CN114477313B - Nickel-cobalt-manganese ternary precursor aging method - Google Patents

Nickel-cobalt-manganese ternary precursor aging method Download PDF

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CN114477313B
CN114477313B CN202111658822.5A CN202111658822A CN114477313B CN 114477313 B CN114477313 B CN 114477313B CN 202111658822 A CN202111658822 A CN 202111658822A CN 114477313 B CN114477313 B CN 114477313B
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aging
cobalt
nickel
ternary precursor
manganese ternary
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CN114477313A (en
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张燕辉
罗宗权
孙宏
岳川丰
刘小翠
王政强
左美华
王东
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Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
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Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a nickel-cobalt-manganese ternary precursor aging method, which comprises the following steps: s1, placing nickel-cobalt-manganese ternary precursor slurry from a synthesis process into an aging tank, and starting the aging tank to stir at 160-300 rpm; s2, adding tetrahydrofuran aqueous solution into an aging tank, and aging for 1-4 hours to obtain aged slurry; s3, the aged slurry is subjected to post treatment to obtain a finished product of the nickel-cobalt-manganese ternary precursor. The advantages are that: 1) The washing effect of the precursor after aging is obviously improved; 2) The alkali consumption is reduced; 3) The wastewater treatment capacity is reduced.

Description

Nickel-cobalt-manganese ternary precursor aging method
Technical Field
The invention relates to a lithium battery production technology, in particular to a lithium ion battery nickel-cobalt-manganese ternary precursor production technology.
Background
The lithium ion battery is mainly composed of a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like. The positive electrode material occupies more than 40% of the total cost of the lithium battery, and the performance of the positive electrode material directly influences various performance indexes of the lithium battery. The ternary precursor is the main raw material of the ternary positive electrode material, in other words, the quality of the ternary precursor directly determines the performance of the ternary positive electrode material.
In the production of ternary battery precursors, the aging process is a key process step in which the purpose of aging is to better wash the precursor later. The conventional ternary precursor production process comprises the steps of introducing a battery-grade nickel sulfate, cobalt sulfate and manganese sulfate solution with a certain concentration ratio into a synthesis kettle, introducing ammonia water and liquid alkali with proper concentrations, and performing primary synthesis of ternary precursor slurry under the protection of nitrogen. After the preparation is finished, dilute alkali is added into an aging tank, and the aging reaction is further finished through stirring. After the slurry is aged, the aged materials are washed by washing equipment (a filter press, a centrifuge and the like), and then are dried, sieved and deironized to produce ternary precursors meeting the requirements.
However, the aging in the aging tank has the following three defects: 1. the slurry discharged from the synthesis kettle is directly added with dilute alkali, and the aging mode has larger demand for the dilute alkali; 2. the slurry discharged from the synthesis kettle is subjected to standing, clear liquid is discharged, and then dilute alkali is added, so that a large amount of material loss is caused; 3. the requirement on the middle volume equipment is high; 4, the wastewater treatment capacity is large; 5. the washing effect of the precursor after aging is poor.
Disclosure of Invention
The invention provides a method for aging a nickel-cobalt-manganese ternary precursor, which aims to improve the washing effect of the aged precursor.
The technical scheme adopted by the invention is as follows: a method for aging a ternary nickel cobalt manganese precursor, comprising the step of using tetrahydrofuran in the aging.
The aging method can be implemented specifically according to the following steps:
s1, placing nickel-cobalt-manganese ternary precursor slurry from a synthesis process into an aging tank, and starting the aging tank to stir at 160-300 rpm;
s2, adding tetrahydrofuran aqueous solution into an aging tank, and aging for 1-4 hours to obtain aged slurry;
s3, the aged slurry is subjected to post treatment to obtain a finished product of the nickel-cobalt-manganese ternary precursor.
As a further improvement of the invention, the concentration of the tetrahydrofuran aqueous solution is 0.2-1 mol/L, and the volume ratio of the added tetrahydrofuran aqueous solution to the nickel-cobalt-manganese ternary precursor slurry is 0.5-2:10.
As a further improvement of the invention, the post-treatment comprises alkali washing, water washing, dehydration, drying, sieving and iron removal which are sequentially carried out.
The invention also discloses a production method of the nickel-cobalt-manganese ternary precursor, which is characterized by comprising the aging method of the nickel-cobalt-manganese ternary precursor.
The invention also discloses the nickel-cobalt-manganese ternary precursor prepared by the nickel-cobalt-manganese ternary precursor production method.
The invention also discloses a production method of the lithium ion battery anode material, which is characterized in that the production raw material comprises the nickel-cobalt-manganese ternary precursor.
The invention also discloses the lithium ion battery anode material prepared by the lithium ion battery anode material production method.
