CN111153445A - Nickel-cobalt-manganese ternary precursor with stable particle size and preparation method and preparation device thereof - Google Patents
Nickel-cobalt-manganese ternary precursor with stable particle size and preparation method and preparation device thereof Download PDFInfo
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- CN111153445A CN111153445A CN202010074834.2A CN202010074834A CN111153445A CN 111153445 A CN111153445 A CN 111153445A CN 202010074834 A CN202010074834 A CN 202010074834A CN 111153445 A CN111153445 A CN 111153445A
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- 239000002245 particle Substances 0.000 title claims abstract description 159
- 239000002243 precursor Substances 0.000 title claims abstract description 104
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 152
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000003513 alkali Substances 0.000 claims abstract description 66
- 239000008139 complexing agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 abstract description 10
- 238000010899 nucleation Methods 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 80
- 239000000243 solution Substances 0.000 description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel-cobalt-manganese ternary precursor with stable particle size, a preparation method and a preparation device thereof, wherein the preparation method comprises the following steps: (1) introducing deionized water into the reaction kettle; (2) introducing alkali liquor; the alkali liquor before being completely diluted forms a high pH environment, and the alkali liquor after being completely diluted forms a low pH environment; (3) introducing a main material flow and a complexing agent into a low-pH environment to generate nickel-cobalt-manganese ternary precursor particles; (4) when the granularity of the nickel-cobalt-manganese ternary precursor particles reaches the qualified range, introducing an auxiliary material flow into a high-pH environment, maintaining the pH of a low-pH environment to be basically unchanged, if the granularity of the nickel-cobalt-manganese ternary precursor is continuously reduced, reducing the flow rate of the auxiliary material flow, otherwise, increasing the flow rate of the auxiliary material flow, and finally preparing the nickel-cobalt-manganese ternary precursor with stable granularity. The invention leads the nucleation and the growth of small particles to be carried out stably at the same time in the reaction process under the premise of controlling the pH value in the reaction kettle to be stable, thereby achieving the purpose of stably controlling the particle size.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel-cobalt-manganese ternary precursor with stable particle size, and a preparation method and a preparation device thereof.
Background
Lithium ion batteries are widely used due to their advantages of high voltage, high specific capacity, environmental protection, etc. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material plays an important role in the performance of the lithium ion battery. The precursor of the anode material is very important for the performance of the anode material. At present, the precursor is mainly produced by adopting a coprecipitation method in China, the method comprises a continuous method and an intermittent method, and the granularity of the precursor influences key indexes such as tap density, compaction density and cycle performance of the anode material.
In the existing continuous process, the particle size is changed by mostly adopting a pH lifting mode. At a higher pH, the precipitation reaction is mainly nucleation and can generate a large amount of fine powder with small particles, and at a lower pH, the precipitation reaction is mainly growth and can form coarse powder with large particles; in addition, in the process of increasing and decreasing the pH, the reaction system has large fluctuation, the nucleation and growth process is unstable, the granularity is difficult to stably control, and the product performance is negatively influenced.
Disclosure of Invention
The invention aims to overcome the technical defects of large particle size fluctuation and unstable control in the production of the lithium battery anode material precursor, and provides a nickel-cobalt-manganese ternary precursor with stable particle size, a preparation method and a preparation device thereof. The invention leads the nucleation and the growth of small particles to be carried out stably at the same time in the reaction process under the premise of controlling the pH value in the reaction kettle to be stable, thereby achieving the purpose of stably controlling the particle size.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) introducing deionized water into the reaction kettle;
(2) introducing alkali liquor into the deionized water; the alkali liquor is gradually diffused in the aqueous solution in the reaction kettle, the concentration is gradually diluted, the alkali liquor before being completely diluted forms a high pH environment, the alkali liquor after being completely diluted forms a low pH environment, and the pH of the high pH environment is greater than that of the low pH environment;
(3) continuously introducing a main material flow and a complexing agent into the low-pH environment, controlling the stirring speed of the reaction kettle, and carrying out coprecipitation reaction to generate nickel-cobalt-manganese ternary precursor particles;
(4) measuring the particle size of the nickel-cobalt-manganese ternary precursor particles at intervals, introducing an auxiliary material flow to the high-pH environment when the particle size of the nickel-cobalt-manganese ternary precursor particles reaches the qualified range of the preset D50 particle size, maintaining the pH of the low-pH environment to be basically unchanged, measuring the particle size of the nickel-cobalt-manganese ternary precursor at intervals, and if the particle size of the nickel-cobalt-manganese ternary precursor is continuously reduced, reducing the flow rate of the auxiliary material flow, otherwise, increasing the flow rate of the auxiliary material flow; when the granularity of the nickel-cobalt-manganese ternary precursor is basically unchanged, maintaining the flow rate of the auxiliary material flow, and finally preparing the nickel-cobalt-manganese ternary precursor with stable granularity;
in the technical scheme, the main material flow and the auxiliary material flow comprise soluble nickel salt solution, soluble cobalt salt solution and soluble manganese salt solution; the flow rate of the main stream is greater than the flow rate of the auxiliary stream.
