CN112607769A - Lithium titanate battery material, preparation method and application thereof - Google Patents

Lithium titanate battery material, preparation method and application thereof Download PDF

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CN112607769A
CN112607769A CN202011508004.2A CN202011508004A CN112607769A CN 112607769 A CN112607769 A CN 112607769A CN 202011508004 A CN202011508004 A CN 202011508004A CN 112607769 A CN112607769 A CN 112607769A
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lithium
ball
lithium titanate
titanium source
source
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游志江
白岩
成信刚
马薇薇
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Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies Co Ltd
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Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies Co Ltd
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Abstract

The invention provides a lithium titanate battery material, and a preparation method and application thereof. The preparation method comprises the following steps: mixing part of a titanium source and a lithium source, and then carrying out ball milling to obtain a primary ball-milled material; mixing the primary ball-milled material with the residual titanium source, and then continuing ball milling to obtain a ball-milled product; and drying, calcining and screening the ball milling product in sequence to obtain the lithium titanate battery material. The titanium source is added in the ball milling process in a grading way, so that part of the titanium source is attached to the ball milling particles, the volatilization of lithium during high-temperature calcination in the later stage can be effectively reduced, and TiO can be formed on the surface of lithium titanate after the calcination2To play as a guideThe effect of the electrolyte can further inhibit the polarization of the electrode caused by high current, and make up for the deficiency of the lithium titanate material. The method is beneficial to improving the utilization rate of a lithium source, improving the conductivity of a lithium titanate sample and improving the stability and the production efficiency of a product.

Description

Lithium titanate battery material, preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a lithium titanate battery material, and a preparation method and application thereof.
Background
The lithium titanate battery mainly comprises a positive electrode (mainly comprising lithium cobaltate, lithium manganate, lithium iron phosphate and ternary materials at present), a negative electrode (adopting lithium titanate), an electrolyte with the capability of transmitting lithium ions and a diaphragm capable of separating the positive electrode from the negative electrode. The work is mainly completed by continuously converting between lithium-poor state and lithium-rich state.
Among lithium titanate batteries, lithium titanate materials are an extremely important component of lithium titanate batteries. At present, the lithium source of the lithium titanate battery material volatilizes when the raw material is sintered, so that the lithium titanate crystal structure has defects, the phase purity of the obtained lithium titanate material is low, and the conductivity cannot be guaranteed, so that the problem of how to improve the lithium titanate sintering process becomes a very key problem.
Disclosure of Invention
The invention mainly aims to provide a lithium titanate battery material, a preparation method and application thereof, so as to solve the problem that the lithium source volatilizes during sintering to cause defects of a lithium titanate crystal structure in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a lithium titanate battery material, the method comprising: mixing part of a titanium source and a lithium source, and then carrying out ball milling to obtain a primary ball-milled material; mixing the primary ball-milled material with the residual titanium source, and then continuing ball milling to obtain a ball-milled product; and drying, calcining and screening the ball milling product in sequence to obtain the lithium titanate battery material.
Further, the mixing mass ratio of part of the titanium source and the lithium source is 1: 0.43-1: 0.54 in terms of mass ratio; preferably the titanium source is selected from TiO2And/or metatitanic acid; preferably, the lithium source is selected from LiOH H2O and lithium carbonate.
Further, the mass ratio of the partial titanium source to the residual titanium source is 1:0.03 to 1: 0.13.
further, mixing part of the titanium source and the lithium source, and then performing ball milling to obtain a primary ball milling material, wherein the primary ball milling material comprises: adding part of a titanium source and a lithium source into a container filled with deionized water, and stirring and dispersing to obtain a dispersion liquid; preferably, the stirring speed is 1750-3500 r/min, the stirring time is 2.5-4 h, and the dispersion liquid is added into a ball mill filled with grinding balls for ball milling to obtain a primary ball milled material; preferably, the rotating speed of the ball mill is 3200-3800 r/min, and the ball milling time is 1.5-2.5 h.
