CN104261465A - Method for preparing titanate, titanic acid and titanium dioxide - Google Patents
Method for preparing titanate, titanic acid and titanium dioxide Download PDFInfo
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- CN104261465A CN104261465A CN201410581104.6A CN201410581104A CN104261465A CN 104261465 A CN104261465 A CN 104261465A CN 201410581104 A CN201410581104 A CN 201410581104A CN 104261465 A CN104261465 A CN 104261465A
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- titanium
- acid
- titanate
- sea urchin
- urchin shape
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title abstract description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title abstract 3
- 241000257465 Echinoidea Species 0.000 claims abstract description 110
- 239000002253 acid Substances 0.000 claims abstract description 71
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims abstract description 3
- FXWGWZQOSOJYOC-UHFFFAOYSA-N propane-1,2,3-triol;titanium Chemical compound [Ti].OCC(O)CO FXWGWZQOSOJYOC-UHFFFAOYSA-N 0.000 claims abstract description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims abstract description 3
- 238000003916 acid precipitation Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000005119 centrifugation Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 abstract 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- 238000007599 discharging Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing titanate, titanic acid and titanium dioxide. The method for preparing titanate comprises the following steps: carrying out hydrolysis reaction on a titanium source to obtain hydrated titanium acid precipitates, wherein the titanium source is selected from one or a composition of more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, titanium ethoxide, titanium propoxide, tetrabutyl titanate, ethylene glycol titanium, glycerol titanium and ammonium fluorotitanate; dispersing the hydrated titanium acid precipitates in an aqueous hydrogen peroxide solution containing strong base for hydrothermal reaction, and thus obtaining sea urchin titanate with a micro-nano hierarchical structure. The method can overcome some defects of titanate, titanic acid and titanium dioxide prepared into nanowire or nanotube structures.
Description
Technical field
The application relates to the preparation of environmental protection, energy field material, particularly relates to the preparation method of a kind of titanate, metatitanic acid and titanium dioxide.
Background technology
Titanate, metatitanic acid and titanium dioxide have broad application prospects in lithium ion battery, photochemical catalysis, dye sensitization solar battery, photocatalytic water and sensor field due to them, have become the focus of Material Field research.Properties and their pattern of above-mentioned titanate, metatitanic acid and titanic oxide material are closely related.
Compared to nanometer monocrystalline particle, one-dimensional material (as nanotube, nano wire) can reduce intergranular crystal boundary, be conducive to current carrier transporting on long axis direction, be the desirable construction unit of assemble nanometer functional device, optoelectronic device structure, be expected to become nano-device functionalization and integrated critical material.Monodimension nanometer material has following Some features: (1), in photocatalysis field, be conducive to photo-generate electron-hole to free migration on long axis direction, reduces the recombination probability of electron hole, improves photocatalysis efficiency; (2), in field of lithium ion battery, major axis is conducive to the effective mobility of electronics, and minor axis is conducive to the quick embedding of lithium ion/embedding and goes out process, and compared to nano particle, one-dimentional structure has good charge-discharge performance; (3), in field of dye-sensitized solar cells, one dimension Nano structure expection can greatly reduce intergranular crystal boundary, is conducive to the transmission of electronics on light anode, greatly can improves the efficiency of battery.
But after titanate, metatitanic acid and titanic oxide material are prepared into the one dimension Nano structure such as nano wire or nanotube, have some shortcomings: as in photocatalysis field, after photochemical catalysis terminates, nano-photocatalyst not easily reclaims; The shortcomings such as in field of lithium ion battery, nano material often has lower tap density, and the Contact of particle and particle is bad, make nano material electrode usually not possess higher volume and capacity ratio and fast charging and discharging performance preferably.
Summary of the invention
Contriver finds through great many of experiments, titanate, metatitanic acid and titanic oxide material is made to receive differentiating stage structure, can while making full use of the nanostructure characteristic of material, the micrometer structure function of good reserved materials.Receiving in differentiating stage structured material, the hierarchy microballoon be made up of 1-dimention nano pipe, nano wire by being a kind of ideal differentiating stage structure of receiving, as sea urchin shape hierarchy microballoon.In photocatalysis field, the 1-dimention nano pipe in this hierarchy, nano wire can promote its photocatalysis efficiency, and micron order ball can accelerate its sedimentation or membrane separating effect.In field of lithium ion battery, composition the 1-dimention nano pipe of hierarchy, the nanostructure of nanometer wire are conducive to electronics and transmit on long axis direction, minor axis be then conducive to lithium ion quick embedding and embedding go out; Meanwhile, this hierarchy entirety is micron order ball, and globosity has good tap density in the preparation of traditional electrode, and the contact between ball and ball particle is more tight, can improve the fast charging and discharging performance of battery to a great extent.
