CN113896251A - Preparation device and preparation method of high-tap-density ternary precursor material - Google Patents
Preparation device and preparation method of high-tap-density ternary precursor material Download PDFInfo
- Publication number
- CN113896251A CN113896251A CN202111027376.8A CN202111027376A CN113896251A CN 113896251 A CN113896251 A CN 113896251A CN 202111027376 A CN202111027376 A CN 202111027376A CN 113896251 A CN113896251 A CN 113896251A
- Authority
- CN
- China
- Prior art keywords
- seed crystal
- reaction kettle
- concentration
- crystal reaction
- thickener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000002243 precursor Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 141
- 238000006243 chemical reaction Methods 0.000 claims abstract description 124
- 239000000243 solution Substances 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000012266 salt solution Substances 0.000 claims abstract description 32
- 239000002562 thickening agent Substances 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000975 co-precipitation Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 12
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 12
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- 229910001453 nickel ion Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229940053662 nickel sulfate Drugs 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000284 extract Substances 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 description 16
- 239000012716 precipitator Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000010405 anode material Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- VVEAQOPVJBGVFY-UHFFFAOYSA-N disodium chloro(dioxido)borane Chemical compound B([O-])([O-])Cl.[Na+].[Na+] VVEAQOPVJBGVFY-UHFFFAOYSA-N 0.000 description 2
- 230000009647 facial growth Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
-
- 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
- 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
- H01M4/50—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
-
- 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 discloses a preparation device of a high-tap ternary precursor material, which comprises a seed crystal reaction kettle (1), a thickener (7) and a seed crystal tank (8), wherein the seed crystal reaction kettle is respectively connected with the thickener and the seed crystal tank, and a pipeline connected between the seed crystal reaction kettle and the seed crystal tank is connected with the thickener; a stirrer (2) and a baffle (5) are arranged in the seed crystal reaction kettle, and a guide cylinder (3) is arranged on the inner wall of the seed crystal reaction kettle (1). The preparation method comprises the following steps: preparing a mixed sulfate solution of nickel, cobalt and manganese; preparing base liquid and introducing protective gas; adding the mixed salt solution, the industrial liquid caustic soda and the ammonia water to the upper layer of the blade and starting a stirrer; the thickener extracts supernatant fluid, returns to the seed crystal reaction kettle and overflows into the seed crystal tank; and introducing the seed crystal particles into a seed crystal reaction kettle to continue reacting to obtain a material with a target particle size, and then processing to obtain the high-tap-density ternary precursor material. The material prepared by the invention has high tap density and good particle uniformity.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation device and a preparation method of a high-tap ternary precursor material.
Background
As a new secondary clean and renewable energy source, the lithium ion battery has the advantages of high energy, high voltage, rapid charge and discharge and the like, is widely applied to the fields of electric tools, mobile phones, digital cameras, notebook computers, instruments and meters and the like, has great potential in the electric automobile industry, and has shown a strong development trend. The anode material is used as a key material of the lithium ion battery, directly influences the performance of the lithium ion battery, the cost accounts for over 40%, and the specific gravity of the anode material in the lithium ion battery is high. The lithium ion battery anode material mainly comprises lithium cobaltate, lithium iron phosphate, lithium manganate, ternary materials of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and the like, wherein the ternary materials have higher reversible capacity and low cost and become the lithium ion power battery anode material with the most application prospect at present, and the structural performance of the ternary anode material is mainly influenced by the physical and chemical properties of a precursor material. The industrialization mode of the ternary precursor material mainly adopts a coprecipitation preparation method, and the structural performance of the ternary precursor material is directly influenced by the control of precipitation and crystallization.
