CN112194203A - Preparation method of nickel-cobalt oxide material - Google Patents
Preparation method of nickel-cobalt oxide material Download PDFInfo
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- CN112194203A CN112194203A CN202011180990.3A CN202011180990A CN112194203A CN 112194203 A CN112194203 A CN 112194203A CN 202011180990 A CN202011180990 A CN 202011180990A CN 112194203 A CN112194203 A CN 112194203A
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- 239000000463 material Substances 0.000 title claims abstract description 52
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 99
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 58
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 208000005156 Dehydration Diseases 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910016985 Ni0.85Co0.15O Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical class [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention discloses a preparation method of a nickel-cobalt oxide material, which comprises the steps of simultaneously introducing prepared nickel sulfate and cobalt sulfate mixed solution, sodium hydroxide solution and ammonia water into a reactor for synthetic reaction; adjusting the stirring speed in three stages, shunting the material to three grading tanks, washing, carrying out solid-liquid separation, drying and calcining to obtain the chemical formula of NixCo1‑xO nickel cobalt oxide material, and the material in the grading tank is recycled as seed crystal. The invention forms a multilevel layered structure inside the particles by regulating and controlling the process of the nickel-cobalt oxide material synthesis process.
Description
Technical Field
The invention relates to the field of inorganic chemistry, in particular to a preparation method of a high nickel-cobalt oxide material with a layered structure.
Background
The coprecipitation method is a commonly used method in mass production of precursors of lithium ion battery materials. In the production process, the nickel-cobalt (or nickel-cobalt-manganese) salt solution prepared according to a certain proportion, sodium hydroxide and ammonia water are commonly introduced into a reactor for precipitation reaction. The resulting hydroxide precursor is generally spheroidal.
With the increasing social requirements for the performance of lithium ion batteries, the production technology of lithium ion battery precursors is facing innovation. Because the too compact precursor is not beneficial to uniform doping of lithium, microcracks are easy to generate due to large internal stress in charge-discharge cycles, and the energy density is low due to the too loose precursor, a layered precursor with a tight inside and a loose outside is required to be constructed in order to improve the cycle performance of the battery precursor. The existing production method is relatively single in process, so that the prepared precursor cannot form the layered structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a high nickel cobalt oxide material with a layered structure.
The invention is realized by the following technical scheme.
A method of preparing a nickel cobalt oxide material, the method comprising the steps of:
(1) preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.85-0.98, wherein the concentration of the mixed solution is 80-120 g/L; simultaneously introducing the mixed solution, a sodium hydroxide solution and ammonia water into a reactor containing a base solution to carry out a synthesis reaction;
(2) the reactor keeps the first stirring speed at 300-400 rpm, simultaneously continuously shunts materials in the reactor to the first grading tank, and stops shunting to the first grading tank when the particle size D50 of solid particles generated by the synthesis reaction reaches 5-5.5 um;
(3) adjusting the reactor to a second stirring speed of 180-300 rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of the solid particles reaches 8-8.5 um;
(4) keeping the second stirring speed of the reactor, continuously shunting the material in the reactor obtained in the step (3) to a third grading tank, and stopping shunting to the third grading tank when the particle size D50 of the solid particles reaches 11-11.5 um;
(5) adjusting the reactor to a third stirring speed of 100-180 rpm, and stopping the reaction when the particle size of the solid particles in the reactor obtained in the step (4) is 14-20 um;
(6) washing, solid-liquid separation, drying and calcining the solid particles obtained in the step (5) to obtain Ni with a chemical formulaxCo1-xO, wherein x is 0.85-0.98.
And (3) further, materials in the first grading tank, the second grading tank and the third grading tank are respectively used as base solutions to be recycled, and the reaction steps are the same as the steps (1) to (6).
Further, the flow rate of the mixed solution in the step (1) is 200-400L/h, the flow rate of the sodium hydroxide solution is 70-130L/h, the flow rate of the ammonia water is 20-60L/h, and the reaction temperature is 30-80 ℃.
