CN116741982A - Manganese nickel cobalt-based lithium ion battery anode material and preparation method thereof - Google Patents
Manganese nickel cobalt-based lithium ion battery anode material and preparation method thereof Download PDFInfo
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- CN116741982A CN116741982A CN202310833952.0A CN202310833952A CN116741982A CN 116741982 A CN116741982 A CN 116741982A CN 202310833952 A CN202310833952 A CN 202310833952A CN 116741982 A CN116741982 A CN 116741982A
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- manganese
- cobalt
- nickel
- lithium ion
- positive electrode
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 239000010405 anode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 48
- 239000011163 secondary particle Substances 0.000 claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- -1 salt ions Chemical class 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 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 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000012716 precipitator Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000010406 cathode material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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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- Inorganic Chemistry (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Manganese nickel cobalt-based lithium ion battery positive electrode material and preparation method thereof, and chemical formula of the prepared manganese nickel cobalt-based lithium ion positive electrode material is LiMn a Ni b Co c O 2 Wherein a+b+c=1, and the microscopic morphology of the spherical secondary particles is that primary particles in the spherical secondary particles are radially distributed and grown in a radial alignment in a rod shape. The preparation method comprises the following steps: a precursor is obtained by adopting a hydrothermal method, urea is used as a precipitator, a dispersing agent is added to regulate the growth direction of the precipitate, a manganese nickel cobalt-based precursor with primary particles growing in a radial manner is obtained, and then the precursor is preparedMixing with a lithium source compound, and calcining at high temperature to obtain the manganese nickel cobalt-based lithium ion anode material with the microscopic morphology. According to the invention, the primary particle crystal growth trend and shape of the manganese-nickel-cobalt-based precursor are regulated and controlled by controlling the addition of the dispersing agent, the growth order of the internal structure of the secondary particles is improved, the grain boundary energy and the lithium ion diffusion resistance are reduced, and the multiplying power performance and the long-cycle stability of the material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of material synthesis, relates to a lithium ion battery positive electrode material and a preparation method thereof, and particularly relates to a manganese nickel cobalt-based lithium ion battery positive electrode material with primary particles radially distributed in spherical secondary particles and a preparation method thereof.
Background
The positive electrode material of the lithium ion battery is one of important factors affecting the performance and safety of the lithium ion battery, and the development thereof has been receiving a great deal of attention. Currently common cathode materials include lithium cobaltate, lithium manganate, lithium iron phosphate and manganese nickel cobalt/nickel cobalt aluminum ternary materials. The practical available capacity of lithium cobaltate is only about half of the theoretical capacity due to the damage of excessive lithium removal to the self structure during deep charging. Although the lithium manganate and lithium iron phosphate materials have better cycling stability, the energy density is lower, and the further development of the lithium manganate and lithium iron phosphate materials is limited. The manganese-nickel-cobalt ternary anode material has higher energy density, and the specific capacity of the manganese-nickel-cobalt ternary anode material can reach 200mAh/g, so that the manganese-nickel-cobalt ternary anode material is widely studied. However, the material has low conductivity, low high-current discharge and low rate performance, and has the phenomenon of serious ground electrode/electrolyte side reaction, so that the capacity is rapidly attenuated in the circulation process.
In order to solve the problems, researchers adopt a surface modification or doping modification method to inhibit side reactions of materials and electrolyte and irreversible phase change of materials, but the problems of poor cycle stability and poor rate performance cannot be essentially solved. The positive electrode material with primary particles distributed radially is prepared by controlling the growth process of the material, has excellent lithium ion transmission capacity and good deformation resistance mechanical property, and becomes an important development direction of the shape design of the future battery material. Therefore, in the precursor synthesis process, a primary particle radioactive growth structure is obtained, and the method is greatly helpful for improving the multiplying power and the cycling stability of the manganese-nickel-cobalt-based ternary positive electrode material, and has great significance for promoting the development of the positive electrode material industry.
