CN108996544B - Lithium titanate material and preparation method thereof - Google Patents
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Abstract
The invention provides a lithium titanate material, a preparation method thereof and a lithium titanate battery containing the lithium titanate material, belonging to the technical field of preparation of a lithium ion battery cathode material, wherein the lithium titanate material has a hollow cubic structure, and on one hand, through the construction of the hollow structure, the specific surface area of the lithium titanate material can be obviously improved, an electron transmission path is shortened, the electron conductivity of the lithium titanate material is improved, and the electrochemical dynamic performance of the lithium titanate material is further improved; on the other hand, through the design of the cubic morphology, the integral stability of the micron-scale cubic morphology can be improved, and meanwhile, the active crystal face of the nano-scale particles can be exposed, so that the rate capability and the electrochemical activity of the lithium titanate material can be improved. Therefore, compared with the lithium titanate in the prior art, the lithium titanate material provided by the invention has the advantages of better specific surface area, more stable structure and higher reaction activity.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery cathode materials, and particularly relates to a lithium titanate material and a preparation method thereof.
Background
The lithium ion battery is a novel green high-energy rechargeable battery appearing in the early 90 s of the 20 th century, has the advantages of good voltage platform, excellent cycle stability and thermal stability, low price and the like, and is widely applied to the fields of mobile phones, notebook computers, portable electric tools, electronic instruments, electric automobiles and the like. Lithium titanate (Li)4Ti5O12) As a common material of a lithium ion battery cathode, the lithium ion battery cathode has the advantages of a zero-strain lithium-releasing and-inserting structure, an ultra-long cycle life, a stable charge-discharge voltage platform, excellent safety performance and the like, is low in price and easy to prepare, and therefore has attracted wide attention, especially in the field of power batteries.
At present, the preparation method of a lithium titanate material commonly used is a high-temperature solid-phase method, which is to grind a lithium source (lithium carbonate or lithium hydroxide) and a titanium source (titanium dioxide) uniformly, and then directly calcine the ground materials in a muffle furnace at a high temperature to prepare the lithium titanate. The preparation method has the advantages of simple process, short flow and the like. However, the above method is to perform chemical lithiation at high temperature, on one hand, the prepared lithium titanate particles are large, the morphology of the lithium titanate particles is not uniform, the size of the lithium titanate particles is not uniform, the electronic conductivity and the ionic conductivity of the generated lithium titanate particles are poor, the large-current charging and discharging of the lithium titanate material are seriously influenced, and the lithium titanate prepared by the above method is easy to collapse in structure and pulverize the particles, so that the rate capability and the cycle performance of the lithium ion battery are seriously limited when the lithium titanate is used as a negative electrode material of the lithium ion battery, and the application of the lithium titanate in a high-power battery system is limited. Although the current market tries to improve the electronic conductivity of the lithium titanate material by adopting methods such as coating, ion doping and the like, the preparation method is complex in process and has less improvement on the conductivity of the prepared lithium titanate material.
Therefore, it is an urgent technical problem to be solved for those skilled in the art how to improve the electron conductivity and rate capability of the existing lithium titanate material and the preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of poor electronic conductivity and rate capability of a lithium titanate material in the prior art, so that the invention provides the lithium titanate material, and further provides a preparation method thereof and a lithium titanate battery containing the lithium titanate material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a lithium titanate material, wherein the lithium titanate has a hollow cubic structure.
The invention also provides a method for preparing the lithium titanate material, which comprises the following steps:
(1) precursor cube CaTiO3Preparation of
Mixing calcium chloride, a titanium source, a high molecular polymer and absolute ethyl alcohol, adding sodium hydroxide, carrying out hydrothermal reaction at 150-180 ℃, and filtering to obtain a solid, namely a precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Precursor cube CaTiO prepared in the step (1)3Mixing with metal organic compound, water and glycol, carrying out hydrothermal reaction at 140-180 ℃, filtering to obtain solidThe body is hollow cubic TiO2；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in the step (2)2Mixing with a lithium source, adding absolute ethyl alcohol to form a reaction system, sealing the reaction system to form a sealed system, heating and stirring to uniformly mix the sealed system, opening the sealed system, heating and stirring until the absolute ethyl alcohol is completely evaporated to obtain white powder, and calcining the white powder at 700 ℃ for 3 hours in an inert gas atmosphere to obtain the hollow cubic Li4Ti5O12。
In the preparation method, in the step (1), the titanium source is isopropyl titanate, tetrabutyl titanate or titanium tetrachloride;
the high molecular polymer is polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 800 or polyethylene glycol 1600.
