temperature luminous multiphase lanthanum molybdate mixed luminescent material Download PDFInfo
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Abstract
A preparation method of a rare earth-free doped room-temperature luminescent multiphase lanthanum molybdate mixed luminescent material relates to the field of luminescent material preparation. The solid raw materials of ammonium heptamolybdate tetrahydrate, lanthanum nitrate and citric acid are dissolved in deionized water and stirred by a magnetic stirrer to form yellow gel. Drying to obtain a yellow cake-shaped gel precursor. And then, carrying out pyrolysis on the precursor to obtain the luminescent material mixed by multiphase lanthanum molybdate at room temperature. Compared with the existing mainstream rare earth europium-doped lanthanum molybdate fluorescent material, the fluorescent material and the preparation method thereof have the advantages of simple preparation and low cost. Meanwhile, the rare earth quenching phenomenon existing in doping rare earth europium is avoided, and a new idea is provided for the preparation of red fluorescent powder.
Description
Technical Field
The invention relates to the field of luminescent material preparation, in particular to rare earth-free doped luminescent multiphase lanthanum molybdate mixed fluorescent powder and a preparation method thereof.
Background
The white light LED as a novel green environment-friendly solid illumination light source has the advantages of low working voltage, low power, high reliability, long service life, environmental friendliness, high energy efficiency and the like, and is the development direction of future illumination light sources. In an LED light source, the performance of the fluorescent powder determines the technical indexes of the LED such as luminous efficiency, color rendering index, color temperature, service life and the like. In the method for obtaining the white light LED by exciting the red, green and blue three-primary-color fluorescent powder by near ultraviolet light, the red fluorescent powder is mainly obtained by doping rare earth.
Rare earth Eu3+The doped lanthanum molybdate is a typical red fluorescent powder, and has good chemical properties and practical application value. The preparation process of europium-doped lanthanum molybdate is a sol-gel method, as described in the patent of 'a near ultraviolet excited high-purity lithium europium-doped lanthanum molybdate red phosphor'. However, Eu, a phenomenon of quenching luminescence due to an excessively high rare earth concentration3+Strict preparation process is required during doping process to prevent Eu3+Is very demanding in terms of the preparation and sintering process.
Unlike the above patent, the present invention does not introduce trace amount of Eu3+In the case of (1), by adjusting the component content, the preparation process and the sintering process, the rare earth-free doped room-temperature luminescent multiphase lanthanum molybdate mixed red phosphor can be prepared, and the material is relatively Eu-containing3+The red fluorescent powder has cheap raw materials, is easy to carry out industrial production, and simultaneously, because Eu is not added3 +And is more environment-friendly. The preparation method of the rare earth-free doped room-temperature luminous multiphase lanthanum molybdate mixed red fluorescent powder provided by the patent has important significance for the research and preparation of white light LEDs.
Disclosure of Invention
The invention aims to provide a preparation method of a rare earth-free doped room-temperature luminescent multiphase lanthanum molybdate mixed luminescent material. The method can successfully prepare the multiphase lanthanum molybdate mixed luminescent material which can emit light at room temperature, and has the advantages of low cost and easy preparation.
The preparation method of the multiphase lanthanum molybdate mixed fluorescent powder comprises the following steps:
step (1) raw materials of lanthanum nitrate and ammonium heptamolybdate tetrahydrate are mixed according to lanthanum oxide (La)2O3): molybdenum oxide (MoO)3) The mass ratio is 1: (1.0-5.2) (wherein the ratio of the optimal luminous effect is 1: 1) is weighed; the mass ratio of the citric acid to the sum of the lanthanum nitrate and the ammonium molybdate is (1-1.2): 1; respectively dissolving lanthanum nitrate, ammonium molybdate and citric acid raw materials to form a lanthanum nitrate solution, an ammonium molybdate solution and a citric acid solution, mixing the three solutions after the lanthanum nitrate solution, the ammonium molybdate solution and the citric acid solution are completely dissolved, and then continuously heating and stirring in a water bath stirring pot to finally obtain uniformly mixed gel;
putting the gel into a corundum crucible, and putting the corundum crucible into a forced air drying oven for forced air drying;
putting the dried gel into a box-type muffle furnace in an air atmosphere for calcining, and performing decomposition reaction to obtain a lanthanum molybdate decomposition body;
and (4) taking out the lanthanum molybdate sintered body, grinding the lanthanum molybdate sintered body by using an agate mortar, and sieving the ground lanthanum molybdate sintered body by using a 200-mesh sieve to obtain the white lanthanum molybdate fluorescent powder with uniform and fine particle size.
In step (1) of the above invention, the ratio of the solid powder to the deionized water when the solution is prepared is 1: 3-4.
In the step (1), the rotation speed of the rotor is 200-500 rpm, and the stirring temperature is 60-150 ℃.
