CN109957400A - A kind of Mn4+The preparation method of ion-activated fluorination matter fluorescent powder - Google Patents

A kind of Mn4+The preparation method of ion-activated fluorination matter fluorescent powder Download PDF

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CN109957400A
CN109957400A CN201711342398.7A CN201711342398A CN109957400A CN 109957400 A CN109957400 A CN 109957400A CN 201711342398 A CN201711342398 A CN 201711342398A CN 109957400 A CN109957400 A CN 109957400A
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preferably
selected
mf
fluorescent powder
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CN201711342398.7A
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朱浩淼
易小东
陈学元
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中国科学院福建物质结构研究所
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Abstract

The present invention provides a kind of Mn4+The preparation method of ion-activated fluorination matter fluorescent powder, preparation method of the invention do not need to form A2MF6Saturated solution, greatly reduce the dosage demand of raw material, the preparation process can synthesize target product at room temperature, facilitate synthesis.And by the addition of precipitating reagent, so that preparation is more convenient, operation is simpler, to simplify synthesis step, and the fluorescent powder being prepared has better optical property.The fluorination matter fluorescent powder can be excited by ultraviolet light to blue light well, especially blue light, and have strong red emission, and the emission peak of the feux rouges is in 600-650nm wave-length coverage.The method of the invention has preparation process simple, time-consuming short, and the material emission quantum yield of preparation is high, is suitble to industrial-scale preparation.

Description

A kind of Mn4+The preparation method of ion-activated fluorination matter fluorescent powder

Technical field

The invention belongs to luminescent material technical fields, and in particular to a kind of Mn4+The system of ion-activated fluorination matter fluorescent powder Preparation Method.

Background technique

In recent decades, white light emitting diode (White Light-Emitting Diode, referred to as WLED) is because of tool Have the advantages that energy-saving and environmental protection, the long-life and greatly paid close attention to, and gradually instead of traditional incandescent lamp, fluorescent lamp.Mesh Before, preparing the most common method of WLED on the market is by blue light GaN chip and yellow light YAG:Ce3+Fluorescent powder combines, wherein yellow Emitting phosphor launches yellow light after absorbing the blue light that GaN chip in part issues, and forms white light with unabsorbed blue light. Since the feux rouges component in yellow fluorescent powder emission spectrum is insufficient, the WLED of this method preparation is cool white optical device, related colour Warm (Correlated Color Temperature, CCT) is typically larger than 4500K, and its colour rendering index (Color Rendering Index, CRI) it is lower, usually less than 80, cause it to be limited by many important applications, such as room lighting. To make up its defect, needs to add red light fluorescent powder appropriate in white light LED part, enhance the red emission of device, make it Warm white optical device is become from cool white optical device, and improves its colour rendering index.

Mn4+Ion-activated fluoride red light fluorescent powder material is ideal red light fluorescent powder material.To this progress Many research work, patent WO 2007/100824 disclose Mn4+The A of activation2MF6(A is K, Na, Rb etc.;M is Ti, Si, Sn, Ge etc.) red light fluorescent powder;Preparation method is by dissolution of raw material in high concentration of hydrofluoric acid, and then heating evaporates into drying, This method has a large amount of toxic hydrogen fluoride gas volatilizations during the preparation process, and preparation process is difficult to control, and is not suitable for industrializing Production;Preparation method disclosed in 102732249 A of patent CN be will the first solution containing the fluoride of tetravalent metal M and The compound of the A of second of solution or solid form containing alkali metal A mixes, and generates precipitating after reacted, obtains product, but The preparation method need to control the factors such as the concentration of two kinds of solution, the speed of mixing and temperature, it is difficult to it is preferable to obtain luminous efficiency Product.

Summary of the invention

In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of AxMFy:Mn4+It is fluorinated matter fluorescent powder Preparation method, the method not necessarily form AxMFySaturated solution, greatly reduce the dosage demand of raw material, the preparation process Target product can be synthesized at room temperature, preparation process is simple, and time-consuming short, the light-emitting phosphor quantum yield being prepared is high, It is suitble to industrial-scale preparation.