The invention patent of patent No. CN103482711A discloses a method for preparing a precursor of a ternary positive electrode material of a lithium ion battery by ultrasonic assistance, wherein an ultrasonic assistance method is adopted in the coprecipitation preparation process and the washing process of the precursor, so that a precursor conforming to the hydroxide with high tap density can be obtained, but the preparation process adopts an ultrasonic assistance mode, the high tap density ternary precursor needs higher shearing force in the synthesis process, the ultrasonic assistance method is adopted in the coprecipitation preparation process of the ternary precursor to prepare the precursor conforming to the hydroxide with high tap density, but the energy consumption in the preparation process is lower than that in the coprecipitation preparation processLarge size and high cost. In the application of patent No. CN111039331A, a certain amount of sodium chloroborate (Na) is added in the process of preparing the high-nickel ternary precursor by a coprecipitation method3B6O10Cl) to adjust the crystal face growth of primary particles in the precursor, so that the interface adhesion among the primary particles is improved, a more compact and dense secondary ball is obtained, sodium chloroborate is added in the coprecipitation process to adjust the crystal face growth of the precursor particles, the interface adhesion is increased, and then the precursor particles which are combined compactly and densely are prepared. The application with the patent number of CN109225069A improves the stability and consistency of products caused by uneven stirring by adding an anti-deposition device at the bottom of the reaction kettle, and prepares a ternary anode precursor material with small particle size, high tap density, narrow distribution and uniformity, but the method directly reduces the effective volume of the reaction kettle, which is equivalent to sacrificing the productivity to improve the consistency of the materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation device and a preparation method for preparing a high-tap ternary precursor material which has high tap density and good particle uniformity and is beneficial to improving the stability and energy density of a cathode material.
The invention adopts the following technical scheme:
the preparation device of the high-tap ternary precursor material is characterized by comprising a seed crystal reaction kettle (1), a thickener (7) and a seed crystal tank (8), wherein the seed crystal reaction kettle (1) is connected with the thickener (7) through a pipeline provided with a valve; install agitator (2) in seed crystal reation kettle (1), draft tube (3) are installed to the inside wall of seed crystal reation kettle (1), and baffle (5) are installed to the lateral wall of seed crystal reation kettle (1).
The device for preparing the high-tap ternary precursor material is characterized in that a stirring paddle (4) is installed on the stirrer (2), the stirring paddle (4) comprises an upper paddle (9) and a lower paddle (6), the upper paddle (9) is installed in the middle of the stirrer (2), and the guide cylinder (3) is installed around the upper paddle (9); the lower paddle (6) is arranged at the lower part of the stirrer (2).
The preparation device of the high tap ternary precursor material is characterized in that the upper-layer paddle (9) is one of a flap-opening paddle and a disc turbine paddle, the blade inclination angle of the upper-layer paddle (9) is 45-75 degrees, the stirring diameter is 0.5-0.8 times of the inner diameter of the guide cylinder (3), and the inner diameter of the guide cylinder (3) is 0.5-0.7 times of the inner diameter of the seed crystal reaction kettle (1).
The device for preparing the high-tap ternary precursor material is characterized in that a valve installed on a pipeline connected between the seed crystal reaction kettle (1) and the seed crystal tank (8) is positioned on a pipeline between the thickener (7) and the seed crystal tank (8).
The preparation method of the preparation device based on the high-tap ternary precursor material is characterized by comprising the following steps of:
step (I): preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions, cobalt ions and manganese ions in the mixed salt solution is x: y (100-x-y), wherein x is more than or equal to 60 and less than or equal to 98, y is more than or equal to 0 and less than or equal to 20, and the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the mixed salt solution is 1-3 mol/L;
step (II): preparing a base solution in a seed crystal reaction kettle, and introducing protective gas into the seed crystal reaction kettle; the base solution comprises industrial liquid alkali and ammonia water, the pH value of the base solution is 11-12.5, the concentration of the ammonia water in the base solution is 5-20 g/L, and the temperature of the base solution is 40-60 ℃;
step (three): adding the mixed salt solution into the upper layer blade height position in a seed crystal reaction kettle at the flow rate of 300-600L/h, the industrial liquid caustic soda with the concentration of 8-12 mol/L at the flow rate of 60-120L/h and the ammonia water with the concentration of 0.5-2 mol/L at the flow rate of 20-50L/h for coprecipitation reaction, and starting a stirrer; extracting supernatant from the materials in the seed crystal reaction kettle through a thickener, returning the materials in the thickener to the seed crystal reaction kettle, and continuously overflowing the materials in the seed crystal reaction kettle to a seed crystal tank when the particle size of the material particles in the seed crystal reaction kettle reaches 0.3-0.6 times of the target particle size;
step (IV): introducing the seed crystal material in the seed crystal groove into a seed crystal reaction kettle, wherein the seed crystal material introduced into the seed crystal reaction kettle is 1/5-1/2 of the volume of the seed crystal reaction kettle; adding the mixed salt solution into the lower paddle height in a seed crystal reaction kettle at the flow rate of 200-400L/h and the industrial liquid caustic soda with the concentration of 8-12 mol/L at the flow rate of 40-100L/h and the ammonia water with the concentration of 0.5-2 mol/L at the flow rate of 10-40L/h, starting a stirrer to continue coprecipitation reaction, and stopping the reaction after precursor particles with target particle size are obtained;
step (V): and (3) sequentially carrying out aging, centrifuging, washing, drying and magnetic foreign matter removal treatment on the precursor particles to obtain the high-tap-density ternary precursor material.