Further, mixing the primary ball-milled material with the residual titanium source, and then continuing ball milling to obtain a ball-milled product comprising: mixing the primary ball-milled material with the residual titanium source and the solvent which are dissolved in advance, and carrying out ball milling to obtain a ball-milled product; preferably the solvent is selected from ethylene glycol, methanol, absolute ethanol or isopropanol; the amount of the solvent added is preferably 50 to 150 g.
Further, in the steps of drying, calcining and screening the ball-milled product in sequence, spray drying is adopted for drying, preferably, the spray drying temperature is 110-205 ℃, and the spray flow in the spray drying process is 5-7 m3H; preferably, the calcination adopts batch sintering, and the sintering temperature is 650-900 ℃ and the time is 180-360 min; more preferably, the temperature is increased to the sintering temperature according to the heating rate of 8-12 ℃/min; preferably, the calcined product is cooled and then sieved, and more preferably, the particle size D of the lithium titanate battery material is obtained after sieving909 to 10 μm, preferably D99Is 14 to 15 μm.
According to a second aspect of the present application, there is provided a lithium titanate battery material prepared by any one of the above-described preparation methods.
According to a third aspect of the present application, there is provided a lithium titanate battery material having a phase purity of 100%.
Further, the particle size D of the lithium titanate battery material 909 to 10 μm, preferably D99Is 14 &15 μm; preferably, the specific surface area of the lithium titanate battery material is 92-97 m2(ii)/g; preferably, the gram capacity of the lithium titanate battery material is 165.4-166.4 mAh/g.
According to a fourth aspect of the present application, there is provided a lithium titanate battery negative electrode sheet comprising any one of the lithium titanate battery materials described above.
According to a fifth aspect of the present application, there is provided a lithium ion battery, including a positive electrode, a negative electrode, an electrolyte, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is any one of the lithium titanate battery negative electrode sheets described above.
By applying the technical scheme of the invention, the titanium source is added in the ball milling process step by step, so that a part of the titanium source is attached to the ball milling particles (namely, the titanium is coated on the outer layer of the lithium), the volatilization of the lithium during the later high-temperature calcination can be effectively reduced, and TiO can be formed on the surface of the lithium titanate after the calcination2The lithium titanate conductive electrode has the function of a conductive agent, and further can inhibit the polarization of the electrode caused by high current, so that the defect of the lithium titanate material is overcome. The method is beneficial to improving the utilization rate of a lithium source, improving the conductivity of a lithium titanate sample, and obviously improving the stability and the production efficiency of products in industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic flow chart of a method for preparing a lithium titanate electrode material according to a preferred embodiment of the invention;
FIG. 2 is a structural view of an electron microscope of a ball-milled product of a comparative example;
FIG. 3 is an electron microscope structural view of a ball-milled product of example 1 of the present invention;
FIG. 4 is an electron microscope structural view of a lithium titanate finished product of a comparative example;
fig. 5 is an electron microscope structural view of a lithium titanate product of example 1 of the present invention;
fig. 6 and 7 show XRD structural diagrams of examples 1 to 17 of the present invention and a comparative example.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background art, in the lithium titanate battery material in the prior art, due to volatilization of a lithium source when a raw material is sintered, a defect occurs in a lithium titanate crystal structure, the phase purity of the obtained lithium titanate material is relatively low, and the conductivity cannot be guaranteed, so that in order to improve the above defect of lithium titanate, the application improves a sintering process, and provides a preparation method of the lithium titanate battery material, which comprises the following steps: mixing part of a titanium source and a lithium source, and then carrying out ball milling to obtain a primary ball-milled material; mixing the primary ball-milled material with the residual titanium source, and then continuing ball milling to obtain a ball-milled product; and drying, calcining and screening the ball milling product in sequence to obtain the lithium titanate battery material.
According to the preparation method, the titanium source is added in a ball milling process in a divided manner, so that a part of the titanium source is attached to ball milling particles (namely, the titanium is coated on the outer layer of lithium), the volatilization of lithium during high-temperature calcination in the later period can be effectively reduced, and TiO can be formed on the surface of lithium titanate after calcination2The lithium titanate conductive electrode has the function of a conductive agent, and further can inhibit the polarization of the electrode caused by high current, so that the defect of the lithium titanate material is overcome. The method is beneficial to improving the utilization rate of a lithium source, improving the conductivity of a lithium titanate sample, and obviously improving the stability and the production efficiency of products in industrial production.
