CN106477624A - A kind of spherical lithium titanate preparation method of gradient-controllable particle diameter - Google Patents
A kind of spherical lithium titanate preparation method of gradient-controllable particle diameter Download PDFInfo
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- CN106477624A CN106477624A CN201610872524.9A CN201610872524A CN106477624A CN 106477624 A CN106477624 A CN 106477624A CN 201610872524 A CN201610872524 A CN 201610872524A CN 106477624 A CN106477624 A CN 106477624A
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- lithium titanate
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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Abstract
The invention provides a kind of spherical lithium titanate preparation method of gradient-controllable particle diameter, including the spherical TiO of different-grain diameter2Preparation, the preparation of lithium titanate precursor and high-temperature calcination.Present invention liquid phase method prepares the spherical lithium titanate material of submicron, prepares the different spherical lithium titanate material of particle diameter by controlling ethanol solution temperature.The spherical lithium titanate of submicron of the technical scheme preparation that the present invention provides reduces specific surface area, thus reducing the water absorption of lithium titanate material, efficiently avoid it and producing gas due to water suction.Again due to the presence of cetylamine molecule in ethanol solution, can control obtain particle diameter different distributions uniformly spherical lithium titanate it is also possible to obtain monodispersed spherical lithium titanate, it is to avoid the agglomeration in high-temperature burning process.
Description
Technical field
The present invention relates to a kind of lithium titanate material is and in particular to a kind of spherical lithium titanate preparation method of gradient-controllable particle diameter.
Background technology
Lithium titanate material has " zero strain " compared to traditional graphite cathode material, discharge platform is high and does not produce SEI
The cycle performance of the features such as film, therefore lithium titanate battery and security performance are greatly improved.
But lithium titanate battery occurs flatulence phenomenon in use, flatulence phenomenon can produce both sides shadow to battery
Ring：One is that flatulence phenomenon makes the internal resistance of cell increase, and promotes battery premature failure, shortens the service life of battery；Two be easily make soft
The rupture of alclad plastic film leads to electrolyte to be revealed, imflammable gas effusion, induces security incident.Therefore, lithium titanate battery will be realized
Scale stored energy application is it is necessary to solve the problems, such as flatulence.
The reason that lithium titanate material produces flatulence is the water absorption on lithium titanate material surface, mainly lithium titanate material
Granule is little and specific surface area makes greatly lithium titanate material water absorption big, and then lithium titanate material is produced in charge and discharge process
Angry body.
In traditional lithium titanate preparation method, the whether lithium titanate material of solid phase method or liquid phase method generation, its particle diameter
All there is certain uncontrollability.The many factors such as crystallization process, temperature schedule, calcinating system, nucleation process are all to material
Shaping has a certain impact, and is difficult to control the particle diameter of material by changing the variable of a certain fixation.
Content of the invention
The present invention is directed to the problems referred to above, and the present invention will prepare the spherical lithium titanate material of submicron by liquid phase method, and lead to
Cross the spherical lithium titanate material controlling ethanol solution temperature controlled to prepare different size of gradient.
In order to achieve the above object, the invention provides adopting following technical proposals：
A kind of spherical lithium titanate preparation method of gradient-controllable particle diameter comprises the steps：
(1) prepare the spherical TiO of different-grain diameter2；
(2) utilize spherical TiO2Prepare lithium titanate precursor；
(3) high-temperature calcination lithium titanate precursor.
A kind of first preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, in step (1), to molten under stirring
There is addition butyl titanate in cetylamine and the dehydrated alcohol of ammonia, centrifugal drying heat treatment obtains the different spherical TiO of particle diameter2.
A kind of second preferred version, dehydrated alcohol, cetylamine and the ammonia of the spherical lithium titanate preparation method of gradient-controllable particle diameter
The mass ratio of water is 120:1:1.
A kind of 3rd preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, dehydrated alcohol temperature is 0～75
℃.
