CN105542768B - A kind of high colour gamut LED MxSr1-xTiO3：The preparation method of the high-purity red light fluorescent powders of Eu3+ - Google Patents
A kind of high colour gamut LED MxSr1-xTiO3：The preparation method of the high-purity red light fluorescent powders of Eu3+ Download PDFInfo
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Abstract
The invention belongs to wet chemistry methods to prepare phosphor technologies field, and in particular to a kind of high colour gamut LED MxSr1‑xTiO3∶Eu3+The preparation method of high-purity red light fluorescent powder.The LED M prepared using sol-gal processxSr1‑xTiO3∶Eu3+(0 x≤0.5 ＜) high-purity red light fluorescent powder, can be obtained M under later stage low temperature calcinationxSr1‑xTiO3∶Eu3+High-purity red light fluorescent powder.Compared with traditional high temperature solid-state method, the later stage needed for sol-gal process, calcination temperature was low, and not high to equipment requirement, energy consumption is relatively low, was suitble to industrialized production；Eu3+ in gained fluorescent powder is uniformly dispersed, and easily enters MxSr1‑xTiO3Middle realization energy transmission；The emission peak half-wave width of gained red light fluorescent powder is relatively narrow, and feux rouges excitation purity is high；Particle size distribution is uniform, is conducive to mix with the uniform of glue in the application of fluorescent powder later stage, is suitble to the use of high colour gamut white light LEDs.
Description
Technical field
The invention belongs to wet chemistry methods to prepare phosphor technologies field, and in particular to a kind of high colour gamut LED MxSr1- xTiO3：Eu3+The preparation method of high-purity red light fluorescent powder.
Background technology
Currently, rare earth luminescent material has become the core material in the fields such as presentation of information, lighting source, photoelectric device.
Wherein, what is be most widely used is the fluorescence that can be excited and be generated different luminescent colors by ultraviolet light-blue light (200~500nm)
Powder material.The high color purity of fluorescent powder, high luminous intensity and the particle size that is evenly distributed can be obviously improved making for LED component
Use performance.Red light fluorescent powder is the essential material of high colour gamut white light LEDs, and red light fluorescent powder basis material includes mainly aluminium at present
Hydrochlorate, silicate, tungstates and titanate etc., but not the red light fluorescent powder of system in excitation purity and luminous intensity exist it is poor
It is different.
2006, Hong Zhanglian et al. mixed object etc. for raw material with alkaline earth carbonate, rare earth nitrades and auxiliary, is restoring
Calcining obtains the SrTiO of Ce, Pr, Eu, Tb, Er, Tm activation at 900~1400 DEG C under atmosphere3Fluorescent powder, find rare earth from
The SrTiO of son activation3Fluorescent powder has higher luminous intensity.In the same year, Zhao Jie et al. is with nano level SrCO3、In3O3、TiO2
And Pr (NO3)3It for raw material, is calcined at 900~1400 DEG C by high temperature solid-state method, has synthesized (Sr1-xInx)TiO3：Pr3+It is red
Emitting phosphor finds (Sr1-xInx)TiO3：Pr3+The stability of fluorescent powder is good, and brightness is higher.2010, Zhou Mingjie et al. was with Pr
(NO3)3、Ca(NO3)2、Sr(NO3)2、Ba(NO3)2, butyl titanate etc. be raw material, gelinite is forged at 900~1500 DEG C
It burns, obtains SrTiO3：Pr3+, M (M can be Ag, Au, Pt or Pd), the luminescent properties of fluorescent powder are excellent.2013, Wang Jiangying
Et al. with Sr (NO3)2、TiOSO4·2H2O、 Eu(NO3)3, Al (fine aluminium piece), tartaric acid etc. be raw material, using colloidal sol-template
Method obtains SrTiO by way of priming by vacuum-drying-heat preservation is repeated3：Eu3+Red light fluorescent powder.