In the above technical solution, the preset particle size D50 is a preset theoretical value of the particle size D50 of the final product nickel-cobalt-manganese ternary precursor.
Preferably, in the step (1), the volume of the reaction kettle is 5m3。
Preferably, in the step (1), the deionized water is added to the reaction kettle 20cm below an overflow port.
Preferably, in the step (1), inert gas is introduced into the reaction kettle.
More preferably, in the step (1), the inert gas is nitrogen.
Preferably, in the step (1), the flow rate of the inert gas is 5-10 m3/h。
Preferably, in the step (1), alkali liquor is introduced into the reaction kettle until the pH value of the system is 10.90-11.60.
More preferably, the lye is a NaOH solution.
Preferably, in the step (1), the complexing agent is introduced into the reaction kettle until the concentration of the complexing agent in the system is 0.3-0.6 mol/L.
Preferably, the complexing agent is ammonia.
Preferably, in the step (1), the temperature of the reaction kettle is increased to 45-65 ℃.
More preferably, in the step (1), the temperature of the reaction kettle is increased to 59.5-60.5 ℃.
Preferably, in the step (2), the alkali liquor is a NaOH solution.
Preferably, in the step (2), the concentration of the alkali liquor is 5-8 mol/L.
More preferably, in the step (2), the concentration of the alkali liquor is 8 mol/L.
Preferably, in the step (2), the flow rate of the alkali liquor is 50-180L/h.
More preferably, in the step (2), the flow rate of the alkali liquor is 50-65L/h.
Preferably, in the step (2), the pH of the high-pH environment is more than 11.40, and the pH of the low-pH environment is 10.40-11.40.
Preferably, in the step (3), the concentration of the main stream is 1.5 mol/L.
Preferably, in the step (3), the flow rate of the main stream is 150 to 300L/h.
More preferably, in step (3), the flow rate of the main stream is 150L/h.
Preferably, in the step (3), the complexing agent is introduced into the reaction kettle until the concentration of the complexing agent in the system is 0.3-0.6 mol/L.
Preferably, in the step (3), the complexing agent is ammonia water.
Preferably, in the step (3), the flow rate of the complexing agent is 5-25L/h.
Preferably, in the step (3), the stirring speed is 150-200 rpm.
Preferably, in the step (4), the certain time interval is 2 h.
Preferably, in the step (4), the preset particle size of D50 is 3 μm to 15 μm.
More preferably, in the step (4), the preset particle size of D50 is 3 μm, 10 μm, or 15 μm.
Preferably, in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 0.9 and 1.1 times of the preset D50 particle size.
More preferably, in the step (4), the preset qualified range of the D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3 ± 0.3 μm, 10 ± 0.5 μm and 15 ± 0.5 μm respectively.
Preferably, in the step (4), the flow rate of the auxiliary stream is 3% to 10% of the flow rate of the main stream.
Preferably, in the step (4), the flow rate of the auxiliary stream is 5-20L/h.
Preferably, in the step (4), when the auxiliary material flow is introduced into the high-pH environment, the flow rate of the main material flow is reduced to be the flow rate of the auxiliary material flow, and the pH of the low-pH environment is maintained to be basically unchanged; since the total stream (main stream + auxiliary stream) and the base stream are unchanged, a low pH environment is achieved with substantially unchanged pH.
Preferably, in the step (4), the pH at which the pH of the low-pH environment is substantially unchanged is ± 0.07 of the pH at the acceptable range.
Preferably, in the step (4), the liquid outlet of the auxiliary material flow in the aqueous solution of the reaction kettle is 2-5 cm away from the liquid outlet of the alkali liquor in the aqueous solution of the reaction kettle.
