CN113471424B - Ternary cathode material of lithium ion battery and preparation method thereof - Google Patents
Ternary cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN113471424B CN113471424B CN202110782251.XA CN202110782251A CN113471424B CN 113471424 B CN113471424 B CN 113471424B CN 202110782251 A CN202110782251 A CN 202110782251A CN 113471424 B CN113471424 B CN 113471424B
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a ternary cathode material of a lithium ion battery, which comprises the following steps: s01, introducing nitrogen into the deionized water to expel oxygen, and removing oxygen dissolved in the water; s02, adding nickel nitrate hexahydrate, cobalt nitrate hexahydrate and anhydrous manganese sulfate to prepare a salt solution, and adding polyethylene glycol into the salt solution; s03, continuously stirring, and adding di-n-butylamine at one time; s04, standing and precipitating for a period of time, taking out the precipitate, and washing, centrifuging and drying to obtain an NCM811 precursor; and S05, mixing the NCM811 precursor with lithium hydroxide monohydrate, then carrying out pre-calcination, then carrying out oxygen-introducing calcination for a period of time, and finally taking out and grinding. The invention also provides a ternary cathode material of the lithium ion battery, which is prepared by the preparation method. The ternary cathode material of the lithium ion battery and the preparation method thereof provided by the invention can avoid the situations of uneven precipitation and difficult pH control, and are beneficial to improving the electrochemical performance stability of the ternary cathode material.
Description
Technical Field
The invention relates to a ternary cathode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium batteries.
Background
The mainstream preparation method of the nickel-cobalt-manganese ternary precursor at present is to perform coprecipitation synthesis by adopting sodium hydroxide and ammonia water under the nitrogen atmosphere, wherein when the sodium hydroxide and the ammonia water solution are mixed, ammonium ions react with the surrounding solution to form a concentration gradient, so that the pH value in the solution is not easy to control. In addition, different precipitants and different precipitant concentrations have a greater effect on the electrochemical performance of the ternary cathode material. The existing preparation method of the nickel-cobalt-manganese ternary precursor can not ensure that the precipitate in the solution is in a balanced state, thereby influencing the electrochemical performance of the final product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ternary cathode material of a lithium ion battery, which can avoid the conditions of uneven precipitation and difficult pH control and is beneficial to improving the electrochemical performance stability of the ternary cathode material, and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a ternary cathode material of a lithium ion battery comprises the following steps:
s01, introducing nitrogen into the deionized water to expel oxygen, and removing oxygen dissolved in the water;
s02, according to nickel: cobalt: adding nickel nitrate hexahydrate, cobalt nitrate hexahydrate and anhydrous manganese sulfate to prepare a salt solution with the manganese molar ratio of 8:1:1, and adding polyethylene glycol solid particles and polyethylene glycol liquid into the salt solution;
s03, continuously stirring, adding di-n-butylamine at one time after the metal salt particles are completely dissolved in the deionized water, and sealing the reaction solution by using a preservative film;
s04, transferring the reaction solution to a large beaker, sealing the beaker by using a preservative film, standing and precipitating for a period of time, taking out the precipitate, and cleaning, centrifuging and drying the precipitate to obtain an NCM811 precursor;
and S05, mixing the NCM811 precursor with lithium hydroxide monohydrate according to the molar ratio of 1:1.05, then carrying out pre-calcination, then carrying out oxygen-introducing calcination for a period of time, and finally taking out and grinding.
In S01, the nitrogen gas is introduced for 2h to expel oxygen.
In S02, the concentration of the salt solution is 1mol/L, and the polyethylene glycol solid particles are polyethylene glycol 6000, and the mass is 2 g; the polyethylene glycol liquid is polyethylene glycol 200, and the volume is 10 ml.
In S03, the stirring speed is 500rpm, the stirring temperature is 90 ℃, the stirring reaction time is 4h, and the adding amount of the di-n-butylamine is 50 ml.
And in S04, standing for 12h, wherein the cleaning comprises three times of deionized water cleaning and one time of alcohol cleaning.
In S05, the precalcination temperature is 500 ℃ and the time is 5 h; the temperature of oxygen introduction and calcination is 800 ℃ and the time is 20 h.
A lithium ion battery ternary cathode material is prepared by the preparation method of the lithium ion battery ternary cathode material.