The preparation method of the preparation device of the high tap density ternary precursor material is characterized in that the process conditions of the coprecipitation reaction in the step (III) are as follows: the reaction temperature is 40-60 ℃, the pH is 10-11, and the concentration of ammonia water is 5-10 g/L; the stirring speed of the stirrer is 200rpm-600 rpm.
The preparation method of the preparation device of the high tap density ternary precursor material is characterized in that the stirring speed of the stirrer in the step (IV) is 200-500 rpm.
The invention has the beneficial technical effects that: in the coprecipitation reaction process of the precursor, a seed crystal process and a seed crystal growth process in the preparation of the precursor are respectively controlled, the shear distribution in the crystallization process of the seed crystal is improved, a certain radial flow is ensured below a feeding position by controlling the structural sizes of a stirrer and a guide cylinder, the rapid mixing of a mixed salt solution and a precipitator in a crystal nucleus area is promoted, the mixing efficiency and the shear distribution in the nucleation and crystallization process of the seed crystal are improved, and the seed crystal with compact particles and good consistency and dispersibility is prepared; by controlling the addition of the seed crystal, the growth rate of the precursor particles is ensured to be consistent and stable in the growth process of the seed crystal, the ordered assembly of the precursor particles is promoted, and the ternary precursor material with high tap density and good uniformity is prepared. The material prepared by the invention has high tap density and good particle uniformity, and is beneficial to improving the stability and energy density of the anode material.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 shows the surface morphology and the cross-sectional morphology of the seed crystal of the ternary precursor material prepared in example 1;
FIG. 3 shows the surface morphology of the finished ternary precursor material with high tap density.
Detailed Description
Referring to fig. 1, the device for preparing a high tap density ternary precursor material of the present invention comprises a seed crystal reaction kettle 1, a thickener 7 and a seed crystal tank 8, wherein the seed crystal reaction kettle 1 is connected with the thickener 7 through a pipeline provided with a valve, the seed crystal reaction kettle 1 is connected with the seed crystal tank 8 through a pipeline provided with a valve, a pipeline connected between the seed crystal reaction kettle 1 and the seed crystal tank 8 is connected with the thickener 7 through a pipeline provided with a valve, and the seed crystal tank 8 is connected with the seed crystal reaction kettle 1 through a pipeline provided with a valve; the valve installed on the pipeline connected between the seed crystal reaction kettle 1 and the seed crystal tank 8 is positioned on the pipeline between the thickener 7 and the seed crystal tank 8. Install agitator 2 in the seed crystal reation kettle 1, agitator 4 is installed to agitator 2, and agitator 4 includes upper paddle 9 and lower floor's paddle 6, and upper paddle 9 is installed in the middle part of agitator 2, and lower floor's paddle 6 is installed in the lower part of agitator 2. The upper layer blade 9 is one of a flap opening type blade and a disc turbine type blade, the blade inclination angle of the upper layer blade 9 is 45-75 degrees, the stirring diameter is 0.5-0.8 times of the inner diameter of the guide shell 3, and the inner diameter of the guide shell 3 is 0.5-0.7 times of the inner diameter of the seed crystal reaction kettle 1. The inner wall of the crystal seed reaction kettle 1 is provided with a guide shell 3, and the guide shell 3 is arranged around the upper paddle 9. The side wall of the seed crystal reaction kettle 1 is provided with a baffle 5.
The preparation method of the preparation device of the high-tap ternary precursor material comprises the following steps:
step (I): preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions, cobalt ions and manganese ions in the mixed salt solution is x: y (100-x-y), wherein x is more than or equal to 60 and less than or equal to 98, y is more than or equal to 0 and less than or equal to 20, and the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the mixed salt solution is 1-3 mol/L; industrial liquid caustic soda with the concentration of 8-12 mol/L is used as a precipitator solution, and ammonia water with the concentration of 0.5-2 mol/L is used as a complexing agent solution.
