CN112300798A - High-color-rendering environment-friendly red fluorescent powder and preparation method thereof - Google Patents
High-color-rendering environment-friendly red fluorescent powder and preparation method thereof Download PDFInfo
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- 238000009877 rendering Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 63
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000227 grinding Methods 0.000 claims abstract description 23
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 17
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 8
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- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
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- 239000000463 material Substances 0.000 claims description 24
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- 238000003756 stirring Methods 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000498 ball milling Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
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- 239000004570 mortar (masonry) Substances 0.000 claims description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000001294 propane Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 21
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- 239000010936 titanium Substances 0.000 abstract description 5
- CCCCITLTAYTIEO-UHFFFAOYSA-N titanium yttrium Chemical compound [Ti].[Y] CCCCITLTAYTIEO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- -1 cation alkaline earth metal Chemical class 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 3
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- 239000006104 solid solution Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NVZBIFPUMFLZLM-UHFFFAOYSA-N [Si].[Y] Chemical compound [Si].[Y] NVZBIFPUMFLZLM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7707—Germanates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/60—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction
- F21K9/64—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction using wavelength conversion means distinct or spaced from the light-generating element, e.g. a remote phosphor layer
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2115/00—Light-generating elements of semiconductor light sources
- F21Y2115/10—Light-emitting diodes [LED]
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Abstract
The invention relates to a high-color-rendering environment-friendly red fluorescent powder and a preparation method thereof, wherein the red fluorescent powder has the following chemical formula: kxMxY2‑xR1‑yGeyO5：aCr3+，bMn4+Wherein M is one of Sr, Ca, Mg and Be, M is Si or Ti, x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than 0.9, a is more than or equal to 0.3 and less than 0.9, b is more than or equal to 0.1 and less than 1.8, and K is2CO3,MCO3,RO2,KMnO4Adding dilute nitric acid solution in sequence, mixing with citric acid aqueous solution, adding oxalic acid to obtain gel, burning, and mixing with Y2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powderPlacing the mixture in a tube furnace for gradient temperature control and high-temperature sintering to obtain fluorescent powder, adopting yttrium germanate or yttrium titanium germanate as a substrate, combining low-valence cation alkaline earth metal codoping, having high light conversion efficiency, stable temperature and chemical properties, and codoping Cr3+，Mn4+The red fluorescent powder is used as a sensitized active ion to generate a high-intensity red emission peak, so that the luminous intensity and luminous efficiency are ensured, the particle size distribution is narrow, the red fluorescent powder can be excited by near ultraviolet and blue light, and the environment-friendly color rendering degree of the red fluorescent powder is improved to meet the requirements of an LED lamp.
Description
Technical Field
The invention relates to high-color-rendering environment-friendly red fluorescent powder and a preparation method thereof, belonging to the technical field of fluorescent powder.
Background
The red, green and blue (RBG) multi-LED chip combined white LED is a white LED module formed by arranging LEDs with different colors according to a certain mode, a blue light or purple light chip is used for exciting a red fluorescent powder luminescent material, the luminescent material generally comprises a main compound and an active dopant, a small amount of activator with photochemical activity is doped in a luminescent substrate material to replace particles on original lattice sites in a substrate crystal to form a luminescent center, excited emission ions lose part of energy by heat or lattice vibration to become an excited state, and the excited emission ions move back to a ground state after part of luminescent transition and heat dissipation to emit light.
The YAG yellow fluorescent powder is combined with three-color-based fluorescent powder by a near ultraviolet chip, the material with high luminous efficiency has poor color rendering, so that white light with high color rendering is difficult to emit, the luminous intensity is easy to generate color temperature shift along with the neonate in a temperature environment, and meanwhile, the red fluorescent powder adopts a sulfide-containing substrate, so that the chemical property is unstable, the phenomenon of lamp death is easy to generate after improper packaging or long-term use, and the pollution risk exists.
Disclosure of Invention
The invention aims to provide high-color-rendering environment-friendly red fluorescent powder and a preparation method thereof aiming at the defects of the prior art3+，Mn4+As the sensitized and activated ions, the red fluorescent powder has narrow particle size distribution, can be excited by near ultraviolet and blue light, and improves the environment-friendly color rendering of the red fluorescent powder so as to meet the requirements of LED lamps while ensuring the luminous intensity and luminous efficiency.
The invention is realized by the following technical scheme:
a high color rendering environment-friendly red fluorescent powder has a chemical formulaComprises the following steps: kxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is one of Sr, Ca, Mg and Be, M is Si or Ti, x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than 0.9, a is more than or equal to 0.3 and less than 0.9, and b is more than or equal to 0.1 and less than or equal to 1.8.