Currently, the Eu reported3+Activate SrTiO3The preparation method of fluorescent powder is mostly high temperature solid-state method, after high-temperature calcination
Activator mixing is uneven in powder, causes phosphor emission peak wider, feux rouges excitation purity is low.Meanwhile obtained by high temperature solid-state method
Fluorescent powder grain particle size is uneven, the strong influence actual use performance of fluorescent powder in the devices.Conventional solid-state method
Gained Eu3+Activate SrTiO3Red light fluorescent powder material directly carries out high-temperature calcination, and activator mixing is uneven in gained fluorescent powder
Even, it is in broadband emission peak to lead to red light fluorescent powder, and feux rouges excitation purity is low, while fluorescent powder grain particle size is uneven.
Invention content
For this purpose, technical problem to be solved by the present invention lies in overcome Eu obtained by conventional solid-state method3+Activate Sr TiO3Feux rouges
Phosphor material powder is due to directly carrying out high-temperature calcination, and activator mixing is uneven in gained fluorescent powder, causes the red light fluorescent powder to be in
Broadband emission peak, feux rouges excitation purity is low, while the non-uniform technical bottleneck of fluorescent powder grain particle size, a kind of high to propose
Colour gamut LED MxSr1-xTiO3：Eu3+The preparation method of high-purity red light fluorescent powder.
In order to solve the above technical problems, a kind of high colour gamut LED M of disclosure of the inventionxSr1-xTiO3： Eu3+It is high-purity red
The preparation method of emitting phosphor, wherein the method is：
1) according to M: Sr=x: 1-x molar ratio, weigh a certain amount of MO or MCO3, by itself and Sr (OH)2·8H2O is mixed
It closes；M element can be one or both of Mg, Ca, Ba, Zn and Cu, wherein 0 x≤0.5 ＜；
According still further to Mx+Sr1-x: Ti=1: 1 molar ratio weighs the Ti (SO of corresponding amount4)2·9H2O；
According still further to Eu: MxSr1-xTiO3=(0.2~10): 100 elemental mole ratios example weighs the Eu of corresponding amount2O3；
2) each substance weighed in step 1) is collectively disposed at HNO3In solution, it is molten to obtain clear mixing for isothermal holding
Liquid；
3) it is C according to molar ratio6H8O7∶Ti(SO4)2=0.4~3.8: 1, weigh C6H8O7·H2O is placed in obtained by step 2)
Mixed solution in, stirring, obtain vitreosol body；
4) by vitreosol body obtained by step 3), mixing processing obtains wet gel body；
5) by wet gel body obtained by step 4), ripening is carried out, xerogel block is obtained；
7) xerogel block obtained by step 5) is carried out gradient increased temperature to handle to 600~850 DEG C, after being cooled to room temperature, then is ground
Mill processing, obtains MxSr1-xTiO3：Eu3+High-purity red light fluorescent powder.
Preferably, the preparation method, wherein in the step 2), HNO3A concentration of the 30% of solution.
Preferably, the preparation method, wherein in the step 2), the temperature of isothermal holding is 5 0~70 DEG C, when
Between be 35~90min.
Preferably, the preparation method, wherein in the step 3), it is that magnetic force stirs to stir used blender
Device is mixed, magnetic rotor rotating speed is 80~320rpm, and mixing time is 15~60mi n.
Preferably, the preparation method, wherein in the step 4), it is magnetic force that used blender, which is mixed,
Blender, magnetic rotor rotating speed be 25~75rpm, heating temperature be 50~80 DEG C, and heating time be 3.5~for 24 hours.
Preferably, the preparation method, wherein in the step 5), the temperature of ripening is 90~170 DEG C, when
Between be 2~16h.
More preferably, the preparation method, wherein in the step 6), the gradient increased temperature is specially：By step
5) gained xerogel block be placed in resistance furnace, with the heating rate of 10 DEG C/min be warming up to 350~400 DEG C heat preservation 2~6h, then with
The heating rate of 5 DEG C/min is warming up to 600~850 DEG C of 6~30h of calcining, takes out after furnace cooling, is then ground.
The above technical solution of the present invention has the following advantages over the prior art：
(1) the LED M that the present invention is prepared using sol-gel methodxSr1-xTiO3：Eu3+(0 x≤0.5 ＜) high-purity feux rouges
Fluorescent powder, (600-850 DEG C) can be obtained M under later stage low temperature calcinationxSr1-xTiO3：Eu3+High-purity red light fluorescent powder.With tradition
High temperature solid-state method compare, the later stage needed for sol-gel method, calcination temperature was low, and not high to equipment requirement, energy consumption is relatively low, be suitble to work
Industry metaplasia is produced.