Disclosure of Invention
The invention aims to provide a manganese nickel cobalt-based lithium ion battery anode material with primary particles radially distributed in spherical secondary particles and a preparation method thereof, and solves the problem of poor multiplying power and cycle stability of the battery material.
The preparation method comprises the steps of obtaining a precursor by adopting a hydrothermal method, utilizing urea as a precipitator, regulating and controlling the growth direction of the precipitate through a dispersing agent to obtain a manganese nickel cobalt-based precursor with primary particles growing radially, mixing the precursor with a lithium source compound, and calcining at a high temperature to obtain the manganese nickel cobalt-based lithium ion positive electrode material with primary particles radially distributed in the spherical secondary particles. The chemical general formula of the prepared manganese nickel cobalt-based lithium ion battery anode material is LiMn a Ni b Co c O 2 Wherein a+b+c=1, the microstructure of the particles is that primary particles in the spherical secondary particles grow in a radial alignment of a rod shape. According to the invention, the primary particle crystal growth trend and shape of the manganese-nickel-cobalt-based precursor are regulated and controlled by controlling the addition of the dispersing agent, the growth order of the internal structure of the secondary particles is improved, the grain boundary energy and the lithium ion diffusion resistance are reduced, and the multiplying power performance and the long-cycle stability of the material are effectively improved.
The preparation method comprises the following specific steps:
the manganese nickel cobalt-based lithium ion battery anode material with primary particles radially distributed in spherical secondary particles is characterized by comprising the following components:
1. the chemical general formula of the positive electrode material is LiMn a Ni b Co c O 2 Wherein a+b+c=1, 0.ltoreq.b.ltoreq.a, 0.ltoreq.c.ltoreq.a, a<1。
2. The microcosmic appearance of the manganese nickel cobalt based lithium ion positive electrode material is that primary particles in spherical secondary particles are grown in a rod-shaped radial directional arrangement.
The preparation method of the manganese nickel cobalt-based lithium ion positive electrode material with primary particles radially distributed in spherical secondary particles comprises the following steps:
firstly, respectively weighing a manganese source compound, a nickel source compound and a cobalt source compound according to a certain molar ratio, dissolving the manganese source compound, the nickel source compound and the cobalt source compound in a deionized solvent, and then adding a certain amount of urea and a dispersing agent. The liquid was placed in a closed reactor and protected under an argon atmosphere. The ultrasonic wave makes the raw materials fully dissolved. And then placing the mixture at 60-90 ℃ for 48-72 h, filtering the precipitate, repeatedly washing to remove impurities, and drying to obtain the manganese-nickel-cobalt-based precursor for directional growth of primary particles in the spherical secondary particles. The method can ensure that the obtained precursor is distributed in the radial direction of primary particles inside spherical secondary particles.
Weighing a lithium source compound and manganese nickel cobalt-based precursors with radial distribution of primary particles in the spherical secondary particles according to a molar ratio, fully grinding and uniformly mixing the manganese nickel cobalt-based precursors, putting the manganese nickel cobalt-based precursors into a muffle air atmosphere, heating the mixture from room temperature to 400-600 ℃, heating the mixture at a heating rate of 5-10 ℃/min, preserving the heat for 2-6 h, heating the mixture to 700-1000 ℃ at the same heating rate, and calcining the mixture for 6-16 h to obtain the manganese nickel cobalt-based lithium ion anode material with radial distribution of the primary particles in the spherical secondary particles.
The solvent in the preparation method is one or more of deionized water, ethanol and the like; the dispersing agent is cetyl trimethyl ammonium bromide and/or dodecyl trimethyl ammonium bromide.
The concentration of metal salt ions in the liquid prepared in the first step in the preparation method is 0.1-0.5 mol/L, and the molar ratio of the metal salt ions to urea is 1: 10-15, wherein the molar ratio of metal salt ions to the dispersing agent is 30-80: 1.
the manganese source compound in the preparation method is one or a mixture of a plurality of manganese sulfate, manganese acetate, manganese oxalate or manganese nitrate.
