CN113213552A - Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof - Google Patents
Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002243 precursor Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000011163 secondary particle Substances 0.000 claims abstract description 22
- -1 lithium transition metal Chemical class 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000011164 primary particle Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 156
- 239000000243 solution Substances 0.000 claims description 65
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 51
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000002585 base Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- 238000000975 co-precipitation Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 6
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 25
- 238000001035 drying Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 229910001437 manganese ion Inorganic materials 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 9
- 229940053662 nickel sulfate Drugs 0.000 description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 9
- 239000012716 precipitator Substances 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 8
- 239000012697 Mn precursor Substances 0.000 description 8
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 8
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 229910001429 cobalt ion Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910001453 nickel ion Inorganic materials 0.000 description 8
- 229910001428 transition metal ion Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a sphere-like porous nickel-cobalt-manganese precursor and a preparation method thereof, wherein the precursor is hydroxide of nickel, cobalt and manganese, and the molecular formula is NixCoyMn1‑x‑y(OH)2，0<x<1,0<y<1. The spherical-like porous nickel-cobalt-manganese precursor is in a hexagonal sheet shape, the thickness of the primary particles is 10 nm-100 nm, the side length of the primary particles is 10 nm-1 mu m, the particle size of the secondary particles is 3-20 mu m, and the pore diameter of the secondary particles is 2-10 nm. The sphere-like porous nickel-cobalt-manganese precursor prepared by the preparation process has regular shape and high tap density, and particularly the porous structure is favorable for high-temperature calcinationAnd the diffusion of lithium salt is promoted in the firing process, and the distribution uniformity of elements is improved. The lithium transition metal layered oxide anode material prepared by the spheroidal porous nickel-cobalt-manganese precursor provided by the invention has higher electrochemical capacity and excellent cycling stability.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a sphere-like porous nickel-cobalt-manganese precursor and a preparation method thereof.
Background
With the continuous development of economic society, the demand of human society for energy is more and more, but the traditional fossil energy is non-renewable resource, and the heavy use of the fossil energy also causes serious environmental problems. Therefore, in order to achieve sustainable development of human society, it is urgently needed to search clean renewable resources to provide inexhaustible power for development of human society. Lithium ion batteries are widely used in various electronic devices and electric vehicles due to their characteristics of high specific capacity, good cycling stability, high safety, etc., and are also used in large-scale applications in the fields of large-scale energy storage systems, etc. Therefore, the nickel-cobalt-manganese precursor material matched with the lithium ion battery of the power automobile is developed, and the nickel-cobalt-manganese precursor material has wide application prospect.
The hydroxide coprecipitation method is a method for preparing a large amount of precursors of the anode materials of the lithium ion batteries. The preparation of the precursor is a method that a transition metal salt mixed solution, an alkali liquor and a complexing agent are added into a reactor filled with a certain amount of base solution in a cocurrent manner, transition metal ions react with a precipitator to generate insoluble precipitates by adjusting the process conditions of stirring speed, complexing agent concentration, pH, feeding speed and the like, and the insoluble precipitates are filtered, washed and dried to obtain the nickel-cobalt-manganese precursor. The method can reduce the precipitation speed of the transition metal ions under the combined action of the precipitator and the complexing agent, so that the transition metal ions can be nucleated and grown together to prepare the precursor with the spheroidal morphology. Compared with the shapes of a rod, a tube, an irregular polyhedron and the like, the spherical precursor is a necessary trend for the development of the lithium ion battery anode material due to the advantages of good fluidity, dispersibility, vibration-like density and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a spherical-like porous nickel-cobalt-manganese precursor and a preparation method thereof. On one hand, the nickel-cobalt-manganese precursor provided by the invention has a sphere-like porous shape, high sphericity, regular shape and high vibration-like density, and the porous structure is favorable for promoting the diffusion of lithium salt in the high-temperature calcination process and improving the distribution uniformity of elements; on the other hand, the primary particles of the sphere-like porous nickel-cobalt-manganese precursor provided by the invention are hexagonal sheets, so that the preferential growth of a crystal face with high electrochemical activity (010) can be effectively promoted, the diffusion of lithium ions is promoted, and the rate capability of the lithium transition metal oxide layered anode material is remarkably improved. The sphere-like nickel-cobalt-manganese precursor provided by the invention is applied to a high-nickel-lithium transition metal oxide layered cathode material, and can effectively improve the performance of the material.