Preferably, in the step (4), the included angle between the liquid outlet direction of the auxiliary material flow in the aqueous solution of the reaction kettle and the liquid outlet direction of the alkali liquor in the aqueous solution of the reaction kettle is 90 °.
Preferably, in the step (4), the particle size is not changed basically, and the particle size of the D50 of the nickel-cobalt-manganese ternary precursor fluctuates between 0.95 and 1.05 times of the preset particle size of D50.
Preferably, in the step (4), the particle size of the D50 of the nickel-cobalt-manganese ternary precursor with stable particle size fluctuates between 0.95 and 1.05 times of the preset particle size of D50.
More preferably, in the step (4), the particle size of the D50 of the nickel-cobalt-manganese ternary precursor with stable particle size fluctuates between 3.05 ± 0.10 μm, 10.00 ± 0.35 μm and 15 ± 0.4 μm respectively.
Preferably, the composition of the main stream and the subsidiary stream is nickel sulfate, cobalt sulfate and manganese sulfate.
More preferably, the ratio of the nickel sulfate, the cobalt sulfate and the manganese sulfate is 8: 1 or 0.9: 0.05 by mole ratio.
In the technical scheme, when the preset particle size of D50 is 3 μm, in the step (2), the pH value of the high-pH environment is greater than 11.40, and the pH value of the low-pH environment is 11.05-11.40; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3 +/-0.3 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment is 11.08 +/-0.05 when the pH value is basically unchanged; in the step (4), the particle size is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3.05 +/-0.10 microns.
In the technical scheme, when the preset particle size of D50 is 10 μm, the pH value of the high-pH environment in the step (2) is more than 11.40, and the pH value of the low-pH environment is 10.65-11.05; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 10 +/-0.5 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment when the pH value is basically unchanged is 10.74 +/-0.07; in the step (4), the particle size is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 10.00 +/-0.35 mu m.
In the technical scheme, when the preset D50 particle size is 15 μm, the pH value of the high-pH environment in the step (2) is more than 11.40, and the pH value of the low-pH environment is 10.48-11.02; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 15 +/-0.5 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment is 10.55 +/-0.05 when the pH value is basically unchanged; in the step (4), the granularity is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 15 +/-0.4 mu m.
The nickel-cobalt-manganese ternary precursor with stable particle size is prepared by the preparation method.
A nickel-cobalt-manganese ternary precursor preparation device with stable particle size comprises a reaction kettle; the reaction kettle comprises a kettle body, a kettle cover arranged at the top of the kettle body, a stirring shaft arranged in the kettle body, a motor arranged outside the kettle body and connected with one end of the stirring shaft in a matching manner, and a stirring paddle arranged in the kettle body and connected with the other end of the stirring shaft in a matching manner; the kettle cover is provided with a main material pipe, an auxiliary material pipe, an alkali liquor pipe, a complexing agent pipe and an air inlet pipe; the liquid outlet of the main material pipe is far away from the liquid outlet of the alkali liquor pipe; the liquid outlet of the auxiliary material pipe is close to the liquid outlet of the alkali liquor pipe; the distance between the liquid outlet of the main material pipe and the liquid outlet of the alkali liquor pipe is larger than the distance between the liquid outlet of the auxiliary material pipe and the liquid outlet of the alkali liquor pipe.
Further, the liquid outlet of the main material pipe and the liquid outlet of the alkali liquor pipe face the stirring shaft respectively.
Further, a 180-degree angle is formed between a horizontal connecting line of the main material pipe and the stirring shaft and a horizontal connecting line of the alkali liquor pipe and the stirring shaft.
Further, a horizontal connecting line of the main material pipe and the stirring shaft and a horizontal connecting line of the complexing agent pipe and the stirring shaft form a 90-degree angle.
Further, the horizontal connecting line of the air inlet pipe and the stirring shaft and the horizontal connecting line of the complexing agent pipe and the stirring shaft form an angle of 180 degrees.
Further, the horizontal distance between the main material pipe and the stirring shaft, the horizontal distance between the alkali liquor pipe and the stirring shaft, the horizontal distance between the complexing agent pipe and the stirring shaft, and the horizontal distance between the air inlet pipe and the stirring shaft are equal.
Further, the distance between the liquid outlet of the auxiliary material pipe and the liquid outlet of the alkali liquor pipe is 2-5 cm.
Further, the extension line of the liquid outlet of the auxiliary material pipe and the extension line of the liquid outlet of the alkaline liquid pipe form an included angle of 90 degrees.