The high-color-rendering environment-friendly red fluorescent powder has the advantages that x is more than or equal to 0.4 and less than or equal to 0.6, y is more than or equal to 0.3 and less than 0.7, a is more than or equal to 0.4 and less than 0.7, and b is more than or equal to 0.6 and less than 1.3.
A preparation method of high-color-rendering environment-friendly red fluorescent powder comprises the following steps:
s1: according to the formula KxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is one of Sr, Ca, Mg and Be, R is Si or Ti, x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than 0.9, a is more than or equal to 0.3 and less than 0.9, b is more than or equal to 0.1 and less than 1.8, and K is weighed according to the proportion of the calculated chemical components2CO3,MCO3,Y2O3,RO2,GeO2,Cr2O3,KMnO4Respectively placing the materials in a mortar for grinding;
s2: will K2CO3,MCO3,RO2,KMnO4Sequentially adding into dilute nitric acid solution, dissolving, stirring and heating at 30-45 deg.C, adding citric acid and K2CO3,MCO3,RO2,KMnO4The mole ratio of the medium cations is (1.5-2.5): 1, adding citric acid into hot water, stirring until the citric acid is clear, mixing all solutions, and fully stirring, wherein the stirring temperature for mixing all the solutions is 75-85 ℃;
s3: adding oxalic acid into the mixed solution in the step 3, heating and preserving heat to obtain gel, wherein the adding amount of the oxalic acid and the citric acid are (3-4): 1, heating at the temperature of 100-2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powder;
s4: placing the precursor powder in a tubular furnace, sintering at high temperature in a reducing atmosphere, wherein the reducing atmosphere in the tubular furnace is one or more of nitrogen, hydrogen, ammonia, methane, acetylene and propane, raising the temperature to 650 plus materials and 690 ℃ within 30min, then preserving the temperature for 1-2h, continuing raising the temperature to 1000 plus materials and 1250 ℃ within 20-40min, then preserving the temperature for 2-4h, then cooling to 840 plus materials and 900 ℃ within 30min, preserving the temperature for 1-2h, taking out the materials after the furnace temperature is cooled to room temperature, further crushing and grinding, performing ball milling treatment during grinding, sorting and collecting by a sorting machine under the wind power traction of a cyclone separator, and performing ultrasonic cleaning, suction filtration and drying by using deionized water to obtain a fluorescent powder product.
The invention has the beneficial effects that:
(1) yttrium germanate or yttrium titanium germanate is used as a substrate, the volume of a garnet crystal package is enhanced, and the garnet crystal package has the characteristics of broad excitation spectrum and emission spectrum, continuity and adjustability, high light conversion efficiency, aging resistance, good temperature and stable chemical performance, so that the excitation spectrum extends to a visible light region and the emission light of a blue LED is effectively absorbed;
(2) k, M is adopted as a combined low-valence cation alkaline earth metal codoping of one of Sr, Ca, Mg and Be, so that the thermal stability and the quantum efficiency are improved, the luminous intensity and the luminous efficiency are ensured, the concentration quenching effect is reduced, and Cr codoping is carried out3+，Mn4+With Cr3+Trivalent transition metal ion as sensitizing ion, Mn4+As active ions, a high-intensity red emission peak is generated, broadband excitation is carried out, relaxation among ions is consumed, and the color rendering property is improved;
(3) adopting a sol-gel method to carry out hydrolysis or chelation reaction to form sol, then gelling and burning to obtain porous particles, further grinding the porous particles so as to form continuous solid solution crystal ions, ensuring that the dispersion performance of a precursor is good and no phase separation is generated, carrying out gradient temperature-controlled high-temperature sintering in a reducing atmosphere to carry out secondary nucleation, reducing surface defects and impure phase generation so as to improve and ensure luminous intensity and luminous efficiency;
in conclusion, the red fluorescent powder has near-infrared broadband emission under the excitation of blue light, ensures the luminous intensity and luminous efficiency, has narrow particle size distribution, can be excited by near ultraviolet and blue light, and improves the environment-friendly color rendering degree of the red fluorescent powder so as to meet the requirements of LED lamps.
Detailed Description
The following examples further illustrate embodiments of the present invention.