In order to achieve the above object, the present invention provides the following technical solutions:
a spherical-like porous Ni-Co-Mn precursor is the hydroxide of Ni, Co and Mn and has the molecular formula of NixCoyMn1-x-y(OH)2, 0<x<1, 0<y<1, primary particles of the sphere-like porous nickel-cobalt-manganese precursor are hexagonal sheets, the thickness of the sphere-like porous nickel-cobalt-manganese precursor is 10 nm-100 nm, the side length of the sphere-like porous nickel-cobalt-manganese precursor is 10 nm-1 mu m, the particle size of secondary particles is 3-20 mu m, and the pore diameter of the secondary particles is 2-10 nm.
The invention also provides the sphere-like porous nickel-cobalt-manganese precursor and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding the mixed solution of nickel, cobalt and manganese, alkali liquor and a complexing agent into a reactor filled with a base solution in a protective atmosphere in a concurrent flow manner for carrying out coprecipitation reaction for 3-24 hours; the base solution is a mixed solution of a sodium hydroxide solution and ammonia water. And controlling the concentration of ammonia water in the base solution to be 8-12 g/L;
(2) and after the reaction is finished, continuing aging at a low stirring speed for 1-10 h. After aging is finished, repeatedly performing vacuum filtration on the obtained nickel-cobalt-manganese precursor solution, washing with deionized water for 3-5 times, and finally performing forced air drying at 80-120 ℃ for 10-30 h to obtain the sphere-like nickel-cobalt-manganese precursor. Wherein the coprecipitation reaction temperature is controlled to be 50-60 ℃, the reaction pH value is controlled to be 10-11.5, and the stirring speed is controlled to be 400-800 rpm.
Preferably, in the mixed solution of sodium hydroxide and ammonia water in the step (1), the molar ratio of the sodium hydroxide to the ammonia water is (0.6-2.0): 1, the concentration of the sodium hydroxide is 1-8 mol/L, and the concentration of the ammonia water is 0.4-10 mol/L.
Preferably, the total concentration of the mixed solution of nickel, cobalt and manganese transition metals in the step (1) is 1.0-2.5 mol/L.
Preferably, in the step (1), the molar flow ratio of the sodium hydroxide to the nickel-cobalt-manganese mixed solution is (1.0-5.0):1, and the molar ratio of the ammonia water to the nickel-cobalt-manganese mixed solution is (1.0-3.0): 1.
Preferably, the adding rate of the nickel-cobalt-manganese mixed solution in the step (1) is 0.32-0.96 mL/min, the adding rate of the complexing agent ammonia water is 0.16-0.48 mL/min, and the adding rate of the sodium hydroxide solution is 0.64-1.92 mL/min.
Preferably, the aging stirring speed in the step (2) is 50-150 rpm, and the aging time is 1-10 h.
The invention provides a sphere-like porous nickel-cobalt-manganese precursor and a preparation method thereof, wherein the precursor is hydroxide of nickel, cobalt and manganese, and the molecular formula is NixCoyMn1-x-y(OH)2, 0<x<1, 0<y<1. The spherical-like porous nickel-cobalt-manganese precursor is in a hexagonal sheet shape, the thickness of the primary particles is 10 nm-100 nm, the side length of the primary particles is 10 nm-1 mu m, the particle size of the secondary particles is 3-20 mu m, and the pore diameter of the secondary particles is 2-10 nm. The present invention takes into account Mn (OH)2Has a solubility product constant higher than that of Ni (OH)2、Co(OH)2The solubility product of the transition metal ion is two orders of magnitude larger, so that the ammonia water is added as a complexing agent, the precipitation speed of the transition metal ion is effectively reduced, and the joint precipitation of the transition metal ion and the hydroxyl ion is realized. In the coprecipitation reaction process, the technological conditions are continuously optimized by controlling the technological conditions such as pH, ammonia water concentration, stirring speed, feeding speed and the like, and the one-time synthesis is successfully carried outThe nickel-cobalt-manganese precursor has thinner flaky particles and spherical-like regular morphology of secondary particles. The lithium ion battery anode material prepared by the sphere-like porous nickel-cobalt-manganese precursor provided by the invention has excellent cycle stability and rate capability.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and embodiments.