The invention has the beneficial effects that: according to the ternary positive electrode material of the lithium ion battery and the preparation method of the ternary positive electrode material, provided by the invention, the di-n-butylamine is added when the NCM811 precursor is prepared, and can be combined with H & lt + & gt in a solution to generate CH3CH2CH2CH2)2NH2 +Can stably supply OH-The method can slowly and uniformly release the crystal-forming ions in the solution, and ensures that the precipitate in the solution is in a balanced state by controlling the concentration of the precipitator in the solution, so that the precipitate is uniformly separated out, and the conditions of non-uniform precipitate and difficult pH control are avoided. At the same time, generated CH3CH2CH2CH2)2NH2 +Can react with nitrate radical in the solution to generate di-n-butylamine nitrate, which is volatile and can take away nitrate radical ions in the aqueous solution, thereby reducing the consumption of later-stage washing water.
Drawings
FIG. 1 is a graph of the internal cycle performance of the ternary cathode material of the lithium ion battery prepared in the invention within 80 times;
FIG. 2 is a first charge-discharge curve diagram of the ternary cathode material of the lithium ion battery prepared in the present invention;
FIG. 3 is a graph of the internal cycle performance of a lithium ion battery ternary cathode material prepared from a commercial precursor for 80 times;
fig. 4 is a first charge-discharge curve diagram of a lithium ion battery ternary cathode material prepared from a commercial precursor.
Detailed Description
The present invention is further described with reference to the accompanying drawings, and the following examples are only for clearly illustrating the technical solutions of the present invention, and should not be taken as limiting the scope of the present invention.
The invention discloses a preparation method of a ternary cathode material of a lithium ion battery, which comprises the following steps:
step one, 1L of deionized water is put in a three-neck flask, nitrogen is introduced into a left port, a condenser pipe is placed into a middle port, a thermometer is inserted into a right port, heating can be properly carried out to promote oxygen discharge when the deionized oxygen in water is discharged through introducing the nitrogen, the nitrogen is introduced to discharge the oxygen for 2 hours, and the oxygen dissolved in the water is removed. Wherein, the purpose of setting up the condenser pipe is avoided a small amount of solution because the higher steam that produces of temperature flows out, can guarantee that follow-up metal salt concentration configuration is accurate.
Step two, according to nickel: cobalt: adding nickel nitrate hexahydrate, cobalt nitrate hexahydrate and anhydrous manganese sulfate to prepare a salt solution with the manganese molar ratio of 8:1:1, and adding polyethylene glycol solid particles and polyethylene glycol liquid into the salt solution. Wherein the concentration of the salt solution is 1mol/L, the polyethylene glycol solid particles are polyethylene glycol 6000, and the mass is 2 g; the polyethylene glycol liquid is polyethylene glycol 200, and the volume is 10 ml.
And step three, continuously stirring, adding the di-n-butylamine at one time after the metal salt particles are completely dissolved in the deionized water, and then sealing all gas outlets of the three-neck flask by using a preservative film to avoid volatilization of the di-n-butylamine. Wherein the stirring speed is 500rpm, the stirring temperature is 90 ℃, the stirring reaction time is 4h, and the adding amount of the di-n-butylamine is 50 ml.
And step four, transferring the reaction solution to a large beaker, sealing the beaker by using a preservative film, standing and precipitating for a period of time, taking out the precipitate, and cleaning, centrifuging and drying the precipitate to obtain the precursor of NCM 811. Wherein the standing and precipitating time is 12h, and the cleaning comprises three times of deionized water cleaning and one time of alcohol cleaning.
And step five, mixing the precursor of the NCM811 with the lithium hydroxide monohydrate according to the molar ratio of 1:1.05, then carrying out pre-calcination, then carrying out oxygen-introduction calcination for a period of time, and finally taking out and grinding to obtain the NCM811 ternary cathode material. Wherein the pre-calcining temperature is 500 ℃, and the time is 5 hours; the temperature of oxygen introduction and calcination is 800 ℃ and the time is 20 h.
The invention also discloses a ternary cathode material of the lithium ion battery, which is prepared by the preparation method of the ternary cathode material of the lithium ion battery. In order to verify the performance of the lithium ion battery ternary cathode material prepared by the method, the method is compared with the lithium ion battery ternary cathode material prepared by a commercial precursor.
FIG. 1 and FIG. 2 are respectively a cycle performance diagram of lithium nickel cobalt manganese oxide within 80 times and a first charge-discharge curve of lithium nickel cobalt manganese oxide. At 0.1C, the specific capacity of initial discharge is as follows: 195.51mAh/g, the coulombic efficiency is: 94.9 percent, and the specific discharge capacity after 80 cycles is as follows: 170.44mAh/g, capacity retention ratio: 87.18 percent.
