CN113104906A - Intermittent nickel-cobalt-manganese ternary precursor preparation process - Google Patents
Intermittent nickel-cobalt-manganese ternary precursor preparation process Download PDFInfo
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- CN113104906A CN113104906A CN202110516963.7A CN202110516963A CN113104906A CN 113104906 A CN113104906 A CN 113104906A CN 202110516963 A CN202110516963 A CN 202110516963A CN 113104906 A CN113104906 A CN 113104906A
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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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- 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
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- 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
- H01M4/50—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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Abstract
The invention relates to a preparation process of an intermittent nickel-cobalt-manganese ternary precursor, which comprises the steps of adding a nickel-cobalt-manganese mixed salt solution with a certain concentration and proportion, a liquid caustic soda with a certain concentration and an ammonia water solution into a reaction kettle, preparing the conditions (including the temperature, the stirring speed, the ammonia concentration and the like of the reaction kettle) for opening the reaction kettle, and introducing a protective gas nitrogen; after reacting for 1-2 hours, materials in the reaction kettle begin to overflow to the intermediate tank, then the overflowed slurry is transferred to a thickener through the intermediate tank diaphragm pump, one part of the slurry in the thickener reflows to the reaction kettle, the other part of mother liquor is discharged through a filter tube, and the reaction materials are circularly concentrated among the three devices to achieve the balance of feeding and discharging; and when the granularity of the reaction material reaches the target granularity, conveying the reaction material to an ageing tank for standing and ageing, and then washing and drying the aged material to obtain the nickel-cobalt-manganese ternary precursor. The invention can prepare the nickel-cobalt-manganese ternary precursor product with extremely narrow particle size distribution of any particle size.
Description
Technical Field
The invention relates to the technical field of preparation of a precursor of a ternary positive electrode material of a lithium ion battery, in particular to a preparation process of an intermittent nickel-cobalt-manganese ternary precursor.
Background
At present, a lithium ion battery is widely applied to the fields of 3C products, electric automobiles and the like as a novel green and environment-friendly power supply; the anode material is a key material determining the chemical performance of the lithium ion battery and is divided into a ternary anode material, lithium cobaltate, lithium manganate, lithium iron phosphate and the like, wherein the ternary anode material has been in the mainstream of the market by virtue of comprehensive performances expressed in the aspects of manufacturing cost, energy density, cycle performance, thermal stability and the like, and the output of the lithium battery anode material in 2019 is 40.4 ten thousand tons according to research data, wherein the output of the ternary anode material is 19.2 ten thousand tons, and the market percentage is 47.52%. The ternary anode material mainly comprises a nickel-cobalt-manganese ternary composite oxide and a nickel-cobalt-aluminum ternary composite oxide, wherein the two composite oxides are prepared by sintering a hydroxide precursor, the currently domestic nickel-cobalt-manganese precursor is mostly prepared by adopting a continuous process, the continuous process has the advantage that normally distributed particles can be prepared, and on the other hand, as the continuous process adopts a feeding mode and overflows and discharges materials, crystal nucleus generation is difficult to control, D0 is generally less than 1um, a certain amount of tiny particles are generated, and the tiny particles can cause overburning in the subsequent sintering process to influence the product performance of the anode material. Although these very small particles can be separated by filtration, this practice results in material loss, indirectly increases manufacturing costs, and is not necessarily desirable. The advantage of batch processes is that they can be made to achieve high compaction densities with very narrow distributions by size particle matching, thereby solving the problems described above.