FIG. 1 is an SEM image of a Ni-Co-Mn precursor prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a Ni-Co-Mn precursor prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a Ni-Co-Mn precursor prepared in example 3 of the present invention;
FIG. 4 is an SEM image of a Ni-Co-Mn precursor prepared in example 4 of the present invention;
FIG. 5 is an SEM image of a Ni-Co-Mn precursor prepared in example 5 of the present invention;
FIG. 6 is an SEM image of a Ni-Co-Mn precursor prepared in example 6 of the present invention;
FIG. 7 is a first charge-discharge curve diagram of the positive electrode material prepared in embodiments 5-7 of the present invention;
FIG. 8 is a graph showing the rate performance of the positive electrode material prepared in examples 5 to 7 of the present invention;
FIG. 9 is a graph of 1C cycle performance of the positive electrode materials prepared in examples 5-7 of the present invention;
Detailed Description
The invention provides a sphere-like porous nickel-cobalt-manganese precursor and a preparation method thereof, wherein the precursor is hydroxide of nickel, cobalt and manganese, and the molecular formula is NixCoyMn1-x-y(OH)2, 0<x<1, 0<y<1. The spherical-like porous nickel-cobalt-manganese precursor is in a hexagonal sheet shape, the thickness of the primary particles is 10 nm-100 nm, the side length of the primary particles is 10 nm-1 mu m, the particle size of the secondary particles is 3-20 mu m, and the pore diameter of the secondary particles is 2-10 nm.
The invention also provides a nickel-cobalt-manganese precursor and a preparation method thereof, wherein the nickel-cobalt-manganese precursor comprises the following steps: the method comprises the following steps:
(1) adding the mixed solution of nickel, cobalt and manganese, alkali liquor and a complexing agent into a reactor filled with a base solution in a protective atmosphere in a concurrent flow manner for carrying out coprecipitation reaction for 3-24 hours; the base solution is a mixed solution of a sodium hydroxide solution and ammonia water. And controlling the concentration of ammonia water in the base solution to be 8-12 g/L;
(2) and after the reaction is finished, continuing aging at a low stirring speed for 1-10 h. After aging is finished, repeatedly performing vacuum filtration on the obtained nickel-cobalt-manganese precursor solution, washing with deionized water for 3-5 times, and finally performing forced air drying at 80-120 ℃ for 10-30 h to obtain the sphere-like nickel-cobalt-manganese precursor. Wherein the coprecipitation reaction temperature is controlled to be 50-60 ℃, the reaction pH value is controlled to be 10-11.5, and the stirring speed is controlled to be 400-800 rpm.
The invention preferably provides a nickel-cobalt-manganese salt solution, a strong alkali solution and ammonia water respectively. In the nickel-cobalt-manganese salt mixed solution, the total concentration of nickel-cobalt-manganese ions is 1.0-3.0 mol/L, and more preferably 1.5-2.0 mol/L. In the nickel-cobalt salt mixed solution of the present invention, the nickel salt is one or more of nickel sulfate, nickel nitrate and nickel chloride, and more preferably a mixture of 2 thereof. The mass ratio of each nickel salt in the mixture is not specifically limited, and researchers in the field can freely select the nickel salt as long as the mass ratio of nickel ions is satisfied; in the nickel-cobalt salt mixed solution of the present invention, the cobalt salt is one or more of cobalt sulfate, cobalt nitrate and cobalt chloride, and more preferably a mixture of 2 thereof. The mass ratio of each cobalt salt in the mixture is not specifically limited, and researchers in the field can freely select the cobalt salt as long as the mass ratio of cobalt ions is satisfied; in the nickel-cobalt salt mixed solution of the present invention, the manganese salt is one or more of nickel sulfate, nickel nitrate and nickel chloride, and more preferably a mixture of 2 thereof. The mass ratio of each manganese salt in the mixture is not specifically limited in the present invention, and a researcher in the field can freely select the manganese salt as long as the mass ratio of the manganese ion is satisfied.