The present invention is to be achieved through the following technical solutions:

A kind of AxMFy:Mn4+It is fluorinated the preparation method of matter fluorescent powder, the preparation method includes the following steps:

(1) Mn will be contained4+Compound and the compound containing alkali metal A and M, or with simple substance or compound containing M And the compound of alkali metal containing A, or solvent is dissolved in the compound of the compound containing alkali metal A and M and alkali metal containing A In, obtain mixed solution;

(2) precipitating reagent is added into the mixed solution of step (1), obtains sediment, A is preparedxMFy:Mn4+Fluoride Fluorescent powder, wherein x is [MFy] ion charge absolute value, M is selected from Si, Ti, Ge, Sn, Zr, Nb, Ta, Y, Ga, in Al One or more of combinations, alkali metal A are selected from Li, Na, K, the combination of Rb, one or more of Cs, y 4,5,6 or 7.

According to the present invention, the method also includes following steps:

(3) by sediment centrifugation, washing, the drying of step (2), solid product A is obtainedxMFy:Mn4+It is fluorinated matter fluorescent powder.

Preferably, the y is 4 or 6, and x is [MFy] ion charge absolute value.

Preferably, the M is selected from Si, Ti, Ge, Sn, Zr, the combination of Nb, one or more of Ta, alternatively, the M is selected From Y, the combination of Ga, one or more of Al;Also preferably Si and/or Ti, or also preferably Al.

Preferably, the alkali metal A is selected from Na and/or K.

According to the present invention, described to contain Mn4+Compound be selected from K2MnF6, Na2MnF6, Li2MnF6, Rb2MnF6Or Cs2MnF6, preferably K2MnF6, Na2MnF6, the also preferably above compound of crystal form.

According to the present invention, the compound containing alkali metal A and M is selected from K2SiF6And/or K2TiF6;It is described to contain M's Simple substance is selected from Si, Ti, Ge, Sn, Zr, Nb, Ta, Y, Ga, the combination of one or more of Al;The compound choosing containing M From SiO2, TiO2, GeO2, SnO2, ZrO2, Nb2O5, Ta2O5, Y2O3, Ga2O3, Al2O3One or more of combination;It is described to contain There is the compound of alkali metal A to be selected from LiF, NaF, NaHF2, KF, KHF2, the combination of RbF, one or more of CsF.

According to the present invention, in step (1), the solvent is selected from hydrofluoric acid solution, it is preferable that the matter of the hydrofluoric acid solution Measure percentage 20-50wt%.

According to the present invention, in step (1), the Mn4+It is 0.1-30%, preferably 1-20% with the molar ratio of M, more preferably For 2-10%.

According to the present invention, in step (1), the Mn4+It is 0.1-15%, preferably 0.5-10% with the molar ratio of A, it is more excellent It is selected as 1-5%.

According to the present invention, in step (2), the precipitating reagent is selected from one or more of methanol, acetone, dehydrated alcohol Combination, preferably methanol.

According to the present invention, in step (2), the volume ratio of the precipitating reagent and solvent is (0.20-2): 1, preferably (0.20-1): 1, also preferably (0.20-0.5): 1.

According to the present invention, in step (2), precipitating reagent is added with given pace;Preferably, the addition rate of the precipitating reagent For 0.02ml/s-10ml/s, preferably 0.05ml/s-3ml/s, also preferably 0.1ml/s-0.5ml/s, more preferably 0.1ml/ s-0.3ml/s.Precipitating reagent is added using different rates, the A of various grain sizes and pattern can be obtainedxMFy:Mn4+Fluoride Fluorescent powder.

According to the present invention, in step (3), through the solid product that centrifugation, wash can further with organic solvent such as Dehydrated alcohol or acetone are washed, preferably acetone, to remove the acid solution of surface residual, then are dried.

