CN106477624B - Preparation method of spherical lithium titanate with controllable gradient particle size - Google Patents
Preparation method of spherical lithium titanate with controllable gradient particle size Download PDFInfo
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- CN106477624B CN106477624B CN201610872524.9A CN201610872524A CN106477624B CN 106477624 B CN106477624 B CN 106477624B CN 201610872524 A CN201610872524 A CN 201610872524A CN 106477624 B CN106477624 B CN 106477624B
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
Abstract
The invention provides a preparation method of spherical lithium titanate with controllable gradient particle size, which comprises the steps of preparing spherical TiO with different particle sizes2The preparation of the lithium titanate precursor and the high-temperature calcination. The invention prepares submicron spherical lithium titanate materials by a liquid phase method, and spherical lithium titanate materials with different particle sizes are prepared by controlling the temperature of an ethanol solution. The submicron spherical lithium titanate prepared by the technical scheme provided by the invention has the advantages that the specific surface area is reduced, so that the water absorption of the lithium titanate material is reduced, and the gas generation caused by water absorption is effectively avoided. And due to the existence of hexadecylamine molecules in the ethanol solution, spherical lithium titanate with different particle sizes and uniform distribution can be obtained under control, and monodisperse spherical lithium titanate can also be obtained, so that the agglomeration phenomenon in the high-temperature calcination process is avoided.
Description
Technical Field
The invention relates to a lithium titanate material, in particular to a preparation method of spherical lithium titanate with controllable gradient particle size.
Background
Compared with the traditional graphite cathode material, the lithium titanate material has the characteristics of zero strain, high discharge platform, no SEI (solid electrolyte interphase) film generation and the like, so that the cycle performance and the safety performance of the lithium titanate battery are greatly improved.
But lithium titanate battery can appear the gas expansion phenomenon in the use, and the gas expansion phenomenon can produce the influence in two aspects to the battery: firstly, the internal resistance of the battery is increased by the gas expansion phenomenon, so that the battery fails in advance, and the service life of the battery is shortened; and secondly, the soft package aluminum-plastic film is easy to break, so that electrolyte is leaked, combustible gas escapes, and safety accidents are induced. Therefore, the problem of flatulence must be solved for realizing large-scale energy storage application of lithium titanate batteries.
One reason for the occurrence of flatulence in lithium titanate materials is the water absorption of the surface of the lithium titanate material, mainly, the water absorption of the lithium titanate material is large due to the small particles and the large specific surface area of the lithium titanate material, and further, the lithium titanate material generates gas in the charge and discharge process.
In the traditional preparation method of lithium titanate, the particle size of the lithium titanate material generated by a solid-phase method or a liquid-phase method has certain uncontrollable property. Many factors such as crystallization process, temperature system, calcination system, nucleation process, etc. all have certain influence on the forming of the material, and it is difficult to control the particle size of the material by changing a certain fixed variable.
Disclosure of Invention
In order to solve the problems, the submicron spherical lithium titanate material is prepared by a liquid phase method, and the spherical lithium titanate materials with controllable gradients and different sizes are prepared by controlling the temperature of an ethanol solution.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the spherical lithium titanate with the controllable gradient particle size comprises the following steps:
(1) preparation of spherical TiO of different particle size2；
(2) Using spherical TiO2Preparing a lithium titanate precursor;
(3) and calcining the lithium titanate precursor at high temperature.
A first preferred scheme of a preparation method of spherical lithium titanate with controllable gradient particle size comprises the steps of (1), adding tetrabutyl titanate into absolute ethyl alcohol dissolved with hexadecyl amine and ammonia water under stirring, and performing centrifugal drying heat treatment to obtain spherical TiO with different particle sizes2。
According to the second preferable scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size, the mass ratio of absolute ethyl alcohol to hexadecylamine to ammonia water is 120:1: 1.
A third preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size is that the temperature of absolute ethyl alcohol is 0-75 ℃.
According to the fourth preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size, the density of ammonia water is 1 g/mL.
A fifth preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size, step (2) is to prepare the spherical TiO with different particle sizes2And adding a lithium source into the ethanol aqueous solution, stirring to obtain a lithium titanate precursor solution, and performing heat treatment to obtain the lithium titanate precursor.
The sixth preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size comprises a lithium source and TiO2Is 0.8: 1.
A seventh preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size, wherein a lithium source is LiOH.
According to an eighth preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size, the heat treatment comprises treatment at 150-180 ℃ for 15-20 hours.
A ninth preferred scheme of the preparation method of the spherical lithium titanate with the controllable gradient particle size is that in the step (3), a lithium titanate precursor is calcined for 8-12 hours at 650-750 ℃.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
(1) the technical scheme provided by the patent controls the temperature of the ethanol solution to further control TiO2The spherical lithium titanate with different particle sizes is finally obtained;
(2) according to the technical scheme provided by the patent, the specific surface area of the submicron spherical lithium titanate is reduced by preparing the submicron spherical lithium titanate, so that the water absorption of the lithium titanate material is reduced, and gas generation caused by water absorption is effectively avoided.
(3) According to the technical scheme provided by the patent, due to the existence of hexadecylamine molecules in an ethanol solution, the spherical lithium titanate with different and uniformly distributed particle sizes can be obtained in a controlled manner, and the monodisperse spherical lithium titanate can be obtained, so that the agglomeration phenomenon of the spherical lithium titanate in the high-temperature calcination process is effectively avoided.