Step (II): preparing a base solution in the seed crystal reaction kettle 1, and introducing protective gas into the seed crystal reaction kettle 1; the base solution is prepared from a precipitator solution and a complexing agent solution, the pH of the base solution is 11-12.5, the concentration of ammonia water in the base solution is 5-20 g/L, and the temperature of the base solution is 40-60 ℃.
Step (three): adding the mixed salt solution at the flow rate of 300-600L/h, the precipitant solution at the flow rate of 60-120L/h and the complexing agent solution at the flow rate of 20-50L/h into the horizontal position of an upper paddle 9 in the seed crystal reaction kettle 1 for coprecipitation reaction, and starting a stirrer 2; the process conditions of the coprecipitation reaction are as follows: the reaction temperature is 40-60 ℃, the pH is 10-11, the concentration of ammonia water is 5-10 g/L, and the stirring speed of the stirring paddle is 200-600 rpm. Extracting supernatant from the material in the seed crystal reaction kettle 1 through a thickener 7, returning the material in the thickener 7 to the seed crystal reaction kettle 1, stabilizing the reaction conditions when the particle size of the material particles in the seed crystal reaction kettle 1 reaches 0.3-0.6 times of the target particle size, and continuously overflowing the material in the seed crystal reaction kettle 1 into a seed crystal tank 8.
Step (IV): introducing the seed crystal material in the seed crystal tank 8 into the seed crystal reaction kettle 1, wherein the seed crystal material introduced into the seed crystal reaction kettle 1 is 1/5-1/2 of the volume of the seed crystal reaction kettle 1; and adding the mixed salt solution at the flow rate of 200-400L/h, the precipitant solution at the flow rate of 40-100L/h and the complexing agent solution at the flow rate of 10-40L/h into the horizontal position of the lower paddle 6 in the seed crystal reaction kettle 1, starting the stirrer 2 to continue the coprecipitation reaction, and stopping the reaction until the precursor particles grow to the target particle size D50. The stirring speed of the stirrer 2 is 200rpm to 500 rpm.
Step (V): and aging the precursor particles to obtain a spherical precursor, and carrying out centrifugation, washing, drying, magnetic foreign matter removal and other treatments to obtain the high-tap-density ternary precursor material.
Example 1
Preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions to cobalt ions to manganese ions in the mixed salt solution is 8:1:1, and the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the mixed salt solution is 2 mol/L; industrial liquid alkali with the concentration of 8mol/L is used as a precipitator solution, and ammonia water with the concentration of 1mol/L is used as a complexing agent solution.
Preparing a base solution in the seed crystal reaction kettle 1, and introducing protective gas into the seed crystal reaction kettle 1; the base solution is prepared from a precipitator solution and a complexing agent solution, the pH of the base solution is 11-11.6, the concentration of ammonia water in the base solution is 5-10 g/L, and the temperature of the base solution is 40-50 ℃.
Adding the mixed salt solution at the flow rate of 600L/h, the precipitant solution at the flow rate of 110L/h-120L/h and the complexing agent solution at the flow rate of 45L/h-50L/h to the horizontal position of an upper layer paddle 9 in the seed crystal reaction kettle 1, and carrying out coprecipitation reaction under the stirring speed of 500rpm-600rpm of a stirring paddle; the upper layer of the blades 9 are hinged opening blades, the blade inclination angle of the upper layer of the blades 9 is 55 degrees, the stirring diameter is 0.65 times of the inner diameter of the guide shell 3, and the inner diameter of the guide shell 3 is 0.7 times of the inner diameter of the crystal seed reaction kettle 1. The process conditions of the coprecipitation reaction are as follows: the reaction temperature is 40-42 ℃, the pH is 10-10.2, and the concentration of ammonia water is 5-6 g/L. Extracting supernatant from the material in the seed crystal reaction kettle 1 through a thickener 7, returning the material in the thickener 7 to the seed crystal reaction kettle 1, stabilizing reaction conditions when the particle size of the material particles in the seed crystal reaction kettle 1 reaches 0.6 times of the target particle size D50, and continuously overflowing the material in the seed crystal reaction kettle 1 into a seed crystal tank 8.