Further, the mass fraction of the sodium hydroxide solution in the step (1) is 20-40%, and the mass fraction of the ammonia water is 12-20%.
Further, the base solution in the step (1) is prepared by sodium hydroxide solution and ammonia water, the pH of the base solution is 10-12, and the ammonia concentration is 5-10 g/L.
Further, the total volume of the base solution is 2m3-5 m3。
Further, in the step (6), 1-4 times of washing with sodium hydroxide solution with the mass fraction of 1% -5% are carried out for 10-40 min each time, and then 2-5 times of washing with pure water with the temperature of 50-100 ℃ are carried out for 10-40 min each time.
Further, the drying temperature of the step (6) is 100-150 ℃.
Further, the calcining temperature in the step (6) is 400-600 ℃, and the calcining time is 4-10 h.
The method has the beneficial technical effects that a multi-stage layered structure is formed inside the particles by regulating and controlling the process of the nickel-cobalt oxide material synthesis process, so that the cycle performance of the battery precursor is improved.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Fig. 2 is an SEM image of the nickel cobalt oxide material obtained by the present invention.
FIG. 3 is a SEM image of the cross section of the Ni-Co oxide material obtained by the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, a method for preparing a nickel-cobalt oxide material includes the steps of:
a method of preparing a nickel cobalt oxide material, the method comprising the steps of:
(1) preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.85-0.98, wherein the concentration of the mixed solution is 80-120 g/L; simultaneously introducing the mixed solution, a sodium hydroxide solution and ammonia water into a reactor containing a base solution to carry out a synthesis reaction; the reactor kettle type reactor is respectively connected with the first grading tank, the second grading tank and the third grading tank through pipelines, and control valves are arranged on the pipelines; the flow rate of the mixed solution is 200-400L/h, the flow rate of the sodium hydroxide solution is 70-130L/h, the flow rate of the ammonia water is 20-60L/h, and the reaction temperature is 30-80 ℃; the mass fraction of the sodium hydroxide solution is 20-40%, and the mass fraction of the ammonia water is 12-20%; the base solution is prepared from sodium hydroxide solution and ammonia water, the pH of the base solution is 10-12, the ammonia concentration is 5-10g/L, and the total volume of the base solution is 2m3-5 m3。
(2) The reactor keeps a first stirring speed of 300-400 rpm, simultaneously materials (which refer to all reaction products in the reactor) in the reactor are continuously shunted to the first grading tank, and when the particle size D50 of solid particles generated by the synthesis reaction reaches 5-5.5 um, shunting to the first grading tank is stopped;
(3) adjusting the reactor to a second stirring speed of 180-300 rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of the solid particles reaches 8-8.5 um;
(4) keeping the second stirring speed of the reactor, continuously shunting the material in the reactor obtained in the step (3) to a third grading tank, and stopping shunting to the third grading tank when the particle size D50 of the solid particles reaches 11-11.5 um;
(5) adjusting the reactor to a third stirring speed of 100-180 rpm, and stopping the reaction when the particle size of the solid particles in the reactor obtained in the step (4) is 14-20 um;
(6) washing the solid particles obtained in the step (5) with sodium hydroxide solution with the mass fraction of 1% -5% for 1-4 times and 10min-40min for each time, then washing with pure water with the temperature of 50 ℃ -100 ℃ for 2-5 times and 10min-40min for each time, then carrying out solid-liquid separation, drying and calcining to obtain Ni with the chemical formulaxCo1-xA nickel cobalt oxide material of O (wherein x is 0.85-0.98); wherein, the drying equipment is used for drying after the preliminary dehydration of the dehydration equipment, the drying temperature is 100 ℃ to 150 ℃, and the calcination is finally carried out in the calcination equipment, the calcination temperature is 400 ℃ to 600 ℃, and the calcination time is 4h to 10 h.
(7) And (4) respectively taking the materials in the first grading tank, the second grading tank and the third grading tank as base solutions for recycling, wherein the reaction steps are the same as the steps (1) to (6).