Example 1:
a preparation method of high-color-rendering environment-friendly red fluorescent powder comprises the following steps:
s1: according to the formula KxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is Ca, R is Ti, x is 0.8, y is 0.5, a is 0.5, b is 1.1, and the raw material K is weighed according to the proportion of the computational chemical components2CO3,MCO3,Y2O3,RO2,GeO2,Cr2O3,KMnO4Respectively placing the materials in a mortar for grinding;
s2: will K2CO3,MCO3,RO2,KMnO4Sequentially adding into dilute nitric acid solution, dissolving, stirring and heating at 35 deg.C, adding citric acid and K2CO3,MCO3,RO2,KMnO4The mole ratio of the medium cations is 2: 1, adding citric acid into hot water, stirring until the citric acid is clear, mixing all solutions, and fully stirring, wherein the stirring temperature for mixing all the solutions is 80 ℃;
s3: adding oxalic acid into the mixed solution obtained in the step 3, and heating and preserving heat to obtain gel, wherein the adding amount of the oxalic acid and the citric acid are 3: 1, heating at 105 ℃ for 8 hours, putting the gel into a muffle furnace for combustion at 220 ℃ for 1 hour, taking out, cooling to room temperature, mixing with Y2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powder;
s4: placing the precursor powder in a tubular furnace, and sintering at high temperature in a reducing atmosphere, wherein the reducing atmosphere in the tubular furnace is nitrogen and hydrogen according to a volume ratio of 9: 1, heating to 680 ℃ within 30min, keeping the temperature for 1.5h, continuing heating to 1100 ℃ within 35min, keeping the temperature for 3h, cooling to 860 ℃ within 30min, keeping the temperature for 2h, taking out the materials after the furnace temperature is cooled to room temperature, further crushing and grinding the materials, performing ball milling treatment during grinding, sorting and collecting the materials by a sorting machine under the wind power traction of a cyclone separator, and performing ultrasonic cleaning, suction filtration and drying by using deionized water to obtain a fluorescent powder product.
Example 2:
a preparation method of high-color-rendering environment-friendly red fluorescent powder comprises the following steps:
s1: according to the formula KxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is Sr, R is Ti, x is 0.4, y is 0.6, a is 0.8, b is 0.8, and the raw material K is weighed according to the proportion of the computational chemical components2CO3,MCO3,Y2O3,RO2,GeO2,Cr2O3,KMnO4Respectively placing the materials in a mortar for grinding;
s2: will K2CO3,MCO3,RO2,KMnO4Sequentially adding into dilute nitric acid solution, dissolving, stirring and heating at 42 deg.C, adding citric acid and K2CO3,MCO3,RO2,KMnO4The mole ratio of the medium cations is 2.5: 1, adding citric acid into hot water, stirring until the citric acid is clear, mixing all solutions, and fully stirring, wherein the stirring temperature for mixing all the solutions is 84 ℃;
s3: adding oxalic acid into the mixed solution obtained in the step 3, and heating and preserving heat to obtain gel, wherein the adding amount of the oxalic acid and the citric acid are 4: 1, heating at 108 ℃ for 8h, putting the gel into a muffle furnace for combustion at 240 ℃ for 1.5h, taking out, cooling to room temperature, mixing with Y2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powder;
s4: putting the precursor powder into a tubular furnace, sintering at high temperature in a reducing atmosphere, wherein the reducing atmosphere in the tubular furnace is ammonia gas, heating to 660 ℃ within 30min, keeping the temperature for 1h, continuing heating to 1200 ℃ within 25min, keeping the temperature for 4h, cooling to 850 ℃ within 30min, keeping the temperature for 1h, taking out the material after the furnace temperature is cooled to room temperature, further crushing and grinding the material, performing ball milling treatment during grinding, sorting and collecting the material by a sorting machine under the wind power traction of a cyclone separator, and performing ultrasonic cleaning, suction filtration and drying by deionized water to obtain a fluorescent powder product.