The mass ratio of the calcium chloride to the titanium source, the high-molecular polymer and the sodium hydroxide is 0.11: 0.33 (0.4-0.5) to 0.24;
the mass ratio of the absolute ethyl alcohol to the high molecular polymer is (40-60) to 1;
the hydrothermal reaction time is 15-20 h;
the obtained solid is respectively washed three times by absolute ethyl alcohol and distilled water and dried overnight at 60 ℃ to obtain precursor cube CaTiO3。
In the above preparation method, in the step (2),
the metal organic compound is disodium ethylene diamine tetraacetate or dipotassium ethylene diamine tetraacetate;
the metal organic compound and the CaTiO3The mass ratio of (2-6) to 1;
the volume ratio of the water to the ethylene glycol is (2-4) to 1;
the time of the hydrothermal reaction is 10-12 h.
The obtained solid is respectively washed three times by absolute ethyl alcohol and distilled water, and is dried at 60 ℃ overnight to obtain the hollow cubic TiO2。
In the preparation method, in the step (3), the lithium source is lithium hydroxide dihydrate;
TiO prepared in the step (2)2With a lithium source as follows: the molar ratio of Li ions is 1 to (0.81-0.85).
The invention also provides a lithium titanate material prepared by the method.
The invention also provides a lithium titanate battery which comprises the lithium titanate material or the lithium titanate material prepared by the preparation method.
The invention also provides application of the lithium titanate material or the lithium titanate material prepared by the preparation method in preparing a lithium ion battery cathode material.
The technical scheme of the invention has the following advantages:
1. the lithium titanate material has a hollow cubic structure, so that on one hand, through the construction of the hollow structure, the specific surface area of the lithium titanate material can be obviously improved, an electron transmission path is shortened, the electronic conductivity of the lithium titanate material is improved, and the electrochemical dynamic performance of the lithium titanate material is further improved; on the other hand, through the design of the cubic morphology, the integral stability of the micron-scale cubic morphology can be improved, and meanwhile, the active crystal face of the nano-scale particles can be exposed, so that the rate capability and the electrochemical activity of the lithium titanate material can be improved. Therefore, compared with the lithium titanate in the prior art, the lithium titanate material provided by the invention has the advantages of better specific surface area, more stable structure and higher reaction activity.
2. The preparation method of the lithium titanate material comprises the steps of firstly regulating and controlling a precursor CaTiO3The synthesis of the method can controllably construct the cubic morphology; then using CaTiO3Self-sacrificing template, i.e. by adding a precursor cubic CaTiO3Controlling the hydrothermal reaction temperature of the metal organic compound, water and glycol within the range of 150-180 ℃, and regulating Ca2+And H in ethylene glycol+Thereby not only inheriting the CaTiO3The cubic structure of (A) constitutes a hollow structure and also realizes the hollow structureControllable regulation and control of wall thickness; finally, chemical lithiation is adopted to synthesize Li with spinel structure4Ti5O12. The synthesized lithium titanate with the hollow cubic structure has uniform size and appearance, good phase purity and crystallinity, and excellent electronic conductivity and rate capability.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows L prepared in example 1 of the present inventioni4Ti5O12、TiO2With CaTiO3XRD pattern of (a);
fig. 2 is an sem (a) and tem (b) of a lithium titanate material of a hollow cubic structure prepared in example 1 of the present invention;
fig. 3 is a diagram showing electrochemical properties of a lithium titanate material having a hollow cubic structure prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. 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. Furthermore, the technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the lithium titanate material with the hollow cubic structure provided by the embodiment comprises the following steps:
(1) precursor cube CaTiO3Preparation of
0.11g of calcium chloride and 0.33g of tetrabutyl titanate were weighed outAdding ester, 0.5g polyethylene glycol (PEG)200 and 35mL absolute ethyl alcohol into a 50mL reaction kettle, and performing ultrasonic treatment at room temperature for 30min to uniformly mix the mixture; then adding 0.24g of sodium hydroxide under continuous stirring, uniformly stirring, sealing the reaction kettle after the sodium hydroxide is dissolved, heating for 20 hours at 150 ℃, filtering after the reaction kettle is cooled to room temperature, respectively washing the obtained solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Taking 75mg of precursor cube CaTiO prepared in the step (1)3Placing the mixture into a 50mL reaction kettle, adding 300mg disodium ethylene diamine tetraacetate (EDTA-2Na), adding 30mL water and 10mL ethylene glycol to form a mixture, performing ultrasonic treatment on the mixture at room temperature for 15min to uniformly mix the mixture, performing hydrothermal reaction at 160 ℃, controlling the reaction time to be 12h, cooling the reaction mixture to room temperature, filtering, respectively washing the obtained beige solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the hollow cube TiO 22；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in the step (2)2Placing in a 100mL beaker, adding lithium hydroxide dihydrate, wherein the TiO2With lithium hydroxide dihydrate as follows: mixing Li ions according to the molar ratio of 1: 0.83, adding 40mL of absolute ethyl alcohol to form a reaction system, sealing the reaction system by using a preservative film to form a sealing system, heating and stirring at 70 ℃ for 12h to uniformly mix the sealing system, tearing off the preservative film to open the sealing system, continuing heating and stirring at 70 ℃ until the absolute ethyl alcohol is completely evaporated to obtain white powder, scraping the obtained white powder out of a beaker, collecting the white powder, filling the white powder into a 10mL crucible, and calcining the white powder at 700 ℃ for 3h in an argon atmosphere to obtain the hollow cubic Li4Ti5O12。
In this example, the hollow cube L was preparedi4Ti5O12、TiO2With CaTiO3The XRD pattern of (A) is shown in figure 1。
Hollow cube L produced in this examplei4Ti5O12The SEM (a) and TEM (b) are shown in FIG. 2, and it can be seen from FIG. 2 that L produced in this examplei4Ti5O12Has a hollow cubic structure.