In the preparation method, the raw materials of the titanium source and the lithium source can be the conventional raw materials. Sources of titanium in this application include, but are not limited to, TiO2Metatitanic acid; lithium sources include, but are not limited to, LiOH H2O and lithium carbonate. The specific amount of the titanium source mixed with the lithium source is not particularly limited, and the titanium source is added in a plurality of times as long as part of the titanium source is added later, so that part of the titanium source is attached to the surface of the ball-milled particles, and the subsequent reduction of the titanium source is facilitatedAnd (3) volatilizing lithium in the calcining process. In order to make the titanium source more effectively and more completely attached to the ball-milled particles, the volatilization of lithium in the calcining process and the formation of TiO on the surface of lithium titanate are more effectively reduced2The conductivity of the lithium titanate electrode material is improved. In a preferred embodiment, the mixing mass ratio of a part of the titanium source and the lithium source is 1:0.43 to 1:0.54, preferably 1: 0.45-1: 0.50. in another preferred embodiment, the mass ratio of the partial titanium source to the residual titanium source is 1:0.03 to 1: 0.13.
the specific conditions in the ball milling step can be reasonably adjusted according to actual conditions. In a preferred embodiment of the present application, mixing a part of the titanium source and the lithium source and ball milling the mixture to obtain a primary ball milled material comprises: adding part of a titanium source and a lithium source into a container filled with deionized water, and stirring and dispersing to obtain a dispersion liquid; preferably, the stirring speed is 1750-3500 r/min, the stirring time is 2.5-4 h, and the dispersion liquid is added into a ball mill filled with grinding balls for ball milling to obtain a primary ball milled material; preferably, the rotating speed of the ball mill is 3200-3800 r/min, and the ball milling time is 1.5-2.5 h.
Mixing the primary ball-milled material with the residual titanium source and then continuing ball milling to obtain a ball-milled product, wherein the ball-milled product is obtained by mixing and ball milling the primary ball-milled material with the residual titanium source and the solvent which are dissolved in advance to obtain the ball-milled product; preferably the solvent is selected from methanol, absolute ethanol or isopropanol; the amount of the solvent added is preferably 50 to 150g, more preferably 80 to 120 g. The solvent is added as a dispersing agent, so that the molecular acting force among ball-milling substances is reduced, and the grinding efficiency is improved. And adding a titanium source and a solvent on the surface of the primarily milled particles to ensure that a part of the titanium source is attached to the surface of the lithium source. The amount of solvent used here is determined by the amount of a portion of the titanium source.
In the step of drying, calcining and screening the ball-milled product in sequence, spray drying is adopted for drying, the preferable spray drying temperature is 110-205 ℃, and the spray flow in the spray drying process is 5-7 m3H; preferably, the calcination adopts batch sintering, the temperature of the sintering is 650-900 ℃, the preferred temperature is 700-820 ℃, the time is 180-360 min, and the preferred time is 180-270 min;preferably, the temperature is increased to the sintering temperature according to 8-12 ℃/min, more preferably according to the heating rate of 10 ℃/min; preferably, the product to be calcined is cooled and then sieved, and more preferably, the particle size D of the lithium titanate battery material is obtained after sieving909 to 10 μm, D99Is 14 to 15 μm.
Spray drying is to atomize the thin material and to vaporize the water rapidly in the contact with hot air to obtain the dry product, which can directly dry the liquid into powder or granule. Spray drying is generally a process in which a spray dryer mechanically disperses the slurry into a mist of particles, which helps to increase the area of water evaporation and speed up the drying process, thereby removing most of the water instantaneously when in contact with hot air. The drying temperature and flow rate are controlled within the above ranges, so that the purpose of rapid drying can be achieved.
The sintering temperature and time are controlled in the range, so that the particles can have good particle size distribution and higher specific surface area. The temperature can be rapidly raised to the target sintering temperature according to the temperature raising rate. Batch sintering is preferably carried out in a muffle furnace. And naturally cooling to a greenhouse after sintering. And cooling and screening to obtain the lithium titanate finished product. Specific particle diameter
In a second exemplary embodiment of the present application, a lithium titanate battery material prepared by any one of the above-described preparation methods is provided. Compared with the traditional hydrothermal method and sol-gel method, the method has the advantages that the product is easier to quantify, and the performance is more stable.