According to the present invention, the temperature of the drying is 50 DEG C -100 DEG C, preferably 50 DEG C -80 DEG C.

According to the present invention, the reaction can carry out at 10-40 DEG C, such as room temperature.

Preferably, the AxMFy:Mn4+Selected from A2MF6:Mn4+, A3MF6:Mn4+Or AMF4:Mn4+

Preferably, the A2MF6:Mn4+Selected from K2TiF6:Mn4+, K2SiF6:Mn4+, Na2SiF6:Mn4+, Na2TiF6:Mn4+, K2GeF6:Mn4+, Na2SnF6:Mn4+, Cs2TiF6:Mn4+Or Cs2SiF6:Mn4+, also preferably K2TiF6:Mn4+, K2SiF6:Mn4+Or Na2SiF6:Mn4+

Preferably, the A3MF6:Mn4+Selected from Na3AlF6:Mn4+, K3AlF6:Mn4+, Li3AlF6:Mn4+, Rb3AlF6:Mn4+, Cs3AlF6:Mn4+, K2NaAlF6:Mn4+, K2LiAlF6:Mn4+, also preferably Na3AlF6:Mn4+、K3AlF6:Mn4+、K2NaAlF6: Mn4+

Preferably, the AMF4:Mn4+Selected from NaYF4:Mn4+Or NaGaF4:Mn4+

The utility model has the advantages that

The present invention provides a kind of Mn4+That activates can be by purple light and blue light activated AxMFy:Mn4+It is fluorinated matter fluorescent powder Preparation method, this method do not need to form AxMFySaturated solution, greatly reduce the dosage demand of raw material, it is described to prepare Journey can synthesize target product at room temperature, facilitate synthesis.And by the addition of precipitating reagent, so that preparation is more convenient, operation is more Add simply, to simplify synthesis step.The fluorination matter fluorescent powder can be excited by ultraviolet light to blue light well, especially Blue light, and have strong red emission, the emission peak of the feux rouges is in 600-650nm wave-length coverage.The method of the invention tool Have that preparation process is simple, time-consuming short, the material emission quantum yield of preparation is high, is suitble to industrial-scale preparation.

Detailed description of the invention

Fig. 1 is the K of embodiment 22NaAlF6:Mn4+The X-ray powder diffraction figure of fluorescent powder.

Fig. 2 is the K of embodiment 22NaAlF6:Mn4+The scanning electron microscope (SEM) photograph of fluorescent powder.

Fig. 3 is the K of embodiment 22NaAlF6:Mn4+The excitation and emission spectra figure of fluorescent powder.

Fig. 4 is the K of embodiment 32TiF6:Mn4+The X-ray powder diffraction figure of fluorescent powder.

Fig. 5 is the K of embodiment 32TiF6:Mn4+The scanning electron microscope (SEM) photograph of fluorescent powder.

Fig. 6 is the K of embodiment 32TiF6:Mn4+The excitation and emission spectra figure of fluorescent powder.

Fig. 7 is the K of embodiment 42SiF6:Mn4+The scanning electron microscope (SEM) photograph of fluorescent powder.

Fig. 8 is the K of embodiment 42SiF6:Mn4+The excitation and emission spectra figure of fluorescent powder.

Specific embodiment

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention Within the scope of.

Instrument and equipment:

In the present invention, the test equipment model MiniFlex2 of the X-ray powder diffraction figure, producer Rigaku, copper Target emanation wavelength is λ=0.154187nm.

In the present invention, the test equipment model JSM-6700F of the scanning electron microscope (SEM) photograph.

In the present invention, the test equipment model FLS980 type (Edinburgh of the excitation and emission spectra figure Instrument)。

Embodiment 1:K2MnF6Preparation

K is prepared according to method described in document Angew.Chem-Ger.Edit.65,304-304 (1953)2MnF6It is brilliant Body.