(2) the LED M that the present invention is prepared using sol-gel methodxSr1-xTiO3：Eu3+(0 x≤0.5 ＜) high-purity feux rouges
Fluorescent powder, compared with conventional solid-state method, the Eu3+ in fluorescent powder obtained by sol-gel method is uniformly dispersed, and easily enters MxSr1-xTiO3
The emission peak half-wave width of middle realization energy transmission, gained red light fluorescent powder is relatively narrow, and feux rouges excitation purity is high.
(3) the LED M that the present invention is prepared using sol-gel methodxSr1-xTiO3：Eu3+(0 x≤0.5 ＜) high-purity feux rouges
Fluorescent powder, compared with conventional solid-state method, fluorescent powder particle size distribution is uniform obtained by sol-gel method, after being conducive to fluorescent powder
It is mixed with the uniform of glue in phase application.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the Ca prepared in embodiment 10.2Sr0.8TiO3：0.02Eu3+The X ray diffracting spectrum of red light fluorescent powder.
Fig. 2 is the Ca prepared in embodiment 10.2Sr0.8TiO3：0.02Eu3+The particle diameter distribution histogram of red light fluorescent powder.
Fig. 3 is the Mg prepared in embodiment 20.1Ba0.4Sr0.5TiO3：0.08Eu3+The emission spectrum of red light fluorescent powder.
Fig. 4 is the Zn prepared in embodiment 30.05Sr0.95TiO3：0.002Eu3+The emission spectrum of red light fluorescent powder.
Specific implementation mode
Present embodiment discloses a kind of high colour gamut LED M for embodiment 1xSr1-xTiO3：Eu3+The system of high-purity red light fluorescent powder
Preparation Method is as follows：
(1) according to Ca: Sr: Ti=0.2: 0.8: 1 molar ratio, weigh the CaCO of 0.395g3Powder, the Sr of 2.126g
(OH)2·8H2Ti (the SO of O and 4.021g4)2·9H2O.According to Eu3+Molar concentration be 4mo% (refer to Eu3+Account for basis material
Ca0.2Sr0.8TiO3Molar concentration), weigh the Eu of 0.070g2O3Powder.
(2) by the CaCO in step 1)3、Sr(OH)2·8H2O、Ti(SO4)2·9H2O and Eu2O3Powder is collectively disposed at
The HNO of 100mL a concentration of 30%3In solution, 90min is kept the temperature at 50 DEG C, obtains clear Ca2+、Sr2+、Ti4+And Eu3+It is mixed
Close solution.
(3) according to C6H8O7(citric acid): Ti=2.25: 1 molar ratio weighs the C of 4.728g6H8O7·H2O is placed in
In the solution of step 2), then solution is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is stirred for 240rpm
45min makes each reactant be uniformly mixed, and obtains vitreosol body.
(4) vitreosol body obtained by step 3) is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is 25rpm, is stirred
It is to be mixed slowly and heated 12h at 80 DEG C to mix device heating temperature, obtains wet gel body.
(5) wet gel body obtained by step 4) is placed in baking oven, 2h is kept the temperature at 150 DEG C and is aged, after furnace cooling
It takes out, obtains xerogel block.
(6) xerogel block obtained by step 5) is placed in resistance furnace, 380 DEG C of guarantors is warming up to the heating rate of 10 DEG C/min
Warm 2h, then heated up 750 DEG C of calcining 18h with the heating rate of 5 DEG C/min, takes out after furnace cooling, be ground to get
Ca0.2Sr0.8TiO3：0.02Eu3+High-purity red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, is specifically shown in Fig. 1, Fig. 2 institute
Show, it is found that the particle median particle diameter of fluorescent powder is 5.4 μm, peak wavelength 619nm, chromaticity coordinates is (x=0.6392, y=
0.3541), the wide about 32nm of emission peak half-wave, feux rouges excitation purity are 98.7%.