Introducing the seed crystal material in the seed crystal tank 8 into the seed crystal reaction kettle 1; and adding the mixed salt solution at the flow rate of 400L/h, the precipitant solution at the flow rate of 90L/h-100L/h and the complexing agent solution at the flow rate of 35L/h-40L/h to the horizontal position of the lower layer paddle 6 in the seed crystal reaction kettle 1, starting the stirrer 2 to continue coprecipitation reaction, and stopping the reaction until precursor particles grow to the target particle size D50. The stirring speed of the stirrer 2 is 450rpm-500 rpm.
And aging the precursor particles to obtain a spherical precursor, and carrying out centrifugation, washing, drying, magnetic foreign matter removal and other treatments to obtain the high-tap-density ternary precursor material.
The surface morphology and the profile morphology of the ternary precursor material seed crystal prepared in example 1 are shown in fig. 2; the surface topography of the finished high tap ternary precursor material is shown in fig. 3.
Example 2
Preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions to cobalt ions to manganese ions in the mixed salt solution is 88:6:6, and the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the mixed salt solution is 2 mol/L; industrial liquid alkali with the concentration of 8mol/L is used as a precipitator solution, and ammonia water with the concentration of 1mol/L is used as a complexing agent solution.
Preparing a base solution in the seed crystal reaction kettle 1, and introducing protective gas into the seed crystal reaction kettle 1; the base solution is prepared from a precipitator solution and a complexing agent solution, the pH of the base solution is 11.2-11.8, the concentration of ammonia water in the base solution is 8-13 g/L, and the temperature of the base solution is 45-55 ℃.
Adding the mixed salt solution at the flow rate of 500L/h, the precipitant solution at the flow rate of 90L/h-100L/h and the complexing agent solution at the flow rate of 40L/h-45L/h to the horizontal position of an upper layer blade 9 in the seed crystal reaction kettle 1, and carrying out coprecipitation reaction under the stirring speed of 450rpm-550rpm of a stirring paddle; the upper layer of the blades 9 are hinged opening blades, the blade inclination angle of the upper layer of the blades 9 is 55 degrees, the stirring diameter is 0.65 times of the inner diameter of the guide shell 3, and the inner diameter of the guide shell 3 is 0.6 times of the inner diameter of the crystal seed reaction kettle 1. The process conditions of the coprecipitation reaction are as follows: the reaction temperature is 50-52 ℃, the pH is 10.4-10.6, and the concentration of ammonia water is 7-8 g/L. Extracting supernatant from the material in the seed crystal reaction kettle 1 through a thickener 7, returning the material in the thickener 7 to the seed crystal reaction kettle 1, stabilizing reaction conditions when the particle size of the material particles in the seed crystal reaction kettle 1 reaches 0.6 times of the target particle size D50, and continuously overflowing the material in the seed crystal reaction kettle 1 into a seed crystal tank 8.
Introducing the seed crystal material in the seed crystal tank 8 into the seed crystal reaction kettle 1; and adding the mixed salt solution at the flow rate of 350L/h, the precipitant solution at the flow rate of 62L/h-70L/h and the complexing agent solution at the flow rate of 28L/h-35L/h to the horizontal position of the lower layer paddle 6 in the seed crystal reaction kettle 1, starting the stirrer 2 to continue coprecipitation reaction, and stopping the reaction until precursor particles grow to the target particle size D50. The stirring speed of the stirrer 2 is 400rpm to 450 rpm.
And aging the precursor particles to obtain a spherical precursor, and carrying out centrifugation, washing, drying, magnetic foreign matter removal and other treatments to obtain the high-tap-density ternary precursor material.
Example 3
Preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions to cobalt ions to manganese ions in the mixed salt solution is 96:2:2, and the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the mixed salt solution is 2 mol/L; industrial liquid alkali with the concentration of 8mol/L is used as a precipitator solution, and ammonia water with the concentration of 1mol/L is used as a complexing agent solution.
Preparing a base solution in the seed crystal reaction kettle 1, and introducing protective gas into the seed crystal reaction kettle 1; the base solution is prepared from a precipitator solution and a complexing agent solution, the pH of the base solution is 11.4-12.0, the concentration of ammonia water in the base solution is 8-15 g/L, and the temperature of the base solution is 50-60 ℃.