A kind of 4th preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, ammonia density is 1g/mL.
A kind of 5th preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, step (2) is different by particle diameter
Spherical TiO2It is added to after ethanol water with lithium source and stir to obtain lithium titanate precursor solution, thermally treated lithium titanate forerunner
Body.
A kind of 6th preferred version, lithium source and the TiO of the spherical lithium titanate preparation method of gradient-controllable particle diameter2Mol ratio be
0.8:1.
A kind of 7th preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, lithium source is LiOH.
A kind of 8th preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, heat treatment is included in 150～180
15～20h is processed at DEG C.
A kind of 9th preferred version of the spherical lithium titanate preparation method of gradient-controllable particle diameter, in step (3), before lithium titanate
Drive body and calcine 8～12h at 650～750 DEG C.
Compared with immediate prior art, the technical scheme that the present invention provides has following excellent effect：
(1) technical scheme that this patent provides is passed through to control the temperature of ethanol solution and then control TiO2Particle diameter, finally
Obtain the different spherical lithium titanate of particle diameter；
(2) technical scheme that this patent provides, reduces its specific surface area by preparing the spherical lithium titanate of submicron, thus
Reduce the water absorption of lithium titanate material, efficiently avoid it and produce gas due to water suction.
(3) technical scheme that this patent provides, due to the presence of cetylamine molecule in ethanol solution, can control and obtain
The different equally distributed spherical lithium titanate of particle diameter, and monodispersed spherical lithium titanate can also be obtained, effectively avoid it
Agglomeration in high-temperature burning process.
Brief description
Fig. 1 is spherical TiO2Prepare schematic diagram；
Fig. 2 is that schematic diagram prepared by the different spherical lithium titanate of particle diameter；
Fig. 3 is the TiO preparing under different temperatures275 DEG C of 50 DEG C of 25 DEG C of 0 DEG C of electron microscopic picture (a) (b) (c) (d)；
Fig. 4 is 75 DEG C of 50 DEG C of 25 DEG C of 0 DEG C of the electron microscopic picture (a) (b) (c) (d) of the lithium titanate prepared under different temperatures.
Specific embodiment
Below in conjunction with the accompanying drawings 1～4 and specific embodiment be described in further detail, technical scheme is carried out clearly
Chu, it is fully described by it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of not making creative work all its
His embodiment, broadly falls into the scope of protection of the invention.
Gradient-controllable particle diameter spherical lithium titanate preparation method, comprises the following steps, such as Fig. 2：
(1) solid-state cetylamine and ammonia are added in the anhydrous ethanol solvent of different temperatures, mechanical agitation, make cetylamine
It is dissolved in formation clear solution in ethanol；The mass ratio of cetylamine, ammonia and dehydrated alcohol is 1:1:120, ammonia density is 1g/
mL.
(2) in the case of being stirred vigorously, butyl titanate is added in above-mentioned solution, tetrabutyl titanate hydrolysis simultaneously form white
Color suspension；
(3) by above-mentioned white suspension through the centrifugal drying spherical TiO different with being thermally treated resulting in particle diameter2, such as Fig. 3；
(4) by different size of spherical TiO2It is added in etoh solvent solution with LiOH, strong agitation makes it mix to fill
Get precursor solution；Lithium source and TiO2Mol ratio be 0.8:1；
(5) precursor solution preparing is transferred in high-temperature high-pressure reaction kettle, obtain lithium titanate after Overheating Treatment
Presoma.
(6) lithium titanate precursor is calcined at a certain temperature and can get the different spherical lithium titanate of particle diameter, such as Fig. 4.
Wherein, cetylamine molecule is made up of amino and alkyl, and wherein amino is hydrophilic group, and alkyl is hydrophobic
Property group, that is, cetylamine be made up of amphiprotic group.Ti (OCH (the CH that butyl titanate hydrolyzes in the presence of ammonia3)2)4-x
(OH) amino group of x or oligomer and cetylamine interacts and reacts, and is to reduce interface under alkyl group
Free energy and the glomerate Ti of shape (OH)4, then pass through and be thermally treated resulting in TiO2Ball, as shown in Figure 1.