Hollow cube L produced in this examplei4Ti5O12FIG. 3 shows the electrochemical performance of the hollow cube L obtained in this example, as can be seen from FIG. 3i4Ti5O12The specific capacities of the alloy materials are 150 mAh g, 111 mAh g and 81mAh g respectively under the heavy current densities of 10C, 60C and 100C-1When the current density returns to 1C, the specific capacity can be increased back to 174mAh g-1And the excellent rate performance is shown.
Example 2
The preparation method of the lithium titanate material with the hollow cubic structure provided by the embodiment comprises the following steps:
(1) precursor cube CaTiO3Preparation of
Weighing 0.11g of calcium chloride, 0.33g of isopropyl titanate, 0.4g of polyethylene glycol (PEG)1600 and 38mL of absolute ethyl alcohol, adding into a 50mL reaction kettle, and performing ultrasonic treatment at room temperature for 30min to uniformly mix; then adding 0.24g of sodium hydroxide under continuous stirring, uniformly stirring, sealing the reaction kettle after the sodium hydroxide is dissolved, heating for 18 hours at 160 ℃, filtering after the reaction kettle is cooled to room temperature, respectively washing the obtained solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Taking 100mg of precursor cube CaTiO prepared in the step (1)3Placing into a 50mL reaction kettle, adding 600mg dipotassium ethylene diamine tetraacetic acid (EDTA-2K), adding 40mL water and 10mL ethylene glycol to form a mixture, performing ultrasonic treatment on the mixture at room temperature for 15min to uniformly mix the mixture, performing hydrothermal reaction at 140 ℃, controlling the reaction time to be 10h, cooling the reaction mixture to room temperature, filtering, respectively washing the obtained beige solid with anhydrous ethanol and distilled water for three times, and performing washing at 60 ℃ to obtain beige solidDrying overnight to obtain the hollow cubic TiO2；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in the step (2)2Placing in a 100mL beaker, adding lithium hydroxide dihydrate, wherein the TiO2With lithium hydroxide dihydrate as follows: mixing Li ions according to the molar ratio of 1: 0.85, adding 40mL of absolute ethyl alcohol to form a reaction system, sealing and sealing the reaction system by using a preservative film to form a sealing system, heating and stirring at 70 ℃ for 12h to uniformly mix the sealing system, tearing off the preservative film to open the sealing system, continuing heating and stirring at 70 ℃ until the absolute ethyl alcohol is completely evaporated to obtain white powder, scraping the obtained white powder out of a beaker, collecting the white powder, filling the white powder into a 10mL crucible, and calcining the white powder at 700 ℃ for 3h in an argon atmosphere to obtain the hollow cubic Li4Ti5O12。
Example 3
The preparation method of the lithium titanate material with the hollow cubic structure provided by the embodiment comprises the following steps:
(1) precursor cube CaTiO3Preparation of
Weighing 0.11g of calcium chloride, 0.33g of butyl titanate, 0.5g of polyethylene glycol (PEG)800 and 35mL of absolute ethyl alcohol, adding into a 50mL reaction kettle, and performing ultrasonic treatment at room temperature for 30min to uniformly mix; then adding 0.24g of sodium hydroxide under continuous stirring, uniformly stirring, sealing the reaction kettle after the sodium hydroxide is dissolved, heating for 15h at 180 ℃, filtering after the reaction kettle is cooled to room temperature, respectively washing the obtained solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Taking 75mg of precursor cube CaTiO prepared in the step (1)3Placing into a 50mL reaction kettle, adding 400mg disodium ethylene diamine tetraacetate (EDTA-2Na), adding 30mL water and 10mL ethylene glycol to form a mixture, performing ultrasonic treatment at room temperature for 15min to mix the mixture uniformly, performing hydrothermal reaction at 180 ℃, and controllingThe reaction time is 12h, the reaction mixture is cooled to room temperature and filtered, the obtained beige solid is respectively washed three times by absolute ethyl alcohol and distilled water and is dried at 60 ℃ overnight, and the hollow cube TiO is obtained2；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in step (2)2Placing in a 100mL beaker, adding lithium hydroxide dihydrate, wherein the TiO2With lithium hydroxide dihydrate as follows: mixing Li ions according to the molar ratio of 1: 0.83, adding 40mL of absolute ethyl alcohol to form a reaction system, sealing the reaction system by using a preservative film to form a sealing system, heating and stirring at 70 ℃ for 12h to uniformly mix the sealing system, tearing off the preservative film to open the sealing system, continuing heating and stirring at 70 ℃ until the absolute ethyl alcohol is completely evaporated to obtain white powder, scraping the obtained white powder out of a beaker, collecting the white powder, filling the white powder into a 10mL crucible, and calcining the white powder at 700 ℃ for 3h in an argon atmosphere to obtain the hollow cubic Li4Ti5O12。