Adding the mixed salt solution at the flow rate of 400L/h, the precipitant solution at the flow rate of 72L/h-80L/h and the complexing agent solution at the flow rate of 35L/h-40L/h to the horizontal position of an upper layer paddle 9 in the seed crystal reaction kettle 1, and carrying out coprecipitation reaction under the stirring speed of a stirring paddle of 400rpm-500 rpm; the upper layer of the blades 9 are hinged opening blades, the blade inclination angle of the upper layer of the blades 9 is 55 degrees, the stirring diameter is 0.65 times of the inner diameter of the guide shell 3, and the inner diameter of the guide shell 3 is 0.5 times of the inner diameter of the crystal seed reaction kettle 1. The process conditions of the coprecipitation reaction are as follows: the reaction temperature is 58-60 ℃, the pH value is 10.8-11, and the concentration of ammonia water is 9-10 g/L. Extracting supernatant from the material in the seed crystal reaction kettle 1 through a thickener 7, returning the material in the thickener 7 to the seed crystal reaction kettle 1, stabilizing reaction conditions when the particle size of the material particles in the seed crystal reaction kettle 1 reaches 0.6 times of the target particle size D50, and continuously overflowing the material in the seed crystal reaction kettle 1 into a seed crystal tank 8.
Introducing the seed crystal material in the seed crystal tank 8 into the seed crystal reaction kettle 1; and adding the mixed salt solution at the flow rate of 300L/h, the precipitant solution at the flow rate of 54L/h-60L/h and the complexing agent solution at the flow rate of 24L/h-30L/h to the horizontal position of the lower layer paddle 6 in the seed crystal reaction kettle 1, starting the stirrer 2 to continue coprecipitation reaction, and stopping the reaction until precursor particles grow to the target particle size D50. The stirring speed of the stirrer 2 is 350-400 rpm.
And aging the precursor particles to obtain a spherical precursor, and carrying out centrifugation, washing, drying, magnetic foreign matter removal and other treatments to obtain the high-tap-density ternary precursor material.
Claims (7)
1. The preparation device of the high-tap ternary precursor material is characterized by comprising a seed crystal reaction kettle (1), a thickener (7) and a seed crystal tank (8), wherein the seed crystal reaction kettle (1) is connected with the thickener (7) through a pipeline provided with a valve; install agitator (2) in seed crystal reation kettle (1), draft tube (3) are installed to the inside wall of seed crystal reation kettle (1), and baffle (5) are installed to the lateral wall of seed crystal reation kettle (1).
2. The apparatus for preparing high tap density ternary precursor material according to claim 1, wherein the stirrer (2) is provided with a stirring paddle (4), the stirring paddle (4) comprises an upper layer paddle (9) and a lower layer paddle (6), the upper layer paddle (9) is arranged in the middle of the stirrer (2), and the guide cylinder (3) is arranged around the upper layer paddle (9); the lower paddle (6) is arranged at the lower part of the stirrer (2).
3. The apparatus for preparing a ternary precursor material with high tap density according to claim 2, wherein the upper layer blade (9) is one of a flap-open type blade and a disc turbine type blade, the blade inclination angle of the upper layer blade (9) is 45-75 °, the stirring diameter is 0.5-0.8 times the inner diameter of the guide cylinder (3), and the inner diameter of the guide cylinder (3) is 0.5-0.7 times the inner diameter of the seed crystal reaction kettle (1).
4. The apparatus for preparing high tap density ternary precursor material according to claim 1, wherein the pipeline-mounted valve connected between the seed reaction kettle (1) and the seed tank (8) is located on the pipeline between the thickener (7) and the seed tank (8).