Further, a main material pipe is formed at the liquid inlet end of the main material pipe and the liquid inlet end of the auxiliary material pipe; the auxiliary material pipe is provided with a flowmeter and a valve.
Further, the stirring paddle is of a single-layer propelling type.
Further, the stirring paddle is provided with three blades.
Further, the lateral wall of reation kettle sets up the overflow mouth, the overflow mouth with the vertical distance of kettle cover is 15 ~ 20 cm.
The basic principle of the invention is as follows:
there are two reactions in the coprecipitation reaction: nucleation and growth of small particles. These two reactions are controlled by pH: nucleation predominates at high pH and growth predominates at low pH. In order to allow nucleation and growth to proceed simultaneously, it is necessary to provide both high and low pH environments in one reaction vessel.
The alkali liquor enters the reaction kettle and then has a concentration dilution process, so that the alkali liquor before complete dilution is used for providing high pH, and the alkali liquor after complete dilution is used for providing low pH for the reaction kettle, thereby having two environments of high pH and low pH. Then, nickel-cobalt-manganese sulfate solution with certain flow is respectively introduced into the two environments, so that the nucleation and the growth are simultaneously carried out.
During nucleation, extremely large amount of small particles are formed, so that a small flow of sulfate solution (called auxiliary material) is needed, and the proportion of the sulfate solution is 3-10% of the total material flow; the nickel-cobalt-manganese sulfate material flow (main material flow + auxiliary material flow) in the total material pipe and the alkali flow are controlled to be unchanged, so that the pH is unchanged; the size of the auxiliary stream is then adjusted according to the particle size, as follows: after opening the auxiliary stream:
a. if the particle size of the material is continuously reduced, the auxiliary material flow is higher, the generated small particles are excessive, and at the moment, the opening of an auxiliary material valve needs to be reduced, so that the number of the small particles is reduced;
b. if the particle size of the material is continuously increased, the auxiliary material flow is low, the generated small particles are few, and at the moment, the opening of an auxiliary material valve needs to be increased, so that the number of the small particles is increased;
in the adjustment process, the change of the granularity is slow, large fluctuation can not be caused, and the nickel-cobalt-manganese ternary precursor is produced continuously (material solution is continuously added into the reaction kettle, and qualified products continuously flow out from an overflow port) and stably (the particle size of D50 of the nickel-cobalt-manganese ternary precursor fluctuates between 0.95 and 1.05 times of the preset particle size of D50) by a single reaction kettle.
Compared with the prior art, the invention has the beneficial effects that:
(1) the main material flow and the auxiliary material flow are fed into a reaction kettle according to a certain proportion, and a certain alkali flow is fed into the reaction kettle to keep the pH value in the reaction kettle at a lower level so as to grow crystal nuclei; the auxiliary material flow is close to the alkali flow, the concentration of the alkali is higher, and the auxiliary material and the alkali meet to quickly nucleate; the crystal nucleus flows to a region with lower pH of the reaction kettle along with stirring, and at the moment, the material of the main material tube is deposited on the crystal nucleus and grows up to form a secondary ball; after the system is stable, the particles in the reaction kettle have a stable particle size value, and when the proportion of the main material and the auxiliary material is adjusted, the particle size value is changed; the proportion of the main material and the auxiliary material is increased, and the granularity is increased; otherwise, the particle size decreases; after the system is stabilized, continuous production can be realized without other subsequent operations through the adjustment, the operation is simple and convenient, and the industrial production is convenient;
(2) on the premise of controlling the pH value in the reaction kettle to be stable, the nucleation and growth of small particles in the reaction process are simultaneously and stably carried out, so that the aim of stably controlling the particle size is fulfilled;
(3) the D50 particle size of the nickel-cobalt-manganese ternary precursor prepared by the method fluctuates between 0.95 and 1.05 times of the preset D50 particle size, and the D50 particle size of the ternary precursor fluctuates slightly.
Drawings
FIG. 1 is a graph showing the particle size and pH change of a ternary precursor in the preparation process of example 1;
FIG. 2 is a graph showing the particle size and pH change of a ternary precursor in the preparation process of example 2;
FIG. 3 is a graph showing the particle size and pH change of the ternary precursor in the preparation process of example 3;
FIG. 4 is a schematic structural view of a ternary precursor production apparatus according to embodiment 4;
FIG. 5 is a schematic piping diagram (top view) of a ternary precursor manufacturing apparatus according to example 4;
FIG. 6 is a schematic view showing the discharge direction of the flows of the alkali solution and the auxiliary materials in the ternary precursor preparing apparatus according to example 4;
FIG. 7 is a graph showing the particle size and pH change of the ternary precursor in the preparation process of comparative example 1.