Disclosure of Invention
The invention aims to provide a preparation process of an intermittent nickel-cobalt-manganese ternary precursor. The method mainly adopts an intermittent process of crystal nucleation and crystal growth to prepare the nickel-cobalt-manganese hydroxide, and adopts a concentrator to circularly control the particle size growth and distribution of the nickel-cobalt-manganese hydroxide in the crystal growth stage; and then alkali washing, water washing and drying processes are carried out to obtain the nickel-cobalt-manganese ternary precursor with extremely narrow distribution.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation process of an intermittent nickel-cobalt-manganese ternary precursor comprises the following steps:
the method comprises the following steps: preparing a mixed salt solution with a certain proportion and concentration by using soluble nickel salt, soluble cobalt salt and soluble manganese salt as raw materials and pure water;
step two: filling the reaction kettle and the thickener with pure water and nitrogen as protective gas; setting the reaction temperature, stirring speed, ammonia concentration and the like to set parameters, and adding the prepared mixed salt, liquid caustic soda and ammonia water according to the set pH value to start feeding. This is the crystal nucleation stage;
step three: maintaining high pH value in the reaction kettle, and after stabilizing for 2-4 hours, reducing the pH value by 0.6-0.8 until the pH value is reduced to below 11.5. This is the crystal nucleus growth stage;
step four: after reacting for 1-2 hours, overflowing the reaction slurry to flow into an intermediate tank, transferring into a concentrator through an intermediate tank circulating pump, concentrating and discharging in the concentrator, returning to the reaction kettle again until the granularity is increased to the target granularity, and then conveying the reactant to an aging tank for aging;
step five: and washing and drying the aged reaction material to obtain a powdery nickel-cobalt-manganese ternary precursor.
Preferably, the mixed salt solution of the first step has a chemical formula of NixCoyMnz(OH)2 The total amount of Ni, Co and Mn is controlled at 110-120g/L, wherein x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.7, y is more than or equal to 0.2 and less than or equal to 0.3, and z is more than or equal to 0.2 and less than or equal to 0.3.
Preferably, the reaction temperature in the second step is controlled to be 50-70 ℃; the stirring speed is controlled at 220-230 r/min; the ammonia concentration is controlled at 9-11 g/L.
Preferably, the high pH value in the third step is controlled to be 12.00-12.10.
Preferably, the amount of the mother liquor discharged by the thickener in the step four needs to be balanced with the feeding amount of the reaction kettle, and an air diaphragm pump is selected as a circulating pump.
Preferably, in the fifth step, the aging time is more than 30min, the washing time is 180-240min, and the drying time is 10-16 hours.
Compared with the prior art, the invention has the following beneficial effects:
the process flow is short, the material waste is less, and the cost is low;
the produced small particles have narrow particle size distribution and high tap density, and are beneficial to improving the performance of the lithium ion anode material prepared at the rear end;
and (III) the process has stable grain size growth in the reaction procedure, is easy to control in a continuous mode, and can prepare narrow-distribution products with any grain size according to the requirements of customers.
Drawings
Fig. 1 is a particle size distribution graph of a nickel-cobalt-manganese ternary precursor provided in embodiment 1 of the present invention; fig. 2, fig. 3, and fig. 4 are electron micrographs of the nickel-cobalt-manganese ternary precursor provided in embodiment 1 of the present invention at 10 micrometers, 5 micrometers, and 1 micrometer, respectively.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the specific examples.
The embodiment of the invention prepares an intermittent nickel-cobalt-manganese ternary precursor with D50 of 3.8um and extremely narrow particle size distribution, and the chemical formula of the precursor is as follows: ni0 .6Co0 .2Mn0 .2 (OH)2The preparation process comprises the following steps:
according to the weight ratio of nickel: cobalt: manganese is 3: 1: 1 molar ratio to prepare a metal salt mixed solution with the total metal concentration of 120g/L, wherein the concentration of the used liquid alkali solution is 32 percent, and the concentration of the used ammonia water is 20 percent. (II) selecting the volume of 10m3Stainless steel reaction kettle with volume of 5m3A stainless steel thickener; adding pure water as a base solution before opening the kettle, raising the temperature in the kettle to 58-62 ℃, controlling the stirring speed at 230r/min for 220 plus materials, adding liquid alkali ammonia water, adjusting the pH value of the base solution to 12.01, introducing nitrogen for protection, starting a metal salt, liquid alkali and ammonia water feeding pump to feed materials simultaneously after the conditions are met, and feeding materials to maintain the pH value to be stable. After reacting for 1-2 hours, after the slurry in the reaction kettle is full, the slurry overflows to the intermediate tank from the overflow pipeline, then is transferred to the concentrator through the intermediate tank delivery pump, and reflows to the reaction kettle after concentration, so that the material circulation is carried out. And (III) after the reaction is carried out for 2 to 4 hours, regulating the pH value to 11.60 for many times, keeping other conditions such as temperature, total alkalinity and the like unchanged, continuing the reaction until the granularity D50 of the materials in the reaction kettle reaches the controlled granularity of 3.8um, and then placing the reaction materials in an ageing tank for standing for 180 min. And (IV) continuously washing the aged material with pure water for 240min, drying the obtained washed material at 80 ℃ for 12h, and finally naturally cooling by air to obtain the nickel-cobalt-manganese ternary precursor with the particle size of 3.8 um.