5. A method for preparing a high tap ternary precursor material based on any of claims 1-4, comprising the steps of:
step (I): preparing a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate; the molar ratio of nickel ions, cobalt ions and manganese ions in the mixed salt solution is x: y (100-x-y), wherein x is more than or equal to 60 and less than or equal to 98, y is more than or equal to 0 and less than or equal to 20, and the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the mixed salt solution is 1-3 mol/L;
step (II): preparing a base solution in a seed crystal reaction kettle, and introducing protective gas into the seed crystal reaction kettle; the base solution comprises industrial liquid alkali and ammonia water, the pH value of the base solution is 11-12.5, the concentration of the ammonia water in the base solution is 5-20 g/L, and the temperature of the base solution is 40-60 ℃;
step (three): adding the mixed salt solution into the upper layer blade height position in a seed crystal reaction kettle at the flow rate of 300-600L/h, the industrial liquid caustic soda with the concentration of 8-12 mol/L at the flow rate of 60-120L/h and the ammonia water with the concentration of 0.5-2 mol/L at the flow rate of 20-50L/h for coprecipitation reaction, and starting a stirrer; extracting supernatant from the materials in the seed crystal reaction kettle through a thickener, returning the materials in the thickener to the seed crystal reaction kettle, and continuously overflowing the materials in the seed crystal reaction kettle to a seed crystal tank when the particle size of the material particles in the seed crystal reaction kettle reaches 0.3-0.6 times of the target particle size;
step (IV): introducing the seed crystal material in the seed crystal groove into a seed crystal reaction kettle, wherein the seed crystal material introduced into the seed crystal reaction kettle is 1/5-1/2 of the volume of the seed crystal reaction kettle; adding the mixed salt solution into the lower paddle height in a seed crystal reaction kettle at the flow rate of 200-400L/h and the industrial liquid caustic soda with the concentration of 8-12 mol/L at the flow rate of 40-100L/h and the ammonia water with the concentration of 0.5-2 mol/L at the flow rate of 10-40L/h, starting a stirrer to continue coprecipitation reaction, and stopping the reaction after precursor particles with target particle size are obtained;
step (V): and (3) sequentially carrying out aging, centrifuging, washing, drying and magnetic foreign matter removal treatment on the precursor particles to obtain the high-tap-density ternary precursor material.
6. The method for preparing a high tap density ternary precursor material as claimed in claim 5, wherein the process conditions of the coprecipitation reaction in step (III) are as follows: the reaction temperature is 40-60 ℃, the pH is 10-11, and the concentration of ammonia water is 5-10 g/L; the stirring speed of the stirrer is 200rpm-600 rpm.
7. The method for preparing a high tap density ternary precursor material according to claim 5, wherein the stirring speed of the stirrer in the step (IV) is 200rpm to 500 rpm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111027376.8A CN113896251A (en) | 2021-09-02 | 2021-09-02 | Preparation device and preparation method of high-tap-density ternary precursor material |
| PCT/CN2022/110992 WO2023029897A1 (en) | 2021-09-02 | 2022-08-09 | Preparation method and preparation apparatus for high tap density ternary precursor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111027376.8A CN113896251A (en) | 2021-09-02 | 2021-09-02 | Preparation device and preparation method of high-tap-density ternary precursor material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113896251A true CN113896251A (en) | 2022-01-07 |
Family
ID=79188465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111027376.8A Pending CN113896251A (en) | 2021-09-02 | 2021-09-02 | Preparation device and preparation method of high-tap-density ternary precursor material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113896251A (en) |
| WO (1) | WO2023029897A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733463A (en) * | 2022-04-18 | 2022-07-12 | 成都思达能环保设备有限公司 | Positive electrode material precursor coprecipitation reaction equipment |
| WO2023029897A1 (en) * | 2021-09-02 | 2023-03-09 | 荆门市格林美新材料有限公司 | Preparation method and preparation apparatus for high tap density ternary precursor material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172892A (en) * | 2017-11-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | Multistage continuity method synthesis size distribution is concentrated, the preparation method of multiple types presoma |
| CN108807968A (en) * | 2018-08-09 | 2018-11-13 | 中国恩菲工程技术有限公司 | Nickel-cobalt-manganese ternary persursor material and its synthetic method |
| CN112174226A (en) * | 2020-09-29 | 2021-01-05 | 荆门市格林美新材料有限公司 | Method for continuously preparing nickel-cobalt-manganese ternary precursor with ultrahigh metal yield |