In the step (1) of the invention, the time from sol to gel is 3 to 5 hours due to different seasons and humidity.
In the step (2) of the invention, the dried sample can be directly put into a corundum crucible to carry out calcination decomposition without post-treatment.
In the step (2) of the invention, the drying temperature is 80-100 ℃, and the drying time is 10-15 hours, so that yellow cake-shaped gel is obtained.
In the step (3), the temperature of the box-type muffle furnace is raised to the decomposition temperature at the heating rate of 10 ℃/min, the oxidative decomposition temperature of the muffle furnace is 650-1000 ℃, and the decomposition heat preservation time is 5-7 hours.
In the step (3), the decomposed lanthanum molybdate phosphor is cooled along with the furnace to obtain a white lanthanum molybdate sintered body.
In the above step (4) of the present invention, the particle size of the sieved lanthanum molybdate powder is usually 40 to 100. mu.m.
The invention has the advantages that: the raw materials are cheap, the production process is simple and easy to operate, the industrial production is easy to carry out, the environment is protected, and a new idea is provided for the preparation of the red fluorescent powder.
Drawings
FIG. 1 is a fluorescence emission (PL) spectrum of three phosphors prepared in examples 1-3.
FIG. 2 is an XRD phase analysis diagram of three phosphors prepared in examples 1-3.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
22.08g of an aqueous solution of ammonium heptamolybdate tetrahydrate, 21.26g of lanthanum nitrate (corresponding to lanthanum oxide (La)2O3): molybdenum oxide (MoO)3) The mass ratio is 4: 6) mixing with 44g of citric acid solution, continuously stirring for 4 hours at a constant temperature of 80 ℃ by using a magnetic stirrer with the rotation speed of 250 revolutions per minute to obtain yellow wet gel, putting the wet gel into an alumina crucible, putting the alumina crucible into an oven with the temperature of 80 ℃ to dry the wet gel for 12 hours to obtain yellow cake-shaped gel, putting the gel into a muffle furnace to decompose, wherein the oxidative decomposition temperature in the muffle furnace is 650 ℃, the decomposition and heat preservation time is 5 hours, the gel undergoes decomposition reaction, cooling, taking out the white powder mixed with multiphase lanthanum molybdate, and testing the fluorescence performance of the white powder mixed with multiphase lanthanum molybdate, wherein a PL (line-of-luminescence) spectrum is drawn in figure 1.
Example 2
20.24g of an aqueous solution of ammonium heptamolybdate tetrahydrate, 23.92g of lanthanum nitrate (corresponding to lanthanum oxide (La)2O3): molybdenum oxide (MoO)3) The mass ratio is 45: 55) mixing with 44g citric acid solution, stirring with a magnetic stirrer rotating at 250 rpm at 80 deg.C for 4 hr to obtain yellow wet gel,putting the wet gel into an alumina crucible, putting the alumina crucible into an oven at 80 ℃ for drying for 12 hours to obtain yellow cake-shaped gel, putting the gel into a muffle furnace for decomposition, wherein the temperature of the muffle furnace for oxidative decomposition is 650 ℃, the time of decomposition and heat preservation is 5 hours, the gel is subjected to decomposition reaction, cooling and taking out to obtain white powdery multiphase lanthanum molybdate mixed fluorescent powder, testing the fluorescent property of the fluorescent powder, and drawing a PL (color-line) spectrum in figure 1.
Example 3
16.56g of an aqueous solution of ammonium heptamolybdate tetrahydrate, 29.24g of lanthanum nitrate (corresponding to lanthanum oxide (La)2O3): molybdenum oxide (MoO)3) The mass ratio is 1: 1) mixing with 47g of citric acid solution, continuously stirring for 5 hours at a constant temperature of 80 ℃ by using a magnetic stirrer with the rotation speed of 250 revolutions per minute to obtain yellow wet gel, putting the wet gel into an alumina crucible, putting the alumina crucible into an oven with the temperature of 80 ℃ for drying for 13 hours to obtain yellow cake-shaped gel, putting the gel into a muffle furnace for decomposition, wherein the temperature of the muffle furnace for oxidative decomposition is 650 ℃, the decomposition and heat preservation time is 5 hours, the gel undergoes decomposition reaction, cooling, then taking out the gel to obtain white powdery multiphase lanthanum molybdate mixed fluorescent powder, and testing the fluorescence performance of the fluorescent powder, wherein a PL spectrum is drawn in figure 1.