The alkali liquor is preferably a sodium hydroxide solution, the molar flow ratio of the sodium hydroxide to the nickel-cobalt-manganese mixed solution is (1.0-5.0):1, and more preferably (1.0-2.0): 1; the concentration of the filtrate is 2.0-8.0 mol/L, preferably 2.0-4.0 mol/L; the molar ratio of the ammonia water to the nickel-cobalt-manganese mixed solution is (1.0-3.0): 1, and preferably (1.0-1.2): 1.
The method comprises the steps of adding a nickel-cobalt-manganese mixed solution, a liquid reducing agent and a complexing agent into a reactor in a parallel flow manner to obtain a spherical-like porous nickel-cobalt-manganese precursor, wherein the pH of a reaction system is adjusted to 10-11.5 by using sodium hydroxide. In the invention, considering that the precipitation speed of nickel-cobalt-manganese ions and hydroxyl ions is too high, ammonia water is used as a complexing agent, so that the transition metal ions and the ammonium ions are preferentially complexed and then precipitated with the hydroxyl ions, thereby effectively reducing the coprecipitation reaction speed and realizing the co-precipitation of three transition metal ions of nickel-cobalt-manganese. And then under the dynamic balance of crystal nucleation and crystal growth, synthesizing the sphere-like nickel-cobalt-manganese precursor with good monodispersity of secondary particles and regular appearance. In the invention, the molecular formula of the nickel-cobalt-manganese precursor is preferably NixCoyMn1-x-y(OH)2, 0<x<1, 0<y<1。
The invention preferably adds the mixed solution of nickel, cobalt and manganese salts and the ammonia solution into the bottom liquid of the reactor in parallel.
The adding speed of the nickel-cobalt-manganese mixed solution is 0.16-1.60 mL/min, preferably 0.32-0.96 mL/min; the adding rate of the complexing agent ammonia water is 0.32-0.80 mL/min, preferably 0.16-0.48 mL/min, and the adding rate of the sodium hydroxide solution is 0.20-2.0 mL/min, preferably 0.64-1.92 mL/min.
In the present invention, the volume of the base solution is preferably (1.0 to 2.0) L.
The temperature of the coprecipitation reaction is 50-60 ℃, and preferably 55 ℃.
After the coprecipitation reaction is finished, the mixture is aged to ensure that the coprecipitation reaction is fully carried out, the particle morphology is more regular, and the sphere-like porous nickel-cobalt-manganese precursor is obtained. The temperature of the aging process is consistent with that of the reaction process, and the stirring speed is 50-150 rpm, preferably 50-100 rpm. The aging time is 1-10 h, preferably 1-3 h.
And after the aging reaction is finished, performing solid-liquid separation on the obtained insoluble precipitate in a vacuum filtration mode and other modes, washing for 3-5 times by using deionized water, using 2L of water for each washing, and drying to obtain the sphere-like nickel-cobalt-manganese precursor. The invention has no special requirements on the solid-liquid separation and washing modes, and the technical personnel in the field can adopt any mode to achieve the purposes of solid-liquid separation and washing.
And after washing, putting the washed precipitate in an air-blast drying oven for drying to obtain the sphere-like porous nickel-cobalt-manganese precursor. The drying temperature is 80-120 ℃, and preferably 80-100 ℃. The drying time is 10-30 h, preferably 15-25 h. The invention has no special requirements on the drying mode, and the person skilled in the art can select the drying mode at will to achieve the purpose of drying.