| CN112169732A (en) * | 2020-08-27 | 2021-01-05 | 荆门市格林美新材料有限公司 | Preparation equipment and method of doped ternary precursor material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7031535B2 (en) * | 2018-09-03 | 2022-03-08 | 住友金属鉱山株式会社 | Method for producing nickel-containing hydroxide |
| CN112582605B (en) * | 2020-11-27 | 2022-11-04 | 万华化学(四川)有限公司 | Preparation method of nickel-cobalt-manganese ternary precursor for reducing sulfur content in continuous production process |
| CN113896251A (en) * | 2021-09-02 | 2022-01-07 | 荆门市格林美新材料有限公司 | Preparation device and preparation method of high-tap-density ternary precursor material |
-
2021
- 2021-09-02 CN CN202111027376.8A patent/CN113896251A/en active Pending
-
2022
- 2022-08-09 WO PCT/CN2022/110992 patent/WO2023029897A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172892A (en) * | 2017-11-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | Multistage continuity method synthesis size distribution is concentrated, the preparation method of multiple types presoma |
| CN108807968A (en) * | 2018-08-09 | 2018-11-13 | 中国恩菲工程技术有限公司 | Nickel-cobalt-manganese ternary persursor material and its synthetic method |
| CN112169732A (en) * | 2020-08-27 | 2021-01-05 | 荆门市格林美新材料有限公司 | Preparation equipment and method of doped ternary precursor material |
| CN112174226A (en) * | 2020-09-29 | 2021-01-05 | 荆门市格林美新材料有限公司 | Method for continuously preparing nickel-cobalt-manganese ternary precursor with ultrahigh metal yield |
Non-Patent Citations (2)
| Title |
|---|
| 孙逢春 等主编: "《电动汽车工程手册 第4卷（动力蓄电池）》", vol. 1, 机械工业出版社, pages: 57 * |
| 廖折军 等: "浓密机在前躯体合成中的应用", vol. 47, no. 19, pages 33 - 34 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023029897A1 (en) * | 2021-09-02 | 2023-03-09 | 荆门市格林美新材料有限公司 | Preparation method and preparation apparatus for high tap density ternary precursor material |
| CN114733463A (en) * | 2022-04-18 | 2022-07-12 | 成都思达能环保设备有限公司 | Positive electrode material precursor coprecipitation reaction equipment |
| CN114733463B (en) * | 2022-04-18 | 2024-04-12 | 成都思达能环保设备有限公司 | Positive electrode material precursor coprecipitation reaction equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023029897A1 (en) | 2023-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113896251A (en) | Preparation device and preparation method of high-tap-density ternary precursor material | |
| CN106745331B (en) | A kind of preparation method of low-sulfur small particle nickel cobalt manganese hydroxide | |
| CN110048118B (en) | High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material | |
| CN107265520B (en) | A kind of preparation method and product of spherical nickel cobalt manganese persursor material | |
| CN101229928B (en) | Method for preparing spherical nickel-cobalt lithium manganate material | |
| CN112777647B (en) | High-nickel hydroxide with narrow particle size distribution and preparation method thereof | |
| CN104269548B (en) | A kind of method optimizing size distribution in nickel cobalt manganese persursor material preparation process | |
| CN109422297B (en) | Method for regulating and controlling nucleation in crystallization process of nickel-cobalt-manganese precursor | |
| CN113373517B (en) | High-nickel single crystal small-particle ternary precursor and continuous preparation method thereof | |
| CN110875472A (en) | Preparation method of micro-nano positive electrode material of lithium battery | |
| CN105047900A (en) | Preparation method and equipment of nano-flake nickel lithium manganate material | |
| CN104649336B (en) | A kind of preparation method of spherical nickel-cobalt aluminium hydroxide presoma | |
| CN108987682B (en) | Preparation method of nickel-rich precursor material capable of preventing particle fracture | |
| CN114014375B (en) | High-nickel quaternary precursor and preparation method thereof | |
| CN104934591A (en) | High-volume-energy-density spherical Li-rich cathode material and preparing method of high-volume-energy-density spherical Li-rich cathode material | |
| CN111072075A (en) | Preparation method of lithium ion battery anode material | |
| CN107658460A (en) | A kind of preparation method of modified nickel-cobalt-manganese multi material | |
| CN110294498B (en) | Intelligent control reaction system for preparing ternary material precursor and preparation method | |
| CN110550668A (en) | Process preparation method of power type single crystal NCM622 type precursor concentrator | |
| CN107565124A (en) | A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof | |
| CN111153445B (en) | Nickel-cobalt-manganese ternary precursor with stable granularity and preparation method and preparation device thereof | |
| CN112479266A (en) | Preparation method of spherical NCM811 cathode material with large-particle stacking structure on surface | |
| CN101062792A (en) | Preparation method of spherical nickel hydroxid | |
| CN114150378B (en) | High-spherical ternary precursor and preparation method thereof | |
| CN211998850U (en) | Nickel-cobalt-manganese ternary precursor preparation device with stable particle size |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220107 |