CN104016345A - Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate - Google Patents

Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate Download PDF

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CN104016345A
CN104016345A CN201410243022.0A CN201410243022A CN104016345A CN 104016345 A CN104016345 A CN 104016345A CN 201410243022 A CN201410243022 A CN 201410243022A CN 104016345 A CN104016345 A CN 104016345A
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titanium carbide
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CN104016345B (en
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张建峰
王红兵
吴玉萍
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Hohai University HHU
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Abstract

The invention discloses a method for preparing a graphene-like two-dimensional laminar titanium carbide nanoplate. The method comprises the following steps: preparing Ti3AlC2 powder by an in-situ hot-pressing solid-liquid reaction; preparing two-dimensional titanium carbide by a chemical liquid phase reaction; performing vacuum calcination post-treatment, and the like. The method can be used for preparing a Ti3AlC2 precursor with excellent crystallinity and high purity under simple process flow, stable process parameters, controllable process, high efficiency, low cost, short time and low pressure; the information that the transverse size of the two dimensional Ti3AlC2 nanoplate prepared by the method can be 5-10 microns, the average thickness of a single layer is about 10-20 nanometers can be found from an SEM picture, the inter-laminar spacing is remarkably enlarged after calcination treatment, and the laminar surface is regular and smooth.

Description

The preparation method of one kind Graphene two-dimensional layer titanium carbide nanometer sheet
Technical field
The invention belongs to the preparing technical field of nano material, relate to particularly a kind of method of synthetic class Graphene two-dimensional layer titanium carbide nanometer sheet.
Background technology
Since the people such as Novoselov and Geim finds Graphene, synthetic, performance and the application of two-dimensional material have become the most interested important research field of material supply section scholars, and academia has started the research boom of a new round to two-dimensional material thus.Material structure, after changing two dimension into by three-dimensional, has shown unique surface tissue and characteristic electron, has had good mechanics, calorifics, electricity and optical property.Being for example that the peelable Graphene obtaining has the performances such as high transmission rate, high thermal conductivity coefficient, high electron mobility and extremely low resistivity lamellar graphite by simple micromechanics stripping method, is the material of the most attractive and scientific research value in recent years.Two-dimensional nanostructure material taking Graphene as Typical Representative has shown wide application prospect comprising in the fields such as field-effect transistor, flexible and transparent electrode, touch-screen, advanced composite material, sensor, support of the catalyst, energy storage device.At present wide concerned class Graphene two-dimensional layer material mainly contains Transition-metal dichalcogenide, transition metal oxide and metal hydroxides, the precursor of these stratified materials because of the Van der Waals interaction force between synusia a little less than, be easy to them to peel off the sheet structure that becomes two-dimentional single or multiple lift.
2011, the Barsoum seminar of Drexel university of the U.S. synthesized the C/N compound (Naguib M., et al., Adv.Mater., 2011,23,4248-4253) of novel two-dimensional layer transition metal.The precursor that they are used for peeling off is that a class is called as M n+1aX nthe ternary layered sintering metal compound (M is early stage transition metal, and A is mainly IIIA or IVA family element, and X is C and/or N element, n=1,2 or 3) of phase.Although A atomic layer chemical activity is stronger, compared with the layer structure material such as graphite, BN weak with interlaminar action power, between the three-dimensional synusia of this compounds, there is extremely strong bond energy and be difficult to be stripped from.Obtain MX phase although MAX mutually at high temperature can decomposed goes out A, in pyrolysis process, the laminate structure of MX is destroyed and change three-dimensional cubic rock salt structure into.The research team of Barsoum has solved this difficult problem, has separated A mutually obtained the two-dimentional MX structured material that original Lamellar character still exists by liquid phase stripping method from the highly stable MAX of chemical property.They will at room temperature be immersed in the aqueous solution of HF containing the MAX powder of aluminium element, and the al atomic layer by MAX in is mutually peeled off, and has synthesized the two-dimentional MX nanometer sheet that laminate structure is still retained.