In a third exemplary embodiment, a lithium titanate battery material having a phase purity of 100% is provided. The lithium titanate battery material has more excellent conductivity, and has obvious effect of improving the stability and production efficiency of products in industrial production.
In a preferred embodiment, the particle size D of the lithium titanate battery material 909 to 10 μm, more preferably D99Is 14 to 15 μm; preferably, the specific surface area of the lithium titanate battery material is 92-97 m2(ii)/g; preferably, the gram capacity of the lithium titanate battery material is 165.4-166.4 mAh/g. The lithium titanate battery material provided by the applicationThe performances are all obviously improved compared with the prior art.
In a fourth exemplary embodiment, a lithium titanate battery negative plate is provided, and the lithium titanate battery negative plate comprises any one of the lithium titanate battery materials described above.
In a fifth exemplary embodiment, a lithium ion battery is provided, which includes a positive electrode, a negative electrode, an electrolyte, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is made of any one of the lithium titanate battery materials.
The advantageous effects of the present application will be further described with reference to specific examples. The following examples were prepared according to the scheme shown in fig. 1. In the following examples, the titanium source is TiO2The lithium source is LiOH. H2O。
Experimental example 1
1) Weighing machine
Accurately weighing 302g of lithium source, 649g of titanium source and 50g of titanium source (the mass ratio is 1:0.08) in a dry environment;
2) premixing
Putting 4.45Kg of deionized water into a charging basket, adding 302g of lithium source and 649g of titanium source (the mass ratio is 0.47:1) during stirring, keeping the rotating speed at 1750r/min, and dispersing for 4 hours;
3) ball mill
After the ball mill was cleaned, 1770g of zirconium balls were added, and the slurry after dispersion was transferred to a dispersion jar. Keeping the rotating speed at 3500rpm, grinding for 2h, adding 50g of pre-dissolved titanium source and 95g of ethylene glycol, and continuing grinding; and transferring the slurry into the material pipe after the grinding is finished. Wherein, fig. 3 shows the structure of the electron microscope after ball milling.
4) Spray drying
Cleaning the spray dryer before each spray drying, setting the inlet air temperature at 205 deg.C, controlling the exhaust air temperature at about 110 deg.C, maintaining the pump speed at 28, and adjusting the flow rate to 6m3And h, starting spray drying after the parameters of the spray dryer are stable.
5) Calcination of
And (3) performing batch sintering by using a muffle furnace, raising the temperature to 750 ℃ of a target sintering temperature at a heating rate of 10 ℃/min, and then keeping the temperature for 180 min. Naturally cooling to room temperature.
6) Sieving
And (3) cooling the sample, and screening to obtain a lithium titanate finished product, wherein fig. 5 shows the electron microscope structure of the lithium titanate finished product.
Experimental example 2
1) Weighing machine
Accurately weighing 302g of lithium source, 659g of titanium source and 40g of titanium source (the mass ratio is 1:0.06) in a dry environment;
2) premixing
Putting 4.45Kg of deionized water into a charging basket, adding 302g of lithium source and 659g of titanium source (the mass ratio is 0.46:1) during stirring, keeping the rotating speed at 1750r/min, and dispersing for 4 hours;
3) ball mill
After the ball mill is cleaned, 1770g of zirconium balls are added, and the dispersed slurry is transferred to a dispersion cylinder and added; keeping the rotating speed of 3450rpm, grinding for 2h, adding 40g of the titanium source dissolved in advance and 95g of ethylene glycol, and continuing grinding; and transferring the slurry into the material pipe after the grinding is finished.
4) Spray drying
Cleaning the spray dryer before each spray drying, setting the inlet air temperature at 205 deg.C, controlling the exhaust air temperature at about 110 deg.C, maintaining the pump speed at 28rpm/min, and adjusting the flow rate to 6m3And h, starting spray drying after the parameters of the spray dryer are stable.
