CN108574094B - Negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a negative electrode material for a lithium ion battery and a preparation method thereof. The preparation method comprises the following steps: dissolving a lithium source in a first solvent to obtain a first solution, and dissolving a titanium source in a second solvent to obtain a second solution; dissolving alkali in a third solvent to obtain an alkaline compound solution; dispersing the nano silicon powder and the carbon nano tube in a fourth solvent to obtain a first mixed solution; dropwise adding the solution into the first mixed solution to obtain a second mixed solution; and precipitating the second mixed solution to obtain a precipitate, and modifying the precipitate to obtain the negative electrode material for the lithium ion battery. The invention increases Li of the lithium titanate material on the basis of ensuring the self lattice structure and zero strain+The capacity is increased, the energy density of the material is increased, the cyclicity and the rate capability of the material are not obviously weakened, the material is prepared by adopting a coprecipitation method, and the material is doped and coated with each other during precipitation to form a laminated or net-shaped structure, so that the coating effect can be effectively improved.
Description
Technical Field
The invention relates to the technical field of batteries, and relates to a negative electrode material for a lithium ion battery and a preparation method thereof.
Background
Nowadays, social energy is in short supply and environmental problems are increasingly severe, and people pay more and more attention to the development of renewable resources and secondary energy; lithium ion batteries are highly appreciated in the present society because of their high efficiency, recyclability, cleanliness and no pollution. At present, different lithium ion batteries have different energy density, cycle performance, temperature resistance, safety performance and rapid charge and discharge performance, but various comprehensive indexes of the lithium ion battery are lacked to be comprehensive and advanced, so that the development of the lithium ion battery with excellent comprehensive performance is a continuous pursuit of researchers in this generation.
Spinel type lithium titanate is a zero strain material, and the parameters of a unit cell hardly change before and after lithium ions are inserted and extracted, so that the spinel type lithium titanate has excellent cycle performance and stable discharge voltage. The lithium titanate battery has excellent cycle performance, temperature resistance, safety performance and rapid charge and discharge performance, but is always subject to the defects of low energy density and high price, so that the doping of the modified lithium titanate material to increase the energy density and reduce the cost has important significance.
Silicon has the largest theoretical specific capacity (3572 mAh/g) in known lithium ion battery negative electrode materials, but the silicon has poor conductivity, large volume change and extremely poor cycle performance. Although the expansion of the carbon-silicon composite material is reduced by the compounding of the carbon-silicon composite material, the problem of the expansion of the carbon-silicon composite material is still solved, the first discharge efficiency is improved, and the cycle life and the safety of the battery are improved. The introduction of lithium titanate can provide good mechanical support for silicon, and a lithium titanate coating layer can effectively inhibit severe volume change of silicon in the processes of lithium removal and lithium insertion, reduce internal contact loss, and further improve internal resistance and lithium removal/insertion.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide a method for preparing a negative electrode material for a lithium ion battery and a negative electrode material prepared by the method, wherein the negative electrode material is prepared by a co-precipitation method, and is doped and coated with each other during precipitation to form a cubic or mesh structure, so that the coating effect can be effectively improved, and the performance of the lithium ion battery adopting the negative electrode material can be further improved.
In order to achieve the above purpose, on one hand, the following technical solutions are adopted in the present application:
a preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving a lithium source in a first solvent to obtain a first solution, and dissolving a titanium source in a second solvent to obtain a second solution;
(2) dissolving alkali in a third solvent to obtain an alkaline compound solution;
(3) dispersing the nano silicon powder and the carbon nano tube in a fourth solvent to obtain a first mixed solution;
(4) dropwise adding the solution obtained in the step (1) and the solution obtained in the step (2) into the first mixed solution obtained in the step (3) to obtain a second mixed solution;
(5) and (5) precipitating the second mixed solution obtained in the step (4) to obtain a precipitate, and modifying the precipitate to obtain the negative electrode material for the lithium ion battery.