Present embodiment discloses a kind of high colour gamut LED M for embodiment 2xSr1-xTiO3：Eu3+The system of high-purity red light fluorescent powder
Preparation Method is as follows：
(1) according to Mg: Ba: Sr: Ti=0.1: 0.4: 0.5: 1 molar ratio, weigh the MgO of 0.040 g,
0.789gBaCO3Powder, the Sr (OH) of 1.329g2·8H2Ti (the S O of O and 4.021g4)2·9H2O.According to Eu3+Mole
A concentration of 1mol% (refers to Eu3+Account for basis material Mg0.1Ba0.4Sr0.5TiO3Molar concentration), weigh the Eu of 0.018g2O3Powder.
(2) by MgO, BaCO in step 1)3、Sr(OH)2·8H2O、Ti(SO4)2·9H2O and Eu2O3Powder is set jointly
In the HNO of 100mL a concentration of 30%3In solution, 45min is kept the temperature at 70 DEG C, obtains clear Mg2+、Ba2+、Sr2+、Ti4+With
And Eu3+Mixed solution.
(3) according to C6H8O7(citric acid): Ti=3.2: 1 ratio weighs the C of 6.724g6H8 O7·H2O is placed in step
2) in solution, then solution is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is that 320rpm is stirred 15min,
So that each reactant is uniformly mixed, obtains vitreosol body.
(4) vitreosol body obtained by step 3) is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is 50rpm, is stirred
It is to be mixed slowly and heated 6h at 65 DEG C to mix device heating temperature, obtains wet gel body.
(5) wet gel body obtained by step 4) is placed in baking oven, 14h is kept the temperature at 90 DEG C and is aged, after furnace cooling
It takes out, obtains xerogel block.
(6) xerogel block obtained by step 5) is placed in resistance furnace, 400 DEG C of guarantors is warming up to the heating rate of 10 DEG C/min
Warm 3h, then with the heating rate of 5 DEG C/min be warming up to 600 DEG C calcining 10h, taken out after furnace cooling, be ground to get
Mg0.1Ba0.4Sr0.5TiO3：0.08Eu3+High-purity red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, as shown in figure 3, hair
The particle median particle diameter of existing fluorescent powder is 2.9 μm, peak wavelength 626nm, and chromaticity coordinates is (x=0.6435, y=0.3577),
The wide about 29nm of emission peak half-wave, feux rouges excitation purity is 99.5%.
Present embodiment discloses a kind of high colour gamut LED M for embodiment 3xSr1-xTiO3：Eu3+The system of high-purity red light fluorescent powder
Preparation Method is as follows：
(1) according to Zn: Sr: Ti=0.05: 0.95: 1 molar ratio, weigh the Zn O powders of 0.041g, the Sr of 2.525g
(OH)2·8H2Ti (the SO of O and 4.021g4)2·9H2O.According to Eu3+Molar concentration be 0.2mol% (refer to Eu3+Account for matrix
Material Zn0.05Sr0.95TiO3Molar concentration), weigh the Eu of 0.004g2O3Powder.
(2) by ZnO, Sr (OH) in step 1)2·8H2O、Ti(SO4)2·9H2O and Eu2O3Powder is collectively disposed at
The HNO of 100mL a concentration of 30%3In solution, 40min is kept the temperature at 70 DEG C, obtains clear Zn2+、Sr2+、Ti4+And Eu3+It is mixed
Close solution.
(3) according to C6H8O7(citric acid): Ti=3.8: 1 ratio weighs the C of 7.985g6H8 O7·H2O is placed in step
2) in solution, then solution is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is that 80rpm is stirred 60min, is made
Each reactant is uniformly mixed, and obtains vitreosol body.
(4) vitreosol body obtained by step 3) is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is 60rpm, is stirred
It is to be mixed slowly and heated 3.5h at 55 DEG C to mix device heating temperature, obtains wet gel body.
(5) wet gel body obtained by step 4) is placed in baking oven, 16h is kept the temperature at 130 DEG C and is aged, after furnace cooling
It takes out, obtains xerogel block.