Example 3:
a preparation method of high-color-rendering environment-friendly red fluorescent powder comprises the following steps:
s1: according to the formula KxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is Be, R is Si, x is 0.7, y is 0.3, a is 0.5, b is 1.7, and the raw material K is weighed according to the proportion of the computational chemical components2CO3,MCO3,Y2O3,RO2,GeO2,Cr2O3,KMnO4Respectively placing the materials in a mortar for grinding;
s2: will K2CO3,MCO3,RO2,KMnO4Sequentially adding into dilute nitric acid solution, dissolving, stirring and heating at 42 deg.C, adding citric acid and K2CO3,MCO3,RO2,KMnO4The mole ratio of the medium cations is 2.5: 1, adding citric acid into hot water, stirring until the citric acid is clear, mixing all solutions, and fully stirring, wherein the stirring temperature for mixing all the solutions is 82 ℃;
s3: adding oxalic acid into the mixed solution obtained in the step 3, and heating and preserving heat to obtain gel, wherein the adding amount of the oxalic acid and the citric acid are 3: 1, heating at 100 ℃, keeping the temperature for 8 hours, putting the gel into a muffle furnace for combustion at 250 ℃ for 1 hour, taking out, cooling to room temperature, and mixing with Y2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powder;
s4: putting the precursor powder into a tubular furnace, sintering at high temperature in a reducing atmosphere, wherein the reducing atmosphere in the tubular furnace is ammonia gas, heating to 685 ℃ within 30min, keeping the temperature for 2h, continuing heating to 1200 ℃ within 40min, keeping the temperature for 2h, then cooling to 885 ℃ within 30min, keeping the temperature for 2h, carrying out gradient temperature control, taking out the material after the furnace temperature is cooled to room temperature, further crushing and grinding the material, carrying out ball milling treatment during grinding, sorting and collecting the material by a sorting machine under the wind power traction of a cyclone separator, and carrying out ultrasonic cleaning, suction filtration and drying by using deionized water to obtain a fluorescent powder product.
The mechanism of the invention is as follows:
the yttrium germanate or yttrium titanium germanate is used as a substrate, has the characteristics of broad excitation spectrum, wide emission spectrum, continuity and adjustability, high light conversion efficiency and aging resistance, utilizes the germanate to enhance the volume of the garnet crystal package so as to extend the excitation spectrum to a visible light region, effectively absorbs the emitted light of a blue LED, has good temperature and chemical stability characteristics, has stable structure from low temperature to melting point, and gradually enhances the emission intensity along with the rise of the temperature;
k, M is adopted to Be a combined low-valence cation alkaline earth metal codoping of one of Sr, Ca, Mg and Be, so that the fluorescent powder generates obvious red shift in wavelength under the excitation of blue light and enters an yttrium silicon germanate or yttrium titanium germanate garnet crystal package, thereby improving the thermal stability and quantum efficiency, ensuring the luminous intensity and efficiency, being beneficial to reducing the concentration quenching effect due to the larger distance between the fluorescent powder and the active ions, and leading the whole body to Be free of S and have high stability and environmental protection;
by co-doping with Cr3+，Mn4+Can be effectively excited by near ultraviolet light and blue light and is made of Cr3+Trivalent transition metal ions as sensitizing ions can absorb excitation energy and transfer the energy to an activator, and Mn is used4+As an active ion, the red fluorescent material has the characteristics of strong charge transfer, easy excitation of a visible region and red light emission in any matrix, generates a high-intensity red emission peak, excites a narrow band to emit in a broadband manner, has long fluorescence service life, is cheap and easy to obtain, generates the phenomena of gravity center downward shift and energy level splitting to cause emission broad-spectrum red shift, has near-infrared broadband emission under the excitation of blue light, and improves the color rendering property;
adopting sol-gel method to mix K2CO3,MCO3,RO2,KMnO4Dissolving in dilute nitric acid solution, adding oxalic acid and citric acid to make metal salt solute and organic matter cosolvent produce hydrolysis or chelation reaction to form sol, then making sol gel and burning to obtain porous granules, further grinding, mixing all the components on atomic or molecular level so as to make the product have finer grain size and lower synthesis temperature to form continuous solid solution crystal ion, and make the dispersion property of precursor good and do not produce phase separation;
the high-temperature sintering method of gradient temperature control in reducing atmosphere is adopted, mutual diffusion and migration among various ions at high temperature are guaranteed, reaction is promoted to be carried out, secondary nucleation is carried out, powder connection crystallinity is improved, surface defects and impurity phase generation are reduced, so that luminous intensity and luminous efficiency are improved and guaranteed, hard aggregate is prevented from increasing crystal grain size and widening grain size distribution, and ball milling treatment is adopted during grinding, and sorting and collection are carried out through a sorting machine under the wind power traction of a cyclone separator;