From the stratiform characteristic of atomic structure, MAX can think that two-dimensional layer transition metal C/N compound and A atomic shell are bonded together mutually.The strong M-X key of MAX in mutually has the feature of covalent linkage, metallic bond and ionic linkage, and M-A key is metallic bond.Compare as the weak Van der Waals interaction supporting structure of graphite and Transition-metal dichalcogenide etc. with other stratified materials, the key of the mutually each interlayer of MAX is too strong and can not be with shearing or any similar mechanical means be broken.But utilize the difference of M-A key and M-X key relative intensity, can remove A atomic shell and not interrupt M-X key by chemical process, thereby gain freedom without the MX thin slice that supports two-dirnentional structure.Three-dimensional MAX phase factor is removed A becomes two-dimentional MX phase later, and it has the MX phase factor of this two-dimensional layer sheet similar attribute and be called as MXene to Graphene.The individual layer synusia thickness of MXene material is less than 1 nanometer, and lateral dimension can reach 10 microns, and resistivity and Graphene are close, and conductivity is good.Although Graphene has attracted more attention than other two-dimensional material, but the weak Van der Waals force of its simple chemical formula and interlayer has limited its practical application, and the interlayer structure that comprises 2～3 kinds of elements of MXene complexity, thereby the combination that may provide a large amount of difference in functionalitys to roll into a ball obtains some comparatively special performances.Theoretical with experiment showed, that this class material may be applied in multiple technical fields, for example catalysis, energy storage device, electrical condenser and lithium ion battery and the enhancing as polymkeric substance equate.
Ti 3alC 2being typical ternary metal ceramic compound, is also the three-layer laminated precursor that is stripped from out at first at most two-dimensional nano sheet of research at present.Ti 3alC 2structure can regard as in the octahedron that C atom is filled in closelypacked Ti atom, Al atom intercalation at Ti 3c 2among synusia.By Ti 3alC 2after powder is immersed in the aqueous solution of HF, HF selectivity acid etching falls Al atomic shell and does not break the laminate structure of Ti-C key and generate two-dimentional Ti 3c 2sheet.Being rich in the water surrounding of fluorion and hydroxyl, Ti 3alC 2after Al atomic shell in parent phase is stripped from, Ti-Al key is replaced by the F ion of surface adsorption and OH ion, and the actual product obtaining is Ti 3c 2f 2and Ti 3c 2(OH) 2nano ply.Document (Khazaei M., et al., Adv..Funct.Mater., 2013,23,2185-2192) utilize density functional theory to calculate the free energy band structure without supporting two-dimentional titanium carbide and derivative thereof, result shows: pure two-dimentional titanium carbide structure has eka-gold attribute, but surface adsorption derivative after the functional group such as OH, F ion be that the semi-conductor of narrow band gap is (as Ti 3c 2f 2and Ti 3c 2(OH) 2band gap be respectively 0.1 and 0.05eV).Open structure, the interlayer weak interaction of two dimension titanium carbide combines than with its electroconductibility with larger surface volume, makes this two-dimensional layered structure material aspect lithium ion battery electrode material, fuel cell, ultracapacitor and water treatment, have good application prospect.For example, document (Naguib M et al., J, ElectroChem.Commun., 2012,16,61-64) is used two-dimentional Ti 2lithium ion battery negative material prepared by C, electrical capacity is high, have extended cycle life, and document (Tang.Q, et al., J.Am.Chem.Soc., 2012,134,16909-16916) utilizes First Principle to study two-dimentional Ti 3c 2storage lithium performance, theoretical prediction shows Ti 3c 2the diffusion of lithium is had to low energy barrier and the high characteristic absorbing, but F or OH ion can cause storing up weakening and the minimizing of reversible capacity of lithium performance in the absorption on synusia surface, its stability also can be affected.