The corresponding part names for the various reference numbers in the figures are:
1-a reaction kettle; 2-kettle body; 3-a kettle cover; 4-stirring shaft; 5, a motor; 6-stirring paddle; 7-a main material pipe; 8-auxiliary material pipe; 9-alkali liquor tube; 10-complexing agent tube; 11-an air inlet pipe; 12-a main feed pipe; 13-a paddle; 14-baffle.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into the reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding NaOH solution until the pH value is 10.9-11.2, and adding ammonia water to the systemThe ammonia water concentration is 0.5-0.6 mol/L, nitrogen is introduced into the reaction kettle, and the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) start-up to prepare 10 μm NCM811 precursor: after the conditions are met, introducing 8mol/L NaOH solution into the reaction kettle, controlling the flow of NaOH to be 56-61L/h, gradually diffusing the NaOH solution in the aqueous solution in the reaction kettle, gradually diluting the concentration of the NaOH solution, and forming a high-pH environment before the NaOH solution is not completely diluted, wherein the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 10.65-11.05; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.8Co0.1Mn0.1SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.5-0.6 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be 0, the ammonia water flow to be 10-15L/h, the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 2.68 mu m, the particle size is increased to 9.5 mu m after the precursor grows for 96 hours and belongs to a qualified range, the auxiliary material is started for 8L/h, the main material is reduced to 142L/h, the pH value of the low-pH environment is maintained to fluctuate within the range of 10.74 +/-0.07, the particle size is measured at intervals of 2 hours, and the particle size test result shows that after the auxiliary material is started, the expansion speed of D10 and D50 is reduced and stabilized, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within 10.00 +/-0.35 mu m, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary precursor with stable particle size is.
Example 2
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding a NaOH solution until the pH value is 11.3-11.6, adding ammonia water until the concentration of ammonia water in the system is 0.3-0.4 mol/L, introducing nitrogen into the reaction kettle, wherein the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) preparation at startup3 μm NCM811 precursor: after the conditions are met, introducing 8mol/L NaOH solution into the reaction kettle, controlling the flow of NaOH to be 58-62L/h, gradually diffusing the NaOH solution in the aqueous solution in the reaction kettle, gradually diluting the concentration of the NaOH solution, and forming a high-pH environment by the NaOH solution before the NaOH solution is not completely diluted, wherein the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 11.05-11.40; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.8Co0.1Mn0.1SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.3-0.4 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be 0, the ammonia water flow to be 5-10L/h, the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 1.42 mu m, the particle size is increased to 2.9 mu m after the growth is 60 hours, the particle size belongs to a qualified range, the starting auxiliary material is 13L/h, the main material is reduced to 137L/h, the pH value of a low pH environment is maintained to fluctuate within the range of 11.08 +/-0.05, the particle size is measured at intervals of 2 hours, and the particle size test result shows that the rising speed of D50 is reduced and stabilized after the auxiliary material is started, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within the range of 3.05 +/-0.10 mu m, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary precursor with stable particle.
Example 3
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding a NaOH solution until the pH value is 10.90-11.00, adding ammonia water until the concentration of ammonia water in the system is 0.5-0.6 mol/L, introducing nitrogen into the reaction kettle, wherein the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) preparing a 15-micron NCM9055 precursor by starting up: after the conditions are met, 8mol/L NaOH solution is introduced into the reaction kettle, the flow of NaOH is controlled to be 55-60L/h, the NaOH solution gradually diffuses in the aqueous solution in the reaction kettle, and the concentration gradually increasesDiluting, wherein the NaOH solution before incomplete dilution forms a high pH environment, and the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 10.48-11.02; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.9Co0.05Mn0.05SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.5-0.6 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be 0, the ammonia water flow to be 20L/h, and the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 4.50 micrometers, the particle size is increased to 14.8 micrometers after the growth is carried out for 106 hours, the particle size belongs to a qualified range, at the moment, the auxiliary material is started to be 6L/h, the main material is reduced to 144L/h, the pH value of a low pH environment is maintained to fluctuate within the range of 10.55 +/-0.05, the particle size is measured at intervals of 2 hours, and the particle size test result shows that after the auxiliary material is started, the expansion speed of D50 is reduced and stabilized, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within 15 +/-0.4 micrometers, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary.