Therefore, the application provides the preparation method of a kind of titanate, metatitanic acid and titanium dioxide, some shortcomings had during to make up and titanate, metatitanic acid and titanic oxide material are prepared into nano wire or nano tube structure.
The application provides a kind of preparation method of titanate, comprising:
Titanium source is obtained hydrated titanium Acid precipitation by hydrolysis reaction, and described titanium source is selected from one or several the combination in titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, titanium ethanolate, titanium propanolate, tetrabutyl titanate, titanium ethylene glycolate, glycerol titanium, ammonium titanium fluoride;
Described hydrated titanium Acid precipitation is dispersed in the aqueous hydrogen peroxide solution containing highly basic and carries out hydro-thermal reaction and obtain to have and receive the sea urchin shape titanate of differentiating stage structure.
Preferably, in the described aqueous hydrogen peroxide solution containing highly basic, paper mill wastewater is 0.01 mole and often rises to 5 moles often liter, and described is 0.1% to 8% containing the volume fraction of hydrogen peroxide in the aqueous hydrogen peroxide solution of highly basic.
Preferably, the described aqueous hydrogen peroxide solution containing highly basic obtains for adding highly basic or add hydrogen peroxide in aqueous hydrogen peroxide solution in strong base solution; Described highly basic is selected from a kind of in sodium hydroxide and potassium hydroxide or their combination.
Preferably, the described hydrated titanium Acid precipitation of purification acquisition is carried out in described titanium source after hydrolysis reaction; Described purification is for removing the foreign ion in hydrated titanium Acid precipitation, and described purification mode adopts the combination of one or several modes in washing-centrifugation, washing-membrane sepn, washing-filtration and dialysis.
Preferably, described hydrolysis reaction generates hydrated titanium Acid precipitation for described titanium source being disperseed direct hydrolysis in deionized water, or described hydrolysis reaction is the aqueous solution by adding alkaline matter to described titanium source, titanium source is hydrolyzed and generates hydrated titanium Acid precipitation.
Preferably, described hydrated titanium Acid precipitation is dispersed in described is 0.001% to 5% containing the massfraction in the aqueous hydrogen peroxide solution of highly basic.
Preferably, the temperature of described hydro-thermal reaction is 60 degrees Celsius to 200 degrees Celsius, and the time of hydro-thermal reaction is 2 to 48 hours.
The application also provides the preparation method of the metatitanic acid of a kind of preparation method based on the above titanate, and the preparation method of this metatitanic acid also comprises:
The described sea urchin shape titanate receiving differentiating stage structure is exchanged to obtain to have through acid and receives the sea urchin shape metatitanic acid of differentiating stage structure.
Preferably, described acid exchanges and comprises:
The described sea urchin shape titanate washing receiving differentiating stage structure is separated;
The sea urchin shape titanate of differentiating stage structure received after described washing being separated is put into acid solution and is carried out hydrogen ion and exchange to obtain to have and receive the sea urchin shape metatitanic acid of differentiating stage structure, described acid solution be selected from nitric acid, hydrochloric acid, sulfuric acid, acetic acid one or several, the concentration of acid solution is 0.0001 mole and often rises to 0.1 mole often liter;
Having of described acquisition is received the sea urchin shape metatitanic acid of differentiating stage structure and carried out washing and be separated.
The application also provides the preparation method of the titanium dioxide of a kind of preparation method based on metatitanic acid as above, and the preparation method of this titanium dioxide also comprises:
Obtained to have through anneal by the described sea urchin shape metatitanic acid receiving differentiating stage structure and receive the sea urchin shape titanium dioxide of differentiating stage structure, described anneal temperature is 300 degrees Celsius to 800 degrees Celsius, and annealing time is 1 little of 5 hours.