Being used at present peeling off A atomic shell, to prepare the typical MAX of two-dimentional MX nanometer sheet be Ti mutually 3alC 2.The integrity degree level and smooth and lattice of this powder synusia has determined quality, pattern and the performance of two-dimensional nano sheet.At preparation Ti 3alC 2powder aspect, for the generation of the impurity phases such as TiC in inhibited reaction process and prevent the generation of thermal explosion phenomenon in building-up process, generally add the sintering aid of low melting point, as Chinese patent CN 1699159A (Zhai Hongxiang, a kind of titanium aluminium carbide powder and the synthetic method taking tin as reaction promoter thereof) and Chinese patent CN 101070248A (Li Shibo, a kind of atmospheric synthesizing method of aluminium-titanium carbonate ceramic powder) in, all make auxiliary agent with Sn, these sintering aids have been solid-solubilized in Ti after reaction 3alC 2lattice in, the destruction that causes lattice imperfection and three-dimensional synusia characteristic, this is unfavorable for the smooth and regular of peeling off of follow-up Al atomic shell and two-dimensional layer surface.In addition, the grain-size of two-dimensional nano material and pattern, condition of surface and microstructure directly affect its physicochemical property and purposes.The performances such as optical, electrical, the thermal and magnetic of nanoparticle uniqueness and catalysis, absorption have size and pattern (Aliofkhazraei M., et al., Two-Dimensional Nanostructures, CRC Press, the 2012) dependency of height.Chemical liquid phase stripping method is prepared two-dimensional layered structure material and is had the features such as technique is simple, process is controlled, efficiency is high, cost is low, but three-layer laminated Ti 3alC 2al atomic shell is mutually after being stripped from, the prepared two-dimentional titanium carbide nanometer sheet of chemical liquid phase reaction inevitably has serious textural defect, as document (Chang F., et al., Mater.Lett., 2013,109,295-297) prepared two-dimentional titanium carbide nanometer sheet lattice defect is more, and synusia is smooth not.Ti prepared by these class methods 3c 2its specific conductivity of synusia can diminish along with increasing of defect.Meanwhile, Ti 3alC 2in the aqueous solution, there is after chemical reaction Ti with HF 3c 2synusia surface can a large amount of OH functional group of absorption, and this functional group increases further variation of aggravating conductivity, has affected the application of two-dimentional titanium carbide nanometer sheet aspect electricity and chemical property.Therefore, prepare that pattern is regular, the little and poor two-dimensional layer titanium carbide of the hydroxy functional group nanometer sheet of smooth surface, grain-size is the key that promotes that the conductivity of this material is fully utilized.
Summary of the invention
Goal of the invention: be to solve the problem that prior art exists, the present invention proposes that a kind of pattern is regular, the preparation method of smooth surface and the poor class Graphene of hydroxy functional group two-dimensional layer titanium carbide nanometer sheet, to improve its electricity and chemical property.
Technical scheme: solving the problems of the technologies described above adopted technical scheme is: first prepare Ti taking Ti, Al and C powder as raw material 3alC 2powder, and then use Ti 3alC 2powder and HF reactant aqueous solution obtain Ti 3c 2, finally to Ti 3c 2carry out after vacuum calcining processing, obtain the smooth complete and two-dimensional layer Ti that conductivity is good of synusia 3c 2nanometer sheet.Particularly, comprise the following steps:
(1) Ti 3alC 2the preparation of powder: will the Ti of the loose bulk that original position solid-liquid reaction obtains occur in the hot pressing furnace of argon shield after Ti, Al and C powder dry grinding moulding 3alC 2, then to the Ti obtaining 3alC 2grind, sieving obtains Ti 3alC 2powder;
(2) preparation of two-dimentional titanium carbide: by the Ti obtaining in step (1) 3alC 2powder is dipped in the aqueous solution of HF, and magnetic agitation issues biochemical liquid phase reaction, obtains suspension, by above-mentioned suspension after filtration, washing, alcohol wash, centrifugal after low-temperature vacuum drying again, obtain two-dimentional titanium carbide powder;
(3) vacuum calcining aftertreatment: the two-dimentional titanium carbide powder obtaining in step (2) is placed in to calcining in vacuum crystallization furnace and obtains class Graphene two-dimensional layer titanium carbide nanometer sheet.
Wherein, in step (1), the mol ratio of Ti, Al and C powder is 3: 1: 2.
In step (1), the condition of dry grinding moulding is: the mixture of Ti, Al and C powder and agate ball in ball grinder are dry mixed to 8～12h by weight at 1: 2, adopt graphite jig moulding, forming pressure is 5～15MPa.
The condition of step (1) situ solid-liquid reaction is: the temperature in hot pressing furnace is warming up to after 1300～1400 DEG C with the speed of 10～25 DEG C/min, under 20～30Mpa pressure, be incubated 20～30 minutes, then be cooled to 50～70 DEG C, obtain loose block Ti 3alC 2.
The sub-sieve sieving in step (1) is 100～200 orders.
In step (2), Ti 3alC 2the mass volume ratio of powder and the HF aqueous solution is (6～10): (100～120) g/ml, and the concentration of the HF aqueous solution is 45～55wt%, temperature is 45～55 DEG C.
