CN113130886A - Preparation method and application of superfine high-nickel ternary precursor - Google Patents
Preparation method and application of superfine high-nickel ternary precursor Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002243 precursor Substances 0.000 title claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 42
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002585 base Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 238000012544 monitoring process Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 claims 4
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 claims 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010405 anode material Substances 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000011437 continuous method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a superfine high-nickel ternary precursor, which comprises the following steps: 1) and (2) simultaneously adding the ternary metal salt solution, the liquid alkali solution and the ammonia water solution in parallel into a reaction kettle containing the base solution, carrying out coprecipitation reaction at a stirring speed of 300-400 r/min, controlling the pH of a reaction system to be 11.0-12.0 and the ammonia concentration to be 4-8 g/L in the reaction process, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 1.5-3.0 mu m, and continuing to react until the materials are completely reacted to obtain the superfine high-nickel ternary precursor. The superfine high-nickel ternary precursor obtained by the method has good shape consistency, especially the superfine sphericity, primary crystal grains and large particles can be kept consistent, the process is simple, the process parameters are easy to control, and the precision is high.
Description
Technical Field
The invention belongs to the technical field of preparation of ternary precursors, and particularly relates to a preparation method and application of a superfine high-nickel ternary precursor.
Background
In the continuous production of the ternary precursor, when the granularity is close to the target granularity, the technological parameters such as addition and subtraction ternary flow, liquid caustic soda flow, ammonia water flow, rotating speed, temperature and the like are usually adopted in a reaction system, so that the reaction system in a growth state generates fluctuation through the change of the technological parameters, and new crystal nuclei and new small particles are generated; in addition, by means of growing and overflowing at the same time, continuous reaction and continuous discharge are realized, and the stable production is good; however, in order to maintain the particle size distribution, the conventional continuous method usually needs to generate small particles by adjusting various process parameters in the reaction process, and the small particles generated by adjusting the parameters generally have a rough morphology, poor sphericity, difficult particle size control and poor index stability.
Disclosure of Invention
In view of the above, the application provides a method for preparing a superfine high-nickel ternary precursor, which solves the problems of inaccurate particle size distribution control and inconsistent particle morphology caused by maintaining particle size distribution by generating small particles by adjusting process parameters in the conventional continuous method.
The invention also aims to provide the application of the superfine high-nickel ternary precursor prepared by the preparation method of the superfine high-nickel ternary precursor in the preparation of the high-nickel ternary precursor by a continuous method.
The third purpose of the invention is to provide the application of the superfine high-nickel ternary precursor prepared by the preparation method of the high-nickel ternary precursor in the anode material of the lithium ion battery.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: a preparation method of an ultrafine high-nickel ternary precursor comprises the following steps:
and (2) simultaneously adding the ternary metal salt solution, the liquid alkali solution and the ammonia water solution in parallel into a reaction kettle containing the base solution, carrying out coprecipitation reaction at a stirring speed of 200-400 r/min, controlling the pH of a reaction system to be 11.0-12.0 and the ammonia concentration to be 4-8 g/L in the reaction process, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 1.5-3.0 mu m, and continuing to react until the materials are completely reacted to obtain the superfine high-nickel ternary precursor.
Preferably, the concentration of ammonia water in the base solution is 4-8 g/L, the temperature of the base solution is 40-60 ℃, and the pH value of the base solution is 11.0-12.0.
Preferably, the feeding speed of the ternary metal salt solution is 100-300L/h.
Preferably, the feeding speed of the liquid caustic soda solution is 50-100L// h.
Preferably, the feeding speed of the ammonia water is 10-30L/h.
Preferably, the ternary metal salt solution is a nickel-cobalt-manganese ternary mixed salt solution, and the concentration of the nickel-cobalt-manganese ternary mixed salt solution is 80-120 g/L.
Preferably, the mass concentration of the liquid caustic soda in the liquid caustic soda solution is 28-32%, and the mass concentration of the ammonia water in the ammonia water solution is 10-20%.
Preferably, the content of nickel in the obtained superfine high-nickel ternary precursor is 80-85 mol%.
Preferably, the nickel-cobalt-manganese ternary mixed salt is dissolved in at least one of a nickel-cobalt-manganese ternary mixed sulfuric acid solution, a nickel-cobalt-manganese ternary mixed hydrochloric acid solution and a nickel-cobalt-manganese ternary mixed nitric acid solution.
The other technical scheme of the invention is realized as follows: the high-nickel ternary precursor prepared by the preparation method of the high-nickel ternary precursor is applied to the anode material of the lithium ion battery.