The invention also provides a preparation method of the cathode material, which is prepared by mixing the nickel-cobalt-manganese precursor prepared by the method with lithium salt. The preparation method is preferably as follows:
and grinding, mixing and uniformly preparing lithium by the prepared nickel-cobalt-manganese precursor and lithium salt to obtain a lithium-prepared precursor.
The lithium source in the present invention is lithium hydroxide monohydrate or lithium carbonate, and preferably lithium hydroxide monohydrate. The molar ratio of the lithium hydroxide to the nickel-cobalt-manganese precursor is preferably (1.01-1.10): 1, and more preferably (1.05-1.08): 1.
And (3) placing the lithium-prepared precursor in a muffle furnace to carry out two-stage roasting in air atmosphere: the calcination temperature in the first stage is preferably 400-500 ℃, and more preferably 450-480 ℃. The calcination time is preferably 3-5 h, and more preferably 4-5 h. The heating rate is preferably 1-5 ℃/min, and more preferably 1-2 ℃/min; the calcination temperature in the second stage is preferably 700-900 ℃, and more preferably 800-850 ℃. The calcination time is preferably 10-15 h, and more preferably 12-15 h. The heating rate is preferably 3-10 ℃/min, and more preferably 3-5 ℃/min.
In order to further explain the present invention, the following detailed description is made on the spheroidal porous nickel-cobalt-manganese precursor and the preparation method thereof in combination with the embodiments, and the scope of the present invention is not limited by the following examples.
Example 1
Nickel sulfate, cobalt sulfate and manganese sulfate which are weighed according to a molar ratio of 0.8:0.1:0.1 and have certain mass are dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be 11. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) respectively pumping the three solutions A, B, C into a continuous reaction kettle CSTR according to the speed of 0.64 ml/min, 1.28 ml/min and 0.32 ml/min in parallel, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =11 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuing stirring and aging for 1 h. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.8Co0.1Mn0.1(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in example 1 was analyzed by scanning electron microscopy. Fig. 1 shows a scanning electron micrograph of a spherical-like nickel-porous cobalt-manganese precursor, fig. 1(a) shows a scanning electron micrograph at a magnification of 5000, and fig. 1(b) shows a scanning electron micrograph at a magnification of 30000. It can be obviously observed from a scanning electron micrograph that the nickel-cobalt-manganese precursor prepared in the embodiment 1 is spheroidal secondary particles formed by stacking primary flaky particles, the thickness of the primary flaky particles is 50-100 nm, the particle size of the secondary particles is 3-5 μm, the sphericity is high, the uniformity is good, and the fluidity is good.
Example 2
Nickel sulfate, cobalt sulfate and manganese sulfate in certain mass are weighed according to the molar ratio of 0.6:0.2:0.2 and dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be 11. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) respectively pumping the three solutions A, B, C into a continuous reaction kettle CSTR according to the parallel flow rate of 2.40 ml/min, 4.80 ml/min and 1.20 ml/min, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =11 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuing stirring and aging for 1 h. Finally, the insoluble precipitate obtained is filtered off under vacuumSolid-liquid separation, washing with deionized water for 5 times, drying in a blast oven at 80 deg.C for 20 h to obtain spherical porous Ni-Co-Mn precursor Ni0.6Co0.2Mn0.2(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in example 2 was analyzed by scanning electron microscopy. Fig. 2 shows a scanning electron micrograph of the spheroidal porous nickel-cobalt-manganese precursor, and fig. 2 shows the scanning electron micrograph at a magnification of 20000 times. It can be obviously observed from a scanning electron micrograph that the nickel-cobalt-manganese precursor prepared in example 2 is spheroidal secondary particles formed by stacking primary fine acicular particles, the thickness of the primary flaky particles is 10 nm-50 nm, the particle size of the secondary particles is 5-10 μm, the sphericity is good, the uniformity is good, and the fluidity is good.