testing and analyzing: the synthesized sample is detected by a Nicolet700 infrared spectrometer and a D/max2550X ray diffractometer, and the tube pressure is 30KV tube flow: 20mA, example KxMxY2-xR1-yGeyO5：aCr3+，bMn4+The excitation spectrum is a wide band spectrum with the peak wavelength of 380-480nm, and the spectral range is 400-4000cm-1Emission peaks are located at about 565nm, 591nm, 600nm and 613nm, and the excitation intensity is higher at 385nm near ultraviolet light and 460nm blue light;
aCr3+the a value of the ions is increased, the number of luminescence centers is increased, the position of an emission peak is not obviously changed, but the emission intensity shows the trend of increasing firstly and then reducing, the distance between activator ions can be shortened by continuously increasing the a value, the relaxation between the ions is consumed, and the phenomena of brightness reduction and concentration quenching are shown; bMn4+The b value of the ions is increased, the density of the luminescence center is improved, the luminescence intensity shows the trend of increasing firstly and then reducing, and the collision probability of the quenching center is increased along with the increase of the doping concentration;
KxMxY2-xthe x value of the ion is increased, so that the luminous intensity is increased and then reduced, the symmetry of a polyhedron around the M ion is reduced, and R1-yGeyIncrease in y value of ion, Cr3+The gravity center of ions is shifted downwards, so that an emission peak generates obvious red shift, the emission peak is sharp, the fluorescent powder prepared in embodiment 1-3 and an LED packaged by a commercial blue InGaN LED chip emit light in a broad spectrum manner, the color rendering indexes are respectively 92, 89 and 84, near-infrared broadband emission is realized under the excitation of blue light, the light emitting intensity and the light emitting efficiency are ensured, the particle size distribution is narrow, the fluorescent powder can be excited by near ultraviolet and blue light, and the environment-friendly color rendering degree of the red fluorescent powder is improved so as to meet the requirements of the LED lamp.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The high-color-rendering environment-friendly red fluorescent powder is characterized by comprising the following chemical formulas: kxMxY2-xR1-yGeyO5：aCr3 +，bMn4+Wherein M is one of Sr, Ca, Mg and Be, M is Si or Ti, x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than 0.9, a is more than or equal to 0.3 and less than 0.9, and b is more than or equal to 0.1 and less than or equal to 1.8.
2. The environment-friendly red phosphor with high color rendering property as claimed in claim 1, wherein x is 0.4-0.6, and y is 0.3-0.7.
3. The environment-friendly red phosphor with high color rendering property as claimed in claim 1, wherein a is 0.4. ltoreq. a < 0.7, and b is 0.6. ltoreq. b < 1.3.
4. The method for preparing high-color-rendering environment-friendly red phosphor according to any one of claims 1 to 3, characterized in that the method comprises:
s1: according to the formula KxMxY2-xR1-yGeyO5：aCr3+，bMn4+Wherein M is one of Sr, Ca, Mg and Be, R is Si or Ti, x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than 0.9, a is more than or equal to 0.3 and less than 0.9, b is more than or equal to 0.1 and less than 1.8, and K is weighed according to the proportion of the calculated chemical components2CO3,MCO3,Y2O3,RO2,GeO2,Cr2O3,KMnO4Respectively placing the materials in a mortar for grinding;
s2: will K2CO3,MCO3,RO2,KMnO4Sequentially adding the solution into a dilute nitric acid solution, dissolving, stirring and heating, adding citric acid into hot water, stirring until the solution is clear, mixing the solutions, and fully stirring;
s3: adding oxalic acid into the mixed solution obtained in the step 3, heating and preserving heat to obtain gel, putting the gel into a muffle furnace for combustion, taking out the gel, cooling to room temperature, and mixing with Y2O3,GeO2,Cr2O3Mixing and grinding to obtain precursor powder;
s4: and (2) placing the precursor powder in a tubular furnace, sintering at high temperature in a reducing atmosphere, taking out the material after the furnace temperature is cooled to room temperature, further crushing and grinding, and performing ultrasonic cleaning, suction filtration and drying by using deionized water to obtain a fluorescent powder product.
5. The method for preparing environment-friendly red phosphor with high color development according to claim 4, wherein the dissolving and stirring temperature in step S2 is 30-45 ℃, the amount of citric acid added and K added2CO3,MCO3,RO2,KMnO4The mole ratio of the medium cations is (1.5-2.5): 1, the stirring temperature for mixing the solutions was 75 to 85 ℃.
6. The method for preparing high-color-rendering environment-friendly red phosphor according to claim 5, wherein the addition amount of oxalic acid and citric acid in step S3 is (3-4): 1, the heating temperature is 100-.
7. The method as claimed in claim 4, wherein the muffle furnace temperature in step S3 is 200-250 deg.C, and the burning time is 1-2 h.
8. The method for preparing high-color-rendering environment-friendly red phosphor according to claim 4, wherein the reducing atmosphere in the step S4 tube furnace is one or more of nitrogen, hydrogen, ammonia, methane, acetylene and propane.
9. The method as claimed in claim 4, wherein the temperature of step S4 is increased to 650-.
10. The method for preparing high-color-rendering environment-friendly red phosphor according to claim 9, wherein the S4 is ground by ball milling and sorted and collected by a sorter under the wind power traction of a cyclone.
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