CN107474836A - A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof - Google Patents

A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof Download PDF

Info

Publication number
CN107474836A
CN107474836A CN201710631241.XA CN201710631241A CN107474836A CN 107474836 A CN107474836 A CN 107474836A CN 201710631241 A CN201710631241 A CN 201710631241A CN 107474836 A CN107474836 A CN 107474836A
Authority
CN
China
Prior art keywords
activation
fluorine
fluorescent powder
red fluorescent
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710631241.XA
Other languages
Chinese (zh)
Inventor
焦桓
周洋
张帅
何地平
王晓明
徐玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN201710631241.XA priority Critical patent/CN107474836A/en
Publication of CN107474836A publication Critical patent/CN107474836A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof, red fluorescence powder formula AxWF6:Mn4+ yThe material of expression forms, and A represents Na or K in formula, when A is Na, x=1, and when A is K, x=3；Y value is 0.01~0.1.It is of the invention first with WO3And AHF2For raw material, in H2A is prepared in atmospherexWF6, then by K2MnF6And AxWF6Low-temperature solid phase reaction doping Mn is carried out in nitrogen atmosphere is fluorinated4+, obtain Mn4+The fluorine tungstate red fluorescent powder of activation.The preparation method of fluorescent material of the present invention is simple and safe, and reaction temperature is relatively low, pollution-free, it is controllable to activate agent content, and prepared red light emitting phosphor is functional, it is launched the wavelength of light and not changed, and is adapted to White-light LED illumination device and backlight etc. to require higher field to luminescent material.