The nickel source compound in the preparation method is one or a mixture of a plurality of nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate.
In the preparation method, the cobalt source compound is one or a mixture of a plurality of cobalt sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate.
In the preparation method, the lithium source is one or a mixture of more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate and lithium carbonate. When the selected lithium source is calcined at high temperature, hetero atoms except lithium and oxygen can be removed in a gas form under high-temperature decomposition, so that the introduction of the hetero atoms is avoided.
The mixing mode in the preparation method is liquid phase mixing or solid phase mixing, and the calcining atmosphere is air.
The invention has the following beneficial effects:
(1) The invention provides a manganese nickel cobalt-based lithium ion battery anode material with primary particles radially distributed in spherical secondary particles and a preparation method thereof. In the precursor preparation process, the radial growth arrangement mode of the primary particles is regulated and controlled by controlling the addition of the dispersing agent, and finally, the manganese nickel cobalt-based lithium ion battery anode material with compact inside and radial distribution of the primary particles is obtained.
(2) The preparation method disclosed by the invention is simple in process, the rate performance is obviously and reliably improved, and the prepared manganese nickel cobalt-based lithium ion battery positive electrode material with primary particles radially distributed in spherical secondary particles has excellent rate performance and long-cycle stability.
Drawings
Fig. 1 is an XRD pattern of a positive electrode material of a manganese nickel cobalt-based lithium ion battery in which primary particles inside spherical secondary particles prepared in example 1 of the present invention are radially distributed and a comparative sample prepared in comparative example 1.
Fig. 2 is an SEM image of a positive electrode material of a manganese nickel cobalt-based lithium ion battery in which primary particles inside spherical secondary particles prepared in example 1 of the present invention are radially distributed, and a comparative sample prepared in comparative example 1.
Fig. 3 is a cross-sectional SEM image of the inside of secondary particles of a manganese nickel cobalt-based lithium ion battery positive electrode material in which primary particles are radially distributed inside spherical secondary particles prepared in example 1 prepared according to the present invention.
Fig. 4 is a graph showing the cycle performance (at 1C magnification) of the positive electrode material of the manganese nickel cobalt-based lithium ion battery in which primary particles inside the spherical secondary particles prepared in example 1 according to the present invention are radially distributed and the comparative sample prepared in comparative example 1.
Fig. 5 is a graph showing the rate performance of the positive electrode material of the manganese nickel cobalt-based lithium ion battery with radial distribution of primary particles inside the spherical secondary particles prepared in example 1 of the present invention and the comparative sample prepared in comparative example 1.
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
Example 1
Nickel acetate, cobalt acetate and manganese acetate were mixed according to 1:1:1 in a molar ratio of 100mL and 0.1 mol/L. Then adding urea, wherein the molar ratio of the urea to the metal ions is 10:1, 0.05g of CTAB was added. The liquid was placed in a closed reactor and protected under an argon atmosphere. The raw materials are fully dissolved by ultrasonic treatment for half an hour. Then placing the mixture in a blast drying oven at 80 ℃ for 72 hours, filtering and drying to obtain a precursor.
And weighing a lithium source compound and a manganese nickel cobalt-based precursor with radial distribution of primary particles in the spherical secondary particles according to a molar ratio, wherein the proportion is 1.1:1, fully grinding and uniformly mixing, then placing the manganese nickel cobalt-based precursor into a muffle furnace air atmosphere, heating to 500 ℃ from room temperature, keeping the temperature at a heating rate of 5 ℃/min, keeping the temperature at 5 h, heating to 850 ℃ at the same heating rate, and calcining for 12 hours to obtain the manganese nickel cobalt-based lithium ion battery anode material with radial distribution of the primary particles in the spherical secondary particles.