And (3) precipitating (namely coprecipitating) the second mixed solution obtained in the step (4), so that the components can be doped and coated with each other during precipitation, a three-layer structure or a net structure is formed, the coating effect is greatly improved, and the performance of the lithium ion battery adopting the cathode material is further improved.
Preferably, in step (1), the first solvent is deionized water;
preferably, the second solvent is an alcohol solvent, such as methanol, ethanol, polyol, or the like;
preferably, the lithium source comprises any 1 or a combination of at least 2 of lithium nitrate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, and lithium isopropoxide;
preferably, the titanium source comprises any 1 or a combination of at least 2 of soluble tetra-n-butyl titanate, tetra-isopropyl titanate, or titanium chloride;
preferably, the molar ratio of the lithium source to the titanium source is 4:5 to 4.5:5, such as 4:5, 4.1:5, 4.3:5, 4.4:5, 4.5:5, and the like;
preferably, the molar ratio of the lithium source to the titanium source is 4.3: 5.
Preferably, in step (2), the moles of the base are equal to the sum of the moles of all metal ions in the first solution;
preferably, the third solvent is deionized water;
preferably, the basic compound is a weak base;
preferably, the basic compound comprises any 1 or a combination of at least 2 of sodium carbonate, sodium bicarbonate or potassium carbonate.
Preferably, in step (3), the fourth solvent is deionized water;
preferably, the molar ratio of the nano silicon powder to the carbon nanotube is 0.8:2 to 1.2: 2; e.g., 0.8:2, 0.9:2, 1:2, 1.1:2, 1.2:2, etc.;
preferably, the molar ratio of the nano silicon powder to the lithium source is 0.8:3 to 1.2:3, such as 0.8:3, 0.9:3, 1:3, 1.1:3, 1.2:3, and the like.
Preferably, in the step (4), the first mixed solution is stirred during the dropwise addition;
preferably, the stirring speed is 500-800r/min, for example, the stirring speed is 500r/min, 550 r/min, 600r/min, 650 r/min, 700 r/min, 750 r/min, 800r/min, etc.;
preferably, the PH value of the system is controlled within the range of 7-9 by controlling the dropping speed;
the crystallinity and the crystal structure can be better controlled by controlling the pH, a large amount of hydroxide is generated due to too strong alkalinity, the hydroxide is changed into an oxide spinel structure instead of a three-dimensional net-shaped and layered structure after ignition, incomplete precipitation is caused due to too weak alkalinity, and the crystallinity is low.
Preferably, the dropping speed of the first solution, the second solution and the first mixed solution is 30 to 60 drops/min, for example, 30 drops/min, 35 drops/min, 40 drops/min, 45 drops/min, 50 drops/min, 55 drops/min, 60 drops/min and the like.
Preferably, in the step (5), precipitating the second mixed solution obtained in the step (4) to obtain a precipitate includes: crystallizing, centrifuging and washing the second mixed solution in microwave to obtain the precipitate;
preferably, the time for crystallization in microwave is 1 to 2 hours, such as 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, etc.;
preferably, during the microwave crystallization, the temperature of the system is controlled to be 80 to 150 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ and the like;
preferably, the microwave environment is provided using a microwave apparatus having a power of 100W-250W, such as 100W, 130W, 180W, 200W, 220W, 250W, etc.
Preferably, in step (5), the modification treatment of the precipitate includes:
(5a) drying and ball-milling the precipitate to obtain a modified lithium titanate precursor I;
(5b) pre-burning, cooling and ball-milling the modified lithium titanate precursor I obtained in the step (5 a) to obtain a modified lithium titanate precursor II;
(5c) and (5) calcining, cooling and ball-milling the modified lithium titanate precursor II obtained in the step (5 b) to obtain the negative electrode material for the lithium ion battery.