In step (2), the speed of magnetic agitation is 1000～2500r/min, and churning time is 6～40 hours.
The centrifugal condition of the suspension obtaining after chemical liquid phase reaction in step (2) after filtration, after washing, alcohol wash is: first the centrifugal 20～30min of 3000～5000r/min removes oarse-grained particle, then centrifugal 10～20min under 8000～10000r/min, collects the solid obtaining.
In step (2), the temperature of low-temperature vacuum drying is 40～60 DEG C, and be 20～30h time of drying.
In step (3), the vacuum tightness in vacuum crystallization furnace is 0.5 × 10 -3～2 × 10 -3pa, calcining temperature is 450～750 DEG C, calcination time is 1～2h.By vacuum calcining, reduce the impact of surface hydroxyl on material, obtain that pattern is regular, smooth surface, two-dimensional layer titanium carbide nanometer sheet that grain-size is little.
Beneficial effect: technical process of the present invention is simple, processing parameter stable, process is controlled, efficiency is high, cost is low, has obtained the Ti that degree of crystallinity is good, purity is high under short period of time, low pressure 3alC 2precursor; From SEM photo, can see two-dimentional Ti prepared by the present invention 3c 2nanometer sheet lateral dimension can reach 5～10 microns, and individual layer mean thickness is about 10～20 nanometers, and after calcination processing, interlamellar spacing obviously increases, and synusia surface is regular smooth.Two-dimentional Ti after calcining 3c 2the thin discs of powder after tabletting machine is colded pressing records resistivity between 0.5～10 Ω cm by four probe method.The present invention can be used for ultracapacitor, lithium ion battery electrode material, catalysis and sorbing material and energy storage device and prepare composite.
Brief description of the drawings
Ti in Fig. 1 embodiment 1 3alC 2the XRD figure spectrum of powder and the two-dimensional layer titanium carbide nanometer sheet that obtains after HF acid etching.
The SEM photo of two-dimentional titanium carbide powder after vacuum calcining in Fig. 2 embodiment 2.
Embodiment
Embodiment 1
Press Ti: Al: C=3: the molar ratio ingredient of 1: 2, its mixture in ball grinder is dry mixed 10 hour by ratio of grinding media to material together with agate ball at 2: 1; The batching mixing is put into graphite jig compacting under the pressure of 5MPa; be placed in afterwards the hot pressing furnace of argon shield; the temperature of hot pressing furnace is warming up to 1350 DEG C with the speed of 15 DEG C/min, then under 25MPa pressure, is incubated 25 minutes, be cooled to and after 60 DEG C, obtain loose block Ti 3alC 2, through broken, ground 200 mesh sieves, obtain Ti 3alC 2powder.By the Ti of 8 grams 3alC 2powder is dipped in the HF aqueous solution of 100mL50wt% under room temperature, reacts 20 hours with the rotating speed magnetic agitation of 1500r/min, obtains suspension; The suspension obtaining is washed to pH value after filtration, repeatedly repeatedly to be cleaned with dehydrated alcohol for after neutrality again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 8000r/min after centrifugal 10 minutes in vacuum drier 40 DEG C dry 24 hours; It is 2 × 10 that powder after vacuum drying treatment is placed in to vacuum tightness -3in the crystallization furnace of pa, 550 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet.To the Ti obtaining 3alC 2powder and the two-dimensional layer titanium carbide nanometer sheet obtaining after HF acid treatment are carried out XRD test, and result as shown in Figure 1.As can be seen from the figure, three-layer laminated Ti 3alC 2in the almost completely dissolve of the strongest characteristic peak at 39 degree places, the Ti that becomes two-dimensional layer after Al is stripped from is described 3c 2.The two-dimentional Ti of preparation 3c 2nanometer sheet lateral dimension is 5～10 microns, and thickness in monolayer is about 10-20 nanometer, the two-dimentional Ti after calcining 3c 2it is 7 Ω cm that the thin discs of powder after tabletting machine is colded pressing records resistivity by four probe method.