5) Calcination of
And (3) performing batch sintering by using a muffle furnace, raising the temperature to the target sintering temperature of 820 ℃ at the heating rate of 10 ℃/min, and then keeping the temperature for 180 min. Naturally cooling to room temperature.
6) Sieving
And (5) cooling the sample, and screening to obtain a lithium titanate finished product.
Example 3
The only difference from example 1 is: 302g of lithium source, 664g of titanium source (mass ratio of first added titanium source to lithium source: 1: 0.45) and 35g of titanium source (second added) (mass ratio of first added titanium source to second added titanium source: 1:0.05) were weighed.
Example 4
The only difference from example 1 is: 302g of lithium source, 669g of titanium source (mass ratio of first addition of titanium source to lithium source: 1: 0.45) and 30g of titanium source (second addition) (mass ratio of 1:0.05) were weighed.
Example 5
The only difference from example 1 is: 302g of lithium source, 679g of titanium source (mass ratio of the first added titanium source to the lithium source: 1: 0.44) and 20g of titanium source (second added) (mass ratio of 1:0.03) were weighed.
Example 6
The only difference from example 1 is: 302g of lithium source, 689g of titanium source (the mass ratio of the first added titanium source to the lithium source is 1: 0.44) and 10g of titanium source (the second added titanium source is 1:0.01) are weighed.
Example 7
The only difference from example 1 is: 302g of lithium source, 694g of titanium source (mass ratio of first addition of titanium source to lithium source: 1: 0.44) and 5g of titanium source (second addition) (mass ratio of 1:0.007) were weighed out.
Example 8
The only difference from example 1 is: 302g of lithium source, 639g of titanium source (mass ratio of first addition of titanium source to lithium source: 1: 0.47), and 60g of titanium source (second addition) (mass ratio of 1:0.09) were weighed.
Example 9
The only difference from example 1 is: 302g of lithium source, 619g of titanium source (the mass ratio of the first added titanium source to the lithium source is 1: 0.49) and 80g of titanium source (the second added titanium source is 1:0.13) are weighed.
Example 10
The only difference from example 1 is: 302g of lithium source, 599g of titanium source (mass ratio of first added titanium source to lithium source: 1: 0.50) and 100g of titanium source (second added) (mass ratio of 1:0.17) were weighed.
Example 11
The only difference from example 1 is: the rotating speed of the ball mill is 3200r/min, and the ball milling time is 2.5 h.
Example 12
The only difference from example 1 is: the rotating speed of the ball mill is 3800r/min, and the ball milling time is 1.5 h.
Example 13
The only difference from example 1 is: the rotating speed of the ball mill is 2800r/min, and the ball milling time is 3 h.
Example 14
The only difference from example 1 is: the stirring speed during dispersion is 1800r/min, the stirring time is 3.5h, the solvent during the second addition of the titanium source is ethylene glycol, and the addition amount is 50 g.
Example 15
The only difference from example 1 is: the stirring speed is 1850r/min during dispersion, the stirring time is 2.5h, the solvent during the second addition of the titanium source is methanol, and the addition amount is 150 g.
Example 16
The only difference from example 1 is: the temperature is increased to 650 ℃ according to the heating rate of 8 ℃/min, and the sintering time is 360 min.
Example 17
The only difference from example 1 is: the temperature is increased to 900 ℃ of the sintering target temperature according to the heating rate of 12 ℃/min, and the sintering time is 180 min.
Comparison example (traditional technology)
1) Weighing machine
Accurately weighing 302g of lithium source and 699g of titanium source in a dry environment;
2) premixing
Putting 4.45Kg of deionized water into a charging basket, adding 302g of lithium source and 699g of titanium source during stirring, keeping the rotating speed at 1750r/min, and dispersing for 4 h;
3) ball mill
After the ball mill is cleaned, 1770g of zirconium balls are added, and the dispersed slurry is transferred to a dispersion cylinder and added; maintaining the rotating speed of 3450rpm, and grinding for 2 h; and transferring the slurry into the material pipe after the grinding is finished. Wherein, fig. 2 shows the structure of an electron microscope of a sample after ball milling of a comparative example.