Description

A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof
Technical field
The invention belongs to luminescent material technical field, and in particular to a kind of Mn4+The fluorine tungstate red fluorescent powder of activation and Its preparation method.
Background technology
At present, luminescent material has become the backing material in the fields such as presentation of information, lighting source, photoelectric device, fluorescence The high luminous intensity of powder and good micro-shape can effectively improve the performance of display, therefore, novel fluorescent material Research and application always one of important research field of materials chemistry and materials physics.
Since invention in 1996, it saves and makes people couple the characteristics of environment-friendly white light-emitting diode (WLEDs) It has been sent in unlimited hope, and luminescent material is for WLEDs every property, such as chromaticity coordinates, associated temperature coefficient etc. have Very important effect.YAG:Ce3+Combined earliest with LED blue chip and produce white light and turn into widely used in WLEDs Business yellow fluorescent powder, but low excitation, Gao Xiang be present due to lacking emitting red light composition in the WLEDs so combined The shortcomings of closing temperature coefficient, it is difficult to applied to general lighting and the backlight of display device.
Although researcher targetedly develops the red fluorescence powder such as nitride, fluoride, preparation condition Harshness makes its manufacturing cost remain high, and the broadband emission of nitride red fluorescent powder and low excitation seriously constrain Its application in display device backlight source.Composition, heat treatment time and the temperature of fluorination matter fluorescent powder are to determine fluorescent material hair An important factor for optical property.By controlling the composition of fluorescent material, heat treatment temperature, time, it can prepare that luminous intensity is high, powder The smooth fluorination matter fluorescent powder of regular particles, particle surface.In recent years, a series of fluoride red fluorescence powder of Mn (IV) activation (formula Aa-xBxMX6:Mn4+ yThe material of expression forms, and M represents Si, Ge, Ti, Sn or Zr in formula, and X represents halogen, and y represents Mn4 +Molal quantity, y value is 0.01~0.10, a=1 or 2, and during wherein a=2, x value is 0~1, and A, B are each independent Represent Na, K, Cs or Rb, during a=1, x value is 0~2, A, B each independent representative Mg, Ba or Zn, and A, B are differed) Red fluorescence powder attracts attention.Such as Mn4+The K of activation2TiF6Excitation spectrum can be ultraviolet and blue with LED well Color chip is luminous to match, and in 500K without obvious light decay.
The preparation method of the fluoride red fluorescence powder of existing Mn (IV) activation generally has 4 classes：(1) room temperature chemical erosion； (2) hydro-thermal method；(3) ion-exchange；(4) coprecipitation method.The Mn (IV) of high quality can be synthesized using these methods The fluoride red fluorescence powder of activation, but be largely to use HF during synthetizing phosphor powder bar none, quite a few Activator ion Mn4+It is present among liquid phase, causes the harm to environment, while there is also potential safety hazard, and in product The concentration of activator ion just can determine that by subsequent analysis.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of luminous intensity is high, granularity is controllable, service life length Mn4+The fluorine tungstate red fluorescent powder of activation, and provide a kind of simple to operate, safety and activator concentration for the red fluorescence powder Controllable preparation method.
Mn used by solution above-mentioned technical problem4+The fluorine tungstate red fluorescent powder formula A of activationxWF6:Mn4+ yTable The material shown forms, and A represents Na or K in formula, when A is Na, x=1, and when A is K, x=3；Y value is 0.01~0.1.
Above-mentioned Mn4+In the fluorine tungstate red fluorescent powder of activation, preferably A represents K, x=3.
Above-mentioned Mn4+In the fluorine tungstate red fluorescent powder of activation, further preferred y value is 0.03~0.05.
Above-mentioned Mn4+The preparation method of the fluorine tungstate red fluorescent powder of activation is made up of following step：
1st, according to AxWF6Stoichiometric proportion, by WO3And AHF2It is well mixed, in H2In atmosphere 200~360 DEG C insulation 2~ 5 hours, obtain AxWF6。
2nd, according to AxWF6:Mn4+ yStoichiometric proportion weigh K2MnF6And AxWF6, polytetrafluoroethylene (PTFE) is put into after well mixed In the reactor of liner, and the plastic tube for filling hydrofluoric acid, wherein A are put into polytetrafluoroethyllining liningxWF6Quality and hydrogen The volume ratio of fluoric acid is 1g:0.02~0.50mL, 80~120 DEG C are incubated 0.5~2 hour in confined conditions, after the completion of reaction Normal temperature is cooled to, product is dried after being washed successively with acetone, deionized water, absolute ethyl alcohol, obtains Mn4+The fluorine tungstates of activation is red Color fluorescent material.
In above-mentioned steps 1, preferably in H2300~340 DEG C are incubated 2~3 hours in atmosphere.
In above-mentioned steps 2, preferably in confined conditions 90~110 DEG C are incubated 1 hour.
In above-mentioned steps 2, the AxWF6Quality and hydrofluoric acid the preferred 1g of volume ratio:0.05~0.25mL, wherein institute The mass fraction for stating hydrogen fluoride in hydrofluoric acid is 30%~49%.
The present invention is using low-temperature solid-phase method synthesis Mn4+The fluorine tungstate red fluorescent powder of activation, compared to other Mn4+Swash Fluoride red fluorescence powder living has the following advantages that：