Embodiment 2
Press Ti: Al: C=3: the molar ratio ingredient of 1: 2 in ball grinder is dry mixed 8 hour by ratio of grinding media to material together with agate ball at 2: 1; The batching mixing is put into compacting under the pressure of graphite jig 10MPa, be placed in afterwards the hot pressing furnace of argon shield, be warming up to 1300 DEG C with the speed of 10 DEG C/min, under 30MPa pressure, be incubated 20 minutes, be cooled to and after 60 DEG C, obtain loose block Ti 3alC 2, after fragmentation, grinding, cross 200 mesh sieves; By the Ti of 6 grams 3alC 2powder is dipped in the HF aqueous solution of 100 milliliters of 50wt% under room temperature, reacts 40 hours with the rotating speed magnetic agitation of 2000r/min; Gained suspension after filtration, is repeatedly washed to pH value and repeatedly cleans with dehydrated alcohol for after neutrality again, then with centrifugal 30 minutes of 4000r/min except the larger particle of degranulation, then with 8000r/min after centrifugal 10 minutes in vacuum drier 50 DEG C dry 30 hours; It is 1 × 10 that powder after vacuum drying treatment is placed in to vacuum tightness -3in the crystallization furnace of pa, 650 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet.The two-dimensional layer titanium carbide nanometer sheet obtaining is carried out to SEM sign, and result as shown in Figure 2, can be found out from scheming, two-dimentional Ti 3c 2nanometer sheet lateral dimension can reach 5-10 micron, and individual layer mean thickness is about 10～20 nanometers, and resistivity is 5 Ω cm.
Embodiment 3
Press Ti: Al: C=3: the molar ratio ingredient of 1: 2 in ball grinder is dry mixed 12 hour by ratio of grinding media to material together with agate ball at 2: 1; The batching mixing is put into compacting under the pressure of graphite jig 5MPa, be placed in afterwards the hot pressing furnace of argon shield, be warming up to 1400 DEG C with the speed of 20 DEG C/min, under 20MPa pressure, be incubated 30 minutes, be cooled to and after 55 DEG C, obtain loose block Ti 3alC 2, after fragmentation, grinding, cross 200 mesh sieves; By the Ti of 10 grams 3alC 2powder was dipped in the HF aqueous solution of 100 milliliters of 50wt% of 50 DEG C, with the rotating speed magnetic agitation reaction of 1000r/min 6 hours; Gained suspension after filtration, is repeatedly washed to pH value and repeatedly cleans with dehydrated alcohol for after neutrality again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 10000r/min after centrifugal 10 minutes in vacuum drier 60 DEG C dry 24 hours; It is 1.5 × 10 that powder after vacuum drying treatment is placed in to vacuum tightness -3in the crystallization furnace of pa, 450 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation 3c 2nanometer sheet lateral dimension is 5-10 micron, and individual layer mean thickness is about 10～20 nanometers, and resistivity is 10 Ω cm.
Embodiment 4
Press Ti: Al: C=3: the molar ratio ingredient of 1: 2 in ball grinder is dry mixed 10 hour by ratio of grinding media to material together with agate ball at 2: 1; The batching mixing is put into compacting under the pressure of graphite jig 15MPa, be placed in afterwards the hot pressing furnace of argon shield, be warming up to 1350 DEG C with the speed of 20 DEG C/min, under 25MPa pressure, be incubated 25 minutes, be cooled to and after 60 DEG C, obtain loose block Ti 3alC 2, through broken, ground 200 mesh sieves; By the Ti of 6 grams 3alC 2powder is dipped in the HF aqueous solution of 100 milliliters of 50wt% under room temperature, reacts 40 hours with the rotating speed magnetic agitation of 1500r/min; Gained suspension after filtration, is repeatedly washed to pH value and repeatedly cleans with dehydrated alcohol for after neutrality again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 8000r/min after centrifugal 10 minutes in vacuum drier 60 DEG C dry 20 hours; It is 0.8 × 10 that powder after vacuum drying treatment is placed in to vacuum tightness -3in the crystallization furnace of pa, 750 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation 3c 2nanometer sheet lateral dimension is 10-20 micron, and individual layer mean thickness is about 10～20 nanometers, and resistivity is 0.5 Ω cm.