Temperature has a certain impact to the liveness of cetylamine molecule, and the liveness of temperature lower cetylamine molecule is lower,
And then more cetylamine molecules are flocked together, form less core in the case of same amount of butyl titanate,
Therefore, the temperature by controlling ethanol solution can obtain spherical TiO of different sizes2.
Design parameter in each embodiment preparation process is as in the table below：
Spherical TiO by gained in the various embodiments described above2Do scanning electron microscope with spherical lithium titanate sample, in same times magnification
Under several, acquired results as shown in Figure 3 and Figure 4, at 0～75 DEG C, increasing with solvent temperature, particle diameter is gradually reduced, also by
This draws, the technical scheme that the present invention provides shows to prepare different spherical of particle diameter by controlling ethanol solution temperature
Lithium titanate material.
Above example only in order to technical scheme to be described rather than be limited, the common skill of art
Art personnel should be appreciated that and the specific embodiment of the present invention can be modified or equivalent with reference to above-described embodiment,
These are all applying for pending claim protection model without departing from any modification of spirit and scope of the invention or equivalent
Within enclosing.
Claims (10)
1. a kind of spherical lithium titanate preparation method of gradient-controllable particle diameter is it is characterised in that methods described comprises the steps：
(1) prepare the spherical TiO of different-grain diameter2；
(2) utilize described spherical TiO2Prepare lithium titanate precursor；
(3) lithium titanate precursor described in high-temperature calcination.
2. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 1 is it is characterised in that described step
Suddenly in (1), in the dehydrated alcohol dissolved with cetylamine and ammonia, under stirring, add butyl titanate, centrifugal drying heat treatment obtains grain
The different spherical TiO in footpath2.
3. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 2 is it is characterised in that described nothing
The mass ratio of water-ethanol, cetylamine and ammonia is 120:1:1.
4. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 2 is it is characterised in that described nothing
Water-ethanol temperature is 0～75 DEG C.
5. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 2 is it is characterised in that described ammonia
Water density is 1g/mL.
6. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 1 is it is characterised in that described step
Suddenly (2) are by spherical TiO different for particle diameter2It is added to after ethanol water with lithium source and stirs to obtain lithium titanate precursor solution, through heat
Process to obtain lithium titanate precursor.
7. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 6 is it is characterised in that described lithium
Source and TiO2Mol ratio be 0.8:1.
8. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 6 is it is characterised in that described lithium
Source is LiOH.
9. the spherical lithium titanate preparation method of a kind of gradient-controllable particle diameter according to claim 6 is it is characterised in that described heat
Process is included in process 15～20h at 150～180 DEG C.
10. a kind of spherical lithium titanate preparation method of gradient-controllable particle diameter according to claim 1 is it is characterised in that described
In step (3), described lithium titanate precursor is calcined at 650～750 DEG C 8～12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180670A (en) * | 2020-01-22 | 2020-05-19 | 河北大学 | Based on controllable TiO2Method for preparing aluminum ion battery anode by microspheres |
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| EP1409409B1 (en) * | 2001-07-20 | 2004-12-22 | Altair Nanomaterials Inc. | Process for making lithium titanate |
| CN101462765A (en) * | 2008-11-24 | 2009-06-24 | 万向电动汽车有限公司 | Method for preparing lithium ionic cell cathode material spinelle lithium titanate |
| CN102167397A (en) * | 2011-03-02 | 2011-08-31 | 东莞宏威数码机械有限公司 | Methods for preparing porous spherical titanium dioxide and light positive pole |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180670A (en) * | 2020-01-22 | 2020-05-19 | 河北大学 | Based on controllable TiO2Method for preparing aluminum ion battery anode by microspheres |
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