Example 4
A nickel-cobalt-manganese ternary precursor preparation device with stable particle size, as shown in fig. 4-6, comprising a reaction kettle 1; the reaction kettle 1 comprises a kettle body 2, a kettle cover 3 arranged at the top of the kettle body 2, a stirring shaft 4 arranged inside the kettle body 2, a motor 5 arranged outside the kettle body 2 and connected with one end of the stirring shaft 4 in a matching manner, and a stirring paddle 6 arranged inside the kettle body 2 and connected with the other end of the stirring shaft 4 in a matching manner; the kettle cover 3 is provided with a main material pipe 7, an auxiliary material pipe 8, an alkali liquor pipe 9, a complexing agent pipe 10 and an air inlet pipe 11; the liquid outlet of the main material pipe 7 is far away from the liquid outlet of the alkali liquor pipe 8; the liquid outlet of the auxiliary material pipe 8 is close to the liquid outlet of the alkali liquor pipe 9; the distance between the liquid outlet of the main material pipe 7 and the liquid outlet of the alkali liquor pipe 9 is larger than the distance between the liquid outlet of the auxiliary material pipe 8 and the liquid outlet of the alkali liquor pipe 9.
The liquid outlet of the main material pipe 7 and the liquid outlet of the alkali liquor pipe 9 face the stirring shaft 4 respectively.
The horizontal connecting line of the main material pipe 7 and the stirring shaft 4 and the horizontal connecting line of the alkali liquor pipe 9 and the stirring shaft 4 form an angle of 180 degrees.
The horizontal connecting line of the main material pipe 7 and the stirring shaft 4 and the horizontal connecting line of the complexing agent pipe 10 and the stirring shaft 4 form a 90-degree angle.
The horizontal line of the air inlet pipe 11 and the stirring shaft 4 is 180 degrees with the horizontal line of the complexing agent pipe 10 and the stirring shaft 4.
The horizontal distance between the main pipe 7 and the stirring shaft 4, the horizontal distance between the alkali liquor pipe 9 and the stirring shaft 4, the horizontal distance between the complexing agent pipe 10 and the stirring shaft 4, and the horizontal distance between the air inlet pipe 11 and the stirring shaft 4 are equal.
The distance between the liquid outlet of the auxiliary material pipe 8 and the liquid outlet of the alkali liquor pipe 9 is 2-5 cm, and granulation is facilitated.
The extension line of the liquid outlet of the auxiliary material pipe 8 and the extension line of the liquid outlet of the alkaline liquid pipe 9 form an included angle of 90 degrees, so that better granulation is facilitated.
The liquid inlet end of the main material pipe 7 and the liquid inlet end of the auxiliary material pipe 8 form a main material pipe 12; the auxiliary material pipe 8 is provided with a flowmeter (not shown in the figure) and a valve (not shown in the figure); the pH can be conveniently kept unchanged by controlling the nickel-cobalt-manganese sulfate material flow (main material flow + auxiliary material flow) in the main material pipe 12 and the alkali flow in the alkali liquor pipe 9 to be unchanged.
The stirring paddle 6 is of a single-layer propelling type.
The stirring paddle 6 is provided with three paddles 13.
The lateral wall of reation kettle 1 sets up overflow mouth (not shown in the figure), the overflow mouth with kettle cover 3's vertical distance is 15 ~ 20 cm.
A baffle plate 14 is arranged in the kettle body 2.