Embodiment 5
Press Ti: Al: C=3: the molar ratio ingredient of 1: 2 in ball grinder is dry mixed 12 hour by ratio of grinding media to material together with agate ball at 2: 1; The batching mixing is put into compacting under the pressure of graphite jig 10MPa, be placed in afterwards the hot pressing furnace of argon shield, be warming up to 1350 DEG C with the speed of 25 DEG C/min, under 20MPa pressure, be incubated 30 minutes, be cooled to and after 65 DEG C, obtain loose block Ti 3alC 2, through broken, ground 200 mesh sieves; By the Ti of 8 grams 3alC 2powder is dipped in the HF aqueous solution of 120 milliliters of 50wt% at 50 DEG C, reacts 6 hours with the rotating speed magnetic agitation of 2500r/min; Gained suspension after filtration, is repeatedly washed to pH value and repeatedly cleans with dehydrated alcohol for after neutrality again, then with centrifugal 30 minutes of 3000r/min except the larger particle of degranulation, then with 10000r/min after centrifugal 10 minutes in vacuum drier 60 DEG C dry 20 hours; It is 0.5 × 10 that powder after vacuum drying treatment is placed in to vacuum tightness -3in the crystallization furnace of pa, 450 DEG C of temperature lower calcinations 2 hours, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation 3c 2nanometer sheet lateral dimension is 12-20 micron, and individual layer mean thickness is about 10～20 nanometers, and resistivity is 8 Ω cm.

Claims (10)

1. the preparation method of a kind Graphene two-dimensional layer titanium carbide nanometer sheet, is characterized in that, comprises the following steps:
(1) Ti 3alC 2the preparation of powder: will the Ti of the loose bulk that original position solid-liquid reaction obtains occur in the hot pressing furnace of argon shield after Ti, Al and C powder dry grinding moulding 3alC 2, then to the Ti obtaining 3alC 2grind, sieving obtains Ti 3alC 2powder;
(2) preparation of two-dimentional titanium carbide: by the Ti obtaining in step (1) 3alC 2powder is dipped in the aqueous solution of HF, and magnetic agitation issues biochemical liquid phase reaction, obtains suspension, by above-mentioned suspension after filtration, washing, alcohol wash, centrifugal after low-temperature vacuum drying again, obtain two-dimentional titanium carbide powder;
(3) vacuum calcining aftertreatment: the two-dimentional titanium carbide powder obtaining in step (2) is placed in to calcining in vacuum crystallization furnace and obtains class Graphene two-dimensional layer titanium carbide nanometer sheet.
2. preparation method according to claim 1, is characterized in that, in step (1), the mol ratio of Ti, Al and C powder is 3: 1: 2.
3. preparation method according to claim 1, it is characterized in that, in step (1), the condition of dry grinding moulding is: the mixture of Ti, Al and C powder and agate ball in ball grinder are dry mixed to 8～12h by weight at 1: 2, adopt graphite jig moulding, forming pressure is 5～15MPa.
4. preparation method according to claim 1, it is characterized in that, the condition of step (1) situ solid-liquid reaction is: the temperature in hot pressing furnace is warming up to after 1300～1400 DEG C with the speed of 10～25 DEG C/min, under 20～30Mpa pressure, be incubated 20～30 minutes, then be cooled to 50～70 DEG C, obtain loose block Ti 3alC 2.
5. preparation method according to claim 1, is characterized in that, the sub-sieve sieving in step (1) is 100～200 orders.
6. preparation method according to claim 1, is characterized in that, in step (2), and Ti 3alC 2the mass volume ratio of powder and the HF aqueous solution is (6～10): (100～120) g/ml, and the concentration of the HF aqueous solution is 45～55wt%, temperature is 45～55 DEG C.
7. preparation method according to claim 1, is characterized in that, in step (2), the speed of magnetic agitation is 1000～2500r/min, and churning time is 6～40 hours.
8. preparation method according to claim 1, it is characterized in that, the centrifugal condition of the suspension obtaining after chemical liquid phase reaction in step (2) after filtration, after washing, alcohol wash is: first the centrifugal 20～30min of 3000～5000r/min removes oarse-grained particle, then centrifugal 10～20min under 8000～10000r/min, collects the solid obtaining.
9. preparation method according to claim 1, is characterized in that, in step (2), the temperature of low-temperature vacuum drying is 40～60 DEG C, and be 20～30h time of drying.
10. preparation method according to claim 1, is characterized in that, in step (3), the vacuum tightness in vacuum crystallization furnace is 0.5 × 10 -3～2 × 10 -3pa, calcining temperature is 450～750 DEG C, calcination time is 1～2h.
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