Preferably, in step (5 a), the precipitate is dried in a vacuum drying oven;
preferably, the temperature of the vacuum drying oven is 80-100 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the like;
preferably, the drying time period is 8-10 hours, such as 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, and the like;
preferably, in the step (5 b), the pre-firing time is 2 to 6 hours, such as 2 hours, 3 hours, 5 hours, 6 hours and the like;
preferably, the temperature of the pre-burning is 300-500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and the like;
preferably, the temperature rise rate during pre-burning is 1-5 ℃ per min, such as 1 ℃, 2 ℃, 3 ℃, 4 ℃, 5 ℃ per min and the like;
preferably, in step (5 c), the calcination time is 6 to 12 hours, such as 6 hours, 7 hours, 9 hours, 10 hours, 12 hours, etc.;
preferably, the calcination temperature is 800-.
Preferably, the ball milling in step (5 a), step (5 b) and step (5 c) is carried out using a small ball mill;
preferably, the rotation speed of the small ball mill is 300-600r/min, such as 300r/min, 350 r/min, 400 r/min, 450 r/min, 500r/min, 550 r/min, 600r/min, etc.
On the other hand, the following technical scheme is adopted in the application:
the negative electrode material for the lithium ion battery is prepared by the preparation method.
Preferably, in the negative electrode material, the doping molar ratio of the carbon nanotube is 20% -30%, for example, the doping molar ratio is 20%, 21%, 23%, 25%, 27%, 29%, 30%, etc.;
the doping molar ratio of the nano silicon powder is 10-20%, for example, the doping molar ratio is 10%, 11%, 13%, 14%, 16%, 17%, 19%, 20%, and the like.
Compared with the prior art, the invention has the following beneficial effects
(1) According to the invention, silicon and carbon nano tubes are doped in the process of forming lithium carbonate crystals, so that the Li + capacity of the lithium titanate material is increased on the basis of ensuring the self lattice structure and zero strain, the energy density of the material is increased, the cyclicity and the rate performance of the material are not obviously weakened, in addition, the lithium titanate material is prepared by adopting a coprecipitation method, and the lithium titanate material is doped and coated with each other during precipitation to form a laminated or net-shaped structure, so that the coating effect can be effectively improved, and the performance of a lithium ion battery adopting the cathode material is further improved.
(2) The modified lithium titanate negative electrode material is prepared by a microwave crystallization method in the crystallization process, and has uniform particle size and good dispersity.
Detailed Description
The present invention will be described below based on examples, but the present invention is not limited to only these examples. Well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, what is meant is "including, but not limited to".
In the description of the present invention, it is to be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
Example 1
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) 7.67g of LiNO was added3Dissolving into 100ml deionized water solution to obtain a first solution, and dissolving 35.67g isopropyl titanate into 100ml ethanol to obtain a second solution;
(2) dissolving 5.724g of sodium carbonate in 100ml of deionized water to obtain an alkaline compound solution;
(3) dispersing 0.3g of nano silicon powder and 0.2g of carbon nano tube in 50ml of deionized water, and stirring and dispersing to obtain a first mixed solution;
(4) under the condition of stirring the first mixed solution, dropwise adding the three solutions obtained in the step (1) and the step (2) into the first mixed solution obtained in the step (3) together, controlling the dropwise adding speed to be about 40 drops per second, controlling the PH value of a system to be 7-9 by controlling the dropwise adding speed of different solutions, and continuously precipitating in the dropwise adding process to obtain a second mixed solution;
(5) after the dropwise addition is finished, crystallizing the system in microwave for 1 h, controlling the temperature of the system to be 120 ℃ through a microwave temperature control system, finishing the crystallization, and centrifugally washing to obtain a precipitate;
(5a) putting the precipitate obtained in the step (5) into a vacuum drying oven, vacuumizing and drying for 8h at 80 ℃, and performing ball milling to obtain a modified lithium titanate precursor I;
(5b) pre-burning the modified lithium titanate precursor I obtained in the step (5 a) at 350 ℃ for 5h, cooling and ball-milling to obtain a modified lithium titanate precursor II;
(5c) and (5) calcining the modified lithium titanate precursor II obtained in the step (5 b) at 900 ℃ for 10h, cooling and ball-milling to obtain the negative electrode material for the lithium ion battery.