Example 1
A preparation method of a nickel-cobalt oxide material comprises the following steps:
(1) preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.85, wherein the concentration of the mixed solution is 80 g/L; simultaneously introducing the mixed solution, sodium hydroxide solution and ammonia water into the reactor for 6m3Carrying out synthetic reaction in a reactor containing a base solution; wherein the mass fraction of the sodium hydroxide solution is 40%, the mass fraction of the ammonia water is 12%, the flow rate of the mixed solution is 200L/h, the flow rate of the sodium hydroxide solution is 130L/h, the flow rate of the ammonia water is 40L/h, and the reaction temperature is 80 ℃; the pH of the base solution is 10, the ammonia concentration is 10g/L, and the total volume of the base solution is 5m3；
(2) Keeping the first stirring speed of the reactor at 400rpm, continuously shunting the materials in the reactor to a first grading tank, stopping shunting to the first grading tank when the particle size D50 of solid particles generated by the synthesis reaction reaches 5.5 um;
(3) adjusting the reactor to a second stirring speed of 300rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of the solid particles reaches 8.5 um;
(4) keeping the second stirring speed of the reactor, continuously shunting the material in the reactor obtained in the step (3) to a third grading tank, stopping shunting the material to the third grading tank when the particle size D50 of the solid particles reaches 11.5 um;
(5) adjusting the reactor to a third stirring speed of 180rpm, and stopping the reaction when the particle size of the solid particles in the reactor obtained in the step (4) is 20 um;
(6) washing the solid particles obtained in the step (5) by using washing equipment with a solid-liquid separation function, and carrying out solid-liquid separation: washing with 5% sodium hydroxide solution for 2 times (each for 40 min), and washing with 80 deg.C pure water for 4 times (each for 30 min); drying the mixture by using drying equipment after primary dehydration by using dehydration equipment, wherein the drying temperature is 120 ℃; finally calcining in calcining equipment at the calcining temperature of 500 ℃ for 8h to obtain the chemical formula of Ni0.85Co0.15O nickel cobalt oxide material.
(7) Adding the materials in the first, second and third grading tanks as base liquid into new 6m3The reaction steps are the same as those in (1) to (6).
Example 2
(1) Preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.9, wherein the concentration of the mixed solution is 100 g/L; simultaneously introducing the mixed solution, sodium hydroxide solution and ammonia water into the reactor for 6m3Carrying out a synthesis reaction in a first reactor containing a base solution; wherein the mass fraction of the sodium hydroxide solution is 20 percent, and the mass fraction of the ammonia water is 16 percent. The flow rate of the mixed solution is 300L/h, the flow rate of the sodium hydroxide solution is 100L/h, the flow rate of the ammonia water is 30L/h, and the reaction temperature is60 ℃; the pH of the base solution is 11, the ammonia concentration is 7g/L, and the total volume of the base solution is 4m3；
(2) The first reactor keeps the first stirring speed at 370rpm, simultaneously the materials in the first reactor are continuously shunted to the first grading tank, the particle size D50 of the solid particles generated by the synthesis reaction reaches 5.4um, and the shunting to the first grading tank is stopped;
(3) adjusting the first reactor to a second stirring speed of 260rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, stopping shunting to the second grading tank when the particle size D50 of solid particles reaches 8.4 um;
(4) keeping the second stirring speed of the first reactor, continuously shunting the material in the first reactor obtained in the step (3) to a third grading tank, stopping shunting to the third grading tank when the particle size D50 of solid particles reaches 11.3 um;
(5) adjusting the first reactor to a third stirring speed of 150rpm, and stopping the reaction when the particle size of the solid particles in the first reactor obtained in the step (4) is 18 um;
(6) washing the solid particles obtained in the step (5) by using washing equipment with a solid-liquid separation function, and carrying out solid-liquid separation: washing with 3% sodium hydroxide solution for 3 times (30 min each time), and washing with 100 deg.C pure water for 5 times (13 min each time); drying the mixture by using drying equipment after primary dehydration by using dehydration equipment, wherein the drying temperature is 120 ℃; finally calcining in calcining equipment at 400 ℃ for 4h to obtain the chemical formula of Ni0.9Co0.1O nickel cobalt oxide material.