Comparative example 1:
nickel acetate, cobalt acetate and manganese acetate were mixed according to 1:1:1 in a molar ratio of 100mL and 0.1 mol/L. Then adding urea, wherein the ratio of the urea to the metal ions is 10:1. the liquid was placed in a closed reactor and protected under an argon atmosphere. The raw materials are fully dissolved by ultrasonic treatment for half an hour. Then placing the mixture in a blast drying oven at 80 ℃ for 72 hours, filtering and drying to obtain a precursor.
And weighing a lithium source compound and a manganese nickel cobalt-based precursor with radial distribution of primary particles in the spherical secondary particles according to a molar ratio, wherein the proportion is 1.1:1, fully grinding and uniformly mixing, then placing the manganese nickel cobalt-based precursor into a muffle furnace air atmosphere, heating to 500 ℃ from room temperature, keeping the temperature at a heating rate of 5 ℃/min, keeping the temperature at 5 h, heating to 850 ℃ at the same heating rate, and calcining for 12 hours to obtain the manganese nickel cobalt-based lithium ion battery anode material with radial distribution of the primary particles in the spherical secondary particles.
XRD of the manganese nickel cobalt-based lithium ion battery positive electrode material with radially distributed primary particles inside the spherical secondary particles prepared in example 1 and the comparative sample prepared in comparative example 1 are shown in figure 1, and the 003 peak intensity of the manganese nickel cobalt-based lithium ion positive electrode material with radially distributed primary particles inside the spherical secondary particles prepared is obviously increased, which indicates that the radially distributed manganese nickel cobalt-based lithium ion battery positive electrode material selectively grows and is beneficial to the diffusion of lithium ions. SEM of the manganese nickel cobalt-based lithium ion battery positive electrode material in which primary particles inside the spherical secondary particles prepared in example 1 were radially distributed and the comparative sample prepared in comparative example 1 are shown in fig. 2. The comparison sample shows a rodlike peanut-like shape, and the diameter of the spherical secondary particles of the manganese nickel cobalt-based lithium ion battery positive electrode material is about 8-12 microns, wherein the primary particles in the spherical secondary particles are radially distributed. Fig. 3 is an SEM image of the distribution of primary particles in the positive electrode material of the manganese nickel cobalt-based lithium ion battery, in which primary particles in the spherical secondary particles are radially distributed, and it can be seen that the primary particles are radially arranged in a rod shape. The cycling performance of the manganese nickel cobalt-based lithium ion battery cathode material with radially distributed primary particles inside the spherical secondary particles prepared in example 1 and the comparative sample prepared in comparative example 1 is shown in fig. 4, it can be seen that the comparative sample has a retention rate of only 46% after 300 cycles at 1C, and the retention rate of the manganese nickel cobalt-based lithium ion battery cathode material with radially distributed primary particles inside the spherical secondary particles is 81%. The ratio properties of the manganese nickel cobalt based lithium ion battery positive electrode material with radially distributed primary particles inside the spherical secondary particles prepared in example 1 and the comparative sample prepared in comparative example 1 are shown in fig. 5, and the specific capacities of the manganese nickel cobalt based lithium ion positive electrode material with radially distributed primary particles inside the spherical secondary particles at 0.2, 0.5, 1, 2, 5 and 10C are 194.8, 187.3, 180.2, 171.8, 157.0 and 141.7 mAh/g, respectively, while the specific capacities of the comparative sample at 0.2, 0.5, 1, 2, 5 and 10C are 191.6, 183.5, 174.9, 164.8, 146.7 and 122.8 mAh/g, respectively, which indicates that the manganese nickel cobalt based lithium ion positive electrode material with radially distributed primary particles inside the spherical secondary particles shows excellent large current discharge capacity and ratio properties.