What the present invention prepared have receives the sea urchin shape titanate of differentiating stage structure, metatitanic acid and titanium dioxide and is made up of 1-dimention nano pipe, nano wire, entirety is micron level spherical, illustrate good cycle performance of lithium ion battery, especially under fast charging and discharging speed, still can keep higher capacity, be a desirable ion cathode material lithium structure.What the present invention prepared have receives the sea urchin shape titanium dioxide of differentiating stage structure and has higher cell container equally, and charging/discharging voltage, is conducive to as lithium ion battery negative material comparatively stably.In addition, what the application prepared have receives the sea urchin shape titanium dioxide of differentiating stage structure and has good photocatalysis performance, because its entirety is micron particles, and can sharp separation recycling after photochemical catalysis terminates.
In sum, the invention has the advantages that:
1, the preparation method that the application provides can prepare respectively to have and receive the sea urchin shape titanate of differentiating stage structure, sea urchin shape metatitanic acid and sea urchin shape titanium dioxide;
2, the sea urchin shape structure that the preparation method that the application provides obtains is made up of 1-dimention nano pipe or nano wire, and while can making full use of one dimension Nano structure characteristic, the micrometer structure function of good reserved materials is that other method cannot realize;
3, the preparation method that provides of the application low in raw material price, be easy to get, production cost is lower; Additive-free in building-up process, safety and environmental protection is pollution-free;
4, the preparation method preparation technology that provides of the application is simple, and processing parameter is easy to control, is easy to large-scale industrial production.
Prepared by the present invention have receives the sea urchin shape metatitanic acid of differentiating stage structure and is for the advantage of lithium ion battery negative material:
1, capacity is high and cycle efficiency good, and repeatedly charge/discharge capacity declines hardly;
2, large capacity is still kept under fast charging and discharging speed.
Prepared by the present invention have receives the sea urchin shape titanium dioxide of differentiating stage structure and is for the advantage of lithium ion battery negative material:
1, comparatively steadily and lower charging/discharging voltage, charge and discharge platform is respectively 1.86 volts and 1.78 volts, is conducive to preparing high-voltage lithium ion batteries as negative material;
2, capacity is high and cycle efficiency good, and repeatedly charge/discharge capacity declines hardly.
Prepared by the present invention have receives the sea urchin shape titanium dioxide of differentiating stage structure and is for light-catalysed advantage:
1, photocatalysis efficiency is high;
2, easily separated recovery, can sedimentation voluntarily after photochemical catalysis.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those skilled in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is preparation method's schema of a kind of titanate of the present invention, metatitanic acid and titanium dioxide;
Fig. 2 is that the sea urchin shape sodium titanate that embodiment 1 prepares (is schemed a) and sea urchin shape metatitanic acid (figure X-ray diffractogram b);
Fig. 3 be embodiment 1 prepare sea urchin shape sodium titanate (figure a), sea urchin shape metatitanic acid (figure b) and sea urchin shape titanium dioxide (figure scanning electron microscope (SEM) photograph c); They are all made up of 1-dimention nano pipe or nano wire, and entirety is micron level spherical;
Fig. 4 be the sea urchin shape metatitanic acid for preparing of embodiment 1 for lithium ion battery: figure a is 50 mAg
-1time capacity circulating figure, figure b is capacity circulating figure under different charge-discharge velocity;
Fig. 5 be the sea urchin shape titanium dioxide for preparing of embodiment 1 for lithium ion battery: figure a is 50 mAg
-1time first charge-discharge capacity plan, figure b be 50 mAg
-1time capacity circulating figure;
Fig. 6 is that the sea urchin shape metatitanic acid that embodiment 1 prepares (is schemed a) He 600 degrees Celsius at 400 degrees Celsius and (schemed the X-ray diffractogram of the sea urchin shape titanium dioxide that anneal obtained after 2 hours b) respectively, wherein 400 degrees Celsius of process after products are Anatase, and 600 degrees Celsius of process after products are the compound phase of Anatase and Rutile Type;
Fig. 7 is that the sea urchin shape titanium dioxide for preparing of embodiment 1 is for the auto-deposition performance schematic diagram in half an hour after photochemical catalysis;
Naoh concentration is changed into 2 moles often liter (to scheme a) He the 4 moles often liter (scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate prepared when scheming b) by Fig. 8 respectively in embodiment 1; Sea urchin shape sodium titanate can obtain the sea urchin shape metatitanic acid that pattern remains unchanged after acid exchanges, and sea urchin shape metatitanic acid can obtain the sea urchin shape titanium dioxide that pattern remains unchanged after anneal.