Compared with the prior art, the single crystal superfine high-nickel ternary precursor synthesized under the conditions of high pH and high stirring speed is 1.5-3.0, the morphology consistency is good, the sphericity is good, the process is simple, the process parameters are easy to control, and the accuracy is high.
Drawings
FIG. 1 is an SEM image of an ultrafine high-nickel ternary precursor obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a ternary precursor obtained in comparative example 1 of the present invention;
FIG. 3 is an SEM image of a ternary precursor obtained in comparative example 2 of the present invention;
fig. 4 is an SEM image of the ternary precursor obtained in comparative example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The particle size of the particles in the process of generating the superfine high-nickel ternary precursor and the particle size of the finally obtained cobaltosic oxide particles are determined by adopting a laser particle size analyzer, and the chemical reagent used in the embodiment of the invention is obtained by a conventional commercial way if no special description is provided.
The embodiment of the invention provides a preparation method of a superfine high-nickel ternary precursor, which comprises the following steps:
simultaneously and concurrently adding a nickel-cobalt-manganese ternary mixed salt solution with the concentration of 80-120 g/L, a liquid caustic soda solution with the mass concentration of 28-32% and an ammonia water solution with the mass concentration of 10-20% into a reaction kettle containing a base solution with the temperature of 40-60 ℃, the ammonia water concentration of 4-8 g/L and the pH of 11.0-12.0 at the feeding speeds of 100-300L/h, 50-100L/h and 10-30L/h respectively, carrying out coprecipitation reaction at the stirring speed of 200-400 r/min, controlling the pH of the reaction system to be 11.0-12.0 in the reaction process, controlling the ammonia concentration to be 4-8 g/L and the temperature to be 40-60 ℃, continuously monitoring the particle size, collecting all particles by using a high-efficiency densifier in the reaction process before the particle size reaches the requirement, continuously reacting in the reaction kettle at any time, and collecting all the particles to return to the reaction kettle when the particle size D50 grows to be 1.5-3.0 mu m, stopping feeding, and continuing to react until the materials are completely reacted to obtain a superfine nickel-cobalt-manganese ternary precursor with the nickel content of 80-85 mol%; the nickel-cobalt-manganese ternary mixed salt solution is at least one of a nickel-cobalt-manganese ternary mixed sulfuric acid solution, a nickel-cobalt-manganese ternary mixed hydrochloric acid solution and a nickel-cobalt-manganese ternary mixed nitric acid solution.
The embodiment of the invention also provides application of the superfine high-nickel ternary precursor prepared by the preparation method of the superfine high-nickel ternary precursor in a lithium ion battery anode material.
After the scheme is adopted, the 1.5-3.0 single crystal superfine high-nickel ternary precursor is synthesized under the conditions of high pH and high stirring speed, the shape consistency is good, the sphericity is good, the process is simple, the process parameters are easy to control, and the accuracy is high
In order that the present invention may be better understood, reference will now be made to the following examples.
Example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, a liquid caustic soda solution with the mass concentration of 30 percent and an ammonia water solution with the mass concentration of 15 percent;
respectively adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, the liquid alkali solution with the mass concentration of 30% and the ammonia water solution with the mass concentration of 15% into a reaction kettle containing base liquid with the temperature of 50 ℃, the ammonia water concentration of 6g/L and the pH of 11.0-11.5 at the same time and in parallel at the feeding speed of 200L/h, 50L/h and 20L/h, carrying out coprecipitation reaction at the stirring speed of 300r/min, controlling the pH of the reaction system to be 11.0-11.5 and the ammonia concentration to be 6g/L in the reaction process, controlling the temperature to be 50 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 2.0 mu m, and continuously reacting until the materials are completely reacted to obtain the superfine nickel-cobalt-manganese ternary precursor.
The content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in example 1 was detected, and it can be seen that the content of nickel was 83 mol%.
Example 2
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 80g/L, a liquid caustic soda solution with the mass concentration of 28% and an ammonia water solution with the mass concentration of 10%;
and (2) simultaneously and concurrently adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 80mol/L, the liquid alkali solution with the mass concentration of 28% and the ammonia water solution with the mass concentration of 10% into a reaction kettle containing a base solution with the temperature of 40 ℃, the ammonia water concentration of 4g/L and the pH of 11.5-12.0 at the feeding speed of 100L/h, 50L/h and 10L/h respectively, carrying out coprecipitation reaction at the stirring speed of 300r/min, controlling the pH of the reaction system to be 11.5-12.0 and the ammonia concentration to be 4g/L in the reaction process, controlling the temperature to be 40 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 1.5 mu m, and continuously reacting until the materials are completely reacted to obtain the superfine nickel-cobalt-manganese ternary precursor with the nickel content of 80 mol%.