Grinding and uniformly mixing the nickel-cobalt-manganese precursor synthesized in the embodiment 2 according to the molar ratio of lithium hydroxide to the nickel-cobalt-manganese precursor of 1.05:1, and then placing the mixture in a muffle furnace in an air atmosphere for presintering for 5 hours at 450 ℃ in a first stage; then calcining at 880 ℃ for 12 h at a second stage; after calcining and sintering, naturally cooling to room temperature along with the furnace to finally obtain the nickel-cobalt-manganese cathode material LiNi0.60Co0.2Mn0.2O2。
The result shows that the material provided by the invention has the initial capacity of 208.7 mAh g of 0.1C-1And the discharge capacity under 5C multiplying power can reach 165.0 mAh g-1. The material has excellent high-rate performance.
Example 3
Nickel sulfate, cobalt sulfate and manganese sulfate in certain mass are weighed according to the molar ratio of 0.6:0.2:0.2 and dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be 11. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) respectively pumping the three solutions A, B, C into a continuous reaction kettle CSTR according to the speed of 1.28 ml/min, 2.56 ml/min and 0.64 ml/min in parallel, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =11 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuing stirring and aging for 1 h. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.6Co0.2Mn0.2(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in example 3 was analyzed by scanning electron microscopy. Fig. 3 shows a scanning electron micrograph of the spheroidal porous nickel-cobalt-manganese precursor, and fig. 3 shows the scanning electron micrograph at a magnification of 100000 times. It can be obviously observed from the scanning electron micrograph that compared with the precursor prepared in example 2, the primary particles of the nickel-cobalt-manganese precursor prepared in example 3 are transformed into flakes, and the sphericity is relatively reduced.
Example 4
Nickel sulfate, cobalt sulfate and manganese sulfate which are weighed according to a molar ratio of 0.65:0.15:0.20 and have certain mass are dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be 11. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) respectively pumping the three solutions A, B, C into a continuous reaction kettle CSTR at the speed of 0.80 ml/min, 1.60 ml/min and 0.40 ml/min in parallel, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =11 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuing stirring and aging for 1 h. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.65Co0.15Mn0.20(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in example 4 was analyzed by scanning electron microscopy. Fig. 4 shows a scanning electron micrograph of the spheroidal porous nickel-cobalt-manganese precursor, and fig. 4 shows the scanning electron micrograph at a magnification of 50000 times. It can be very obviously observed from a scanning electron micrograph that compared with the nickel-cobalt-manganese precursor of the embodiments 2 and 3, the primary nano flaky particles of the nickel-cobalt-manganese precursor prepared in the embodiment 4 are thicker, the particle diameter of the secondary particles of the particles is 3-6 μm, the sphericity becomes worse, and the fluidity becomes worse.
Example 5
Nickel sulfate, cobalt sulfate and manganese sulfate which are weighed according to a molar ratio of 0.32:0.04:0.0.44 and have certain mass are dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be maintained at 10. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) co-currently pumping the three solutions A, B, C into a continuous reaction kettle CSTR according to the speed of 0.64 ml/min, 1.28 ml/min and 0.32 ml/min respectively, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =10 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuously stirring and aging for 1 h. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.32Co0.04Mn0.44(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in the embodiment 5 was analyzed by a scanning electron microscope. Fig. 5 shows a scanning electron micrograph of the spheroidal porous nickel-cobalt-manganese precursor. FIG. 5a shows a SEM image at a magnification of 5000, and FIG. 5b shows a SEM image at a magnification of 20000. It can be obviously observed from a scanning electron microscope photo that the nickel-cobalt-manganese precursor prepared in the embodiment 5 is spheroidal secondary particles formed by stacking primary flaky particles, the primary flaky particles are thinner, the particle size of the secondary particles is 3-10 μm, the sphericity is high, the morphology is regular, the uniformity is good, and the flowability is good.