Embodiment
Technical scheme in the application is understood better in order to make those skilled in the art person, below in conjunction with the accompanying drawing in the embodiment of the present application, technical scheme in the embodiment of the present application is clearly and completely described, obviously, described embodiment is only some embodiments of the present application, instead of whole embodiments.Based on the embodiment in the application, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all should belong to the scope of protection of the invention.
Embodiment 1
Please refer to Fig. 1, under agitation condition, 0.5 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 3 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 1 mole often liter and hydrogen peroxide concentration is in the aqueous solution of 2%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By described sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 5 times, centrifugation.Add the salpeter solution of 0.01 mole often liter subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of lower vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get and to receive the sea urchin shape metatitanic acid of differentiating stage structure described in part and put into Noah's ark, in 400 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape anatase phase titanium dioxide of differentiating stage structure.
The X-ray diffractogram of the sea urchin shape sodium titanate that the present embodiment prepares and sea urchin shape metatitanic acid as shown in Figure 2.In Fig. 2, figure a is the X-ray diffractogram of the sea urchin shape sodium titanate that the present embodiment prepares, and figure b is the X-ray diffractogram of the sea urchin shape metatitanic acid that the present embodiment prepares.
The scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate that the present embodiment prepares, sea urchin shape metatitanic acid and sea urchin shape titanium dioxide as shown in Figure 3.In Fig. 3, figure a is the scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate that the present embodiment prepares, and figure b is the scanning electron microscope (SEM) photograph of the sea urchin shape metatitanic acid that the present embodiment prepares, and figure c is the scanning electron microscope (SEM) photograph of the sea urchin shape titanium dioxide that the present embodiment prepares.As can be seen from Figure 3, they are all made up of 1-dimention nano pipe or nano wire, and entirety is micron level spherical, i.e. sea urchin shape.
The sea urchin shape metatitanic acid that the present embodiment prepares for lithium ion battery capacity circulating figure as shown in Figure 4.In Fig. 4, figure a is 50 mAg
-1time capacity circulating figure, figure b is capacity circulating figure under different charge-discharge velocity.As seen from Figure 4, the sea urchin shape metatitanic acid prepared by the present embodiment is used for the advantage of lithium ion battery negative material and is: 1, capacity is high and cycle efficiency good, and repeatedly charge/discharge capacity declines hardly; 2, large capacity is still kept under fast charging and discharging speed.
The sea urchin shape titanium dioxide that the present embodiment prepares for lithium ion battery capacity circulating figure as shown in Figure 5.In Fig. 5, figure a is 50 mAg
-1time first charge-discharge capacity plan, figure b be 50 mAg
-1time capacity circulating figure.As seen from Figure 5, the sea urchin shape titanium dioxide prepared of the present embodiment is for the advantage of lithium ion battery negative material: 1, comparatively steadily and lower charging/discharging voltage, charge and discharge platform is respectively 1.86 volts and 1.78 volts, is conducive to preparing high-voltage lithium ion batteries as negative material; 2, capacity is high and cycle efficiency good, and repeatedly charge/discharge capacity declines hardly; 3, large capacity is still kept under fast charging and discharging speed.
The X-ray diffractogram of the sea urchin shape titanium dioxide that the sea urchin shape metatitanic acid that the present embodiment prepares obtains after 2 hours at 400 degrees Celsius and 600 degrees Celsius of lower anneal respectively as shown in Figure 6.In Fig. 6, the X-ray diffractogram of the figure a sea urchin shape titanium dioxide that to be sea urchin shape metatitanic acid obtain after 2 hours 400 degrees Celsius of lower anneal, processing after product at this temperature is Anatase; The X-ray diffractogram of the figure b sea urchin shape titanium dioxide that to be sea urchin shape metatitanic acid obtain after 2 hours 600 degrees Celsius of lower anneal, processes the compound phase that after product is Anatase and Rutile Type at this temperature.