The content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in example 2 is detected, and the detected content of nickel is 80 mol%.
Example 3
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 120mol/L, a liquid caustic soda solution with the mass concentration of 32% and an ammonia water solution with the mass concentration of 20%;
respectively adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 120g/L, the liquid alkali solution with the mass concentration of 32% and the ammonia water solution with the mass concentration of 20% into a reaction kettle containing a base solution with the temperature of 60 ℃, the ammonia water concentration of 8g/L and the pH of 11.3-11.6 at the same time and in parallel at the feeding speed of 300L/h, 100L/h and 30L/h, carrying out coprecipitation reaction at the stirring speed of 350r/min, controlling the pH of the reaction system to be 11.3-11.6 and the ammonia concentration to be 8g/L in the reaction process, controlling the temperature to be 60 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 3.0 mu m, and continuously reacting until the materials are completely reacted to obtain the superfine nickel-cobalt-manganese ternary precursor with the nickel content of 85 mol%.
The content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in example 3 was detected, and it can be seen that the content of nickel was 85 mol%.
Comparative example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, a liquid caustic soda solution with the mass concentration of 30 percent and an ammonia water solution with the mass concentration of 15 percent;
respectively adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, the liquid alkali solution with the mass concentration of 30% and the ammonia water solution with the mass concentration of 15% into a reaction kettle containing base liquid with the temperature of 50 ℃, the ammonia water concentration of 6g/L and the pH of 11.0-11.5 at the same time and in parallel at the feeding speed of 200L/h, 50L/h and 20L/h, carrying out coprecipitation reaction at the stirring speed of 100r/min, controlling the pH of the reaction system to be 11.0-11.5 and the ammonia concentration to be 6g/L in the reaction process, controlling the temperature to be 50 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 2.0 mu m, and continuously reacting until the materials are completely reacted to obtain the nickel-cobalt-manganese ternary precursor.
And (3) detecting the content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in the comparative example 1, wherein the detected content of nickel is less than 80 mol%.
Comparative example 2
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, a liquid caustic soda solution with the mass concentration of 30 percent and an ammonia water solution with the mass concentration of 15 percent;
respectively adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, the liquid alkali solution with the mass concentration of 30% and the ammonia water solution with the mass concentration of 15% into a reaction kettle containing base liquid with the temperature of 50 ℃, the ammonia water concentration of 6g/L and the pH of 10.5-11.0 at the same time and in parallel at the feeding speeds of 200L/h, 50L/h and 20L/h, carrying out coprecipitation reaction at the stirring speed of 300r/min, controlling the pH of the reaction system to be 10.5-11.0 and the ammonia concentration to be 6g/L in the reaction process, controlling the temperature to be 50 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 2.0 mu m, and continuously reacting until the materials are completely reacted to obtain the nickel-cobalt-manganese ternary precursor.
And (3) detecting the content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in the comparative example 2, wherein the detected content of nickel is less than 80 mol%.
Comparative example 3
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed to prepare a nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, a liquid caustic soda solution with the mass concentration of 30 percent and an ammonia water solution with the mass concentration of 15 percent;
respectively adding the nickel-cobalt-manganese ternary mixed sulfuric acid solution with the concentration of 100mol/L, the liquid alkali solution with the mass concentration of 30% and the ammonia water solution with the mass concentration of 15% into a reaction kettle containing a base solution with the temperature of 50 ℃, the ammonia water concentration of 6g/L and the pH of 10.5-11.0 at the same time and in parallel at the feeding speeds of 200L/h, 50L/h and 20L/h, carrying out coprecipitation reaction at the stirring speed of 100r/min, controlling the pH of the reaction system to be 10.5-11.0 and the ammonia concentration to be 6g/L in the reaction process, controlling the temperature to be 50 ℃, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 2.0 mu m, and continuously reacting until the materials are completely reacted to obtain the nickel-cobalt-manganese ternary precursor.
And (3) detecting the content of nickel in the superfine nickel-cobalt-manganese ternary precursor obtained in the comparative example 3, wherein the detected content of nickel is less than 80 mol%.