(6) xerogel block obtained by step 5) is placed in resistance furnace, 350 DEG C of guarantors is warming up to the heating rate of 10 DEG C/min
Warm 4h, then with the heating rate of 5 DEG C/min be warming up to 800 DEG C calcining 6h, taken out after furnace cooling, be ground to get
Zn0.05Sr0.95TiO3：0.002Eu3+High-purity red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, as shown in figure 4, finding
The particle median particle diameter of fluorescent powder is 7. 1 μm, peak wavelength 623nm, and chromaticity coordinates is (x=0.6484, y=0.3505), hair
The wide about 33nm of peak half-wave is penetrated, feux rouges excitation purity is 98.6%.
Present embodiment discloses a kind of high colour gamut LED M for embodiment 4xSr1-xTiO3：Eu3+The system of high-purity red light fluorescent powder
Preparation Method is as follows：
(1) according to Cu: Sr: Ti=0.25: 0.75: 1 molar ratio, weigh the Cu O powders of 0.199g, the Sr of 1.993g
(OH)2·8H2Ti (the SO of O and 4.021g4)2·9H2O.According to Eu3+Molar concentration be 10mol% (refer to Eu3+Account for matrix material
Expect Cu0.25Sr0.75TiO3Molar concentration), weigh the Eu of 0.176g2O3Powder.
(2) by CuO, Sr (OH) in step 1)2·8H2O、Ti(SO4)2·9H2O and Eu2O3Powder is collectively disposed at
The HNO of 100mL a concentration of 30%3In solution, 35min is kept the temperature at 65 DEG C, obtains clear Cu2+、Sr2+、Ti4+And Eu3+It is mixed
Close solution.
(3) according to C6H8O7(citric acid): Ti=0.4: 1 ratio weighs the C of 0.841g6 H8O7·H2O is placed in step
2) in solution, then solution is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is that 160rpm is stirred 55min,
So that each reactant is uniformly mixed, obtains vitreosol body.
(4) vitreosol body obtained by step 3) is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is 75rpm, is stirred
It is to be mixed slowly and heated for 24 hours, obtain wet gel body at 70 DEG C to mix device heating temperature.
(5) wet gel body obtained by step 4) is placed in baking oven, 9h is kept the temperature at 110 DEG C and is aged, after furnace cooling
It takes out, obtains xerogel block.
(6) xerogel block obtained by step 5) is placed in resistance furnace, 360 DEG C of guarantors is warming up to the heating rate of 10 DEG C/min
Warm 6h, then with the heating rate of 5 DEG C/min be warming up to 850 DEG C calcining for 24 hours, taken out after furnace cooling, be ground to get
Cu0.25Sr0.75TiO3：0.05Eu3+High-purity red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, finds the particle of fluorescent powder
Median particle diameter is 9.3 μm, peak wavelength 621nm, and chromaticity coordinates is (x=0.6382, y=0.3519), and emission peak half-wave is wide about
For 35nm, feux rouges excitation purity is 98.2%.
Present embodiment discloses a kind of high colour gamut LED M for embodiment 5xSr1-xTiO3：Eu3+The system of high-purity red light fluorescent powder
Preparation Method is as follows：
(1) according to Ba: Sr: Ti=0.5: 0.5: 1 molar ratio, weigh the BaCO of 0.987g3Powder, the Sr of 1.329g
(OH)2·8H2Ti (the SO of O and 4.021g4)2·9H2O.According to Eu3+Molar concentration be 7mol% (refer to Eu3+Account for matrix material
Expect Ba0.5Sr0.5TiO3Molar concentration), weigh the Eu of 0.123 g2O3Powder.
(2) by the BaCO in step 1)3、Sr(OH)2·8H2O、Ti(SO4)2·9H2O and Eu2O3Powder is collectively disposed at
The HNO of 100mL a concentration of 30%3In solution, 60min is kept the temperature at 55 DEG C, obtains clear Ba2+、Sr2+、Ti4+And Eu3+It is mixed
Close solution.
(3) according to C6H8O7((citric acid): the ratio of Ti=1.21 weighs the C of 2.522g6H8O7·H 2O is placed in step 2)
Solution in, then solution is placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 200rpm be stirred 30min, make
Each reactant is uniformly mixed, and obtains vitreosol body.