(7) Adding the materials in the first, second and third grading tanks as base liquid into new 4m3The reaction steps are the same as those in (1) to (6).
Example 3
(1) Preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.94, wherein the concentration of the mixed solution is 110 g/L; simultaneously introducing the mixed solution, sodium hydroxide solution and ammonia water into the reactor for 6m3Carrying out a synthesis reaction in a first reactor containing a base solution; wherein the sodium hydroxide solutionThe mass fraction of the ammonia water is 30 percent, and the mass fraction of the ammonia water is 20 percent. The flow rate of the mixed solution is 350L/h, the flow rate of the sodium hydroxide solution is 70L/h, the flow rate of ammonia water is 60L/h, and the reaction temperature is 30 ℃; the pH of the base solution is 12, the ammonia concentration is 5g/L, and the total volume of the base solution is 2m3；
(2) The first reactor keeps the first stirring speed at 340rpm, simultaneously, the materials in the first reactor are continuously shunted to the first grading tank, the particle size D50 of solid particles generated by the synthesis reaction reaches 5.2um, and the shunting to the first grading tank is stopped;
(3) adjusting the first reactor to a second stirring speed of 220rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of solid particles reaches 8 um;
(4) keeping the second stirring speed of the first reactor, continuously shunting the material in the first reactor obtained in the step (3) to a third grading tank, stopping shunting to the third grading tank when the particle size D50 of solid particles reaches 11.1 um;
(5) adjusting the first reactor to a third stirring speed of 100rpm, and stopping the reaction when the particle size of the solid particles in the first reactor obtained in the step (4) is 16 um;
(6) washing the solid particles obtained in the step (5) by using washing equipment with a solid-liquid separation function, and carrying out solid-liquid separation: washing with 1% sodium hydroxide solution for 20min for 4 times, and washing with 60 deg.C pure water for 40min for 2 times; drying the mixture by using drying equipment after primary dehydration by using dehydration equipment, wherein the drying temperature is 100 ℃; finally calcining in calcining equipment at 600 ℃ for 10h to obtain the chemical formula of Ni0.94Co0.06O nickel cobalt oxide material.
(7) Adding the materials in the first, second and third grading tanks as base liquid into new 2m3The reaction steps are the same as those in (1) to (6).
Example 4
(1) Preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.98, wherein the concentration of the mixed solution is 120 g/L;simultaneously introducing the mixed solution, sodium hydroxide solution and ammonia water into the reactor for 6m3Carrying out a synthesis reaction in a first reactor containing a base solution; wherein the mass fraction of the sodium hydroxide solution is 40 percent, and the mass fraction of the ammonia water is 18 percent. The flow rate of the mixed solution is 400L/h, the flow rate of the sodium hydroxide solution is 110L/h, the flow rate of ammonia water is 20L/h, and the reaction temperature is 70 ℃; the pH of the base solution is 12, the ammonia concentration is 8g/L, and the total volume of the base solution is 3m3；
(2) The first reactor keeps the first stirring speed at 300rpm, simultaneously, the materials in the first reactor are continuously shunted to the first grading tank, the particle size D50 of solid particles generated by the synthesis reaction reaches 5um, and the shunting to the first grading tank is stopped;
(3) adjusting the first reactor to a second stirring speed of 180rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of solid particles reaches 8.1 um;
(4) keeping the second stirring speed of the first reactor, continuously shunting the material in the first reactor obtained in the step (3) to a third grading tank, stopping shunting to the third grading tank when the particle size D50 of solid particles reaches 11 um;
(5) adjusting the first reactor to a third stirring speed of 120rpm, wherein the particle size of the solid particles in the first reactor obtained in the step (4) is 14um, and stopping the reaction;
(6) and (3) washing the solid particles obtained in the step (5) by using washing equipment with a solid-liquid separation function, and performing solid-liquid separation: washing with 4% sodium hydroxide solution for 10min for 1 time, and washing with 50 deg.C pure water for 25min for 3 times; drying the mixture by using drying equipment after primary dehydration by using dehydration equipment, wherein the drying temperature is 140 ℃; finally calcining in calcining equipment at 550 ℃ for 6h to obtain the chemical formula of Ni0.98Co0.02O nickel cobalt oxide material.