Example 6
Nickel sulfate, cobalt sulfate and manganese sulfate which are weighed according to a molar ratio of 0.32:0.04:0.0.44 and have certain mass are dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be maintained at 10.5. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
And (3) co-currently pumping the A, B, C solutions into a continuous reaction kettle CSTR according to the speed of 0.64 ml/min, 1.28 ml/min and 0.32 ml/min respectively, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt solution to be 2:1 in the feeding process, keeping the pH =10.5 +/-0.02 all the time, adjusting the stirring speed to be 50 rpm after the feeding is finished, and continuously stirring and aging for 1 h. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.32Co0.04Mn0.44(OH)2。
The morphology of the spheroidal porous nickel-cobalt-manganese precursor prepared in the embodiment 6 was analyzed by a scanning electron microscope. Fig. 6 shows a scanning electron micrograph of the spheroidal porous nickel-cobalt-manganese precursor. FIG. 6a shows a SEM image at a magnification of 5000, and FIG. 6b shows a SEM image at a magnification of 20000. It can be obviously observed from a scanning electron microscope photo that the nickel-cobalt-manganese precursor prepared in the embodiment 6 is a sphere-like secondary particle formed by stacking primary flaky particles, the primary flaky particles are relatively thin, the particle size of the secondary particle is 3-10 μm, the sphericity is high, the morphology is regular, the uniformity is good, and the fluidity is good.
Example 7
Nickel sulfate, cobalt sulfate and manganese sulfate which are weighed according to a molar ratio of 0.32:0.04:0.0.44 and have certain mass are dissolved in deionized water to prepare a metal salt solution A with the total concentration of nickel, cobalt and manganese ions of 2 mol/L.
Weighing a certain mass of sodium hydroxide, and dissolving the sodium hydroxide in deionized water to prepare a sodium hydroxide precipitator solution B with the concentration of 4 mol/L.
Deionized water is added into concentrated ammonia water with a certain volume to prepare a dilute ammonia water solution C with the concentration of 2.8 mol/L.
Deionized water was added to a volume of concentrated ammonia to dilute 1.5L of ammonia solution and added to a 5L continuous coprecipitation reactor (CSTR) as a base solution.
And stirred at a certain speed and a water bath was performed to heat the reaction kettle to 55 ℃. After the reaction temperature stabilized, a certain amount of 4 mol/L sodium hydroxide precipitant solution was manually added, and the pH of the base solution was adjusted to be 11. At this time, high-purity nitrogen gas is introduced as a shielding gas to prevent Mn2+And Ni2+Oxidation of (2). And introducing protective gas for 30 min to remove dissolved oxygen in the reaction kettle.
Pumping the A, B, C solutions into a continuous reaction kettle CSTR at the speed of 0.64 ml/min, 1.28 ml/min and 0.32 ml/min in parallel respectively, controlling the molar ratio of ammonia water to transition metal salt to be 1.2:1 and the molar flow ratio of sodium hydroxide to transition metal salt to be 2:1 in the feeding process, keeping the pH =11 +/-0.02 all the time, and feedingAfter completion, the stirring speed was adjusted to 50 rpm, and stirring and aging were continued for 1 hour. Finally, carrying out vacuum filtration solid-liquid separation on the obtained insoluble precipitate, washing with deionized water for 5 times, and drying in a blowing oven at 80 ℃ for 20 h to obtain a spheroidal porous nickel-cobalt-manganese precursor Ni0.32Co0.04Mn0.44(OH)2。
Example 8
The nickel-cobalt-manganese precursors synthesized in the above embodiments 5, 6 and 7 are ground and mixed uniformly in a molar ratio of lithium hydroxide to nickel-cobalt-manganese precursor of 1.05:1, 1.05:1 and 1.05:1, and then placed in a muffle furnace in an air atmosphere at 480 ℃ for a first-stage presintering for 5 hours; then calcining at 800 ℃ for 12 h at a second stage at high temperature; after calcining and sintering, naturally cooling to room temperature along with the furnace to finally obtain the nickel-cobalt-manganese cathode material Li1.2Ni0.32Co0.04Mn0.44O2。
Fig. 7 is a first charge-discharge curve diagram of the cathode material obtained by the spheroidal nickel-cobalt-manganese precursors prepared in examples 5, 6 and 7, and it can be seen from the diagram that the primary flaky particles of the nickel-cobalt-manganese precursor are relatively thin and the secondary particles have regular shapes, and the prepared cathode material has more excellent first specific capacity. Fig. 8 is a graph of 1C cycle performance of the obtained cathode materials of the spheroidal nickel-cobalt-manganese precursors prepared in examples 5, 6 and 7. Fig. 9 is a rate performance graph of the obtained cathode material of the spheroidal porous nickel-cobalt-manganese precursor prepared in example 5, example 6 and example 7. The result shows that the nickel-cobalt-manganese cathode material prepared by the invention has excellent cycling stability and rate capability.