The operation process of this embodiment is as follows:
(1) as shown in fig. 4 and 5, a main material pipe 7, an auxiliary material pipe 8, an alkali liquor pipe 9, a complexing agent pipe 10 and an air inlet pipe 11 are installed in a reaction kettle 1, and main material nickel cobalt manganese sulfate, auxiliary material nickel cobalt manganese sulfate, alkali liquor, ammonia water and nitrogen are respectively introduced into the reaction kettle 1; the main material pipe 7, the alkali liquor pipe 9, the complexing agent pipe 10 and the air inlet pipe 11 are arranged in a mode of forming a central angle of 90 degrees with each other, and the liquid outlet directions of the main material pipe 7, the alkali liquor pipe 9 and the complexing agent pipe 10 in the reaction kettle 1 are aligned to the circle center of the reaction kettle 1; a branch pipe, namely an auxiliary material pipe 8, is added on the main material pipe 7 and is positioned 2-5 cm near the alkali liquor pipe 9, the liquid outlet direction of the branch pipe and the alkali liquor outlet direction form 90 degrees (as shown in fig. 6), the flow of the auxiliary material pipe 8 is controlled by a valve, a liquid inlet end of the main material pipe 7 and a liquid inlet end of the auxiliary material pipe 8 form a main material pipe 12, the nickel cobalt manganese sulfate material flow (the main material flow and the auxiliary material flow) and the alkali flow in the main material pipe 12 are controlled to be unchanged, and the pH is unchanged;
(2) adding clear water into the reaction kettle 1 to a position 20cm below an overflow port, then introducing a certain amount of alkali and ammonia water, and starting to continuously introduce nickel-cobalt-manganese sulfate, alkali, ammonia water and nitrogen gas for coprecipitation reaction after a system is stable;
(3) when the granularity is qualified, the auxiliary material valve is opened, the opening degree is 3-10%, and then the size of the auxiliary material flow is adjusted according to the granularity size, wherein the auxiliary material flow is as follows: after the flow of the auxiliary material is turned on,
a. if the particle size of the material is continuously reduced, the auxiliary material flow is higher, the generated small particles are excessive, and at the moment, the opening of an auxiliary material valve needs to be reduced, so that the number of the small particles is reduced;
b. if the particle size of the material is continuously increased, the auxiliary material flow is low, the generated small particles are few, and at the moment, the opening of an auxiliary material valve needs to be increased, so that the number of the small particles is increased;
in the adjusting process, the change of the granularity is slow, large fluctuation can not be caused, and the continuous and stable production of the nickel-cobalt-manganese ternary precursor by a single reaction kettle is finally realized.
Comparative example 1
The method for preparing the ternary precursor with the D50 particle size of 10 mu m by the conventional process comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding NaOH solution until the pH value is 10.9-11.2, adding ammonia water to 0.5-0.6 mol/L, introducing nitrogen into the reaction kettle, and introducing the nitrogen into the reaction kettleThe speed is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) start-up to prepare 10 μm NCM811 precursor: after the conditions are met, 8mol/L NaOH solution is introduced into the reaction kettle, the flow of NaOH is controlled to be 56-61L/h, and sulfate Ni with the material flow of 1.5mol/L is continuously introduced0.8Co0.1Mn0.1SO4Controlling the material flow to be 150L/h, controlling the flow of ammonia water to be 10-15L/h, controlling the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the material liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 2.68 mu m, when the particle size is increased to 9.5 mu m after the precursor grows for 96 hours, the alkali flow is increased gradually, the pH is increased, when the pH is over 11.4, small particles are generated in a reaction kettle, when the D10 is decreased, the alkali flow is decreased, the pH is reduced, the pH is maintained at 11.2-11.4, the particle size starts to grow, and the D50 particle size of the finally prepared nickel cobalt manganese ternary precursor has large fluctuation, namely 10.10 +/-1.00 mu m.
Effects of the embodiment
In the embodiment 1, the preset D50 particle size of the nickel-cobalt-manganese ternary precursor is 10 mu m; the particle size fluctuation of the nickel-cobalt-manganese ternary precursor D50 prepared in example 1 is small and is 10.00 +/-0.35 mu m (see FIG. 1); the nickel-cobalt-manganese ternary precursor D50 prepared by the conventional process has large particle size fluctuation, and the particle size fluctuation is 10.10 +/-1.00 mu m (see figure 7).