(7) Adding the materials in the first, second and third grading tanks as base liquid into new 6m3The reaction steps are the same as those in (1) to (6).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (9)
1. A method of preparing a nickel cobalt oxide material, the method comprising the steps of:
(1) preparing a mixed solution of nickel sulfate and cobalt sulfate according to the molar ratio of Ni (Ni + Co) of 0.85-0.98, wherein the concentration of the mixed solution is 80-120 g/L; simultaneously introducing the mixed solution, a sodium hydroxide solution and ammonia water into a reactor containing a base solution to carry out a synthesis reaction;
(2) the reactor keeps the first stirring speed at 300-400 rpm, simultaneously continuously shunts materials in the reactor to the first grading tank, and stops shunting to the first grading tank when the particle size D50 of solid particles generated by the synthesis reaction reaches 5-5.5 um;
(3) adjusting the reactor to a second stirring speed of 180-300 rpm, continuously shunting the material in the reactor obtained in the step (2) to a second grading tank, and stopping shunting to the second grading tank when the particle size D50 of the solid particles reaches 8-8.5 um;
(4) keeping the second stirring speed of the reactor, continuously shunting the material in the reactor obtained in the step (3) to a third grading tank, and stopping shunting to the third grading tank when the particle size D50 of the solid particles reaches 11-11.5 um;
(5) adjusting the reactor to a third stirring speed of 100-180 rpm, and stopping the reaction when the particle size of the solid particles in the reactor obtained in the step (4) is 14-20 um;
(6) washing, solid-liquid separation, drying and calcining the solid particles obtained in the step (5) to obtain Ni with a chemical formulaxCo1-xO, wherein x is 0.85-0.98.
2. The method according to claim 1, wherein the materials in the first classifying trough, the second classifying trough and the third classifying trough are respectively recycled as base solutions, and the reaction steps are the same as the steps (1) to (6).
3. The method according to any one of claims 1 to 2, wherein the flow rate of the mixed solution in the step (1) is 200 to 400L/h, the flow rate of the sodium hydroxide solution is 70 to 130L/h, the flow rate of the ammonia water is 20 to 60L/h, and the reaction temperature is 30 ℃ to 80 ℃.
4. The method according to any one of claims 1 to 2, wherein the sodium hydroxide solution in the step (1) has a mass fraction of 20 to 40% and the aqueous ammonia has a mass fraction of 12 to 20%.
5. The method according to any one of claims 1 to 2, wherein the base solution in step (1) is prepared from a sodium hydroxide solution and ammonia water, the base solution has a pH of 10 to 12, and the ammonia concentration is 5 to 10 g/L.
6. The method of claim 5, wherein the total volume of the base solution is 2m3-5m3。
7. The method according to any one of claims 1 to 2, wherein the step (6) is carried out by washing with 1 to 5 mass percent sodium hydroxide solution for 1 to 4 times, 10 to 40min each time, and then washing with 50 to 100 ℃ pure water for 2 to 5 times, 10 to 40min each time.
8. The method according to any one of claims 1 to 2, wherein the drying temperature in step (6) is 100 ℃ to 150 ℃.
9. The method as claimed in any one of claims 1 to 2, wherein the calcination temperature in step (6) is 400 ℃ to 600 ℃ and the calcination time is 4h to 10 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011180990.3A CN112194203A (en) | 2020-10-29 | 2020-10-29 | Preparation method of nickel-cobalt oxide material |
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| CN114261997A (en) * | 2021-12-28 | 2022-04-01 | 广西中伟新能源科技有限公司 | Nickel-cobalt hydroxide and preparation method thereof, nickel-cobalt oxide, lithium ion battery positive electrode material, positive electrode, battery and electric equipment |
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