Example 4
The preparation method of the lithium titanate material with the hollow cubic structure provided by the embodiment comprises the following steps:
(1) precursor cube CaTiO3Preparation of
Weighing 0.11g of calcium chloride, 0.33g of titanium tetrachloride, 0.5g of polyethylene glycol (PEG)400 and 35mL of absolute ethyl alcohol, adding into a 50mL reaction kettle, and performing ultrasonic treatment at room temperature for 30min to uniformly mix; then adding 0.24g of sodium hydroxide under continuous stirring, uniformly stirring, sealing the reaction kettle after the sodium hydroxide is dissolved, heating for 15h at 160 ℃, filtering after the reaction kettle is cooled to room temperature, respectively washing the obtained solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Taking 75mg of precursor cube CaTiO prepared in the step (1)3Placing the mixture into a 50mL reaction kettle, adding 200mg of ethylene diamine tetraacetic acid dipotassium (EDTA-2K) and addingAdding 20mL of water and 10mL of ethylene glycol to form a mixture, performing ultrasonic treatment on the mixture at room temperature for 15min to uniformly mix the mixture, performing hydrothermal reaction at 160 ℃, controlling the reaction time to be 12h, cooling the reaction mixture to room temperature, filtering, respectively washing the obtained beige solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the hollow cubic TiO2；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in step (2)2Placing in a 100mL beaker, adding lithium hydroxide dihydrate, wherein the TiO2With lithium hydroxide dihydrate as follows: mixing Li ions according to the molar ratio of 1: 0.81, adding 40mL of absolute ethyl alcohol to form a reaction system, sealing and sealing the reaction system by using a preservative film to form a sealing system, heating and stirring at 70 ℃ for 12h to uniformly mix the sealing system, tearing off the preservative film to open the sealing system, continuing heating and stirring at 70 ℃ until the absolute ethyl alcohol is completely evaporated to obtain white powder, scraping the obtained white powder out of a beaker, collecting the white powder, filling the white powder into a 10mL crucible, and calcining the white powder at 700 ℃ for 3h in an argon atmosphere to obtain the hollow cubic Li4Ti5O12。
Example 5
The preparation method of the lithium titanate material with the hollow cubic structure provided by the embodiment comprises the following steps:
(1) precursor cube CaTiO3Preparation of
Weighing 0.11g of calcium chloride, 0.33g of isopropyl titanate, 0.5g of polyethylene glycol (PEG)200 and 25.3mL of absolute ethyl alcohol, adding into a 50mL reaction kettle, and performing ultrasonic treatment at room temperature for 30min to uniformly mix; then adding 0.24g of sodium hydroxide under continuous stirring, uniformly stirring, sealing the reaction kettle after the sodium hydroxide is dissolved, heating for 15h at 170 ℃, filtering after the reaction kettle is cooled to room temperature, respectively washing the obtained solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Taking 75mg of precursor cube CaTiO prepared in the step (1)3Putting the mixture into a 50mL reaction kettle, adding 200mg disodium ethylene diamine tetraacetate (EDTA-2Na), adding 40mL water and 10mL ethylene glycol to form a mixture, performing ultrasonic treatment on the mixture at room temperature for 15min to uniformly mix the mixture, performing hydrothermal reaction at 150 ℃, controlling the reaction time to be 12h, cooling the reaction mixture to room temperature, filtering, respectively washing the obtained beige solid with absolute ethyl alcohol and distilled water for three times, and drying at 60 ℃ overnight to obtain the hollow cube TiO 22；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in step (2)2Placing in a 100mL beaker, adding lithium hydroxide dihydrate, wherein the TiO2With