Example 2
(1) Dissolving 7.78g of LiOH in 100ml of deionized water to obtain a first solution, and dissolving 42.74g of n-butyl titanate in 100ml of ethanol to obtain a second solution;
(2) dissolving 5.724g of sodium carbonate in 100ml of deionized water to obtain an alkaline compound solution;
(3) 0.48g of nano silicon powder and 0.24g of carbon nano tubes are dispersed in 100ml of deionized water, and stirred and dispersed to form a turbid liquid, which is called as a first mixed solution.
(4) Under the condition of stirring the first mixed solution, dropwise adding the three solutions obtained in the step (1) and the step (2) into the first mixed solution obtained in the step (3) together, controlling the dropwise adding speed to be about 40 drops per second, controlling the PH value of a system to be 7-9 by controlling the dropwise adding speed of different solutions, and continuously precipitating in the dropwise adding process to obtain a second mixed solution;
(5) after the dropwise addition is finished, crystallizing the system in microwave for 2 hours, controlling the temperature of the system to be 140 ℃ through a microwave temperature control system, finishing the crystallization, and centrifugally washing to obtain a precipitate;
(5a) putting the precipitate obtained in the step (5) into a vacuum drying oven, vacuumizing and drying for 10 hours at 100 ℃, and performing ball milling to obtain a modified lithium titanate precursor I;
(5b) pre-burning the modified lithium titanate precursor I obtained in the step (5 a) at 450 ℃ for 3h, cooling and ball-milling to obtain a modified lithium titanate precursor II;
(5c) and (5) calcining the modified lithium titanate precursor II obtained in the step (5 b) at 1000 ℃ for 8h, cooling and ball-milling to obtain the negative electrode material for the lithium ion battery.
Comparative example
Dispersing titanium dioxide, lithium carbonate, nano-silicon and a conductive agent in ethanol, stirring to obtain precursor slurry, atomizing, drying, granulating and grading the precursor slurry to obtain powder, carrying out heat treatment on the powder, firstly heating to 1000 ℃ at the speed of 10 ℃/min, then carrying out heat preservation for 0.5 hour, naturally cooling, crushing and screening to obtain the cathode material.
And (3) performance testing:
except that the negative electrode materials are different, other components and contents of the examples and the comparative examples are the same, and the contents of lithium titanate, silicon and carbon in the examples and the comparative examples are also the same.
The prepared lithium ion battery is tested for performance, such as battery capacity, battery cycle times, rate charge and discharge performance and the like.
The test results are shown in table 1:
table 1 lithium ion battery negative electrode material performance test results of examples and comparative examples
| Item | Capacity of battery | Battery cycle number with capacity maintained above 90% | 6C charge-discharge efficiency |
| Example 1 | 115Wh/Kg | 3092 times | 97% |
| Example 2 | 110Wh/Kg | 2980 times | 95% |
| Comparative example | 85Wh/Kg | 2457 times | 87% |
As can be seen from table 1, the lithium ion battery prepared by the preparation method of the present application has better performance than the existing lithium ion battery.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Those skilled in the art will readily appreciate that the above-described preferred embodiments may be freely combined, superimposed, without conflict.
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.