The sea urchin shape titanium dioxide that the present embodiment prepares for the auto-deposition performance in half an hour after photochemical catalysis as shown in Figure 7.The sea urchin shape titanium dioxide for preparing of the present embodiment is for having easily separated recovery during photochemical catalysis as seen from Figure 7, can the advantage of sedimentation voluntarily after photochemical catalysis.
The scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate prepared when naoh concentration being changed into respectively in the present embodiment 2 moles often liter and 4 moles often liter as shown in Figure 8.In Fig. 8, the scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate prepared when figure a is and naoh concentration is changed into respectively 2 moles often liter; The scanning electron microscope (SEM) photograph of the sea urchin shape sodium titanate that figure b prepares when being and naoh concentration being changed into respectively 4 moles often liter.In the present embodiment, sea urchin shape sodium titanate can obtain the sea urchin shape metatitanic acid that pattern remains unchanged after acid exchanges, and sea urchin shape metatitanic acid can obtain the sea urchin shape titanium dioxide that pattern remains unchanged after anneal.
Embodiment 2
Please refer to Fig. 1, under agitation condition, 0.5 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 3 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 1 mole often liter and hydrogen peroxide concentration is in the aqueous solution of 2%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 3 times, centrifugation.Add the salpeter solution of 0.01 mole often liter subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part described sea urchin shape metatitanic acid and put into Noah's ark, in 600 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape Anatase of differentiating stage structure and the titanium dioxide of Rutile Type compound crystalline phase.
Embodiment 3
Please refer to Fig. 1, under agitation condition, 1 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 5 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of concentration of potassium hydroxide be 2 moles often liter and hydrogen peroxide concentration is in the aqueous solution of 6%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the sea urchin shape potassium titanate of differentiating stage structure.By described sea urchin shape potassium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 5 times, centrifugation.Add 0.1 mole of often liter of salpeter solution subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by K
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part described sea urchin shape metatitanic acid and put into Noah's ark, in 400 degrees Celsius of lower anneal 3 hours, obtain sea urchin shape anatase phase titanium dioxide.
Embodiment 4
Please refer to Fig. 1, under agitation condition, 1 gram of titanyl sulfate is scattered in 30 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 5 times by 30 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 2 moles often liter and hydrogen peroxide concentration is in the aqueous solution of 2%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 120 degrees Celsius, constant temperature 24 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By described sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 4 times, centrifugation.Add 0.01 mole of often liter of salpeter solution subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part described sea urchin shape metatitanic acid and put into Noah's ark, in 500 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 5
Please refer to Fig. 1, under agitation condition, 1 milliliter of titanium isopropylate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 3 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 0.5 mole often liter and hydrogen peroxide concentration is in the aqueous solution of 5%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 160 degrees Celsius, constant temperature 12 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By described sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 5 times, centrifugation.Add 0.01 mole of often liter of salpeter solution subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part sea urchin shape metatitanic acid and put into Noah's ark, in 400 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 6
Please refer to Fig. 1, under agitation condition, 2 milliliters of titanium tetrachlorides are scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 5 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 2 moles often liter and hydrogen peroxide concentration is in the aqueous solution of 5%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 120 degrees Celsius, constant temperature 24 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By described sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 3 times, centrifugation.Add the salpeter solution of 0.1 mole often liter subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part described sea urchin shape metatitanic acid and put into Noah's ark, in 400 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 7
Please refer to Fig. 1, under agitation condition, 2 milliliters of tetrabutyl titanates are scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by the centrifugation of above-mentioned hydrated titanium Acid precipitation, wash 5 times by 50 ml deionized water respectively afterwards, centrifugation obtains the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing to be dispersed in 40 milliliters of naoh concentrations be 1 mole often liter and hydrogen peroxide concentration is in the aqueous solution of 2%.Stir after 1 hour, mixed solution is transferred in water heating kettle, be heated to 180 degrees Celsius, constant temperature 12 hours, prepare to have and receive the sea urchin shape sodium titanate of differentiating stage structure.By described sea urchin shape sodium titanate solid transfer in beaker, ultrasonic disperse, with deionized water wash 3 times, centrifugation.Add 0.01 mole of often liter of salpeter solution subsequently to solution souring, ultrasonic and standing 6 hours, make H
+ion is completely by Na
+out, with deionized water wash, centrifugation, 60 degrees Celsius of vacuum-dryings, obtain having and receive the sea urchin shape metatitanic acid of differentiating stage structure in ion-exchange.Get part described sea urchin shape metatitanic acid and put into Noah's ark, in 400 degrees Celsius of lower anneal 2 hours, obtain having and receive the sea urchin shape anatase phase titanium dioxide of differentiating stage structure.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of present invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (10)
1. a preparation method for titanate, is characterized in that, comprising:
Titanium source is obtained hydrated titanium Acid precipitation by hydrolysis reaction, and described titanium source is selected from one or several the combination in titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, titanium ethanolate, titanium propanolate, tetrabutyl titanate, titanium ethylene glycolate, glycerol titanium, ammonium titanium fluoride;
Described hydrated titanium Acid precipitation is dispersed in the aqueous hydrogen peroxide solution containing highly basic and carries out hydro-thermal reaction and obtain to have and receive the sea urchin shape titanate of differentiating stage structure.