Claims (9)
1. The preparation method of the multiphase lanthanum molybdate mixed fluorescent powder is characterized by comprising the following steps of:
step (1) raw materials of lanthanum nitrate and ammonium heptamolybdate tetrahydrate are mixed according to lanthanum oxide (La)2O3): molybdenum oxide (MoO)3) The mass ratio is 1: (1.0-5.2) (wherein the ratio of the optimal luminous effect is 1: 1) is weighed; the mass ratio of the citric acid to the sum of the lanthanum nitrate and the ammonium molybdate is (1-1.2): 1; respectively dissolving lanthanum nitrate, ammonium molybdate and citric acid raw materials to form a lanthanum nitrate solution, an ammonium molybdate solution and a citric acid solution, mixing the three solutions after the lanthanum nitrate solution, the ammonium molybdate solution and the citric acid solution are completely dissolved, and then continuously heating and stirring in a water bath stirring pot to finally obtain uniformly mixed gel;
putting the gel into a corundum crucible, and putting the corundum crucible into a forced air drying oven for forced air drying;
putting the dried gel into a box-type muffle furnace in an air atmosphere for calcining, and performing decomposition reaction to obtain a lanthanum molybdate decomposition body;
and (4) taking out the lanthanum molybdate sintered body, grinding the lanthanum molybdate sintered body by using an agate mortar, and sieving the ground lanthanum molybdate sintered body by using a 200-mesh sieve to obtain the white lanthanum molybdate fluorescent powder with uniform and fine particle size.
2. The method of claim 1, wherein in step (1), the ratio of solid powder to deionized water in preparing the solution is 1: 3-4.
3. The method as claimed in claim 1, wherein the rotor speed is 200-500 rpm and the stirring temperature is 60-150 ℃ during the step (1).
4. The method for preparing a multiphase lanthanum molybdate mixed fluorescent powder according to claim 1, wherein in the step (2), the drying temperature is 80-100 ℃ and the drying time is 10-15 hours, so that yellow cake-like gel is obtained.
5. The method as claimed in claim 1, wherein in the step (3), the temperature of the box-type muffle furnace is raised to the decomposition temperature at a heating rate of 10 ℃/min, the oxidation decomposition temperature of the muffle furnace is 650-1000 ℃, and the decomposition holding time is 5-7 hours.
6. The method of claim 1, wherein in step (3), the decomposed lanthanum molybdate phosphor is furnace cooled to obtain a white lanthanum molybdate sintered body.
7. The method of claim 1, wherein in step (4), the sieved lanthanum molybdate powder has a particle size of about 40 to about 100 microns.
8. A heterogeneous lanthanum molybdate mixed phosphor prepared according to the method of any of claims 1 to 7.
9. A multiphase lanthanum molybdate mixed phosphor prepared according to the method of any of claims 1-7 wherein the phases comprise the following: la2(MoO4)3、La2O3、MoO3And La2MoO6And the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133929A (en) * | 2021-12-22 | 2022-03-04 | 国网浙江省电力有限公司双创中心 | Method for preparing doped scheelite-type nano fluorescent particles by sol-gel method |
| CN116443932A (en) * | 2023-06-07 | 2023-07-18 | 武汉姜一三新材料科技有限公司 | Preparation method of rare earth molybdate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU857214A1 (en) * | 1978-06-19 | 1981-08-23 | Ордена Трудового Красного Знамени институт физики АН Белорусской ССР | Luminophore based lantanum molybdate |
| CN1569368A (en) * | 2004-05-10 | 2005-01-26 | 西安交通大学 | Method for preparing nm-class composite rare earth molybdenum material by sol-gal process |
| CN1888134A (en) * | 2006-05-18 | 2007-01-03 | 四川大学 | Functional molybdate film and its prepn |
| CN107970944A (en) * | 2017-12-05 | 2018-05-01 | 惠州学院 | A kind of preparation method and applications of compound molybdate tiny balloon |
-
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- 2021-08-18 CN CN202110951854.8A patent/CN113549456B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU857214A1 (en) * | 1978-06-19 | 1981-08-23 | Ордена Трудового Красного Знамени институт физики АН Белорусской ССР | Luminophore based lantanum molybdate |
| CN1569368A (en) * | 2004-05-10 | 2005-01-26 | 西安交通大学 | Method for preparing nm-class composite rare earth molybdenum material by sol-gal process |
| CN1888134A (en) * | 2006-05-18 | 2007-01-03 | 四川大学 | Functional molybdate film and its prepn |
| CN107970944A (en) * | 2017-12-05 | 2018-05-01 | 惠州学院 | A kind of preparation method and applications of compound molybdate tiny balloon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133929A (en) * | 2021-12-22 | 2022-03-04 | 国网浙江省电力有限公司双创中心 | Method for preparing doped scheelite-type nano fluorescent particles by sol-gel method |
| CN114133929B (en) * | 2021-12-22 | 2023-09-22 | 国网浙江省电力有限公司双创中心 | Method for preparing doped scheelite-like nano fluorescent particles by sol-gel method |
| CN116443932A (en) * | 2023-06-07 | 2023-07-18 | 武汉姜一三新材料科技有限公司 | Preparation method of rare earth molybdate |
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