1st, the preparation temperature of red fluorescence powder of the present invention is relatively low, simple to operate, and reaction time is short, and course of reaction is easy to control System, there is great business potential.
2nd, the preparation method of red fluorescence powder of the present invention is green, needs substantial amounts of hydrofluoric acid phase with precipitation synthetic method Than only needing extremely a small amount of hydrofluoric acid in reaction, about precipitating the 1/500 of synthetic method, and major part has been volatilized for gas Reaction is participated in, solves pollution problem serious in product building-up process, and reduce potential safety hazard.
3rd, the ratio of activator is controllable in preparation method of the present invention, will not cause activator wastage of material, save medicine, Cost is low.
4th, the red fluorescence powder stability prepared by the present invention is high, fluorescence intensity is high, service life length, entirely appropriate white light The requirement of LED component, there is important industrial application value.
Brief description of the drawings
Fig. 1 is K prepared by embodiment 13WF6:Mn4+ 0.01The X-ray diffractogram of red fluorescence powder.
Fig. 2 is K prepared by embodiment 13WF6:Mn4+ 0.01The stereoscan photograph of red fluorescence powder.
Fig. 3 is K prepared by embodiment 13WF6:Mn4+ 0.01The X-ray energy analysis chart of red fluorescence powder.
Fig. 4 is K prepared by embodiment 1~33WF6:Mn4+ 0.01、K3WF6:Mn4+ 0.03And K3WF6:Mn4+ 0.04Red fluorescence powder Launching light spectrogram.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
K used in example below2MnF6Preparation method be：By 6.4g KMnO4With 128.0g KHF2It is placed in In 1000mL plastic measuring glass, add in the aqueous hydrogen fluoride solution that 420mL mass fractions are 49%, ice bath stirs in confined conditions It is completely dissolved to solid, the H that 5.10mL mass fractions are 30% is then added dropwise2O2The aqueous solution, drip rear stirring at normal temperature 30 Minute, stratification, outwell supernatant liquor, hydrofluoric acid and acetone respectively washing 3 times of precipitation mass fraction 20%, 60 DEG C of dryings 4 hours, obtain K2MnF6。
Embodiment 1
1st, according to K3WF6Stoichiometric proportion, by 10g WO3With 19.62g KHF2It is well mixed, it is transferred in corundum boat, In H2340 DEG C are incubated 2 hours in atmosphere, after the completion of reaction, are down to normal temperature naturally, obtain K3WF6。
2nd, according to K3WF6:Mn4+ 0.01Stoichiometric proportion weigh 0.4151g K3WF6With 0.0024g K2MnF6, in mortar In be fully ground it is well mixed after be put into the reactor of polytetrafluoroethyllining lining, and be put into and fill in polytetrafluoroethyllining lining The plastic tube of 0.025mL hydrofluoric acid (hydrogen fluoride mass fraction is 49%), 110 DEG C are incubated 1 hour in confined conditions, have reacted After be cooled to normal temperature, after product is washed with acetone, deionized water, absolute ethyl alcohol successively, 60 DEG C dry 2 hours, obtain K3WF6: Mn4+ 0.01Red fluorescence powder.
Embodiment 2
The step 1 of the present embodiment is same as Example 1, obtains K3WF6.In the step 2 of the present embodiment, according to K3WF6:Mn4 + 0.03Stoichiometric proportion weigh 0.4151g K3WF6With 0.0072g K2MnF6, other steps are identical with the step 2 of embodiment 1, Obtain K3WF6:Mn4+ 0.03Red fluorescence powder.
Embodiment 3
The step 1 of the present embodiment is same as Example 1, obtains K3WF6.In the step 2 of the present embodiment, according to K3WF6:Mn4 + 0.04Stoichiometric proportion weigh 0.4151g K3WF6With 0.0096g K2MnF6, other steps are identical with the step 2 of embodiment 1, Obtain K3WF6:Mn4+ 0.04Red fluorescence powder.
Fluorescent material prepared by embodiment 1~3 is lighted using the F-4600 XRFs test of Hitachi, Ltd's production Performance measurement, the TM3030 types desk type scanning electronic microscope (SEM) produced using HIT observe product grain Pattern, the type x-ray powder diffraction instruments of Rigaku mini flex 6000 produced using Rigaku Co., Ltd. are entered to product (test condition is row material phase analysis：CuK α are radiated, voltage 40KV, electric current 15mA, and scanning range is 10 °~60 °, scanning Speed is 10 °/min, and step-length is 0.02 °), as a result see Fig. 1~3.
As seen from Figure 1, the diffraction maximum and K of the fluorescent material prepared by embodiment 13WF6Standard card is consistent, and thing compare it is pure, There is no obvious dephasign.From Figure 2 it can be seen that prepared fluorescent powder grain size uniform, at 10~25 μm or so.As seen from Figure 3, institute Contain tetra- kinds of elements of K, W, F, Mn in the fluorescent material of preparation.The result of complex chart 1 and Fig. 3, illustrate K has been prepared3WF6:Mn4 + 0.01.From fig. 4, it can be seen that the fluorescent material prepared by embodiment 1~3, under 460nm exciting lights, emission peak is located at 630nm, category In Mn4+'s2Eg→4A2gCharacteristic transition is launched, and illustrates that sample glows, and luminous intensity is high, and excitation is preferable, available for white light LED。
Embodiment 4
1st, according to NaWF6Stoichiometric proportion, by 10g WO3With 11.12g NaHF2It is well mixed, it is transferred to corundum boat In, in H2200 DEG C are incubated 2 hours in atmosphere, after the completion of reaction, are down to normal temperature naturally, obtain NaWF6。
2nd, according to NaWF6:Mn4+ 0.01Stoichiometric proportion weigh 0.3208g NaWF6With 0.0024g K2MnF6, other steps Suddenly it is identical with the step 2 of embodiment 1, obtain NaWF6:Mn4+ 0.01Red fluorescence powder.