Claims (20)
1. A preparation method of a negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) dissolving a lithium source in a first solvent to obtain a first solution, and dissolving a titanium source in a second solvent to obtain a second solution;
(2) dissolving alkali in a third solvent to obtain an alkaline compound solution; the third solvent is deionized water, and the alkaline compound is weak base and comprises any 1 or the combination of at least 2 of sodium carbonate, sodium bicarbonate or potassium carbonate;
(3) dispersing the nano silicon powder and the carbon nano tube in a fourth solvent to obtain a first mixed solution; the fourth solvent is deionized water, the molar ratio of the nano silicon powder to the carbon nano tube is 0.8: 2-1.2: 2, and the molar ratio of the nano silicon powder to the lithium source is 0.8: 3-1.2: 3;
(4) dropwise adding the solution obtained in the step (1) and the solution obtained in the step (2) into the first mixed solution obtained in the step (3) to obtain a second mixed solution; stirring the first mixed solution in the dropping process, wherein the stirring speed is 500-800r/min, controlling the pH value of the system within the range of 7-9 by controlling the dropping speed, and the dropping speed of the first solution, the second solution and/or the alkaline compound solution is 30-60 drops/min;
(5) precipitating the second mixed solution obtained in the step (4) to obtain a precipitate, and modifying the precipitate to obtain a negative electrode material for the lithium ion battery;
in the step (5), precipitating the second mixed solution obtained in the step (4) to obtain a precipitate includes:
crystallizing, centrifuging and washing the second mixed solution in microwave to obtain the precipitate;
the crystallization time in microwave is 1 to 2 hours;
in the microwave crystallization process, the temperature of the system is controlled to be 80-150 ℃;
and a microwave instrument is adopted to provide a microwave environment, and the power of the microwave instrument is 100W-250W.
2. The method according to claim 1, wherein in the step (1), the first solvent is deionized water.
3. The method according to claim 1, wherein in the step (1), the second solvent is an alcohol solvent.
4. The production method according to claim 1, wherein in step (1), the second solvent is methanol, ethanol, or a polyhydric alcohol.
5. The method according to claim 1, wherein in step (1), the lithium source comprises any 1 or a combination of at least 2 of lithium nitrate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, and lithium isopropoxide.
6. The method of claim 1, wherein in step (1), the titanium source comprises any 1 or a combination of at least 2 of soluble tetra-n-butyl titanate, tetra-isopropyl titanate, or titanium chloride.
7. The production method according to claim 1, wherein in step (1), the molar ratio of the lithium source to the titanium source is 4:5 to 4.5: 5.
8. The method according to claim 1, wherein in the step (5), the modification treatment of the precipitate comprises:
(5a) drying and ball-milling the precipitate to obtain a modified lithium titanate precursor I;
(5b) pre-burning, cooling and ball-milling the modified lithium titanate precursor I obtained in the step (5 a) to obtain a modified lithium titanate precursor II;
(5c) and (5) calcining, cooling and ball-milling the modified lithium titanate precursor II obtained in the step (5 b) to obtain the negative electrode material for the lithium ion battery.
9. The method according to claim 8, wherein in the step (5 a), the precipitate is dried in a vacuum drying oven.
10. The method according to claim 9, wherein in the step (5 a), the temperature of the vacuum drying oven is 80 to 100 ℃.
11. The method according to claim 8, wherein the drying time in the step (5 a) is 8 to 10 hours.
12. The method of claim 8, wherein in the step (5 b), the pre-firing time is 2 to 6 hours.
13. The method as set forth in claim 8, wherein the pre-firing temperature in step (5 b) is 300-500 ℃.
14. The production method according to claim 8, wherein in the step (5 b), the temperature increase rate at the time of the pre-firing is 1 to 5 ℃ per minute.
15. The method according to claim 8, wherein in the step (5 c), the calcination time is 6 to 12 hours.
16. The method as claimed in claim 8, wherein the calcination temperature in step (5C) is 800-1000 ℃.
17. The method according to claim 8, wherein the ball milling in the step (5 a), the step (5 b) and the step (5 c) is carried out by using a small ball mill.
18. The method as claimed in claim 17, wherein the rotation speed of the small ball mill is 300-600 r/min.
19. A negative electrode material for a lithium ion battery, characterized by being produced by the production method according to any one of claims 1 to 18.
20. The negative electrode material of claim 19, wherein the carbon nanotubes account for 20-30% of the negative electrode material by mole;
the nano silicon powder accounts for 10-20% of the mole ratio of the cathode material.
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