Claims (10)
1. A manganese nickel cobalt-based lithium ion battery anode material is characterized in that the chemical general formula of the anode material is LiMn a Ni b Co c O 2 Wherein a+b+c=1, 0.ltoreq.b.ltoreq.a, 0.ltoreq.c.ltoreq.a, a<1, a step of; the microcosmic appearance of the manganese nickel cobalt-based lithium ion positive electrode material is that primary particles in spherical secondary particles are radially distributed and are in radial directional arrangement and growth in a rod shape.
2. A method for preparing the positive electrode material of the manganese-nickel-cobalt-based lithium ion battery as claimed in claim 1, which is characterized by comprising the following steps:
firstly, respectively weighing a manganese source compound, a nickel source compound and a cobalt source compound according to a certain molar ratio, dissolving the manganese source compound, the nickel source compound and the cobalt source compound in a solvent, and then adding a certain amount of urea and a dispersing agent; placing the liquid in a closed reactor, protecting under argon atmosphere, and fully dissolving the raw materials by ultrasonic; then placing for 48-72 h at 60-90 ℃, finally filtering the precipitate, repeatedly washing to remove impurities, and drying to obtain a manganese-nickel-cobalt-based precursor for directional growth of primary particles in the spherical secondary particles; the obtained precursor is radially distributed in the primary particles inside the spherical secondary particles;
and step two, weighing a lithium source compound and a manganese nickel cobalt-based precursor with radially distributed primary particles in the spherical secondary particles according to a molar ratio, fully grinding and uniformly mixing the manganese nickel cobalt-based precursor with the proportion of 1-1.2:1, putting the mixture into the air atmosphere of a muffle furnace, and carrying out a heating and calcining process to obtain the manganese nickel cobalt-based lithium ion positive electrode material with radially distributed primary particles in the spherical secondary particles.
3. The method for preparing the positive electrode material of the manganese-nickel-cobalt-based lithium ion battery according to claim 2, wherein the heating and calcining process in the second step is specifically as follows: and (3) raising the temperature from room temperature to 400-600 ℃, keeping the temperature for 2-6 hours at a temperature raising rate of 5-10 ℃/min, raising the temperature to 700-1000 ℃ at the same temperature raising rate, and calcining for 6-16 hours.
4. The method for preparing a positive electrode material of a manganese-nickel-cobalt-based lithium ion battery according to claim 2, wherein the solvent is one or two of deionized water and ethanol; the dispersing agent is cetyl trimethyl ammonium bromide and/or dodecyl trimethyl ammonium bromide.
5. The method for preparing a positive electrode material of a manganese-nickel-cobalt-based lithium ion battery according to claim 2, wherein the concentration of metal salt ions in the liquid prepared in the first step is 0.1-0.5 mol/L, and the molar ratio of the metal salt ions to urea is 1: 10-15, wherein the molar ratio of metal salt ions to the dispersing agent is 30-80: 1.
6. the method for preparing a manganese nickel cobalt-based lithium ion battery positive electrode material according to claim 2, wherein the manganese source compound is a mixture of one or more of manganese sulfate, manganese acetate, manganese oxalate and manganese nitrate.
7. The method for preparing a manganese nickel cobalt based lithium ion battery positive electrode material according to claim 2, wherein the nickel source compound is a mixture of one or more of nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate.
8. The method for preparing a manganese-nickel-cobalt-based lithium ion battery positive electrode material according to claim 2, wherein the cobalt source compound is a mixture of one or more of cobalt sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate.
9. The method for preparing the positive electrode material of the manganese-nickel-cobalt-based lithium ion battery according to claim 2, wherein the lithium source is one or a mixture of more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate and lithium carbonate, and the selected lithium source is used for removing hetero atoms except lithium and oxygen in a gas form under high-temperature decomposition during high-temperature calcination, so that the introduction of the hetero atoms is avoided.
10. The method for preparing the positive electrode material of the manganese-nickel-cobalt-based lithium ion battery according to claim 2, wherein the mixing mode is liquid phase mixing or solid phase mixing, and the calcining atmosphere is air.
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