(4) vitreosol body obtained by step 3) is placed on magnetic stirring apparatus, control magnetic rotor rotating speed is 35rpm, is stirred
It is to be mixed slowly and heated 16h at 50 DEG C to mix device heating temperature, obtains wet gel body.
(5) wet gel body obtained by step 4) is placed in baking oven, 12h is kept the temperature at 170 DEG C and is aged, after furnace cooling
It takes out, obtains xerogel block.
(6) xerogel block obtained by step 5) is placed in resistance furnace, 385 DEG C of guarantors is warming up to the heating rate of 10 DEG C/min
Warm 5h, then with the heating rate of 5 DEG C/min be warming up to 700 DEG C calcining 30h, taken out after furnace cooling, be ground to get
Ba0.5Sr0.5TiO3：0.035Eu3+High-purity red light fluorescent powder.Dependence test is carried out to gained fluorescent powder, finds the particle of fluorescent powder
Median particle diameter is 6.7 μm, peak wavelength 625nm, and chromaticity coordinates is (x=0.6435, y=0.3577), and emission peak half-wave is wide about
For 31nm, feux rouges excitation purity is 99.3%.
Technique described in embodiment 1-5 can be obtained micron-sized LED M under later stage low temperature calcinationxSr1-xTiO3：Eu3+
The particle size distribution of high-purity red light fluorescent powder, fluorescent powder is uniform, and feux rouges excitation purity is high.It is obtained using sol-gal process
MxSr1-xTiO3：Eu3+(0 x≤0.5 ＜) fluorescent powder grain particle diameter distribution is uniform, and emission peak half-wave width is relatively narrow, feux rouges excitation purity
Height is suitble to the use of high colour gamut white light LEDs.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (3)
1. a kind of LED MxSr1-xTiO3：Eu3+The preparation method of red light fluorescent powder, which is characterized in that the method is：
1) according to M：Sr=x：The molar ratio of 1-x weighs a certain amount of MO or MCO3, by itself and Sr (OH)2·8H2O is mixed；M members
Element is one or both of Mg, Ca, Ba, Zn and Cu, wherein 0 x≤0.5 ＜；
According still further to Mx+Sr1-x：Ti=1：1 molar ratio weighs the Ti (SO of corresponding amount4)2·9H2O；
According still further to Eu：MxSr1-xTiO3=(0.2~10)：100 elemental mole ratios example, weighs the Eu of corresponding amount2O3；
2) each substance weighed in step 1) is collectively disposed at HNO3In solution, isothermal holding obtains clear mixed solution；
3) it is C according to molar ratio6H8O7：Ti(SO4)2=0.4~3.8：1 weighs C6H8O7·H2O is placed in the mixing obtained by step 2)
In solution, stirring obtains vitreosol body；
4) by vitreosol body obtained by step 3), mixing processing obtains wet gel body；
5) by wet gel body obtained by step 4), ripening is carried out, xerogel block is obtained；
6) xerogel block obtained by step 5) is carried out gradient increased temperature to handle to 600~850 DEG C, after being cooled to room temperature, then grinds place
Reason, obtains MxSr1-xTiO3：Eu3+Red light fluorescent powder；
In the step 2), the temperature of isothermal holding is 50~70 DEG C, and the time is 35~90min；
In the step 3), it is magnetic stirring apparatus to stir used blender, and magnetic rotor rotating speed is 80~320rpm, stirring
Time is 15~60min；
In the step 4), it is magnetic stirring apparatus that used blender, which is mixed, and magnetic rotor rotating speed is 25~75rpm,
Heating temperature be 50~80 DEG C, and heating time be 3.5~for 24 hours；
In the step 5), the temperature of ripening is 90~170 DEG C, and the time is 2~16h.
2. preparation method as described in claim 1, which is characterized in that in the step 2), HNO3A concentration of the 30% of solution.
3. preparation method as claimed in claim 2, which is characterized in that in the step 6), the gradient increased temperature is specially：It will
Xerogel block is placed in resistance furnace obtained by step 5), and 350~400 DEG C of 2~6h of heat preservation are warming up to the heating rate of 10 DEG C/min,
600~850 DEG C of 6~30h of calcining are warming up to the heating rate of 5 DEG C/min again, takes out after furnace cooling, is then ground.
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