The invention also discloses a lithium battery comprising the positive electrode material of the lithium ion battery.
The beneficial effects of the invention are as follows: 1) The washing effect of the precursor after aging is obviously improved; 2) The alkali consumption is reduced; 3) The wastewater treatment capacity is reduced.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples.
Embodiment one:
aging the nickel-cobalt-manganese ternary precursor according to the following steps:
(1) Will be 4m 3 Placing the qualified nickel-cobalt-manganese ternary precursor slurry with the granularity D50 of 4.5 mu m in an aging tank, and starting the aging tank to stir at 200rpm;
(2) Adding 0.4m into an aging tank 3 0.5mol/L tetrahydrofuran aqueous solution, aging for 2 hours to obtain aged slurry;
(3) Pumping the aged slurry into a centrifuge for spin-drying, and then adding 0.8m 3 The concentration of (2) is 1.1mol/L dilute alkali, and spin-drying is carried out after alkali washing.
(4) After the alkali washing is finished, adding 1.5m 3 Washing with pure water, and spin-drying to obtain the washed centrifugal material.
Embodiment two:
aging the nickel-cobalt-manganese ternary precursor according to the following steps:
(1) Will be 4m 3 Placing the qualified nickel-cobalt-manganese ternary precursor slurry with the granularity D50 of 5.6 mu m in an aging tank, and starting the aging tank to stir at 200rpm;
(2) Adding 0.4m into an aging tank 3 0.8mol/L tetrahydrofuran aqueous solution, aging for 3 hours to obtain aged slurry;
(3) Pumping the aged slurry into a centrifuge for spin-drying, and then adding 0.8m 3 The concentration of (2) is 1.1mol/L dilute alkali, and spin-drying is carried out after alkali washing.
(4) After the alkali washing is finished, adding 1.5m 3 Washing with pure water, and spin-drying to obtain the washed centrifugal material.
Comparative example one:
this comparative example is a control experiment of example two, and was conducted in the same steps and conditions as in example two, except that: no auxiliary agent is used in the aging. The method comprises the following specific steps:
aging the nickel-cobalt-manganese ternary precursor according to the following steps:
(1) Will be 4m 3 Putting the nickel-cobalt-manganese ternary precursor slurry with the D50 of 5.6 mu m, which is the same batch as the second embodiment, into an aging tank, starting the aging tank to stir at 200rpm, and aging for 3 hours to obtain aged slurry;
(2) Pumping the aged slurry into a centrifuge for spin-drying, and then adding 0.8m 3 The concentration of (2) is 1.1mol/L dilute alkali, and spin-drying is carried out after alkali washing.
(3) After the alkali washing is finished, adding 1.5m 3 Washing with pure water, and spin-drying to obtain the washed centrifugal material.
Comparative example two:
this comparative example is a control experiment of example two, and was conducted in the same steps and conditions as in example two, except that: and (3) replacing the tetrahydrofuran aqueous solution with an equivalent amount of dilute alkali solution with equal concentration in the ageing process. The method comprises the following specific steps:
(1) Will be 4m 3 Putting the nickel-cobalt-manganese ternary precursor slurry with the D50 of 5.6 mu m, which is the same batch as the second embodiment, into an ageing tank, and starting the ageing tank to stir at 200rpm;
(2) Adding 0.4m into an aging tank 3 A dilute alkali solution with the concentration of 0.8mol/L is aged for 3 hours to obtain aged slurry;
(3) Pumping the aged slurry into a centrifuge for spin-drying, and then adding 0.8m 3 The concentration of (2) is 1.1mol/L dilute alkali, and spin-drying is carried out after alkali washing.
(4) After the alkali washing is finished, adding 1.5m 3 Washing with pure water, and spin-drying to obtain the washed centrifugal material.
Sodium and sulfur content detection:
the centrifuge materials described in the above examples and comparative examples were subjected to sodium and sulfur content detection, respectively.
The detection method comprises the following steps:
1. after the centrifugal washing of the materials is finished, the materials are discharged into a containing container, then 9g of the materials are sampled (3 g of the materials on the upper surface, the middle and the lower surface of the container are respectively sampled) and are placed into a PE bag for sulfur content detection, and the average is obtained after the two times of measurement. The test results are shown in Table 1.
2. The sodium content of the sample was measured by using an ICP elemental analyzer, and the average was taken from the two measurements. The test results are shown in Table 1.
Table 1 table of the results of sodium and sulfur content detection of the centrifugal materials
Figure BDA0003449011440000031
As can be seen from table 1, the sodium-sulfur content of the centrifuge material washed by the second embodiment treated by adding tetrahydrofuran aqueous solution is significantly lower than that of the centrifuge material which is not treated by tetrahydrofuran aqueous solution or by ageing by dilute alkali solution under the same condition, which indicates that the sodium-sulfur ion content of the nickel-cobalt manganese precursor slurry can be significantly reduced by ageing by tetrahydrofuran aqueous solution, and the washing effect of the precursor after ageing is significantly improved. The inventor believes that the reason for this may be related to the fact that the use of an aqueous tetrahydrofuran solution for ageing can open the lamellae between the particles of the ternary nickel cobalt manganese precursor, and that subsequent washing is easier to remove sodium-sulphur impurities inside the precursor.