By 0.45g KMnO4With 9g KHF2It is dissolved in 30mL hydrofluoric acid (49%), stirs 20 minutes, then gradually instill about 1.2mL hydrogen peroxide (30wt.%) gradually generates the precipitating of yellow in solution, obtains sediment after solution is filtered, clear with acetone It is dried 2 hours after washing at 60 DEG C and obtains K2MnF6

Embodiment 2:K2NaAlF6:Mn4+It is fluorinated the preparation of matter fluorescent powder

The K that 0.00741g embodiment 1 is prepared2MnF6、0.8197g NaAlO2、0.1182g KHF2It is dissolved in In 10mL hydrofluoric acid (49wt.%) solution, stirring dissolves it sufficiently in 5 minutes, and precipitating reagent then is added dropwise with the rate of 0.2mL/s After methanol 10mL, 10mL methanol all drips, continue stirring 5 minutes at room temperature, stop stirring and take out sediment, be centrifuged, And cleaned 2 times with acetone, 60 DEG C of drying, obtain product K in air atmosphere2NaAlF6:Mn4+It is fluorinated matter fluorescent powder.

Fig. 1 is K2NaAlF6:Mn4+It is fluorinated the X-ray powder diffraction figure of matter fluorescent powder, shows that the product of synthesis is square phase K2NaAlF6;Fig. 2 is K2NaAlF6:Mn4+It is fluorinated the scanning electron microscope (SEM) photograph of matter fluorescent powder, it can be seen that powder diameter is at 1 μm or so; Fig. 3 is K2NaAlF6:Mn4+It is fluorinated the excitation and emission spectra figure of matter fluorescent powder.It can be seen that K2NaAlF6:Mn4+Fluoride is glimmering Light powder has strong absorption in blue region, and has strong transmitting in red light region.

Moreover, it will be understood by those skilled in the art that passing through K in feed change2MnF6Quality, in other synthesis In the case that condition is constant, different Mn can be prepared4+The sample of doping concentration.

Embodiment 3:K2TiF6:Mn4+It is fluorinated the preparation of matter fluorescent powder

The K that 0.00741g embodiment 1 is prepared2MnF6、0.2401g K2TiF6It is dissolved in 10mL hydrofluoric acid In (49wt.%) solution, stirring dissolves it sufficiently in 5 minutes, and precipitation agent methanol 10mL then is added dropwise with the rate of 0.2mL/s, After 10mL methanol all drips, continue stirring 5 minutes at room temperature, stops stirring and take out sediment, be centrifuged, and clear with acetone It washes 2 times, 60 DEG C of drying, obtain product K in air atmosphere2TiF6:Mn4+Fluoride red light fluorescent powder.

Fig. 4 is K2TiF6:Mn4+It is fluorinated the X-ray powder diffraction figure of matter fluorescent powder, shows that the product of synthesis is hexagonal phase K2TiF6;Fig. 5 is K2TiF6:Mn4+It is fluorinated the scanning electron microscope (SEM) photograph of matter fluorescent powder, powder diameter is at 10 μm or so;Fig. 6 is K2TiF6:Mn4+It is fluorinated the excitation and emission spectra figure of matter fluorescent powder.It can be seen that K2TiF6:Mn4+Matter fluorescent powder is fluorinated in blue light There is strong absorption in region, and has strong transmitting in red light region.

Moreover, it will be understood by those skilled in the art that K is added by changing2MnF6Quality, in other synthesis items In the case that part is constant, different Mn can be prepared4+The sample of doping concentration.

Embodiment 4:K2SiF6:Mn4+It is fluorinated the preparation of matter fluorescent powder

The K that 0.00741g embodiment 1 is prepared2MnF6、0.0601g SiO2、0.1562g KHF2It is dissolved in 10mL In hydrofluoric acid (49wt.%) solution, stirring dissolves it sufficiently in 5 minutes, and precipitation agent methanol then is added dropwise with the rate of 0.2mL/s After 10mL, 10mL methanol all drip, continue stirring 5 minutes at room temperature, stops stirring and take out sediment, centrifugation is used in combination Acetone cleans 2 times, and 60 DEG C of drying, obtain product K in air atmosphere2SiF6:Mn4+Fluoride red light fluorescent powder.