lithium hydroxide dihydrate as follows: mixing Li ions according to the molar ratio of 1: 0.84, adding 40mL of absolute ethyl alcohol to form a reaction system, sealing and sealing the reaction system by using a preservative film to form a sealing system, heating and stirring at 70 ℃ for 12h to uniformly mix the sealing system, tearing off the preservative film to open the sealing system, continuing heating and stirring at 70 ℃ until the absolute ethyl alcohol is completely evaporated to obtain white powder, scraping the obtained white powder out of a beaker, collecting the white powder, filling the white powder into a 10mL crucible, and calcining the white powder at 700 ℃ for 3h in an argon atmosphere to obtain the hollow cubic Li4Ti5O12。
In the embodiment of the invention, the high molecular polymer is selected from polyethylene glycol 200, polyethylene glycol 800 or polyethylene glycol 1600, and the reaction energy on the surface of the lithium titanate material can be changed by selecting the polyethylene glycols with different polymerization degrees, so that a cubic structure with uniform appearance and size is formed, and the defects of non-uniform appearance and non-uniform size in the conventional synthesis method are overcome.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A method for preparing a lithium titanate material is characterized by comprising the following steps:
(1) precursor cube CaTiO3Preparation of
Mixing calcium chloride, a titanium source, a high molecular polymer and absolute ethyl alcohol, adding sodium hydroxide, carrying out hydrothermal reaction at 150-180 ℃, and filtering to obtain a solid, namely a precursor cube CaTiO3；
(2) Hollow cubic TiO2Preparation of
Precursor cube CaTiO prepared in the step (1)3Mixing the solid with a metal organic compound, water and ethylene glycol, carrying out hydrothermal reaction at 140-180 ℃, and filtering to obtain a solid, namely the hollow cubic TiO2；
(3) Hollow cubic Li4Ti5O12Preparation of
TiO prepared in the step (2)2Mixing with a lithium source, adding absolute ethyl alcohol to form a reaction system, sealing the reaction system to form a sealed system, heating and stirring to uniformly mix the sealed system, opening the sealed system, heating and stirring until the absolute ethyl alcohol is completely evaporated to obtain white powder, and calcining the white powder at 700 ℃ for 3 hours in an inert gas atmosphere to obtain the hollow cubic Li4Ti5O12。
2. The method according to claim 1, wherein, in step (1),
the titanium source is isopropyl titanate, tetrabutyl titanate or titanium tetrachloride;
the high molecular polymer is polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 800 or polyethylene glycol 1600.
3. The method according to claim 1, wherein, in step (1),
the mass ratio of the calcium chloride to the titanium source, the high molecular polymer and the sodium hydroxide is 0.11: 0.33: (0.4-0.5): 0.24;
the mass ratio of the absolute ethyl alcohol to the high molecular polymer is (40-60): 1;
the hydrothermal reaction time is 15-20 h;
the obtained solid is respectively washed three times by absolute ethyl alcohol and distilled water and dried overnight at 60 ℃ to obtain precursor cube CaTiO3。
4. The method according to any one of claims 1 to 3, wherein, in step (2),
the metal organic compound is disodium ethylene diamine tetraacetate or dipotassium ethylene diamine tetraacetate;
the metal organic compound and the CaTiO3The mass ratio of (2-6): 1;
the volume ratio of the water to the glycol is (2-4) to 1;
the time of the hydrothermal reaction is 10-12 h.
5. The method according to any one of claims 1 to 3, wherein, in step (2),
the obtained solid is respectively washed three times by absolute ethyl alcohol and distilled water, and is dried at 60 ℃ overnight to obtain the hollow cubic TiO2。
6. The method according to any one of claims 1 to 3, wherein, in step (3),
the lithium source is lithium hydroxide dihydrate;
TiO prepared in the step (2)2With a lithium source as follows: molar ratio of Li ions 1: (0.81-0.85) mixing.
7. A lithium titanate material prepared by the process of any one of claims 1-6.
8. A lithium titanate battery, characterized by comprising the lithium titanate material prepared by the preparation method of any one of claims 1 to 6.
9. Use of the lithium titanate material prepared by the preparation method of any one of claims 1 to 6 in the preparation of a negative electrode material of a lithium ion battery.
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