Claims (6)
1. A preparation process of an intermittent nickel-cobalt-manganese ternary precursor comprises the following steps:
the method comprises the following steps: preparing a mixed salt solution with a certain proportion and concentration by using soluble nickel salt, soluble cobalt salt, soluble manganese salt and pure water;
step two: filling the reaction kettle and the thickener with pure water and nitrogen as protective atmosphere; setting the reaction temperature, the stirring speed, the ammonia concentration and the like to a set standard, adding the prepared metal salt, the liquid caustic soda and the ammonia water according to the set pH value, and starting feeding; this is the nucleation stage;
step three: maintaining high pH value in the reaction kettle, and after maintaining for 2-4 hours, reducing the pH value by 0.6-0.8 until the pH value is reduced to below 11.5; this is the crystal nucleus growth stage;
step four: after reacting for 1-2 hours, the reaction slurry overflows and flows into the intermediate tank; transferring the overflow liquid into a concentrator through a middle tank circulating pump; concentrating and discharging in a concentrator, and returning the materials to the reaction kettle again until the granularity is increased to the target granularity; then conveying the reaction materials to an ageing tank for ageing;
step five: and washing and drying the aged reaction material to obtain a powdery nickel-cobalt-manganese ternary precursor.
2. The mixed salt solution of claim one having the formula: nixCoyMnz(OH)2Wherein x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.7, y is more than or equal to 0.2 and less than or equal to 0.3, and z is more than or equal to 0.2 and less than or equal to 0.3; the total amount of the nickel, cobalt and manganese metals is controlled at 110-120 g/L.
3. The reaction temperature according to claim one is controlled at 50-70 ℃; the stirring speed is controlled at 220-230 r/min; the ammonia concentration is controlled at 9-11 g/L.
4. The high pH of the composition is controlled to be 12.0-12.1.
5. The method of claim one, wherein the amount of the mother liquor discharged from the thickener is balanced with the amount of the feed in the reaction vessel, and the air diaphragm pump is used as the circulating pump, and the aging time is more than 30 min.
6. The washing time is 180-240min according to claim one; the drying time is 10-16 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477313A (en) * | 2021-12-31 | 2022-05-13 | 宜宾光原锂电材料有限公司 | Nickel-cobalt-manganese ternary precursor aging method |
| CN117466344A (en) * | 2023-12-27 | 2024-01-30 | 河南科隆新能源股份有限公司 | Micro-powder-free positive electrode material precursor and preparation method thereof |
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| CN107814418A (en) * | 2017-11-16 | 2018-03-20 | 湖南中伟新能源科技有限公司 | A kind of batch (-type) nickel cobalt aluminium forerunner's preparation |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
| CN110600683A (en) * | 2018-06-13 | 2019-12-20 | 浙江帕瓦新能源股份有限公司 | Preparation method of semi-continuous ternary precursor |
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- 2021-05-12 CN CN202110516963.7A patent/CN113104906A/en active Pending
Patent Citations (4)
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| CN107611383A (en) * | 2017-08-25 | 2018-01-19 | 浙江华友钴业股份有限公司 | A kind of preparation method of the nickel-cobalt-manganese ternary presoma of low-sulfur high-tap density |
| CN107814418A (en) * | 2017-11-16 | 2018-03-20 | 湖南中伟新能源科技有限公司 | A kind of batch (-type) nickel cobalt aluminium forerunner's preparation |
| CN110600683A (en) * | 2018-06-13 | 2019-12-20 | 浙江帕瓦新能源股份有限公司 | Preparation method of semi-continuous ternary precursor |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477313A (en) * | 2021-12-31 | 2022-05-13 | 宜宾光原锂电材料有限公司 | Nickel-cobalt-manganese ternary precursor aging method |
| CN114477313B (en) * | 2021-12-31 | 2023-07-11 | 宜宾光原锂电材料有限公司 | Nickel-cobalt-manganese ternary precursor aging method |
| CN117466344A (en) * | 2023-12-27 | 2024-01-30 | 河南科隆新能源股份有限公司 | Micro-powder-free positive electrode material precursor and preparation method thereof |
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Application publication date: 20210713 |