Fig. 7 is K2SiF6:Mn4+It is fluorinated the scanning electron microscope (SEM) photograph of matter fluorescent powder;Fig. 8 is K2SiF6:Mn4+It is fluorinated matter fluorescent powder Excitation and emission spectra figure.It can be seen from the figure that K2SiF6:Mn4+Fluorination matter fluorescent powder has strong absorption in blue region, And there is strong transmitting in red light region.

Moreover, it will be understood by those skilled in the art that K is added by changing2MnF6Quality, in other synthesis items In the case that part is constant, different Mn can be prepared4+The sample of doping concentration.

Embodiment 5:Na2SiF6:Mn4+It is fluorinated the preparation of matter fluorescent powder

The K that 0.00741g embodiment 1 is prepared2MnF6、0.0601g SiO2、0.124g NaHF2It is dissolved in 10mL In hydrofluoric acid (49wt.%) solution, stirring dissolves it sufficiently in 5 minutes, and precipitation agent methanol then is added dropwise with the rate of 0.2mL/s After 10mL, 10mL methanol all drip, continue stirring 5 minutes at room temperature, stops stirring and take out sediment, centrifugation is used in combination Acetone cleans 2 times, and 60 DEG C of drying, obtain product Na in air atmosphere2SiF6:Mn4+Fluoride red light fluorescent powder.

Moreover, it will be understood by those skilled in the art that Na is added by changing2MnF6Quality, in other synthesis items In the case that part is constant, different Mn can be prepared4+The sample of doping concentration.

Embodiment 6:K2GeF6:Mn4+It is fluorinated the preparation of matter fluorescent powder

The K that 0.00741g embodiment 1 is prepared2MnF6、0.0726g Ge、0.1562g KHF2It is dissolved in 10mL hydrogen In fluoric acid (49wt.%) solution, stirring dissolves it sufficiently in 5 minutes, and precipitation agent methanol then is added dropwise with the rate of 0.2mL/s After 10mL, 10mL methanol all drip, continue stirring 5 minutes at room temperature, stops stirring and take out sediment, centrifugation is used in combination Acetone cleans 2 times, and 60 DEG C of drying, obtain product K in air2GeF6:Mn4+Fluoride red light fluorescent powder.

Moreover, it will be understood by those skilled in the art that K is added by changing2MnF6Quality, in other synthesis items In the case that part is constant, different Mn can be prepared4+The sample of doping concentration.

More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention Within the scope of shield.

Claims (9)