In the embodiment 2, the preset D50 particle size of the nickel-cobalt-manganese ternary precursor is 3 μm; the particle size fluctuation of the nickel-cobalt-manganese ternary precursor D50 prepared in example 2 is small and is 3.05 +/-0.10 mu m (see FIG. 2); the nickel-cobalt-manganese ternary precursor D50 prepared by the conventional process has large particle size fluctuation, and the particle size fluctuation is 3.10 +/-0.50 mu m.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (10)
1. A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size is characterized by comprising the following steps:
(1) introducing deionized water into the reaction kettle;
(2) introducing alkali liquor into the deionized water; the alkali liquor is gradually diffused in the aqueous solution in the reaction kettle, the concentration is gradually diluted, the alkali liquor before being completely diluted forms a high pH environment, the alkali liquor after being completely diluted forms a low pH environment, and the pH of the high pH environment is greater than that of the low pH environment;
(3) continuously introducing a main material flow and a complexing agent into the low-pH environment, controlling the stirring speed of the reaction kettle, and carrying out coprecipitation reaction to generate nickel-cobalt-manganese ternary precursor particles;
(4) measuring the particle size of the nickel-cobalt-manganese ternary precursor particles at intervals, when the particle size of the nickel-cobalt-manganese ternary precursor particles reaches a qualified range of a preset D50 particle size, introducing an auxiliary material flow into the high-pH environment, maintaining the pH of the low-pH environment to be basically unchanged, measuring the particle size of the nickel-cobalt-manganese ternary precursor at intervals, if the particle size of the nickel-cobalt-manganese ternary precursor is continuously reduced, reducing the flow rate of the auxiliary material flow, otherwise, increasing the flow rate of the auxiliary material flow; when the granularity of the nickel-cobalt-manganese ternary precursor is basically unchanged, maintaining the flow rate of the auxiliary material flow, and finally preparing the nickel-cobalt-manganese ternary precursor with stable granularity;
the components of the main material flow and the auxiliary material flow are soluble nickel salt solution, soluble cobalt salt solution and soluble manganese salt solution; the flow rate of the main stream > the flow rate of the subsidiary stream.
2. The method for preparing the nickel-cobalt-manganese ternary precursor with stable particle size according to claim 1, wherein in the step (2), the pH of the high-pH environment is greater than 11.40, and the pH of the low-pH environment is 10.40-11.40.
3. The method for preparing the nickel-cobalt-manganese ternary precursor with stable particle size according to claim 1, wherein in the step (4), the flow rate of the auxiliary stream is 3-10% of the flow rate of the main stream.
4. The method according to claim 1, wherein in the step (4), when the auxiliary material flow is introduced into the high-pH environment, the flow rate of the main material flow is reduced, and the flow rate of the main material flow is reduced to the flow rate of the auxiliary material flow, so as to maintain the pH of the low-pH environment substantially constant; the pH at which the pH in the low pH environment is substantially unchanged is within 0.07 of the pH at which the acceptable range is defined.
5. The method for preparing the nickel-cobalt-manganese ternary precursor with stable particle size according to claim 1, wherein in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 0.9 and 1.1 times of the preset D50 particle size; the granularity basically does not change, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 0.95 and 1.05 times of the preset D50 particle size.
6. The nickel-cobalt-manganese ternary precursor with stable particle size is prepared by the preparation method of the nickel-cobalt-manganese ternary precursor with stable particle size according to any one of claims 1-5.
7. The device for preparing the nickel-cobalt-manganese ternary precursor with stable particle size is characterized by comprising a reaction kettle (1); the reaction kettle (1) comprises a kettle body (2), a kettle cover (3) arranged at the top of the kettle body (2), a stirring shaft (4) arranged inside the kettle body (2), a motor (5) arranged outside the kettle body (2) and connected with one end of the stirring shaft (4) in a matching manner, and a stirring paddle (6) arranged inside the kettle body (2) and connected with the other end of the stirring shaft (4) in a matching manner; the kettle cover (3) is provided with a main material pipe (7), an auxiliary material pipe (8), an alkali liquor pipe (9), a complexing agent pipe (10) and an air inlet pipe (11); the liquid outlet of the main material pipe (7) is far away from the liquid outlet of the alkali liquor pipe (8); the liquid outlet of the auxiliary material pipe (8) is close to the liquid outlet of the alkali liquor pipe (9); the distance between the liquid outlet of the main material pipe (7) and the liquid outlet of the alkali liquor pipe (9) is greater than the distance between the liquid outlet of the auxiliary material pipe (8) and the liquid outlet of the alkali liquor pipe (9).
8. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 7, wherein the horizontal line between the main pipe (7) and the stirring shaft (4) and the horizontal line between the alkali liquor pipe (9) and the stirring shaft (4) is 180 °; and the included angle between the extension line of the liquid outlet of the auxiliary material pipe (8) and the extension line of the liquid outlet of the alkaline liquid pipe (9) is 90 degrees.
9. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 7, wherein the distance between the liquid outlet of the auxiliary pipe (8) and the liquid outlet of the alkaline liquid pipe (9) is 2-5 cm.
10. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 7, wherein the inlet of the main material pipe (7) and the inlet of the auxiliary material pipe (8) form a main material pipe (12); the auxiliary material pipe (8) is provided with a flowmeter and a valve.
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