4) Spray drying
Cleaning the spray dryer before each spray drying, setting the inlet air temperature at 205 deg.C, controlling the exhaust air temperature at about 110 deg.C, maintaining the pump speed at 28rpm/min, and adjusting the flow rate to 6m3And h, starting spray drying after the parameters of the spray dryer are stable.
5) Calcination of
And (3) performing batch sintering by using a muffle furnace, raising the temperature to the target sintering temperature of 820 ℃ at the heating rate of 10 ℃/min, and then keeping the temperature for 180 min. Naturally cooling to room temperature.
6) Sieving
And (5) cooling the sample, and screening to obtain a lithium titanate finished product. Fig. 4 shows an electron microscope structure of the finished product.
And (3) detection:
the lithium titanate finished products prepared in the above examples and comparative examples are detected from the angles of electron microscope structure, particle size, specific surface area, comparative example, gram volume and the like. Wherein the particle size distribution is measured using a laser particle sizer, the specific surface area is measured using a BET method, and the phase structure and the phase purity ratio are measured by XRD (see fig. 6 and 7, in which the vertical line on the abscissa is a standard card, fig. 6 is a comparative example and examples 1 to 9 in the order from the bottom up, fig. 7 is a comparative example and examples 10 to 17 in the order from the bottom up, the comparative example has a fine hetero-peak at a position of 28 indicated by an arrow, and when the phase purity reaches about 99.90%, a specific purity value can be calculated by an instrument, but the XRD shows the same for all examples. The gram capacity is measured by mixing a lithium titanate material with a superconducting carbon black binder, uniformly stirring to prepare a negative electrode plate respectively, forming a lithium ion battery with a metal lithium plate positive plate and 1M LiPF6-EC/DMC (volume ratio of 1:1) electrolyte, and assembling a button cell in a glove box filled with argon.
Specific detection results are shown in tables 1 to 3 below.
Table 1: particle size comparison of different processes
Figure BDA0002845469440000081
Figure BDA0002845469440000091
Table 2: relationship between different processes and specific surface area, phase purity after sintering and gram volume
Figure BDA0002845469440000092
Figure BDA0002845469440000101
Table 3: normal temperature battery multiplying power data of different technology
Rate capability 5C charged/%) 5C discharge/%) 10C charged/%) 10C discharge/%)
Comparison example (traditional technology) 96.89 94.59 92.47 92.68
Example 1 97.15 95.61 93.26 93.35
Example 2 97.13 95.62 93.68 93.33
Example 3 97.25 96.59 93.48 93.21
Example 4 96.98 95.49 93.25 93.26
Example 5 96.99 95.19 93.15 93.34
Example 6 96.95 94.64 93.08 93.02
Example 7 96.92 94.61 93.05 92.71
Example 8 97.14 96.15 93.33 93.28
Example 9 97.16 96.25 93.28 92.86
Example 10 96.94 96.18 92.97 92.76
Example 11 96.98 96.24 93.16 93.24
Example 12 97.16 96.34 93.24 93.17
Example 13 97.18 96.28 93.58 93.17
Example 14 97.25 96.28 93.26 93.16
Example 15 97.16 95.67 93.54 93.24
Example 16 97.19 95.89 93.24 93.25
Example 17 97.02 95.48 93.16 93.22
It can be seen from the above embodiments that, according to the present application, the raw material for preparing lithium titanate is improved in the preparation process, and the amount of the titanium source added in several times is reasonably adjusted, so that not only is the volatilization of lithium in the calcination process achieved, and the defects of the finished product are reduced, such that the phase ratio can reach 100% at most, but also TiO is formed on the surface of the calcined lithium titanate2The conductivity of the lithium titanate as an electrode material is improved. Improve subsequent titaniumThe stability and the production efficiency of the industrial production of the lithium ion negative plate and the lithium ion battery.
The method can be applied to the preparation of lithium titanate cathode materials, but is not limited to the field, and can also be applied to the battery fields of lithium iron phosphate, lithium manganate and the like based on the same principle.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A preparation method of a lithium titanate battery material is characterized by comprising the following steps:
mixing part of a titanium source and a lithium source, and then carrying out ball milling to obtain a primary ball-milled material;
mixing the primary ball-milled material with the residual titanium source, and then continuing ball milling to obtain a ball-milled product;
and drying, calcining and screening the ball-milled product in sequence to obtain the lithium titanate battery material.