Claims (5)

1. The aging method of the nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of:
s1, placing nickel-cobalt-manganese ternary precursor slurry from a synthesis process into an aging tank, and starting the aging tank to stir at 160-300 rpm;
s2, adding tetrahydrofuran aqueous solution into an aging tank, and aging for 1-4 hours to obtain aged slurry;
s3, the aged slurry is subjected to post treatment to obtain a finished product of the nickel-cobalt-manganese ternary precursor.
2. The aging method of the nickel-cobalt-manganese ternary precursor according to claim 1, wherein the aging method comprises the following steps of: the concentration of the tetrahydrofuran aqueous solution is 0.2-1 mol/L.
3. The aging method of the nickel-cobalt-manganese ternary precursor according to claim 2, wherein the aging method comprises the following steps of: the volume ratio of the added tetrahydrofuran aqueous solution to the nickel-cobalt-manganese ternary precursor slurry is 0.5-2:10.
4. A method for aging a ternary nickel cobalt manganese precursor according to any one of claims 1 to 3, characterized in that: the post-treatment comprises alkali washing, water washing, dehydration, drying, sieving and iron removal which are sequentially carried out.
5. The production method of the nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of: comprising a nickel cobalt manganese ternary precursor aging process according to any one of claims 1 to 4.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807976A (en) * 2018-08-09 2018-11-13 中国恩菲工程技术有限公司 Nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution and preparation method thereof
CN113104906A (en) * 2021-05-12 2021-07-13 罗钢 Intermittent nickel-cobalt-manganese ternary precursor preparation process

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CN102092798A (en) * 2010-12-01 2011-06-15 兰州金川新材料科技股份有限公司 Method for continuously synthesizing precursor of lithium ion battery positive material
CN106910877B (en) * 2017-03-20 2018-05-15 深圳市沃特玛电池有限公司 A kind of nickel cobalt lithium aluminate forerunner's preparation
CN111362318B (en) * 2020-03-04 2021-02-19 江门市科恒实业股份有限公司 Nickel-cobalt-manganese carbonate and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807976A (en) * 2018-08-09 2018-11-13 中国恩菲工程技术有限公司 Nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution and preparation method thereof
CN113104906A (en) * 2021-05-12 2021-07-13 罗钢 Intermittent nickel-cobalt-manganese ternary precursor preparation process

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