Comparative example 1 is different from example 1 in the stirring speed during the coprecipitation reaction, and comparative example 2 is different from example 1 in the pH of the reaction system during the coprecipitation reaction; comparative example 3 is different from example 1 in that the stirring rate at the time of the coprecipitation reaction and the pH of the reaction system are different, and the reaction parameters in the above examples and comparative examples are specifically shown in Table 1:
table 1 reaction parameters of examples 1 to 3 and comparative examples 1 to 3
In order to verify whether the shapes of the particles of the ternary precursor prepared by the embodiment are consistent and whether the sphericity is good or not, the ternary precursors obtained in the embodiment 1 and the comparative example 1, the comparative example 2 and the comparative example 3 are taken as examples to be respectively subjected to electron microscope scanning detection, as shown in fig. 1, fig. 2, fig. 3 and fig. 4, it can be seen from fig. 1 that the shapes of the ultrafine ternary precursor particles obtained by the invention are consistent and the sphericity is good, while the shapes of the ultrafine ternary precursor particles obtained in the comparative example 1, the comparative example 2 and the comparative example 3 are poor and the sphericity is poor, and the ultrafine ternary precursor particles are relatively loose.
In addition, as can be seen from the SEM image of the ternary precursor obtained in example 1 compared with the SEM of the ultrafine ternary precursor obtained in the comparative example, on the premise of determining the respective concentrations, flow ratios, and base solution concentrations of the ternary metal salt solution, the precipitant solution, and the complexing agent, a high pH value and a high stirring rate are key factors for successfully preparing the ternary precursor having good morphology consistency and good sphericity.
In conclusion, the 1.5-3.0 monocrystalline superfine high-nickel ternary precursor synthesized under the conditions of high pH and high stirring speed has good shape consistency, good sphericity, simple process and simple and accurate control of process parameters.
Example 4
The embodiment discloses application of the superfine nickel-cobalt-manganese ternary precursor prepared in the embodiment 1 in a lithium ion battery anode material.
And (2) mixing the superfine nickel-cobalt-manganese ternary precursor prepared in the example 1 with a lithium source, placing the mixture in a muffle furnace, calcining the mixture at 800 ℃, and cooling to obtain the nickel-cobalt-manganese lithium positive electrode material.
The material is used as the anode material of the lithium ion battery, the metal lithium sheet is used as the cathode, the button cell is assembled for charge and discharge test, and the result is as follows: the charging and discharging voltage range is 3.1-4.8V, and after the cycle is carried out for 200 times at the multiplying power of 0.5C, the reversible capacity is 415mAh/g, which shows that the obtained battery still has better reversible capacity by taking the superfine nickel-cobalt-manganese ternary precursor as the raw material for preparing the lithium ion battery anode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an ultrafine high-nickel ternary precursor is characterized by comprising the following steps:
and (2) simultaneously adding the ternary metal salt solution, the liquid alkali solution and the ammonia water solution in parallel into a reaction kettle containing the base solution, carrying out coprecipitation reaction at a stirring speed of 200-400 r/min, controlling the pH of a reaction system to be 11.0-12.0 and the ammonia concentration to be 4-8 g/L in the reaction process, continuously monitoring the particle size, stopping feeding when the particle size D50 reaches 1.5-3.0 mu m, and continuing to react until the materials are completely reacted to obtain the superfine high-nickel ternary precursor.
2. The method for preparing the superfine high-nickel ternary precursor according to claim 1, wherein the concentration of ammonia water in the base solution is 4-8 g/L, the temperature of the base solution is 40-60 ℃, and the pH of the base solution is 11.0-12.0.
3. The preparation method of the superfine high-nickel ternary precursor as claimed in claim 2, wherein the feeding speed of the ternary metal salt solution is 100-300L/h.
4. The method for preparing the superfine high-nickel ternary precursor according to claim 3, wherein the feeding speed of the liquid caustic soda solution is 50-100L/h.
5. The method for preparing the superfine high-nickel ternary precursor according to claim 4, wherein the feeding speed of the ammonia water is 10-30L/h.
6. The method for preparing the superfine high-nickel ternary precursor according to claim 5, wherein the ternary metal salt solution is a nickel-cobalt-manganese ternary mixed salt solution, and the concentration of the nickel-cobalt-manganese ternary mixed salt solution is 80-120 g/L.
7. The method for preparing the superfine high-nickel ternary precursor according to claim 6, wherein the mass concentration of the liquid caustic soda in the liquid caustic soda solution is 28-32%, and the mass concentration of the ammonia water in the ammonia water solution is 10-20%.
8. The preparation method of the superfine high-nickel ternary precursor according to claim 6, wherein the content of nickel in the obtained superfine high-nickel ternary precursor is 80-85 mol%.
9. The method of claim 7, wherein the Ni-Co-Mn ternary mixed salt solution is at least one of a Ni-Co-Mn ternary mixed sulfuric acid solution, a Ni-Co-Mn ternary mixed hydrochloric acid solution, and a Ni-Co-Mn ternary mixed nitric acid solution.
10. The application of the high-nickel ternary precursor prepared by the preparation method of the high-nickel ternary precursor according to any one of claims 1 to 8 in the positive electrode material of the lithium ion battery.
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