2. The production method according to claim 1, wherein a mixing mass ratio of the partial titanium source and the lithium source is 1:0.43 to 1: 0.54;
preferably the titanium source is selected from TiO2And/or metatitanic acid;
preferably, the lithium source is selected from LiOH H2O and lithium carbonate.
3. The production method according to claim 1, wherein the mass ratio of the partial titanium source to the remaining titanium source is 1:0.03 to 1: 0.13.
4. the method according to any one of claims 1 to 3, wherein mixing a part of the titanium source and the lithium source and then performing ball milling to obtain a primary ball-milled material comprises:
adding the part of the titanium source and the lithium source into a container filled with deionized water, and stirring and dispersing to obtain a dispersion liquid; preferably, the stirring speed is 1750 to 3500r/min, the stirring time is 2.5 to 4 hours,
adding the dispersion liquid into a ball mill filled with grinding balls for ball milling to obtain a primary ball milled matter; preferably, the rotating speed of the ball mill is 3200-3800 r/min, and the ball milling time is 1.5-2.5 h.
5. The preparation method of claim 4, wherein the initial ball-milled material is mixed with the remaining titanium source and then ball-milled continuously to obtain a ball-milled product comprising:
mixing and ball-milling the primary ball-milled material with the pre-dissolved residual titanium source and the pre-dissolved solvent to obtain a ball-milled product;
preferably the solvent is selected from ethylene glycol, methanol, absolute ethanol or isopropanol;
the addition amount of the solvent is preferably 50 to 150 g.
6. The preparation method of claim 4, wherein in the steps of drying, calcining and screening the ball-milled product in sequence, the drying is spray drying, preferably the spray drying temperature is 110-205 ℃, and the spray flow in the spray drying process is 5-7 m3/h；
Preferably, the calcination adopts batch sintering, the temperature of the sintering is 650-900 ℃, and the time is 180-360 min; more preferably, the temperature is increased to the sintering temperature according to the heating rate of 8-12 ℃/min;
preferably, after the calcined product is cooled, the step of screening is performed, and more preferably, the particle size D of the lithium titanate battery material is obtained after screening909 to 10 μm, preferably D99Is 14 to 15 μm.
7. A lithium titanate battery material prepared by the preparation method of any one of claims 1 to 6.
8. A lithium titanate battery material is characterized in that the phase purity of the lithium titanate battery material is 100%.
9. The lithium titanate battery material of claim 8, wherein the particle size D of the lithium titanate battery material909 to 10 μm, preferably D99Is 14 to 15 μm;
preferably, the specific surface area of the lithium titanate battery material is 92-97 m2/g；
Preferably, the gram capacity of the lithium titanate battery material is 165.4-166.4 mAh/g.
10. A lithium titanate battery negative electrode sheet, characterized in that the lithium titanate battery negative electrode sheet comprises the lithium titanate battery material of any one of claims 7 to 9.
11. A lithium ion battery, comprising a positive electrode, a negative electrode, an electrolyte and a diaphragm arranged between the positive electrode and the negative electrode, wherein the negative electrode is the lithium titanate battery negative electrode sheet of claim 10.
CN202011508004.2A 2020-12-18 2020-12-18 Lithium titanate battery material, preparation method and application thereof Pending CN112607769A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031110A (en) * 2021-10-03 2022-02-11 湖北钛时代新能源有限公司 Preparation and synthesis method of lithium titanate material for lithium ion battery
CN116081682A (en) * 2023-01-30 2023-05-09 湖北钛时代新能源有限公司 Preparation method and application of lithium titanate material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031110A (en) * 2021-10-03 2022-02-11 湖北钛时代新能源有限公司 Preparation and synthesis method of lithium titanate material for lithium ion battery
CN116081682A (en) * 2023-01-30 2023-05-09 湖北钛时代新能源有限公司 Preparation method and application of lithium titanate material
CN116081682B (en) * 2023-01-30 2024-01-19 湖北钛时代新能源有限公司 Preparation method and application of lithium titanate material

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