Drawings
FIG. 1 shows a spherical TiO2A preparation schematic diagram;
FIG. 2 is a schematic diagram of the preparation of spherical lithium titanate with different particle sizes;
FIG. 3 shows TiO prepared at different temperatures2The electron microscope pictures of (a)0 ℃ (b)25 ℃ (c)50 ℃ (d)75 ℃;
FIG. 4 shows the electron micrographs of lithium titanate prepared at different temperatures (a)0 deg.C (b)25 deg.C (c)50 deg.C (d)75 deg.C.
Detailed Description
The following detailed description is given with reference to fig. 1 to 4 and specific embodiments to clearly and completely describe the technical solutions of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the spherical lithium titanate with the controllable gradient particle size comprises the following steps as shown in figure 2:
(1) adding solid hexadecylamine and ammonia water into absolute ethanol solvents with different temperatures, and mechanically stirring to dissolve the hexadecylamine in ethanol to form a transparent solution; the mass ratio of the hexadecylamine to the ammonia water to the absolute ethyl alcohol is 1:1:120, and the density of the ammonia water is 1 g/mL.
(2) Under the condition of violent stirring, tetrabutyl titanate is added into the solution, and the tetrabutyl titanate is hydrolyzed to form white suspension;
(3) centrifugally drying and heat treating the white suspension to obtain spherical TiO with different particle sizes2As in fig. 3;
(4) mixing different sizes of spherical TiO2Adding LiOH and the solvent into ethanol solution, and intensively stirring to fully mix the mixture to obtain precursor solution; lithium source and TiO2In a molar ratio of 0.8: 1;
(5) and transferring the prepared precursor solution into a high-temperature high-pressure reaction kettle, and performing heat treatment to obtain a lithium titanate precursor.
(6) The lithium titanate precursor is calcined at a certain temperature to obtain spherical lithium titanate with different particle sizes, as shown in figure 4.
Wherein, the hexadecylamine molecule is composed of amino and alkyl, wherein, the amino is a hydrophilic group, and the alkyl is a hydrophobic group, namely, the hexadecylamine is composed of amphoteric group. Ti (OCH (CH)) hydrolyzed by tetrabutyl titanate under the action of ammonia water3)2)4-x (OH) x or the interaction of the oligomer and the amino group of hexadecylamine, and under the alkyl group, to form a spherical Ti (OH) for lowering the interfacial free energy4Followed by heat treatment to obtain TiO2A ball as shown in figure 1.
The temperature has certain influence on the activity of the hexadecylamine molecules, the lower the temperature is, the lower the activity of the hexadecylamine molecules is, so that more hexadecylamine molecules are aggregated together, and fewer nuclei are formed under the condition of the same amount of tetrabutyl titanate, therefore, TiO with different spherical sizes can be obtained by controlling the temperature of the ethanol solution2。
The specific parameters during the preparation of each example are set forth in the following table:
the spherical TiO obtained in each example2And a spherical lithium titanate sample is taken as a scanning electron microscope, under the same magnification, the obtained result is shown in fig. 3 and fig. 4, the particle size is gradually reduced along with the increase of the temperature of the solvent at 0-75 ℃, and the technical scheme provided by the invention shows that the spherical lithium titanate materials with different particle sizes can be prepared by controlling the temperature of the ethanol solution.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and it should be understood by those of ordinary skill in the art that the specific embodiments of the present invention can be modified or substituted with equivalents with reference to the above embodiments, and any modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims to be appended.
Claims (6)
1. A preparation method of spherical lithium titanate with controllable gradient particle size is characterized by comprising the following steps:
(1) preparation of spherical TiO of different particle size2；
(2) Using the spherical TiO2Preparing a lithium titanate precursor;
(3) calcining the lithium titanate precursor at a high temperature;
in the step (1), tetrabutyl titanate is added into absolute ethyl alcohol dissolved with hexadecylamine and ammonia water under stirring, and spherical TiO with different particle sizes is obtained through centrifugal drying and heat treatment2；
The mass ratio of the absolute ethyl alcohol to the hexadecylamine to the ammonia water is 120:1: 1;
the temperature of the absolute ethyl alcohol is 0-75 ℃;
the density of the ammonia water is 1 g/mL.
2. The method of claim 1, wherein the step (2) is performed by mixing different sized TiO spheres2And adding a lithium source into the ethanol aqueous solution, stirring to obtain a lithium titanate precursor solution, and performing heat treatment to obtain the lithium titanate precursor.
3. The method of claim 2, wherein the source of lithium and the TiO are selected from the group consisting of2Is 0.8: 1.
4. The method of claim 2, wherein the lithium source is LiOH.
5. The method of claim 2, wherein the heat treatment comprises treatment at 150-180 ℃ for 15-20 hours.
6. The method of claim 1, wherein in the step (3), the lithium titanate precursor is calcined at 650-750 ℃ for 8-12 h.
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| 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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| CN104091939A (en) * | 2014-06-30 | 2014-10-08 | 北京工业大学 | Hydrothermal synthesis preparation method for spherical Li4Ti5O12 |
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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 |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
| CN102718256A (en) * | 2012-06-23 | 2012-10-10 | 三峡大学 | Preparation method for titania microspheres with adjustable grain sizes |
| CN104091939A (en) * | 2014-06-30 | 2014-10-08 | 北京工业大学 | Hydrothermal synthesis preparation method for spherical Li4Ti5O12 |
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