1. a kind of AxMFy:Mn4+It is fluorinated the preparation method of matter fluorescent powder, the preparation method includes the following steps:
(1) Mn will be contained4+Compound and the compound containing alkali metal A and M, or with the simple substance containing M or compound and contain The compound of alkali metal A, or be dissolved in solvent with the compound of the compound containing alkali metal A and M and alkali metal containing A, it obtains To mixed solution;
(2) precipitating reagent is added into the mixed solution of step (1), obtains sediment, obtains AxMFy:Mn4+It is fluorinated matter fluorescent powder, In, x is [MFy] ion charge absolute value, M be selected from Si, Ti, Ge, Sn, Zr, Nb, Ta, Y, Ga, one or more of Al Combination, alkali metal A be selected from Li, Na, K, the combination of Rb, one or more of Cs, y 4,5,6 or 7.
2. the method according to claim 1, wherein the method also includes following steps:
(3) by sediment centrifugation, washing, the drying of step (2), solid product A is obtainedxMFy:Mn4+It is fluorinated matter fluorescent powder.
3. method according to claim 1 or 2, which is characterized in that the y is 4 or 6, and x is [MFy] ion charge it is exhausted To value.
Preferably, the M is selected from Si, Ti, Ge, Sn, Zr, the combination of Nb, one or more of Ta, alternatively, the M is selected from Y, The combination of one or more of Ga, Al;Also preferably Si and/or Ti, or also preferably Al.
Preferably, the alkali metal A is selected from Na and/or K.
4. method according to any one of claim 1-3, which is characterized in that described to contain Mn4+Compound be selected from K2MnF6, Na2MnF6, Li2MnF6, Rb2MnF6Or Cs2MnF6, preferably K2MnF6, Na2MnF6, also preferably crystal form is upper State compound.
Preferably, the compound containing alkali metal A and M is selected from K2SiF6And/or K2TiF6;The simple substance containing M is selected from The combination of one or more of Si, Ti, Ge, Sn, Zr, Nb, Ta, Y, Ga, Al;The compound containing M is selected from SiO2, TiO2, GeO2, SnO2, ZrO2, Nb2O5, Ta2O5, Y2O3, Ga2O3, Al2O3One or more of combination;It is described to contain alkali gold The compound for belonging to A is selected from LiF, NaF, NaHF2, KF, KHF2, the combination of RbF, one or more of CsF.
5. method according to any of claims 1-4, which is characterized in that in step (1), the solvent is selected from hydrogen fluorine Acid solution, it is preferable that the mass percent 20-50wt% of the hydrofluoric acid solution.
Preferably, in step (1), the Mn4+Molar ratio with M is 0.1-30%, preferably 1-20%, more preferably 2- 10%.
Preferably, in step (1), the Mn4+Molar ratio with A is 0.1-15%, preferably 0.5-10%, more preferably 1- 5%.
6. method according to any one of claims 1-5, which is characterized in that in step (2), the precipitating reagent is selected from first The combination of one or more of alcohol, acetone, dehydrated alcohol, preferably methanol.
Preferably, in step (2), the volume ratio of the precipitating reagent and solvent is (0.20-2): 1, preferably (0.20-1): 1, also Preferably (0.20-0.5): 1.
Preferably, in step (2), precipitating reagent is added with given pace;Preferably, the addition rate of the precipitating reagent is 0.02ml/s-10ml/s, preferably 0.05ml/s-3ml/s, also preferably 0.1ml/s-0.5ml/s, more preferably 0.1ml/s- 0.3ml/s。
7. method according to claim 1 to 6, which is characterized in that in step (3), by being centrifuged, washing To solid product can further be washed with organic solvent such as dehydrated alcohol or acetone, preferred acetone is residual to remove surface Remaining acid solution, then be dried.
Preferably, the temperature of the drying is 50 DEG C -100 DEG C, preferably 50 DEG C -80 DEG C.
Preferably, the reaction carries out at 10-40 DEG C, such as carries out at 25 DEG C.
8. method according to any one of claims 1-7, which is characterized in that the AxMFy:Mn4+Selected from A2MF6:Mn4+, A3MF6:Mn4+Or AMF4:Mn4+
9. method according to claim 1 to 8, which is characterized in that the A2MF6:Mn4+Selected from K2TiF6:Mn4 +, K2SiF6:Mn4+, Na2SiF6:Mn4+, Na2TiF6:Mn4+, K2GeF6:Mn4+, Na2SnF6:Mn4+, Cs2TiF6:Mn4+Or Cs2SiF6:Mn4+, also preferably K2TiF6:Mn4+, K2SiF6:Mn4+Or Na2SiF6:Mn4+
Preferably, the A3MF6:Mn4+Selected from Na3AlF6:Mn4+, K3AlF6:Mn4+, Li3AlF6:Mn4+, Rb3AlF6:Mn4+, Cs3AlF6:Mn4+, K2NaAlF6:Mn4+, K2LiAlF6:Mn4+, also preferably Na3AlF6:Mn4+、K3AlF6:Mn4+、K2NaAlF6: Mn4+
Preferably, the AMF4:Mn4+Selected from NaYF4:Mn4+Or NaGaF4:Mn4+
CN201711342398.7A 2017-12-14 2017-12-14 A kind of Mn4+The preparation method of ion-activated fluorination matter fluorescent powder CN109957400A (en)

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