2. the preparation method of titanate as claimed in claim 1, it is characterized in that: in the described aqueous hydrogen peroxide solution containing highly basic, paper mill wastewater is 0.01 mole and often rises to 5 moles often liter, and described is 0.1% to 8% containing the volume fraction of hydrogen peroxide in the aqueous hydrogen peroxide solution of highly basic.
3. the preparation method of titanate as claimed in claim 1, is characterized in that: the described aqueous hydrogen peroxide solution containing highly basic obtains for adding highly basic or add hydrogen peroxide in aqueous hydrogen peroxide solution in strong base solution; Described highly basic is selected from a kind of in sodium hydroxide and potassium hydroxide or their combination.
4. the preparation method of titanate as claimed in claim 1, is characterized in that: described titanium source is carried out purification and obtained described hydrated titanium Acid precipitation after hydrolysis reaction; Described purification is for removing the foreign ion in hydrated titanium Acid precipitation, and described purification mode adopts the combination of one or several modes in washing-centrifugation, washing-membrane sepn, washing-filtration and dialysis.
5. the preparation method of titanate as claimed in claim 1, it is characterized in that: described hydrolysis reaction generates hydrated titanium Acid precipitation for described titanium source being disperseed direct hydrolysis in deionized water, or, described hydrolysis reaction is the aqueous solution by adding alkaline matter to described titanium source, titanium source is hydrolyzed and generates hydrated titanium Acid precipitation.
6. the preparation method of titanate as claimed in claim 1, is characterized in that: it is 0.001% to 5% containing the massfraction in the aqueous hydrogen peroxide solution of highly basic that described hydrated titanium Acid precipitation is dispersed in described.
7. the preparation method of titanate as claimed in claim 1, is characterized in that: the temperature of described hydro-thermal reaction is 60 degrees Celsius to 200 degrees Celsius, and time of hydro-thermal reaction is 2 little of 48 hours.
8., based on a preparation method for the metatitanic acid of the preparation method of titanate described in claim 1 to 7 any one, it is characterized in that, also comprise:
The described sea urchin shape titanate receiving differentiating stage structure is exchanged to obtain to have through acid and receives the sea urchin shape metatitanic acid of differentiating stage structure.
9. the preparation method of metatitanic acid as claimed in claim 8, is characterized in that, described acid exchanges and comprises:
The described sea urchin shape titanate washing receiving differentiating stage structure is separated;
The sea urchin shape titanate of differentiating stage structure received after described washing being separated is put into acid solution and is carried out hydrogen ion and exchange to obtain to have and receive the sea urchin shape metatitanic acid of differentiating stage structure, described acid solution be selected from nitric acid, hydrochloric acid, sulfuric acid, acetic acid one or several, the concentration of acid solution is 0.0001 mole and often rises to 0.1 mole often liter;
Having of described acquisition is received the sea urchin shape metatitanic acid of differentiating stage structure and carried out washing and be separated.
10. based on a preparation method for the titanium dioxide of the preparation method of the metatitanic acid as described in claim 8 to 9 any one, it is characterized in that, also comprise:
Obtained to have through anneal by the described sea urchin shape metatitanic acid receiving differentiating stage structure and receive the sea urchin shape titanium dioxide of differentiating stage structure, described anneal temperature is 300 degrees Celsius to 800 degrees Celsius, and annealing time is 1 little of 5 hours.
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