The foregoing is directed to the preferred embodiment of the present invention, and it is understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (7)
1. The spherical-like porous nickel-cobalt-manganese precursor is characterized in that the precursor is hydroxide of nickel, cobalt and manganese, and molecules of the hydroxideIs of the formula NixCoyMn1-x-y(OH)2, 0<x<1, 0<y<1, primary particles of the sphere-like porous nickel-cobalt-manganese precursor are hexagonal sheets, the thickness of the sphere-like porous nickel-cobalt-manganese precursor is 10 nm-100 nm, the side length of the sphere-like porous nickel-cobalt-manganese precursor is 10 nm-1 mu m, the particle size of secondary particles is 3-20 mu m, and the pore diameter of the secondary particles is 2-10 nm.
2. The preparation method of the quasi-spherical porous nickel-cobalt-manganese precursor of claim 1, which is characterized by comprising the following steps:
(1) adding the mixed solution of nickel, cobalt and manganese, alkali liquor and a complexing agent into a reactor filled with a base solution in a protective atmosphere in a concurrent flow manner for carrying out coprecipitation reaction for 3-24 hours; the base solution is a mixed solution of a sodium hydroxide solution and ammonia water. And controlling the concentration of ammonia water in the base solution to be 8-12 g/L;
(2) and after the reaction is finished, continuing aging at a low stirring speed for 1-10 h. After aging is finished, repeatedly performing vacuum filtration on the obtained nickel-cobalt-manganese precursor solution, washing with deionized water for 3-5 times, and finally performing forced air drying at 80-120 ℃ for 10-30 h to obtain the sphere-like nickel-cobalt-manganese precursor.
Wherein the coprecipitation reaction temperature is controlled to be 50-60 ℃, the reaction pH value is controlled to be 10-11.5, and the stirring speed is controlled to be 400-800 rpm.
3. The preparation method according to claim 2, wherein in the mixed solution of sodium hydroxide and ammonia water in the step (1), the molar ratio of sodium hydroxide to ammonia water is (0.6-2.0): 1, the concentration of sodium hydroxide is 1-8 mol/L, and the concentration of ammonia water is 0.4-10 mol/L.
4. The preparation method according to claim 2, wherein the total concentration of the mixed solution of nickel-cobalt-manganese transition metals in the step (1) is 1.0-3.0 mol/L.
5. The preparation method according to claim 2, wherein the molar flow ratio of the sodium hydroxide to the nickel-cobalt-manganese mixed solution in the step (1) is (1.0-5.0):1, and the molar ratio of the ammonia water to the nickel-cobalt-manganese mixed solution is (1.0-3.0): 1.
6. The preparation method of claim 2, wherein the rate of adding the nickel-cobalt-manganese mixed solution in the step (1) is 0.32-0.96 mL/min, the rate of adding the complexing agent ammonia water is 0.16-0.48 mL/min, and the rate of adding the sodium hydroxide solution is 0.64-1.92 mL/min.
7. The preparation method according to claim 2, wherein the aging stirring speed in the step (2) is 50 to 150 rpm.
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