Fig. 3 and fig. 4 are a cycle performance graph and a first charge-discharge curve of nickel cobalt lithium manganate prepared by a commercial precursor within 80 times respectively. At 0.1C, the specific capacity of the first discharge is as follows: 184.5mAh/g, coulombic efficiency: 82.7 percent, and the specific discharge capacity after 80 cycles is as follows: 170.5 mAh/g, capacity retention ratio: 92.4 percent.
According to the data comparison, the ternary cathode material prepared by using the di-n-butylamine has excellent performance and good stability.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (7)
1. A preparation method of a ternary cathode material of a lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
s01, introducing nitrogen into the deionized water to expel oxygen, and removing oxygen dissolved in the water;
s02, as per nickel: cobalt: adding nickel nitrate hexahydrate, cobalt nitrate hexahydrate and anhydrous manganese sulfate to prepare a salt solution with the manganese molar ratio of 8:1:1, and adding polyethylene glycol solid particles and polyethylene glycol liquid into the salt solution;
s03, continuously stirring, adding di-n-butylamine at one time after the metal salt particles are completely dissolved in the deionized water, and sealing the reaction solution by using a preservative film;
s04, transferring the reaction solution to a large beaker, sealing the beaker with a preservative film, standing and precipitating for a period of time, taking out the precipitate, and cleaning, centrifuging and drying the precipitate to obtain an NCM811 precursor;
and S05, mixing the NCM811 precursor with lithium hydroxide monohydrate according to the molar ratio of 1:1.05, then carrying out pre-calcination, then carrying out oxygen-introducing calcination for a period of time, and finally taking out and grinding.
2. The preparation method of the ternary cathode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: in S01, the nitrogen gas is introduced for 2h to expel oxygen.
3. The preparation method of the ternary cathode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: in S02, the concentration of the salt solution is 1mol/L, and the polyethylene glycol solid particles are polyethylene glycol 6000, and the mass is 2 g; the polyethylene glycol liquid is polyethylene glycol 200, and the volume is 10 ml.
4. The preparation method of the ternary cathode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: in S03, the stirring speed is 500rpm, the stirring temperature is 90 ℃, the stirring reaction time is 4h, and the adding amount of the di-n-butylamine is 50 ml.
5. The preparation method of the ternary cathode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: and in S04, standing for 12h, wherein the cleaning comprises three times of deionized water cleaning and one time of alcohol cleaning.
6. The preparation method of the ternary cathode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: in S05, the precalcination temperature is 500 ℃ and the time is 5 h; the temperature of oxygen introduction and calcination is 800 ℃ and the time is 20 h.
7. A ternary cathode material of a lithium ion battery is characterized in that: the ternary cathode material for the lithium ion battery is prepared by the preparation method of the ternary cathode material for the lithium ion battery as claimed in any one of claims 1 to 6.
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CN113264560A (en) * | 2021-05-17 | 2021-08-17 | 青海师范大学 | Double-coated NCM811 cathode material and preparation method thereof |
CN113308763B (en) * | 2021-05-21 | 2022-09-27 | 青海师范大学 | Method and device for preparing mesoporous nanotube by combining centrifugal spinning with chelating coordination reaction |
CN114349075A (en) * | 2022-01-05 | 2022-04-15 | 合肥国轩高科动力能源有限公司 | Preparation method of coated metal element-doped ternary positive electrode material, prepared positive electrode material and application thereof |
CN114906885B (en) * | 2022-05-23 | 2024-02-02 | 青海师范大学 | High-magnification positive electrode material of lithium ion battery and preparation method thereof |
CN115036499A (en) * | 2022-05-30 | 2022-09-09 | 青海师范大学 | Titanium dioxide-doped lithium battery positive electrode material and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
CN106935824A (en) * | 2017-03-21 | 2017-07-07 | 深圳市沃特玛电池有限公司 | A kind of preparation method of tertiary cathode material |
WO2018121100A1 (en) * | 2016-12-30 | 2018-07-05 | 徐茂龙 | Method for preparing power-type and high-capacity modified nca anode material |
CN109546143A (en) * | 2018-11-27 | 2019-03-29 | 中南大学湘雅医院 | A kind of tertiary cathode material and preparation method thereof with porous structure |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
WO2018121100A1 (en) * | 2016-12-30 | 2018-07-05 | 徐茂龙 | Method for preparing power-type and high-capacity modified nca anode material |
CN106935824A (en) * | 2017-03-21 | 2017-07-07 | 深圳市沃特玛电池有限公司 | A kind of preparation method of tertiary cathode material |
CN109546143A (en) * | 2018-11-27 | 2019-03-29 | 中南大学湘雅医院 | A kind of tertiary cathode material and preparation method thereof with porous structure |
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