Claims (8)

  1. A kind of 1. Mn4+The fluorine tungstate red fluorescent powder of activation, it is characterised in that：Red fluorescence powder formula AxWF6:Mn4+ y The material of expression forms, and A represents Na or K in formula, when A is Na, x=1, and when A is K, x=3；Y value be 0.01~ 0.1。
  2. 2. Mn according to claim 14+The fluorine tungstate red fluorescent powder of activation, it is characterised in that：Described A represents K, X=3.
  3. 3. Mn according to claim 1 or 24+The fluorine tungstate red fluorescent powder of activation, it is characterised in that：The y's takes It is worth for 0.03~0.05.
  4. A kind of 4. Mn described in claim 14+The preparation method of the fluorine tungstate red fluorescent powder of activation, it is characterised in that it by Following step forms：
    (1) according to AxWF6Stoichiometric proportion, by WO3And AHF2It is well mixed, in H2200~360 DEG C of insulations 2~5 are small in atmosphere When, obtain AxWF6；
    (2) according to AxWF6:Mn4+ yStoichiometric proportion weigh K2MnF6And AxWF6, polytetrafluoroethyllining lining is put into after well mixed Reactor in, and the plastic tube for filling hydrofluoric acid, wherein A are put into polytetrafluoroethyllining liningxWF6Quality and hydrofluoric acid Volume ratio be 1g:0.02~0.50mL, 80~120 DEG C are incubated 0.5~2 hour in confined conditions, are cooled down after the completion of reaction To normal temperature, product is dried after being washed successively with acetone, deionized water, absolute ethyl alcohol, obtains Mn4+The fluorine of activation is tungstate red glimmering Light powder.
  5. 5. Mn according to claim 44+The preparation method of the fluorine tungstate red fluorescent powder of activation, it is characterised in that：Step Suddenly in (1), in H2300~340 DEG C are incubated 2~3 hours in atmosphere.
  6. 6. Mn according to claim 44+The preparation method of the fluorine tungstate red fluorescent powder of activation, it is characterised in that：Step Suddenly in (2), 90~110 DEG C are incubated 1 hour in confined conditions.
  7. 7. the Mn according to claim 4 or 64+The preparation method of the fluorine tungstate red fluorescent powder of activation, it is characterised in that： In step (2), the AxWF6Quality and the volume ratio of hydrofluoric acid be 1g:0.05~0.25mL.
  8. 8. Mn according to claim 74+The preparation method of the fluorine tungstate red fluorescent powder of activation, it is characterised in that：Step Suddenly in (2), the mass fraction of hydrogen fluoride is 30%~49% in the hydrofluoric acid.
CN201710631241.XA 2017-07-28 2017-07-28 A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof Pending CN107474836A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710631241.XA CN107474836A (en) 2017-07-28 2017-07-28 A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710631241.XA CN107474836A (en) 2017-07-28 2017-07-28 A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof

Publications (1)

Publication Number Publication Date
CN107474836A true CN107474836A (en) 2017-12-15

Family

ID=60596788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710631241.XA Pending CN107474836A (en) 2017-07-28 2017-07-28 A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107474836A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433626A (en) * 2016-09-22 2017-02-22 陕西师范大学 Method for preparing Mn(IV)-activated fluoride red fluorescent powder

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433626A (en) * 2016-09-22 2017-02-22 陕西师范大学 Method for preparing Mn(IV)-activated fluoride red fluorescent powder

Similar Documents

Publication Publication Date Title
CN106433626B (en) A kind of preparation method of the fluoride red fluorescence powder of Mn (IV) activation
CN106800930B (en) A kind of oxyfluoride red fluorescence powder and preparation method thereof of Mn (IV) activation
CN101475801B (en) Antimonate series luminescent material for white light LED and preparation thereof
CN103911147A (en) Near-infrared long-afterglow fluorescent powder and preparation method thereof
CN106832311B (en) Eu-MOF multicolor luminous crystal material, Tb-MOF green light crystal material and preparation method thereof
CN108350356A (en) Metal fluoride red-emitting phosphor and use its light-emitting component
CN107474835A (en) A kind of fluooxycolumbate red fluorescence powder of Mn (IV) activation and preparation method thereof
CN113583656A (en) Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof
CN105950143A (en) Red phosphor, preparation method thereof and light emitting device using red phosphor
CN104130774B (en) A kind of Chlorosilicate phosphor powder and preparation method thereof
CN106433624A (en) Uniform-appearance and high-color-purity Mn4+ activated red fluoride luminescent material prepared by using micro-emulsion method
CN102146286A (en) Tungstate matrix upper conversion white light emitting material and preparation method thereof
CN102286284B (en) Method for synthesizing unidimensional red long-afterglow phosphor material
CN114181104A (en) N-acetyl ethylenediamine metal halide low-dimensional perovskite single crystal material, preparation method and application thereof
CN108359460A (en) A kind of fluoride red fluorescence powder and preparation method thereof of Mn (IV) activation
CN104212457B (en) Fluoroborosilicate-based red phosphor, and preparation method and application thereof
CN106833643B (en) A kind of green emitting phosphor and preparation method thereof of ultraviolet/near ultraviolet excitation
CN107474836A (en) A kind of Mn4+Fluorine tungstate red fluorescent powder of activation and preparation method thereof
CN111100634A (en) Long-afterglow fluorescent material and preparation method thereof
CN110511755A (en) A kind of indigo plant is light activated to mix the molybdate red luminescent material of Mn4+
CN107353901A (en) A kind of Mn4+Fluorine molybdate red phosphor of activation and preparation method thereof
CN106590657B (en) A kind of lutetium aluminate green fluorescent powder and its preparation method and application
CN102295927A (en) Fluorescent powder for white LED (Light Emitting Diode) and preparation method thereof
CN109734940A (en) A kind of preparation method of the luminous canopy film of rare earth silicate base composite red color
CN105295916B (en) A kind of silicate green fluorescent powder and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171215